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WO2013018473A1 - Feuille métallique comportant une couche de revêtement et procédé de fabrication associé, électrode de cellule secondaire et procédé de fabrication associé, et cellule secondaire au lithium-ion - Google Patents

Feuille métallique comportant une couche de revêtement et procédé de fabrication associé, électrode de cellule secondaire et procédé de fabrication associé, et cellule secondaire au lithium-ion Download PDF

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Publication number
WO2013018473A1
WO2013018473A1 PCT/JP2012/066439 JP2012066439W WO2013018473A1 WO 2013018473 A1 WO2013018473 A1 WO 2013018473A1 JP 2012066439 W JP2012066439 W JP 2012066439W WO 2013018473 A1 WO2013018473 A1 WO 2013018473A1
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WIPO (PCT)
Prior art keywords
layer
active material
metal foil
coating layer
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/066439
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English (en)
Japanese (ja)
Inventor
了一 小黒
直文 徳原
勇 曹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Furukawa Electric Co Ltd
Original Assignee
Furukawa Electric Co Ltd
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Filing date
Publication date
Application filed by Furukawa Electric Co Ltd filed Critical Furukawa Electric Co Ltd
Priority to KR1020147005454A priority Critical patent/KR20140051375A/ko
Priority to CN201280037317.1A priority patent/CN103718346A/zh
Priority to JP2012551413A priority patent/JP5435519B2/ja
Publication of WO2013018473A1 publication Critical patent/WO2013018473A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0628—In vertical cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a metal foil with a coating layer that is particularly excellent as an electrode for a lithium ion secondary battery. Moreover, this invention relates to the electrode for secondary batteries using the said metal foil with a coating layer, and the lithium ion secondary battery using this electrode.
  • Lithium ion secondary batteries are used as an indispensable power source for mobile phones, mobile terminals, laptop computers and the like.
  • Copper foil is generally used for the current collector on the negative electrode side of the lithium ion secondary battery.
  • carbon particles are applied as a negative electrode active material layer on the surface of a copper foil having a smooth front and back, and further pressed to form a negative electrode.
  • An electrolytic copper foil having a small difference in surface roughness between the front and back surfaces is produced by appropriately selecting a water-soluble polymer substance, a surfactant, an organic sulfur-based compound, chlorine ions, and the like and adding a trace amount.
  • a typical known technique discloses a method for producing an electrolytic copper foil in which a compound having a mercapto group, a chloride ion, a low molecular weight glue having a molecular weight of 10,000 or less, and a high molecular weight polysaccharide are added to an electrolytic solution. (See Patent Document 2).
  • the electrolytic copper foil (current collector) produced by the production method is coated with graphite particles as an active material on the front and back, and further heated and pressed to form a copper foil with an active material layer,
  • the negative electrode for a lithium ion secondary battery is used.
  • a negative electrode for a lithium ion secondary battery intended for high capacity is formed by depositing, for example, silicon as an amorphous silicon thin film or a microcrystalline silicon thin film on a base metal foil manufactured by a CVD method or a sputtering method. ing. Since the thin film layer of the active material prepared by such a method is in close contact with the current collector, it has been found that it exhibits good charge / discharge cycle characteristics (see Patent Document 4).
  • the volume of silicon active material expands by a maximum of about 4 times due to occlusion of lithium ions during charging, and shrinks by discharging lithium ions during discharging. To do. Due to the expansion and contraction of the volume of the active material layer accompanying charging and discharging, not only the active material peels from the current collector, but also a phenomenon in which stress acts on the current collector is a problem.
  • the volume of silicon active material expands by a maximum of about 4 times due to occlusion of lithium ions during charging, and shrinks by discharging lithium ions during discharging. To do. Due to the expansion and contraction of the volume of the active material layer accompanying charging and discharging, not only the active material peels from the current collector, but also a phenomenon in which stress acts on the current collector is a problem.
  • the present invention relates to a lithium ion secondary battery using a negative electrode in which an active material mainly composed of silicon, germanium, or tin is applied and deposited on a current collector.
  • the main object of the present invention is to provide a lithium ion secondary battery that does not cause breakage of the electric current, has high adhesion between the active material and the current collector, and can maintain stable secondary battery characteristics for a long time. It aims at providing the metal foil as an electrical power collector for electrodes, especially an electrolytic copper foil.
  • the present invention applies not only to the electrolytic copper foil but also to a metal foil employed as a current collector for a lithium ion secondary battery used for the same purpose as the electrolytic copper foil.
  • a metal foil employed as a current collector for a lithium ion secondary battery used for the same purpose as the electrolytic copper foil For the current collector of the secondary battery electrode, which does not cause wrinkles and does not break the current collector, has high adhesion between the active material and the current collector, and can maintain stable secondary battery characteristics for a long time
  • An object is to provide a metal foil.
  • the present invention relaxes the difference in conductivity at the adhesive interface between the metal foil for the current collector of the lithium ion secondary battery electrode and the active material, improves the conductivity of the active material layer, and increases the volume of the lithium ion secondary battery.
  • One purpose is to increase the energy density per unit.
  • the present invention particularly relates to a current collector in a lithium ion secondary battery using an active material layer-attached metal foil, in which an active material mainly composed of silicon, germanium, or tin is applied and deposited on a current collector (metal foil).
  • Lithium ion secondary that does not cause wrinkles in the body, does not cause breakage of the current collector, has high adhesion between the active material and the current collector (metal foil), and can maintain stable secondary battery characteristics for a long time
  • the metal foil with a coating layer of the present invention is characterized in that a coating layer is provided on at least one surface of the untreated metal foil, and the coating layer contains free metal particles.
  • the coating layer is preferably a remeltable resin composition layer containing free metal particles.
  • the covering layer is preferably an active material layer containing free metal particles.
  • the coating layer is a remeltable resin composition layer containing free metal particles, and an active material layer is preferably provided on the resin composition layer.
  • a roughened layer is provided on at least one surface of the untreated metal foil, a coating layer is provided on the roughened layer, and the coating layer contains free metal particles. It is characterized by being.
  • the free metal particles contained in the coating layer are preferably metal particles released from the roughening treatment layer.
  • the coating layer provided on the roughening treatment layer is preferably a resin composition layer that can be remelted. Moreover, it is preferable that the coating layer provided on the said roughening process layer is an active material layer. Moreover, it is preferable that the coating layer provided on the roughening treatment layer is a layer in which an active material layer is provided on a remeltable resin composition layer.
  • the particle size of the free metal particles is preferably 0.05 ⁇ m to 3.5 ⁇ m.
  • the roughening treatment layer is preferably a roughening treatment layer containing at least one metal of copper, nickel, manganese, iron, chromium, tungsten, molybdenum, vanadium, and indium.
  • the electrode for a secondary battery of the present invention is characterized in that an active material layer is provided on at least one surface of a metal foil, and the active material layer contains free metal particles.
  • a remeltable resin composition layer in which free metal particles are dispersed is provided on at least one surface of a metal foil, and an active material layer is provided on the resin composition. It is characterized by.
  • the electrode for a secondary battery of the present invention is provided with a roughening treatment layer on at least one surface of a metal foil, an active material layer is provided on the roughening treatment layer, and the active material layer contains free metal particles. Preferably it is.
  • the electrode for a secondary battery of the present invention is provided with a roughening treatment layer on at least one surface of a metal foil, a resin composition layer in which free metal particles are dispersed is provided on the roughening treatment layer, and the resin composition An active material layer is provided thereon.
  • the electrode for a secondary battery of the present invention is provided with a roughening treatment layer on at least one surface of a metal foil, and a remeltable resin composition layer in which free metal particles are dispersed on the roughening treatment layer, An active material layer is provided on the resin composition.
  • the particle size of the free metal particles is preferably 0.05 ⁇ m to 3.5 ⁇ m.
  • the roughening treatment layer is a roughening treatment layer formed by treatment in a plating bath containing at least one metal of copper, nickel, manganese, iron, chromium, tungsten, molybdenum, vanadium, and indium. Is preferred.
  • a film or a release paper is provided on at least the outermost surface of the secondary battery electrode.
  • the method for producing a metal foil with a coating layer according to the present invention is a method for producing a metal foil with a coating layer in which a coating layer containing free metal particles is provided on at least one side of an untreated metal foil, the cathode foil being electrolyzed on the surface of the metal foil.
  • a current greater than the limiting current density is passed, a roughening treatment layer having a particle size of 0.1 ⁇ m to 3.5 ⁇ m is applied, a coating layer is formed on the roughening treatment layer, A part is mixed in the coating layer as free metal particles.
  • the coating layer is preferably a resin composition layer that can be remelted. Moreover, it is preferable that the said coating layer is an active material layer. Moreover, it is preferable that the said coating layer is a resin composition layer which can be remelted, and the active material layer is provided on this resin composition.
  • the method for producing a metal foil with a coating layer according to the present invention is a method for producing a metal foil with a coating layer in which a coating layer containing free metal particles is provided on at least one side of an untreated metal foil, and the surface of the metal foil is electrolytically plated. Then, a current exceeding the limit current density is passed, and a roughening treatment layer having a particle size of 0.1 ⁇ m to 3.5 ⁇ m is applied.
  • an active material On the roughening treatment layer, an active material, a binder, and, if necessary, a thickener, a slurry, The active material mixture is added and mixed to form an active material layer, and the metal foil on which the active material layer is formed is dried and added so that the metal-treated particles are incorporated into the active material layer as a conductive additive. And the roughened particles are contained as free metal particles in the active material layer.
  • the method for producing a metal foil with a coating layer of the present invention is a method for producing a metal foil with a coating layer in which a coating layer containing free metal particles is provided on at least one side of the metal foil, and the surface of the metal foil is electrolytically plated.
  • a current is passed over the limit current density, a roughening treatment layer having a particle diameter of 0.1 ⁇ m to 3.5 ⁇ m is applied, a resin composition layer is formed on the roughening treatment layer, and the resin composition layer is formed on the resin composition layer.
  • an active material, a binder, and a thickener and slurry are added if necessary, and a mixed active material mixture is applied to form an active material layer, and the resin composition layer and the metal foil on which the active material layer is formed
  • the roughening-treated particles are dried and pressurized so as to be incorporated into the resin composition layer as free metal particles.
  • cathodic electroplating is used, but anodic electroplating has the same effect.
  • the resin composition layer formed on the roughening treatment layer is preferably a remeltable resin.
  • the electrode for a secondary battery according to the present invention is characterized in that the metal foil produced by the method for producing a metal foil with a coating layer is used as a current collector.
  • a roughened layer having a particle size of 0.1 ⁇ m to 3.5 ⁇ m is formed by electrolytic plating on the surface of an untreated metal foil to cause a current to flow beyond a limit current density.
  • the metal foil in which the active material layer is formed in the first and second steps is dried and pressurized so that the roughened particles are incorporated into the active material layer as a conductive additive, and the roughened particles are activated as free metal particles. It comprises a drying and pressurizing step to be contained in the material layer.
  • a roughened layer having a particle size of 0.1 ⁇ m to 3.5 ⁇ m is formed by applying an electric current exceeding the limit current density by electrolytic plating on the surface of the metal foil.
  • Burn plating Surface roughening treatment step
  • resin composition layer forming step for forming a resin composition layer on the roughening treatment layer, active material, binder, and thickener and slurry added if necessary
  • An active material granulation step of mixing the active material a first active material film forming step of applying the active material mixture granulated in the active material granulation step on one surface of the resin composition layer,
  • the roughened particles are dried and pressurized so that the treated particles are taken into the active material layer as a conductive additive. Characterized by comprising the dry pressing step to be contained in the active material layer as a free metal particles.
  • the resin composition is preferably a resin composition that can be remelted.
  • the lithium ion secondary battery of the present invention is a secondary battery incorporating the electrode.
  • the metal foil having the coating layer of the present invention has a remeltable resin composition layer in which free metal particles are mixed as a coating layer on the surface of the metal foil, for example, an active material layer provided on the surface of the coating layer Adhesiveness is improved, and excellent effects such as relaxation of electrolysis between the metal foil and the active material layer are obtained.
  • the metal foil for a current collector of a lithium ion secondary battery electrode of the present invention when the foil is used as a current collector, the metal constituting the roughening treatment layer is mixed into the active material layer, so that it is conductive. Improves the energy density per volume of the lithium ion secondary battery.
  • the metal foil of the present invention when used as a current collector, the generation of wrinkles and the like can be suppressed against the expansion and contraction of the active material that occurs during charging and discharging, and the energy density per volume of the lithium ion secondary battery Can be increased. Further, to provide a metal foil for a current collector of a lithium ion secondary battery electrode having stable output performance for a long time because the current collector is not stress-ruptured and the adhesiveness between the active material and the current collector is high. Can do.
  • the lithium ion secondary battery of the present invention uses a metal foil for the negative electrode of the battery, wrinkles and the like are not generated in the current collector due to charge and discharge, and the energy density per volume of the lithium ion secondary battery is increased.
  • the current collector is not stress-ruptured and the adhesiveness between the active material and the current collector is high, a lithium ion secondary battery with stable output performance for a long time can be provided.
  • Step 1 Metal particles made of copper, nickel, manganese, iron, chromium, tungsten, molybdenum, vanadium, and indium are prepared.
  • the particle size of the metal particles is preferably in the range of 0.1 ⁇ m to 3.5 ⁇ m.
  • One type or a combination of two or more types of metal particles is selected depending on the conductivity of the resin composition to be mixed.
  • Step 2 Preparation of remeltable resin composition
  • a remeltable resin composition is prepared.
  • commercially available thermoplastic resin compositions for example, vinylidene fluoride resin (hereinafter PVDF)] and thermosetting resin compositions (for example, thermosetting polyimide resin) can be used.
  • PVDF vinylidene fluoride resin
  • thermosetting resin compositions for example, thermosetting polyimide resin
  • Step 3 Preparation of conductive resin composition
  • the free metal particles selected in Step 1 are mixed into the remeltable resin composition selected in Step 2 to create a resin composition imparted with conductivity.
  • Step 4 the resin composition containing metal particles is coated on the surface of a metal foil (copper foil, aluminum foil, etc.).
  • the coating can be performed by a general method such as a press method.
  • a thermosetting polyimide resin is employed as the thermosetting resin composition, dissolved in a solvent with free metal particles added to the resin, and applied to the surface of the metal foil, and then the thermosetting polyimide resin.
  • the solvent is evaporated so as to become a B-stage resin and dried to form a remeltable resin layer containing free metal particles (B-stage resin) on the surface of the metal foil.
  • FIG. 2 is a schematic view of the metal foil 10 with a coating layer in which the resin composition layers 11 and 12 that can be remelted are provided on both surfaces of the metal foil 10. As shown in the figure, free metal particles are dispersed in the coating layers 11 and 12. In FIG. 2, the composition layers 11 and 12 are provided on both surfaces of the metal foil 10, but if only one surface is satisfactory, it is not necessary to provide the composition layers on both surfaces.
  • Second Embodiment A second embodiment for producing a metal foil with a coating layer of the present invention will be described with reference to a flowchart shown in FIG.
  • Step 21 (Preparation of free metal particles) Metal particles made of copper, nickel, manganese, iron, chromium, tungsten, molybdenum, vanadium, and indium are prepared.
  • the particle size of the metal particles is preferably in the range of 0.1 ⁇ m to 3.5 ⁇ m.
  • One type or two or more types of metal particles are selected depending on the conductivity of the active material layer to be mixed.
  • Step 22 An active material mixture is prepared by mixing an active material, a binder, and, if necessary, conductive carbon black or a thickener and a slurry.
  • an active material mixture for example, polyimide is mixed as a binder.
  • Step 23 (formulation)
  • the free metal particles of Step 1 are mixed into the active material mixture prepared in Step 2 to impart conductivity to the active material layer.
  • Step 24 (coating)
  • the active material mixture blended in step 3 is applied to one side of a metal foil (copper foil, aluminum foil, etc.) 30 and coated.
  • the coating can be performed by a general method such as a press method.
  • FIG. 4 is a schematic view of a metal foil with a coating layer in which an active material layer 32 is provided on one side of the metal foil 30. As shown in the figure, free metal particles 34 are dispersed in a gap between the active materials 33 in the coating layer (active material layer) 32.
  • the active material layer 32 is provided on one surface of the metal foil 30, but when it is necessary to provide the active material layer 32 on both surfaces, an active material layer is provided on both surfaces of the foil in the following steps.
  • Step 25 The active material mixture of step 3 is applied and coated on the other surface of the metal foil (copper foil, aluminum foil, etc.).
  • the coating can be performed by a general method such as a press method.
  • surface or both surfaces by the above process can be manufactured.
  • Step 31 Metal particles made of copper, nickel, manganese, iron, chromium, tungsten, molybdenum, vanadium, and indium are prepared.
  • the particle size of the metal particles is preferably in the range of 0.1 ⁇ m to 3.5 ⁇ m.
  • One type or a combination of two or more types of metal particles is selected depending on the conductivity of the resin composition to be mixed.
  • Step 32 Preparation of remeltable resin composition
  • a remeltable resin composition is prepared.
  • a commercially available thermoplastic resin composition for example, vinylidene fluoride resin (hereinafter referred to as PVDF)
  • a thermosetting resin composition for example, a thermosetting polyimide resin
  • Step 33 (formulation)
  • the metal composition selected in step 31 is mixed into the meltable resin composition selected in step 32 to create a resin composition imparted with conductivity.
  • Step 34 the resin composition containing metal particles is coated on the surface of a metal foil (copper foil, aluminum foil, etc.).
  • the coating can be performed by a general method such as a press method.
  • a thermosetting polyimide resin is employed as the thermosetting resin composition, dissolved in a solvent with free metal particles added to the resin, and applied to the surface of the metal foil, and then the thermosetting polyimide resin.
  • the solvent is evaporated so as to become a B-stage resin and dried to form a remeltable resin layer containing metal particles (B-stage resin) on the surface of the metal foil.
  • Step 35 An active material mixture is prepared by mixing an active material, a binder, and, if necessary, conductive carbon black or a thickener and a slurry.
  • an active material mixture for example, polyimide is mixed as a binder.
  • Step 36 formation of active material layer
  • An active material layer is formed with the active material mixture blended in step 35 on the resin composition layer (coating layer) formed in step 34.
  • FIG. 6 is a schematic view of a metal foil with a coating layer in which a resin composition layer is provided on one surface of a metal foil 30 and an active material layer 32 is provided on the surface of the composition layer. As shown in the figure, free metal particles 33 are dispersed in the composition layer, and a part of the free metal particles enters the active material layer 32 thereon.
  • reference numeral 37 denotes a binder.
  • the composition layer and the active material layer 32 are provided on one surface of the metal foil 30. However, when it is necessary to provide both surfaces, the composition layer and the active material layer are provided on both surfaces.
  • Step 37 (Create electrode)
  • the metal foil with an active material layer prepared in step 35 is formed for an electrode.
  • Step 38 Battery creation
  • the electrode created in step 36 is incorporated into the positive electrode or the negative electrode to complete the battery.
  • Step 41 surface roughening process
  • the metal foil 1 is guided to the surface roughening treatment tank 2, and metal particles are grown on the surface of the metal foil 1 by plating to form the roughened metal layer 3.
  • the metal foil 1 is guided to the roughening treatment tank 2 through the feeding electrode 20 and passes between the plating electrodes 22, 24, and 26 arranged in the roughening treatment tank 2.
  • the plating electrodes 22, 24, and 26 are arranged at three locations to roughen both surfaces of the metal foil 1.
  • the electrode 26 is omitted. can do.
  • the roughening process conditions will be described later.
  • the roughened metal layer 3 is guided to the water washing tank 4 and washed with water.
  • the metal foil washed with water is guided to the antirust treatment tank 5 and a rust preventive agent is applied to the surface of the roughened metal layer 3.
  • a rust prevention process can be abbreviate
  • Step 42 Formation of remeltable resin composition layer
  • the resin composition is coated on the surface of the metal foil (copper foil, aluminum foil, etc.) on which the roughened layer is formed in step 2.
  • the coating method can be performed by a general method such as a press method.
  • the resin composition is melted in a solvent and roughened in step 41. The method of applying to will be described.
  • the resin composition is dissolved in a solvent and filled in the container 6.
  • the metal foil provided with the rust prevention layer is guided to the container 6 (filled with a resin composition dissolved in a solvent), and a solution made of the resin composition is applied to the surface.
  • Step 43 drying process After applying the resin composition to the surface of the metal foil, the solvent is evaporated and dried by the solvent evaporation device 8.
  • Step 44 The dried metal foil with a resin composition layer is wound on a winder 11.
  • a remeltable resin layer containing metal particles on the surface of the metal foil as shown in FIG. Resin can be formed.
  • FIG. 8 it demonstrates still in detail about the formation process of the remeltable resin composition layer of step 42.
  • the roughening treatment layer formed by the plating method is preferably applied by roughening treatment by burnt plating.
  • the roughened layer applied by burnt plating maintains an unhealthy state in which the roughened particles fall off (powder off).
  • a metal foil is immersed and passed through a tank 6 of a solution in which, for example, vinylidene fluoride resin (hereinafter referred to as PVDF) is dissolved in a 1-methyl-2-pyrrolidone (NMD) solvent on the roughened surface.
  • PVDF vinylidene fluoride resin
  • NMD 1-methyl-2-pyrrolidone
  • thermosetting polyimide resin is used as the remeltable resin composition
  • the polyimide is dissolved in an appropriate solvent by adjusting the weight ratio, and the solution vessel 6 is roughened by the burnt plating as described above.
  • the treated copper foil is immersed and passed through. Thereafter, the solvent is evaporated over a predetermined period of time so that the thermosetting polyimide resin becomes a B-stage resin, dried, and attached to the surface of the metal foil.
  • the metal foil with a coating layer in which the roughened particles are mixed into the B-stage resin can be produced.
  • the resin composition layer is applied and dried on the dendritic rough particle layer adhering in such a brittle state. Dendritic roughened particles are destroyed during application of the resin composition, during expansion / contraction during drying, or in subsequent steps, and the broken particles are dispersed in the resin composition layer as shown in FIG. It is taken in in the resin composition layer.
  • Step 51 surface roughening process
  • the metal foil 1 is guided to the surface roughening treatment tank 2, and metal particles are grown on the surface of the metal foil I by plating to form the roughened metal layer 3.
  • the metal foil 1 is guided to the roughening treatment tank 2 through the feeding electrode 20 and passes between the plating electrodes 22, 24, and 26 arranged in the roughening treatment tank 2.
  • plating electrodes 22, 24, and 26 are arranged at three locations for roughening both surfaces of the metal foil 1.
  • the electrode 26 is omitted. can do.
  • the roughening process conditions will be described later.
  • the roughened metal layer 3 is guided to the water washing tank 4 and washed with water.
  • the metal foil washed with water is guided to the antirust treatment tank 5 and a rust preventive agent is applied to the surface of the roughened metal layer 3.
  • a rust prevention process can be abbreviate
  • Step 52 active material mixture creation process
  • An active material, a binder, and, if necessary, conductive carbon black or a thickener and a slurry are mixed to prepare an active material mixture 8, and the active material mixture 8 is supplied to the hoppers 6 and 7.
  • Step 53 first active material layer forming step
  • the surface of the metal foil subjected to the surface roughening treatment is rust-prevented with the rust-preventing treatment layer 5, and the active material mixture 8 is poured uniformly from the hopper 6 onto one surface thereof. 8 is dried to form an active material layer 31.
  • Step 54 (second active material layer forming step) Next, the active material mixture 8 is poured uniformly from the hopper 7 onto the other surface and dried by the drying device 10 to form the active material layer 32.
  • Step 55 drying / pressurizing process
  • a metal foil with an active material layer having active material layers 31 and 32 formed on both sides is passed through a press 11 and heated and pressurized.
  • the active material layers 31 and 32 are uniformly adhered to the surface of the metal foil, and are moved by being pressed against the roughened particles in the pressing step, as shown in FIG.
  • Roughened metal particles 35 that are not fixed to the foil I are separated from the base metal foil 1 and taken into and dispersed in the active material layer 31 (32), so that the interface between the active material layer 31 (32) and the base metal foil 1 is dispersed.
  • Improve conductivity In the figure, 33 is an active material, 37 is a binder and a conductive material to be added if necessary.
  • the distribution of the roughened metal particles is characterized by being concentrated on the base metal foil side and decreasing toward the outermost surface of the active material layer.
  • Step 56 Winding process
  • the pressed and dried metal foil with the active material layer is taken up by the winder 12 and conveyed to the manufacturing process of the electrode (step 47) and battery (step 48) as the next process.
  • Step 61 surface roughening process
  • the metal foil 1 is guided to the surface roughening treatment tank 2, and metal particles are grown on the surface of the metal foil I by plating to form the roughened metal layer 3.
  • the metal foil 1 is guided to the roughening treatment tank 2 through the feeding electrode 20 and passes between the plating electrodes 22, 24, and 26 arranged in the roughening treatment tank 2.
  • plating electrodes 22, 24, and 26 are disposed at three locations for roughening both surfaces of the metal foil 1.
  • the electrode 26 is omitted. can do. The roughening process conditions will be described later.
  • the roughened metal layer 3 is guided to the water washing tank 4 and washed with water.
  • the metal foil washed with water is guided to the antirust treatment tank 5 and a rust preventive agent is applied to the surface of the roughened metal layer 3.
  • a rust prevention process can be abbreviate
  • Step 62 active material mixture creation process
  • An active material, a binder, and, if necessary, conductive carbon black or a thickener and a slurry are mixed to prepare an active material mixture 8, and the active material mixture 8 is supplied to the hoppers 6 and 7.
  • Step 63 first active material layer forming step
  • the surface of the metal foil subjected to the surface roughening treatment is subjected to a rust prevention treatment with the rust prevention treatment layer 5, and the active material mixture 8 is poured uniformly from one surface of the hopper 6 to form an active material layer 31.
  • the surface of the active material layer 31 is supplied with a plastic film or release paper 13 from the film supply roll 15 (when it is not necessary to distinguish between the plastic film and the release paper, both are simply expressed as the film 13) and attached.
  • Step 64 (second active material layer forming step)
  • the active material mixture 8 is uniformly poured from the hopper 7 into the film 13 supplied from the supply roll 14 of the film 13, and the active material mixture 8 conveyed from the film 13 is applied to the other surface of the surface-roughened metal foil. Then, the active material layer 32 is formed.
  • Step 65 drying / pressurizing process
  • the metal foil with an active material layer having active material layers 31 and 32 formed on both sides is heated and pressurized through a dryer 9 and a press 11.
  • the active material layers 31 and 32 are uniformly adhered to the surface of the metal foil, and some of the metal particles of the roughened metal layer 3 grown by the surface treatment in this pressing step are active material. Incorporated into the layer.
  • Step 66 Winding process
  • the pressed and dried metal foil with an active material layer is taken up by the winder 12 and conveyed to the electrode / battery manufacturing process, which is the next process.
  • the film 13 is provided on the active material layer 32. Therefore, the active material layer 32 and the active material layer 32 are not in direct contact with each other when wound on the winder (for example, bobbin) 12, and the active material layer is not damaged by winding.
  • the trouble at the time of battery assembly can be reduced by using the same thing as the separator used for the electrode of a lithium ion secondary battery, for example.
  • it when it is not necessary to cover the active material layer surface with a film, it can be deleted after the active material layer drying step.
  • Seventh Embodiment A seventh embodiment for manufacturing a metal foil with a coating layer according to the present invention will be described with reference to a flowchart shown in FIG. 13 and a manufacturing apparatus shown in FIG.
  • Step 71 surface roughening process
  • the metal foil 1 is guided to the surface roughening treatment tank 2, and metal particles are grown on the surface of the metal foil I by plating to form the roughened metal layer 3.
  • the metal foil 1 is guided to the roughening treatment tank 2 through the feeding electrode 20 and passes between the plating electrodes 22, 24, 26 arranged in the roughening treatment tank 2.
  • plating electrodes 22, 24, and 26 are disposed at three locations for roughening both surfaces of the metal foil 1.
  • the electrode 26 is omitted. can do. The roughening process conditions will be described later.
  • the roughened metal layer 3 is guided to the water washing tank 4 and washed with water.
  • the metal foil washed with water is guided to the antirust treatment tank 5 and a rust preventive agent is applied to the surface of the roughened metal layer 3.
  • a rust prevention process can be abbreviate
  • Step 72 A remeltable resin composition is supplied to one side of the roughened metal foil.
  • the remeltable resin composition a commercially available thermoplastic resin composition can be used. In the present embodiment, as described above, it is preferable to select a resin composition that can adhere to the active material layer provided on the resin composition layer. As shown in FIG. 13, a film 40 of a remeltable resin composition is supplied to one side of the metal foil 1, and both are attached by a pressure roll 41. If necessary, thermocompression bonding.
  • Step 73 active material mixture creation process
  • the active material, binder, conductive carbon black or thickener and slurry are mixed as necessary, and the active material mixture 8 is supplied to the hoppers 6 and 7.
  • the active material mixture 8 is supplied to the hoppers 6 and 7.
  • the active material 31 and the metal foil 1 are in close contact with the remeltable resin composition layer 40.
  • polyimide is used as a binder to form a homogeneous slurry coating film. Is preferred.
  • Step 74 (first active material layer forming step)
  • the active material mixture 8 is uniformly poured from the hopper 6 into the metal foil whose one surface is coated with the remeltable resin composition 40, and the active material mixture 8 is dried by the drying device 9 to form the active material layer 31.
  • Step 75 (second remeltable resin composition layer forming step)
  • a remeltable resin composition film 42 is supplied to the other surface of the metal foil 1, and the both are pasted by the pressure roll 41. If necessary, thermocompression bonding.
  • Step 76 (second active material layer forming step)
  • the active material mixture 8 is uniformly poured from the hopper 7 onto the surface of the remeltable resin composition film 42, and is dried by the drying device 10 to form the active material layer 32.
  • Step 77 drying / pressurizing process
  • a metal foil with an active material layer having active material layers 31 and 32 formed on both sides is passed through a press 11 and heated and pressurized.
  • the active material layers 31 and 32 are uniformly adhered to the surface of the metal foil via the remeltable resin composition layers 40 and 42.
  • a part of the metal particles of the roughened metal layer 3 grown by the surface treatment is taken into the resin composition layer that can be remelted in the attaching step and the heating / pressurizing step.
  • the roughened metal particles 35 move away from the surface of the metal foil in a remeltable resin composition layer sticking step and an active material layer pressurizing step, and can be remelted.
  • the conductivity at the interface between the active material layer 31 (32) and the metal foil 1 is improved.
  • 33 is an active material
  • 37 is a binder and a conductive material to be added if necessary.
  • the distribution of the roughened metal particles is characterized by being concentrated on the metal foil side and decreasing toward the active material layer side.
  • Step 78 Winding process
  • the pressed and dried metal foil with an active material layer is taken up by the winder 12 and conveyed to the electrode / battery manufacturing process, which is the next process.
  • the labor at the time of battery assembly can be reduced.
  • Step 81 surface roughening process
  • the metal foil 1 is guided to the surface roughening treatment tank 2, and metal particles are grown on the surface of the metal foil I by plating to form the roughened metal layer 3.
  • the metal foil 1 is guided to the roughening treatment tank 2 through the feeding electrode 20 and passes between the plating electrodes 22, 24, 26 arranged in the roughening treatment tank 2.
  • plating electrodes 22, 24, and 26 are disposed at three locations for roughening both surfaces of the metal foil 1.
  • the electrode 26 is omitted. can do. The roughening process conditions will be described later.
  • the roughened metal layer 3 is guided to the water washing tank 4 and washed with water.
  • the metal foil washed with water is guided to the antirust treatment tank 5 and a rust preventive agent is applied to the surface of the roughened metal layer 3.
  • a rust prevention process can be abbreviate
  • Step 82 (Remeltable resin composition layer forming step)
  • a remeltable resin composition layer 40 is supplied to both surfaces of the roughened metal foil 1.
  • the remeltable resin composition a commercially available thermoplastic resin composition can be used.
  • a remeltable resin composition film 40 is supplied to both surfaces of the metal foil 1, and both are pasted with a pressure-bonding roll 41. If necessary, thermocompression bonding.
  • the labor at the time of battery assembly can be reduced.
  • Step 83 active material mixture creation process
  • the active material, binder, conductive carbon black or thickener and slurry are mixed as necessary, and the active material mixture 8 is supplied to the hoppers 6 and 7.
  • the active material mixture 8 is supplied to the hoppers 6 and 7.
  • the active material 31 and the metal foil 1 are in close contact with the remeltable resin composition layer 40.
  • polyimide is used as a binder to form a homogeneous slurry coating film. Is preferred.
  • Step 84 (first active material layer forming step)
  • the active material mixture 8 is poured uniformly from the hopper 6 onto one surface of the metal foil on which the remeltable resin composition layer is formed, the active material layer 31 is formed, and a film is supplied to the surface of the active material layer 31
  • the film 13 is supplied from the roll 15 and attached.
  • Step 85 (second active material layer forming step)
  • the active material mixture 8 is uniformly poured from the hopper 7 into the film 13 supplied from the supply roll 14 of the film 13, and the active material mixture 8 conveyed from the film 13 is coated with a remeltable resin composition layer
  • the active material layer 32 is formed by supplying the other surface of the foil.
  • Step 86 drying / pressurizing process
  • a metal foil with an active material layer having active material layers 31 and 32 formed on both sides is passed through a press 11 and heated and pressurized.
  • the active material layers 31 and 32 are uniformly adhered to the surface of the metal foil via the remeltable resin composition layers 40 and 42.
  • a part of the metal particles of the roughened metal layer 3 grown by the surface treatment is taken into the resin composition layer that can be remelted in the attaching step and the heating / pressurizing step.
  • Step 87 winding process
  • the pressed and dried metal foil with an active material layer is taken up by the winder 12 and conveyed to the electrode / battery manufacturing process, which is the next process.
  • the film 13 is provided on the active material layer 32. Therefore, the active material layer 32 and the active material layer 32 are not in direct contact with each other when wound on the winder (for example, bobbin) 12, and the active material layer is not damaged by winding. Moreover, the trouble at the time of battery assembly can be reduced by using the same thing as the separator used for the electrode of a lithium ion secondary battery. In addition, when it is not necessary to cover the active material layer surface with a film, it can be deleted after the active material layer drying step.
  • Step 88 The metal foil having the prepared active material layer is finished into a battery electrode.
  • Step 89 The battery is completed by incorporating the above electrode into the battery.
  • the metal foil provided with the active material layer as the coating layer can be directly used as a battery electrode because the active material layer is formed on the surface of the metal foil. Therefore, a metal suitable for the current collector constituting the battery electrode is selected as the metal foil.
  • a metal suitable for the current collector constituting the battery electrode is selected as the metal foil.
  • an aluminum foil is selected as the positive electrode of the lithium ion secondary battery
  • a copper foil is selected as the negative electrode.
  • an electrolytic copper foil may be selected and described as the metal foil, but the electrolytic copper foil can be replaced with a rolled copper foil.
  • Lithium ion secondary that does not cause wrinkles in the current collector, does not cause breakage of the current collector, has high adhesion between the active material and the current collector metal foil, and can maintain stable secondary battery characteristics for a long time
  • any metal foil that can be selected as a battery electrode metal foil with an active material layer
  • the roughening process layer is provided by the burnt plating method which sends the electric current more than the limiting current density in an electrolytic bath on the surface of metal foil, for example, copper foil, in the surface roughening process.
  • the roughening layer formed by the roughening process by the burnt plating method is formed in a dendritic shape, and the tip of the dendritic roughening layer is formed brittle.
  • a roughened layer is formed on the surface of the base metal foil having a surface roughness Rz of 0.5 to 5 ⁇ m by a burnt plating method.
  • the particle size is preferably grown to 0.1 ⁇ m to 3 ⁇ m.
  • the difference in roughness Rz between the front and back surfaces of the base metal foil is 2.5 ⁇ m or less.
  • the cathode electrolytic plating It is preferable to apply by the burn plating method.
  • the plating method is not limited to the burn plating method as long as the metal particles grown by the surface treatment can be grown in the above preferred range.
  • the surface of the metal foil is subjected to a surface roughening treatment, and the grown tip portion of the particle roughening treatment layer is a step of providing an active material layer on the surface of the roughening treatment layer.
  • any method can be adopted as long as it is a plating method provided with the strength of dropping and dispersing.
  • a metal foil having a smooth surface is selected, and a current is passed beyond the limit current density in the electrolytic bath, so that the particle size is 0.1 ⁇ m to 3 ⁇ m.
  • a dendritic roughening treatment layer of .5 ⁇ m is formed so that the surface roughness Rz of the roughening treatment layer is 0.5 to 5 ⁇ m and the difference in surface roughness Rz between the front and back surfaces is 2.5 ⁇ m or less. Is preferred.
  • the crystal structure of the cross section is preferably composed of fine granular crystals. This is because when the crystal structure of the copper foil is a granular crystal, the difference in roughness between the front and back surfaces can be reduced, and the difference in the roughness Rz value after applying the roughened particles can be further reduced. If the copper foil has a columnar crystal structure, the difference between the front and back roughness becomes large, and it becomes difficult to eliminate the difference even after the roughening treatment.
  • the metal foil for a lithium ion secondary battery electrode of the present invention has a particle size of 0 by burnt plating (hereinafter sometimes simply referred to as burnt plating) in which a current equal to or higher than the limiting current density in the electrolytic bath is applied to the front and back surfaces of the base metal foil.
  • burnt plating a current equal to or higher than the limiting current density in the electrolytic bath is applied to the front and back surfaces of the base metal foil.
  • a layer of roughened particles of 1 ⁇ m to 3 ⁇ m is provided, the surface roughness Rz of each surface is 0.5 to 5 ⁇ m, and the difference between the front and back surface roughness Rz is 2.5 ⁇ m or less.
  • the roughening particles are applied to the surface of the base copper foil, thereby improving and improving the adhesion with the active material and changing the volume accompanying expansion and contraction inside the battery. Stress relaxation can be absorbed by the void space obtained by roughening.
  • the material for forming the roughened layer is Cu roughened particles, or particles containing Cu, the main component of which is Fe, Ni, Cr, W, Mo, V, or a plurality thereof. It is preferable that By forming a roughened layer with roughened particles comprising Cu or a copper alloy composition containing Cu as a main component, the adhesion between the roughened particles and the base copper foil is improved, and the particle size of the roughened particles is reduced. By appropriately controlling the current density (limit current density) of the burnt plating, it becomes easy to arbitrarily adjust the surface roughness Rz value.
  • the copper foil as the metal foil may be an electrolytic copper foil or a rolled copper foil, the surface roughness is about 0.8 to 2.0 ⁇ m, and the grain boundary structure at room temperature is from a granular crystal having a particle size of 5 ⁇ m or less.
  • the tensile strength (TS) is 300 MPa or more at room temperature
  • the elongation (E) is 3.5% or more
  • the copper capable of maintaining the tensile strength after 150 ° C. ⁇ 15 hours is 250 MPa or more.
  • a foil is particularly preferred.
  • the tensile strength (T.S) of the metal foil decreases and the elongation (E) tends to increase.
  • the strength (TS) of the current collector (metal foil) is low, the battery will expand and contract regardless of the roughening treatment.
  • the metal foil cannot be absorbed and cracks occur in the metal foil.
  • the tensile strength is 300 MPa or more and the elongation is 3.5% or more.
  • the crystal structure grain size is preferably 5 ⁇ m or less.
  • the drying conditions at this time are generally about 100 to 200 ° C. and about 5 to 20 hours. If the current collector (metal foil) is plastically deformed or softened at this time, the foil breaks and breaks during charging and discharging for the reasons described above, so the strength (hardness) of the foil after the drying process Is also an important component of physical properties.
  • the additive composition concentration in the electrolytic solution during the electrolytic foil production is changed to MPS (3-mercapto 1-
  • a foil production method is recommended in which 3 to 10 ppm of sodium propanesulfonate), 15 to 20 ppm of HEC (hydroxyethyl cellulose / polymer polysaccharide), and 30 to 70 ppm of animal glue are set.
  • the surface area ratio after the roughening particle application treatment is preferably 2.5 to 5 times.
  • the surface area ratio is measured by using KEYENCE VK-8500 to measure the area of 2500 ⁇ m 2 (50 ⁇ m ⁇ 50 ⁇ m) on the surface of the metal foil. Based on this value, the base metal foil (before roughening) and the area after roughening Is expressed as a ratio. That is, when the surface area ratio is 1, it means that the surface area does not change before and after the roughening treatment. When the area after the roughening treatment is 5000 ⁇ m 2 , the surface area ratio is doubled.
  • the tensile strength (TS) and elongation (E) of the present invention are values measured by a method defined in Japanese Industrial Standard (JISK6251).
  • the surface roughness Rz is a ten-point average roughness and an arithmetic surface roughness defined in Japanese Industrial Standards (JIS B0601-1994), and is a value measured with a general-purpose surface roughness meter.
  • the surface roughness Rz of the front and back surfaces of the base metal foil is preferably a smooth surface of 0.5 to 5 ⁇ m.
  • the burnt plating method is a plating method in which a current equal to or higher than the limiting current density in the electrolytic bath is passed, and is suitable as a roughening treatment method for imparting uniform unevenness to the surface of a smooth base metal foil. The front and back surfaces of the metal foil are roughened by this burnt plating method.
  • Patent Document 5 Japanese Patent Publication No. 53-393766
  • Patent Document 5 after forming a grainy copper plating layer by “yake plating”, “capsule plating” is performed on the grainy copper plating layer so as not to impair the uneven shape, This is a technique for forming a smooth, rough copper-like copper layer that does not drop off (does not fall off) granular copper by forming a smooth plating layer.
  • the present invention does not implement the capsule plating technique pointed out in Patent Document 5, and is in a state of roughening treatment by burnt plating, that is, an unhealthy state in which the roughened particles fall off (powder off). It is characterized by holding.
  • the reason why the process is stopped only by the burn plating is as follows.
  • burnt plating is applied to the surface of the base metal foil, dendritic roughened particles uniformly adhere to the front and back surfaces of the foil.
  • the roughening particles extending in a dendritic shape are attached to the front and back surfaces of the foil in a brittle state where the tip is easily broken and dropped off.
  • an active material is apply
  • the burnt plating layer does not become an obstacle in the process of creating the active material layer.
  • the active material composition is applied, dried, and subjected to a heat and pressure press process, an unnecessary solvent that has formed the active material in a slurry state is volatilized and the active material is solidified.
  • the dendritic particles fall off, but the dropped coarse particles are taken into the active material layer, and the portion where the dendritic active material does not fall off constitutes the roughening (unevenness) of the copper foil surface.
  • the active material layer is firmly bonded to the front and back of the copper foil with a binder.
  • the active material layer is formed in a state where the tip portion extended in a dendritic state enters the active material layer and the copper particles are liberated in the active material.
  • the base part is formed with a roughened shape on the surface of the copper foil along the shape of the active material, not only improving the adhesion between the active material and the copper foil, but also the internal residual stress compared to the conventional roughened copper foil Therefore, the conductivity is increased and the battery negative electrode with less heat generation is obtained.
  • the active material composition is exposed to a high temperature of 300 ° C. during the application, drying, heating, and pressure pressing processes, the roughened particles in the base portion are sintered and fixed to the copper foil surface. .
  • the roughening tank 2 is replaced with a conductive aqueous solution containing a polymer dispersion medium, and copper is applied to the surface of the untreated copper foil.
  • a treatment for depositing nanoparticles can also be handled.
  • the copper particles become smaller and later formed into the negative electrode of the battery, the copper nanoparticles can come into contact with the active material without any gaps, so that the conductivity with the negative electrode current collector can be further improved.
  • capsule plating is not performed after burnt plating as in the past.
  • the roughened particles are not fixed to the base metal foil, and the active material is pressed against the roughened particles by the pressure of the heating / pressurizing step (press) and moved, so that the roughened particles become active. It can move in a state where a part is taken into the active material layer along the shape of the material, and the contact area between the roughened particles and the active material is maximized.
  • the roughened particles are fixed to the base metal foil.
  • the base metal foil is also broken.
  • an active material that occludes lithium by alloying with a material that occludes and releases lithium can be selected.
  • silicon, germanium, tin, lead, zinc, magnesium, sodium, aluminum, potassium, indium and the like are known.
  • silicon or tin is preferred as a negative electrode active material in recent years because it is preferred because of its high theoretical capacity and ease of handling.
  • the negative electrode active material layer of the lithium ion secondary battery is preferably an active material layer containing silicon or tin as a main component in addition to graphite, and particularly preferably a layer containing silicon as a main component.
  • the active material layer is preferably an amorphous layer or a microcrystalline layer.
  • the active material layer is preferably an amorphous silicon layer or a microcrystalline silicon layer.
  • the current collector is thin, and it is preferable that the secondary battery is lightweight and light in design.
  • the metal foil copper foil is selected for the negative electrode current collector, and aluminum is selected for the positive electrode current collector.
  • the active material layer is formed by coating and depositing on one surface or front and back surfaces of the current collector. When the active material layer is formed on the front and back of the current collector, the surface roughness Rz on both sides of the current collector is in the range of 0.5 to 5 ⁇ m, and the difference between the Rz values on the front and back is 2.5 ⁇ m or less. It is preferable.
  • the thickness of the current collector is preferably about 8 ⁇ m for a thin one and about 20 ⁇ m for a thick one. If the thickness is 8 ⁇ m or less, the strength of the foil (as a current collector) cannot be maintained, and crack fracture occurs when the active material expands and contracts. If the thickness exceeds 20 ⁇ m, the battery characteristics can be satisfied, but the battery itself is large and heavy.
  • the Rz values on the front and back surfaces are in the range of 0.5 to 5 ⁇ m.
  • the Rz value is lower than the lower limit, the adhesion due to the anchor effect with the active material layer becomes poor, and when the Rz value is higher than the upper limit value, the active material does not uniformly enter the concaves corresponding to the roughened irregularities, and the current collector and the active material This is not preferable because the adhesion of the layer becomes insufficient.
  • the surface roughness is large between the front and back surfaces, the thickness of the active material is different on both sides in the active material coating process, which causes a problem in battery electrode characteristics. Therefore, the difference in the roughness Rz between the front and back sides is set to 2.5 ⁇ m or less. That is, when the difference in roughness Rz between the front and back surfaces is 2.5 ⁇ m or more, the thickness of the active material is different on both sides in the active material coating process, and sufficient battery electrode characteristics cannot be obtained.
  • the lithium ion secondary battery of the present invention comprises a negative electrode on which an active material layer mainly composed of graphite, silicon, or tin is applied and deposited as an active material for a lithium ion secondary battery; A positive electrode using a substance to be released, a nonaqueous electrolyte, and a separator are provided.
  • the non-aqueous electrolyte used in the lithium ion secondary battery of the present invention is an electrolyte in which a solute is dissolved in a solvent
  • the solvent of the non-aqueous electrolyte is not particularly limited as long as it is a solvent used in a lithium ion secondary battery.
  • examples include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
  • a mixed solvent of cyclic carbonate and chain carbonate is used. Is used.
  • a mixed solvent of a cyclic carbonate and an ether solvent such as 1,2-dimethoxyethane or 1,2-diethoxyethane, or a chain ester such as ⁇ -butyrolactone, sulfolane, or methyl acetate may be used.
  • the solute of the nonaqueous electrolyte is not particularly limited as long as it is a solute used for a lithium ion secondary battery.
  • LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 , LiClO 4 Examples include Li 2 B 10 Cl 10 and Li 2 B 12 Cl 12 .
  • a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride with an electrolytic solution, or an inorganic solid electrolyte such as LiI or Li 3 N can be used.
  • a polymer electrolyte such as polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride
  • an electrolytic solution or an inorganic solid electrolyte such as LiI or Li 3 N
  • the electrolyte of the lithium ion secondary battery of the present invention can be used without restriction unless it is decomposed by the voltage at the time of charge / discharge or storage.
  • the positive electrode active material used for the positive electrode and LiCoO 2, LiNiO 2, LiMn 2 O4, LiMnO 2, LiCo 0.5 Ni 0.5 O 2, LiNi 0.7 Co 0.2 Mn 0.1 lithium-containing transition metal oxides such as O 2, MnO
  • the metal oxide that does not contain lithium such as 2 can be used without limitation as long as the material can accept and release lithium ions in the battery.
  • conductive metal fine particles dropped roughening treatment layer
  • the active material layer in a drying / pressurizing process and the like, and appropriately dispersed in the active material layer.
  • the conductivity of the active material layer is improved, and the negative electrode current collector can be prevented from wrinkling and cracking during charging / discharging, and the energy density per volume of the lithium ion secondary battery is increased and stable for a long time.
  • a lithium ion secondary battery that maintains the performance can be provided.
  • a film is interposed to protect the surface of the active material layer overlapped.
  • a film is present on one surface, when the metal foil with an active material layer is wound up, an accident in which the active material layers are in contact with each other and possibly damaged can be prevented.
  • this metal foil with an active material layer is used as an electrode of a secondary battery, if the film is made of the same material as the battery electrode separator, the separator can be shared as an electrode, and there is no need to remove it.
  • the battery separator is an important material that separates the positive electrode and the negative electrode in the battery and retains the electrolytic solution to ensure the ionic conductivity between the positive electrode and the negative electrode.
  • microporous membranes made of polyethylene (ultra-high molecular weight PE) or polypropylene (PP) are used for lithium ion batteries.
  • PP / PE / PP There are three types of layer structure, PP / PE / PP.
  • TG glass transition point
  • polyethylene ultra high molecular weight PE
  • Examples 1 and 4 and Comparative Example 1 copper foil is used as the metal foil.
  • An electrolytic solution for foil production was prepared by adding MPS, HEC and chloride ions having the composition shown in Table 1 as additives to the acidic copper electrolytic bath.
  • MPS is sodium 3-mercapto-1-propanesulfonate
  • HEC high molecular polysaccharide
  • glue is a low molecular weight glue having a molecular weight of 3000.
  • the chloride ion concentration was adjusted to 30 ppm, the chloride ion concentration is appropriately changed depending on the electrolysis conditions, and is not limited to this concentration.
  • an electrolytic copper foil having a thickness of 10 ⁇ m was prepared under the electrolysis conditions (current density, liquid temperature) shown in Table 1.
  • Table 2 shows the surface roughness Rz and mechanical properties of the electrolytic copper foil that was made.
  • each measured value shown in Table 2 is a value measured as follows. [Measurement of foil thickness, tensile strength (TS), elongation (E)] These are actual values measured with a micrometer, and tensile strength (TS) and elongation (E) are values measured using a tensile tester (type 1122 manufactured by Instron).
  • the surface roughness Rz is a value measured with a stylus type surface roughness meter (SE-3C type manufactured by Kosaka Laboratory).
  • the rust prevention treatment tank 5 may be spread and rust prevention treatment may be performed so that the copper foil is not discolored and lightly dried before slurry application.
  • Table 3 shows the characteristic values after applying the roughened particles.
  • Table 3 shows the characteristic values after applying the roughening particles by the burnt plating.
  • Example 4 the feed roll shown in FIG. 8 was used as a cathode and the feed electrode 20 was used as an anode, and roughening was performed under the following conditions.
  • Surface roughening conditions In normal electrolytic copper plating solution (copper sulfate 40-250 g / l, sulfuric acid 30-210 g / l, hydrochloric acid 10-80 ppm, additives such as brightener specified by the manufacturer) The temperature was kept at 18 to 32 ° C., and the current density was 1 A / dm 2 or more. When the current density was lower than 1 A / dm 2, it was found that the amount of copper plating was too small and almost no copper fine particles were deposited. Therefore, Example 4 was performed at 8 A / dm 2 . If the current density is increased, a large amount of copper fine particles are precipitated. Therefore, if necessary, the amount of copper fine particles deposited may be controlled by controlling the current density.
  • Examples 2 and 3 In Examples 2 and 3, rolled copper foil was used, and the same surface treatment as in Example 1 was performed on the copper foil.
  • Example 2 and Comparative Example 2 In this example, a low roughness rolled copper foil (Tough Bitch) manufactured by Nippon Foil Co., Ltd. was used.
  • Example 3 In this example, a copper alloy foil (C14410) containing tin (0.15 wt%) manufactured by Nippon Foil Co., Ltd. was used.
  • Example 4 In Example 4, the same electrolytic copper foil as used in Example 1 was used.
  • the feeding roll 0 was a cathode, the feeding electrode 0 was an anode, and copper fine particles (0.1 ⁇ m) were used under the same surface roughening treatment conditions as in Example 1. ⁇ 3.5 ⁇ m) is produced on the foil surface and then washed in the treatment tank 4 with water.
  • the tank for water washing shows one tank in FIG. 2, you may increase the tank for water washing as needed.
  • a rust prevention treatment tank 5 may be provided to prevent the copper foil from discoloring in a subsequent drying step, and the rust prevention treatment may be performed and lightly dried before slurry application.
  • the characteristic values after the application of the roughened particles are also shown in Table 3.
  • Active Material Granulation Silicon was employed as the active material, and silicon (SiO), acetylene black, PVDF (polyvinylidene fluoride), and NMP (N-methyl-2-pyrrolidone) were mixed to form a slurry. Formation of active material layer The active material in the form of a slurry was used as a current collector for the copper foils of the examples and comparative examples, and coated on the current collector, heated and dried, and heated and pressed to form a silicon-based deposited layer. A copper foil with an active material layer was prepared as (active material layer). The active material mixture was adjusted to a suitable slurry viscosity with a demonstrable solvent so that it could be easily applied by a curtain coater. Moreover, although the method of apply
  • a thickener or a conductive aid for adjusting the viscosity is added and kneaded as necessary, with the active material and binder as main components.
  • the kneaded active material mixture is applied to the surface of the metal foil on which the metal particles are deposited, and after drying, the metal particles and the active material are in strong contact with each other by a hot roll press. As a result, the contact resistance between the active material layer and the current collector (metal foil) can be reduced.
  • the contact area with the metal foil can be increased to the maximum as compared with the copper foil subjected to normal cup cell plating, and can contribute to cycle characteristics as a battery.
  • the assembly and evaluation of the negative electrode current collector were performed under the following conditions.
  • a three-electrode beaker cell was produced in a glove box under an argon gas atmosphere using the produced negative electrode current collector as an electrode.
  • the beaker cell was configured by immersing a counter electrode (positive electrode), a working electrode (negative electrode), and a reference electrode in an electrolytic solution placed in a glass container.
  • As the electrolytic solution an electrolytic solution in which 1 mol / liter of LiPF 6 was dissolved in a solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 3: 7 was used. Lithium metal was used as the counter electrode and the reference electrode.
  • Example 2 a rolled copper foil is used as the base copper foil, the same roughening treatment as that of the electrolytic copper foil in Example 1 is performed, and the roughened rolled copper foil is used as a current collector.
  • the battery was assembled and the battery characteristics were evaluated. The results are shown in Table 3 together with Example 1.
  • Comparative Example 1 used the same untreated copper foil as Example 1, but the difference in roughness Rz value between both surfaces after the roughening treatment was large, and thus the discharge capacity retention after 100 cycles of charge / discharge efficiency was high. It became unsatisfactory. Moreover, in the comparative example 1, the crack fracture
  • the present invention it is possible to increase the energy density per volume of the lithium ion secondary battery, to suppress the occurrence of deformation such as wrinkles and crack fracture of the current collector during charging and discharging, It is possible to provide a lithium ion secondary battery that can be downsized with a long lifetime in which the capacity does not decrease even when the discharge cycle is repeated.

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Abstract

La présente invention concerne une feuille en cuivre électrolytique destinée à être utilisée dans un collecteur qui présente des caractéristiques constantes de cellule secondaire au Li, qui n'entraîne pas de plissures dans le collecteur utilisé dans une cellule secondaire au Li, qui ne se rompt pas, et qui présente une haute cohésion au matériau actif et au collecteur. Cette feuille métallique (feuille en cuivre) qui comporte une couche de revêtement est dotée de la couche de revêtement sur au moins un côté d'un film métallique non traité, la couche de revêtement contenant des particules métalliques libres.
PCT/JP2012/066439 2011-07-29 2012-06-27 Feuille métallique comportant une couche de revêtement et procédé de fabrication associé, électrode de cellule secondaire et procédé de fabrication associé, et cellule secondaire au lithium-ion Ceased WO2013018473A1 (fr)

Priority Applications (3)

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KR1020147005454A KR20140051375A (ko) 2011-07-29 2012-06-27 피복층 부착 금속박 및 그 제조방법, 이차전지용 전극 및 그 제조방법, 및 리튬이온 이차전지
CN201280037317.1A CN103718346A (zh) 2011-07-29 2012-06-27 有被覆层金属箔及其制造方法、二次电池用电极及其制造方法、以及锂离子二次电池
JP2012551413A JP5435519B2 (ja) 2011-07-29 2012-06-27 リチウムイオン二次電池負極電極用被覆層付き金属箔及びその製造方法、リチウムイオン二次電池負極用電極及びその製造方法、リチウムイオン二次電池

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JP2011-166863 2011-07-29
JP2011166863 2011-07-29

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016039160A1 (fr) * 2014-09-08 2016-03-17 オートリブ ディベロップメント エービー Dispositif de retenue d'un occupant de véhicule
JP2019140057A (ja) * 2018-02-15 2019-08-22 Tdk株式会社 負極集電体、負極及びリチウム二次電池
JP2019140055A (ja) * 2018-02-15 2019-08-22 Tdk株式会社 負極集電体、負極及びリチウム二次電池
JP2019140056A (ja) * 2018-02-15 2019-08-22 Tdk株式会社 負極集電体、負極及びリチウム二次電池
JP2021521330A (ja) * 2018-04-11 2021-08-26 ハッチンソン テクノロジー インコーポレイテッドＨｕｔｃｈｉｎｓｏｎ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃｏｒｐｏｒａｔｅｄ フラックスを用いずに付与されるはんだにおけるボイドを減少させるまたは除去するためのメッキ方法
WO2025028031A1 (fr) * 2023-07-28 2025-02-06 ウシオ電機株式会社 Procédé de fabrication d'électrode et dispositif de fabrication d'électrode

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Publication number Priority date Publication date Assignee Title
TWI553161B (zh) 2016-03-02 2016-10-11 華碩電腦股份有限公司 電極的製作方法
KR20190076769A (ko) * 2017-12-22 2019-07-02 주식회사 포스코 리튬 금속 음극, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
TWI791776B (zh) * 2018-02-23 2023-02-11 日商古河電氣工業股份有限公司 電解銅箔、以及使用該電解銅箔之鋰離子二次電池用負極、鋰離子二次電池、覆銅積層板及印刷電路板
KR102869518B1 (ko) 2020-02-18 2025-10-10 삼성에스디아이 주식회사 음극 및 이를 포함하는 전고체 이차전지

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07312219A (ja) * 1994-03-24 1995-11-28 Fuji Photo Film Co Ltd 非水二次電池と充電法
JP2002246020A (ja) * 2001-02-13 2002-08-30 Sony Corp 活物質およびこれを用いた非水電解質電池、ならびに電極の製造方法
JP2004296108A (ja) * 2003-03-25 2004-10-21 Toshiba Corp 非水電解質電池
JP2005353384A (ja) * 2004-06-10 2005-12-22 Mitsui Mining & Smelting Co Ltd キャリア箔付金属箔及びそのキャリア箔付金属箔の製造方法並びにそのキャリア箔付金属箔を用いた非水電解液二次電池の集電体
JP2006040652A (ja) * 2004-07-26 2006-02-09 Matsushita Electric Ind Co Ltd 蓄電素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07312219A (ja) * 1994-03-24 1995-11-28 Fuji Photo Film Co Ltd 非水二次電池と充電法
JP2002246020A (ja) * 2001-02-13 2002-08-30 Sony Corp 活物質およびこれを用いた非水電解質電池、ならびに電極の製造方法
JP2004296108A (ja) * 2003-03-25 2004-10-21 Toshiba Corp 非水電解質電池
JP2005353384A (ja) * 2004-06-10 2005-12-22 Mitsui Mining & Smelting Co Ltd キャリア箔付金属箔及びそのキャリア箔付金属箔の製造方法並びにそのキャリア箔付金属箔を用いた非水電解液二次電池の集電体
JP2006040652A (ja) * 2004-07-26 2006-02-09 Matsushita Electric Ind Co Ltd 蓄電素子

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016039160A1 (fr) * 2014-09-08 2016-03-17 オートリブ ディベロップメント エービー Dispositif de retenue d'un occupant de véhicule
JP2019140057A (ja) * 2018-02-15 2019-08-22 Tdk株式会社 負極集電体、負極及びリチウム二次電池
JP2019140055A (ja) * 2018-02-15 2019-08-22 Tdk株式会社 負極集電体、負極及びリチウム二次電池
JP2019140056A (ja) * 2018-02-15 2019-08-22 Tdk株式会社 負極集電体、負極及びリチウム二次電池
JP2021521330A (ja) * 2018-04-11 2021-08-26 ハッチンソン テクノロジー インコーポレイテッドＨｕｔｃｈｉｎｓｏｎ Ｔｅｃｈｎｏｌｏｇｙ Ｉｎｃｏｒｐｏｒａｔｅｄ フラックスを用いずに付与されるはんだにおけるボイドを減少させるまたは除去するためのメッキ方法
US11674235B2 (en) 2018-04-11 2023-06-13 Hutchinson Technology Incorporated Plating method to reduce or eliminate voids in solder applied without flux
JP7408566B2 (ja) 2018-04-11 2024-01-05 ハッチンソン テクノロジー インコーポレイテッド フラックスを用いずに付与されるはんだにおけるボイドを減少させるまたは除去するためのメッキ方法
WO2025028031A1 (fr) * 2023-07-28 2025-02-06 ウシオ電機株式会社 Procédé de fabrication d'électrode et dispositif de fabrication d'électrode

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KR20140051375A (ko) 2014-04-30

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