WO2021066091A1 - 電解コンデンサ及び電解コンデンサの製造方法 - Google Patents

電解コンデンサ及び電解コンデンサの製造方法 Download PDF

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Publication number
WO2021066091A1
WO2021066091A1 PCT/JP2020/037411 JP2020037411W WO2021066091A1 WO 2021066091 A1 WO2021066091 A1 WO 2021066091A1 JP 2020037411 W JP2020037411 W JP 2020037411W WO 2021066091 A1 WO2021066091 A1 WO 2021066091A1
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Prior art keywords
layer
resin
plating
electrolytic capacitor
plating layer
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PCT/JP2020/037411
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English (en)
French (fr)
Japanese (ja)
Inventor
康浩 玉谷
和哉 楠田
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to CN202080069076.3A priority Critical patent/CN114503229A/zh
Priority to JP2021551447A priority patent/JP7248141B2/ja
Publication of WO2021066091A1 publication Critical patent/WO2021066091A1/ja
Priority to US17/657,711 priority patent/US20220223349A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/008—Terminals
    • H01G9/012—Terminals specially adapted for solid capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure

Definitions

  • the present invention relates to an electrolytic capacitor and a method for manufacturing an electrolytic capacitor.
  • Patent Document 1 discloses a multilayer ceramic capacitor.
  • electrode paste is dipped on each of the first and second surfaces of the capacitor body, dried, and then baked to form a base film for the external electrode, and on the fifth surface of the capacitor body. It is manufactured by printing an electrode paste on each of both ends in the length direction, drying it, and then performing a baking process to form another base film for an external electrode so as to be continuous with the base film.
  • Patent Document 2 describes a method of forming an external electrode on a ceramic capacitor. Specifically, it has a first paste layer forming step of screen printing on the end face of the element body and a second paste layer forming step of screen printing on the main surface of the element body. A first baking step is performed, and after the second paste layer forming step, a second baking step is performed.
  • the electrode paste is screen-printed on a ceramic body and then baked at a high temperature of 600 to 800 ° C., and the composition, rheology, or printing of the electrode paste is performed.
  • the conditions and the like are suitable for the baking process.
  • an electrolytic capacitor such as a solid electrolytic capacitor
  • the periphery of a laminate including a capacitor element including an anode having a dielectric layer on the surface and a cathode facing the anode is sealed with a resin molded body and resin molded. It may be assumed that an external electrode is formed on the body.
  • an inner layer plating layer that directly contacts the cathode and the anode, an outer layer plating layer that directly contacts the solder, and a resin electrode for preventing cracks in the external electrode are used as a method of forming an external electrode on the surface of the resin molded body.
  • An inner layer plating layer that directly contacts the cathode and the anode, an outer layer plating layer that directly contacts the solder, and a resin electrode for preventing cracks in the external electrode are used as a method of forming an external electrode on the surface of the resin molded body.
  • the inner plating layer is required to have high adhesion to the anode or cathode.
  • Ni plating has excellent adhesion to the anode and cathode, but is easily oxidized. Therefore, it is conceivable that the inner plating layer has a two-layer structure consisting of a Ni plating layer and a plating layer (for example, an Ag plating layer) for preventing oxidation of Ni plating.
  • the outer plating layer is required to have high solder wettability. However, if the Sn plating layer having high solder wettability is provided directly on the surface of the resin electrode layer, the adhesion is lowered.
  • the outer layer plating layer it is necessary to first form a Ni plating layer on the surface of the resin electrode layer and then provide a Sn plating layer on the surface of the Ni plating layer. Then, the outer electrode has a five-layer structure of two inner layer plating layers (Ni / Ag), a resin electrode layer, and two outer layer plating layers (Ni / Sn).
  • an object of the present invention is to provide an electrolytic capacitor capable of suppressing an increase in manufacturing cost and ESR, and a method for manufacturing the electrolytic capacitor.
  • the electrolytic capacitor of the present invention has a rectangular shape including an anode having a dielectric layer on its surface, a laminate including a capacitor element including a cathode facing the anode, and a sealing resin that seals the periphery of the laminate. It is formed on the resin molded body, the first external electrode formed on the first end surface of the resin molded body and electrically connected to the anode exposed from the first end face, and the second end surface of the resin molded body.
  • An electrolytic capacitor including a second external electrode electrically connected to the cathode exposed from the second end face, the first external electrode and the second external electrode are the above-mentioned resin molded body.
  • the method for manufacturing an electrolytic capacitor of the present invention includes a step of preparing a laminate including an anode having a dielectric layer on its surface and a capacitor element including a cathode facing the anode, and sealing the periphery of the laminate with a sealing resin.
  • a method for manufacturing an electrolytic capacitor comprising a step of forming a second external electrode electrically connected to the cathode exposed from the second end surface on the second end surface of the resin molded body.
  • the step of forming the electrode and the step of forming the second external electrode are a step of electroless Ag plating or a step of electroless Cu plating on the first end face or the second end face of the resin molded body, respectively. And the resin electrode layer forming step.
  • an electrolytic capacitor and a method for manufacturing the same, which can suppress an increase in manufacturing cost and ESR.
  • FIG. 1 is a perspective view schematically showing an example of the electrolytic capacitor of the present invention.
  • FIG. 2 is a cross-sectional view taken along the line AA of the electrolytic capacitor shown in FIG.
  • FIG. 3 is a graph showing the relationship between the film thickness of the electroless Ag plating layer and ESR in Examples 1 to 5.
  • FIG. 4 is a graph showing the relationship between the film thickness of the electroless Cu plating layer and ESR in Examples 6 to 10.
  • FIG. 5 is a graph showing the relationship between the film thickness of the electroless Ni plating layer and ESR in Comparative Examples 1 to 3.
  • the electrolytic capacitor of the present invention and a method for manufacturing the same will be described.
  • the present invention is not limited to the following configurations, and can be appropriately modified and applied without changing the gist of the present invention. It should be noted that a combination of two or more desirable configurations of each embodiment of the present invention described below is also the present invention.
  • FIG. 1 is a perspective view schematically showing an example of the electrolytic capacitor of the present invention.
  • FIG. 1 shows a rectangular parallelepiped resin molded body 9 constituting the electrolytic capacitor 1.
  • the resin molded body 9 has a length direction (L direction), a width direction (W direction), and a thickness direction (T direction), and has a first end surface 9a and a second end surface 9b facing each other in the length direction. I have.
  • the first external electrode 11 is formed on the first end surface 9a
  • the second external electrode 13 is formed on the second end surface 9b.
  • the resin molded body 9 includes a bottom surface 9c and a top surface 9d facing each other in the thickness direction. Further, the resin molded body 9 includes a first side surface 9e and a second side surface 9f facing each other in the width direction.
  • the surface of the electrolytic capacitor or resin molded body along the length direction (L direction) and the thickness direction (T direction) is referred to as an LT surface, and is referred to as an LT surface in the length direction (L direction) and the width direction (L direction).
  • the surface along the W direction is called the LW surface
  • the surface along the thickness direction (T direction) and the width direction (W direction) is called the WT surface.
  • FIG. 2 is a cross-sectional view taken along the line AA of the electrolytic capacitor shown in FIG.
  • the capacitor element 20 includes an anode 3 having a dielectric layer 5 on its surface and a cathode 7 facing the anode 3.
  • a plurality of capacitor elements 20 are laminated to form a laminated body 30, and the periphery of the laminated body 30 is sealed with a sealing resin 8 to form a resin molded body 9.
  • the laminated capacitor elements 20 may be bonded to each other via a conductive adhesive (not shown).
  • the first external electrode 11 is formed on the first end surface 9a of the resin molded body 9, and the first external electrode 11 is electrically connected to the anode 3 exposed from the first end surface 9a.
  • a second external electrode 13 is formed on the second end surface 9b of the resin molded body 9, and the second external electrode 13 is electrically connected to the cathode 7 exposed from the second end surface 9b.
  • the end portion of the valve acting metal foil 3a constituting the capacitor element 20 on the second end surface 9b side is sealed with the sealing resin 8, and the valve acting metal foil 3a and the solid electrolyte layer 7a or the conductive layer 7b are separated from each other. Not in direct contact.
  • insulation treatment is applied such that the end portion of the valve acting metal foil 3a on the second end surface 9b side is covered with the dielectric layer 5
  • the valve acting metal foil 3a is on the second end surface 9b side.
  • the edge of the solid electrolyte layer 7a and the conductive layer 7b may be covered with the solid electrolyte layer 7a.
  • the anode 3 constituting the capacitor element 20 has a valve acting metal foil 3a at the center, and has a porous layer (not shown) such as an etching layer on the surface.
  • a dielectric layer 5 is provided on the surface of the porous layer.
  • valve acting metal examples include simple metals such as aluminum, tantalum, niobium, titanium, zirconium, magnesium and silicon, or alloys containing these metals. Among these, aluminum or an aluminum alloy is preferable.
  • the shape of the valve acting metal is not particularly limited, but it is preferably flat, more preferably foil.
  • the porous layer is preferably an etching layer that has been etched with hydrochloric acid or the like. Valve action before etching
  • the thickness of the metal leaf is preferably 60 ⁇ m or more, and preferably 180 ⁇ m or less. Further, the thickness of the valve acting metal foil (core portion) that has not been etched after the etching treatment is preferably 10 ⁇ m or more, and preferably 70 ⁇ m or less.
  • the thickness of the porous layer is designed according to the withstand voltage and capacitance required for the electrolytic capacitor, but the total thickness of the porous layers on both sides of the valve acting metal foil is preferably 10 ⁇ m or more, and 120 ⁇ m or less. Is preferable.
  • the anode 3 is drawn out to the first end surface 9a of the resin molded body 9 and is electrically connected to the first external electrode 11.
  • the dielectric layer is preferably made of an oxide film of the valve acting metal.
  • an aluminum foil is used as a valve acting metal substrate, oxidation to form a dielectric layer by anodic oxidation in an aqueous solution containing boric acid, phosphoric acid, adipic acid, or a sodium salt or ammonium salt thereof.
  • a film can be formed.
  • the dielectric layer is formed along the surface of the porous layer to form pores (recesses).
  • the thickness of the dielectric layer is designed according to the withstand voltage and capacitance required for the electrolytic capacitor, but is preferably 10 nm or more, and preferably 100 nm or less.
  • the cathode 7 constituting the capacitor element 20 includes a solid electrolyte layer 7a formed on the dielectric layer 5, a conductive layer 7b formed on the solid electrolyte layer 7a, and a cathode extraction layer formed on the conductive layer 7b. It is made by laminating 7c.
  • An electrolytic capacitor provided with a solid electrolyte layer as a part of the cathode can be said to be a solid electrolytic capacitor.
  • Examples of the material constituting the solid electrolyte layer include conductive polymers having pyrroles, thiophenes, anilines and the like as skeletons.
  • Examples of the conductive polymer having thiophenes as a skeleton include PEDOT [poly (3,4-ethylenedioxythiophene)], and PEDOT: PSS complexed with polystyrene sulfonic acid (PSS) as a dopant. It may be.
  • a treatment liquid containing a monomer such as 3,4-ethylenedioxythiophene is used to form a polymer film such as poly (3,4-ethylenedioxythiophene) on the surface of the dielectric layer. It is formed by a method, a method of applying a dispersion of a polymer such as poly (3,4-ethylenedioxythiophene) to the surface of the dielectric layer, and drying.
  • a method of applying a dispersion of a polymer such as poly (3,4-ethylenedioxythiophene) to the surface of the dielectric layer, and drying.
  • the solid electrolyte layer can be formed in a predetermined region by applying the above-mentioned treatment liquid or dispersion liquid onto the dielectric layer by sponge transfer, screen printing, spray coating, dispenser, inkjet printing or the like.
  • the thickness of the solid electrolyte layer is preferably 2 ⁇ m or more, and preferably 20 ⁇ m or less.
  • the conductive layer is provided to electrically and mechanically connect the solid electrolyte layer and the cathode extraction layer.
  • it is preferably a carbon layer, a graphene layer or a silver layer formed by applying a conductive paste such as a carbon paste, a graphene paste or a silver paste.
  • a conductive paste such as a carbon paste, a graphene paste or a silver paste.
  • it may be a composite layer in which a silver layer is provided on the carbon layer or the graphene layer, or a mixed layer in which the carbon paste or the graphene paste and the silver paste are mixed.
  • the conductive layer can be formed by forming a conductive paste such as carbon paste on the solid electrolyte layer by sponge transfer, screen printing, spray coating, dispenser, inkjet printing, or the like. It is preferable to laminate the cathode extraction layer in the next step in a viscous state before drying.
  • the thickness of the conductive layer is preferably 2 ⁇ m or more, and preferably 20 ⁇ m or less.
  • the cathode lead-out layer can be formed of a metal leaf or a printed electrode layer.
  • a metal foil it is preferably composed of at least one metal selected from the group consisting of Al, Cu, Ag and alloys containing these metals as main components.
  • the resistance value of the metal foil can be reduced and the ESR can be reduced.
  • a metal foil having a surface coated with carbon or titanium by a film forming method such as sputtering or vapor deposition may be used as the metal foil. It is more preferable to use carbon-coated Al foil.
  • the thickness of the metal foil is not particularly limited, but from the viewpoint of handling in the manufacturing process, miniaturization, and reduction of ESR, it is preferably 20 ⁇ m or more, and preferably 50 ⁇ m or less.
  • the cathode extraction layer can be formed in a predetermined region by forming the electrode paste on the conductive layer by sponge transfer, screen printing, spray coating, dispenser, inkjet printing, or the like.
  • the electrode paste an electrode paste containing Ag, Cu, or Ni as a main component is preferable.
  • the thickness of the print electrode layer can be made thinner than when the metal foil is used, and in the case of screen printing, the thickness can be 2 ⁇ m or more and 20 ⁇ m or less. Is.
  • the cathode lead-out layer 7c is drawn out to the second end surface 9b of the resin molded body 9 and electrically connected to the second external electrode 13.
  • the sealing resin 8 constituting the resin molded product 9 contains at least a resin, preferably a resin and a filler.
  • the resin for example, it is preferable to use an epoxy resin, a phenol resin, a polyimide resin, a silicone resin, a polyamide resin, a liquid crystal polymer, or the like.
  • the form of the sealing resin 8 either a solid resin or a liquid resin can be used.
  • the filler for example, silica particles, alumina particles, metal particles and the like are preferably used. It is more preferable to use a material containing silica particles in the solid epoxy resin and the phenol resin.
  • a resin mold such as a compression mold or a transfer mold
  • a compression mold it is preferable to use a compression mold.
  • a molding method such as a dispensing method or a printing method. It is preferable that the laminate 30 of the capacitor element 20 composed of the anode 3, the dielectric layer 5, and the cathode 7 is sealed with the sealing resin 8 by the compression mold to form the resin molded body 9.
  • the resin molded body 9 has a rectangular parallelepiped shape, and has an upper surface 9d and a lower surface 9c which are LW surfaces, a first side surface 9e and a second side surface 9f which are LT surfaces, and a first end surface 9a and a second end surface which are WT surfaces. Has 9b.
  • the resin molded body 9 has an R (radius of curvature) chamfered at the corners formed by barrel polishing after the resin molding.
  • R radius of curvature
  • it is softer than a ceramic body and it is difficult to form R at the corners by barrel polishing, but R can be reduced by adjusting the composition, particle size, shape, barrel processing time, etc. of the media. Can be formed.
  • the first external electrode and the second external electrode in the electrolytic capacitor of the present invention are an Ag plating layer or Cu plating formed on the surface of the anode exposed from the first end surface of the resin molded body or the surface of the cathode exposed from the second end surface. It has a layer and a resin electrode layer containing a conductive component and a resin component formed on the surface of an Ag plating layer or a Cu plating layer. Further, an outer layer plating layer may be provided on the outside of the resin electrode layer.
  • the number of layers of the inner layer plating layer is one, and when two layers of a Ni plating layer and an Ag plating layer are provided as the inner layer plating layer. Since the number of interfaces is smaller than that, the interface resistance is reduced and the ESR can be lowered. Further, when the inner layer plating layer is an Ag plating layer or a Cu plating layer, the ESR can be lowered as compared with the case where the inner layer plating layer is a Ni plating layer (1 layer).
  • the resin electrode layer shown in FIG. 2 is a printed resin electrode layer formed by screen printing of an electrode paste.
  • FIG. 2 shows the layer structure of the first external electrode 11 and the second external electrode 13 included in the electrolytic capacitor 1.
  • the first external electrode 11 includes an Ag plating layer or a Cu plating layer 11a, a resin electrode layer 11b, and an outer layer plating layer 11c.
  • the second external electrode 13 includes an Ag plating layer or a Cu plating layer 13a, a resin electrode layer 13b, and an outer layer plating layer 13c.
  • the Ag plating layer or Cu plating layer 11a is preferably formed by a zincate treatment.
  • the zincate treatment is a treatment for removing oxides on the surface of a metal to be plated and forming a zinc (Zn) film on the surface. That is, the surface of the aluminum foil of the anode 3 exposed from the first end surface of the resin molded body 9 is etched with an acid containing nitric acid as a main component to remove the oxide film of the anode 3, and then Zn plating is performed.
  • the gyere treatment is performed by both single gyere (pickling) and double gyere (peeling).
  • the Ag plating layer or the Cu plating layer 11a is formed by performing replacement plating by electroless Ag plating or electroless Cu plating.
  • the Ag plating layer or Cu plating layer 13a formed on the surface of the cathode extraction layer 7c can also be formed by the same method as the Ag plating layer or Cu plating layer 11a formed on the surface of the anode 3, but the zincate treatment can be performed. Does not have to be done.
  • Al is contained in the cathode extraction layer 7c, it is preferable to perform a zincate treatment. That is, it is preferable that the first end face and / or the second end face of the resin molded product is subjected to a zincate treatment, followed by an electroless Ag plating step or an electroless Cu plating step.
  • the thickness of the Ag plating layer is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, and 0.2 ⁇ m or more and 1.0 ⁇ m or less. Is more preferable.
  • the thickness of the Ag plating layer is within the above range, the ESR reduction effect can be obtained even with a relatively thin film thickness.
  • the thickness of the Cu plating layer is preferably 0.2 ⁇ m or more and 4.0 ⁇ m or less, and 0.5 ⁇ m or more and 2.0 ⁇ m or less. Is more preferable.
  • the thickness required for the plating layer is secured and the ESR is sufficiently low.
  • the thickness of the Ag plating layer or Cu plating layer is measured by measuring the size of the line drawn in the direction perpendicular to the first end face or the second end face in the cross-section micrograph taken with the cross section (LT plane) as shown in FIG. Determined by doing.
  • the thickness of each Ag plating layer or Cu plating layer formed corresponding to each anode or cathode extraction layer shall be measured, and the average value of the thickness of at least 5 Ag plating layers or Cu plating layers shall be measured. Determines the thickness of the Ag plating layer or the Cu plating layer.
  • the resin electrode layers 11b and 13b contain a conductive component and a resin component.
  • the conductive component preferably contains Ag, Cu, Ni, Sn or the like as a main component
  • the resin component preferably contains an epoxy resin, a phenol resin or the like as a main component.
  • the resin electrode layer is a resin electrode layer containing Ag.
  • the specific resistance of Ag is small, so that ESR can be reduced.
  • the resin electrode layer preferably contains a conductive component of 67% by weight or more and 97% by weight or less, and preferably contains a resin component of 3% by weight or more and 33% by weight or less. Further, it is more preferable to contain the conductive component in an amount of 72% by weight or more and 95% by weight or less, and more preferably to contain the resin component in an amount of 5% by weight or more and 28% by weight or less. Further, it is more preferable to contain the conductive component in an amount of 78% by weight or more and 95% by weight or less, and further preferably to contain the resin component in an amount of 5% by weight or more and 22% by weight or less. Further, it is particularly preferable that the conductive component is contained in an amount of 79% by weight or more and 89% by weight or less, and it is particularly preferable that the resin component is contained in an amount of 11% by weight or more and 21% by weight or less.
  • the resin electrode layer is preferably a printed resin electrode layer formed by screen printing of the electrode paste.
  • the electrode paste is an Ag electrode paste containing an Ag filler containing Ag as a conductive component and a resin
  • the resin electrode layer is more preferably an Ag printing resin electrode layer formed by screen printing.
  • the external electrode can be flattened as compared with the case where the electrode paste is formed by a dip. That is, the film thickness uniformity of the first external electrode and the second external electrode is improved.
  • the flatness of the first external electrode and the second external electrode is measured in the cross-sectional view as shown in FIG. 2, the variation in the thickness of the first external electrode measured from the first end surface of the resin molded body and the resin molded body
  • the variation in the thickness of the second external electrode measured from the second end surface of the above is preferably 30 ⁇ m or less. Further, it is more preferable that the thickness variation is 20 ⁇ m or less. Further, it is more preferable that the thickness variation is 5 ⁇ m or less.
  • the thickness variation of the first external electrode and the second external electrode at three points that divide the laminated body from the upper surface to the bottom surface into four equal parts and a total of five points on the upper surface and the bottom surface It can be obtained from the difference between the maximum value and the minimum value of the thickness. It is also possible to measure the thickness at a plurality of points in a non-destructive manner using a fluorescent X-ray film thickness meter, a laser displacement meter, or the like.
  • the electrode paste preferably contains 60% by weight or more and 95% by weight or less of the conductive component, and contains 3% by weight of the resin component. As mentioned above, it is preferable to contain 30% by weight or less. Further, it is more preferable that the conductive component is contained in an amount of 65% by weight or more and 90% by weight or less, and it is more preferable that the resin component is contained in an amount of 5% by weight or more and 25% by weight or less. Further, it is more preferable to contain the conductive component in an amount of 70% by weight or more and 90% by weight or less, and further preferably to contain the resin component in an amount of 5% by weight or more and 20% by weight or less.
  • the conductive component is contained in an amount of 75% by weight or more and 85% by weight or less, and it is particularly preferable that the resin component is contained in an amount of 10% by weight or more and 20% by weight or less.
  • the electrode paste may contain an organic solvent, and it is preferable to use a glycol ether-based solvent as the organic solvent.
  • a glycol ether-based solvent for example, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether and the like can be mentioned.
  • you may use an additive if necessary. Additives are useful in adjusting the rheology of electrode pastes, especially the thixophilicity.
  • the content of the additive is preferably less than 5% by weight based on the weight of the electrode paste.
  • An outer layer plating layer may be provided on the surface of the resin electrode layer.
  • the outer plating layer is preferably a Ni plating layer or a Sn plating layer.
  • the outer layer plating layer has a first outer layer plating layer formed on the surface of the resin electrode layer and a second outer layer plating layer formed on the surface of the first outer layer plating layer. May be.
  • the first outer layer plating layer is preferably a Ni plating layer
  • the second outer layer plating layer is preferably a Sn plating layer.
  • the electrolytic capacitor of the present invention can be manufactured by the method for manufacturing an electrolytic capacitor of the present invention.
  • the method for manufacturing an electrolytic capacitor of the present invention includes a step of preparing a laminate including an anode having a dielectric layer on its surface and a capacitor element including a cathode facing the anode, and sealing the periphery of the laminate with a sealing resin.
  • a method for manufacturing an electrolytic capacitor comprising a step of forming a second external electrode electrically connected to the cathode exposed from the second end surface on the second end surface of the resin molded body.
  • the step of forming the electrode and the step of forming the second external electrode are a step of electroless Ag plating or a step of electroless Cu plating on the first end face or the second end face of the resin molded body, respectively.
  • the resin electrode layer forming step comprising a step of forming a second external electrode electrically connected to the cathode exposed from the second end surface on the second end surface of the resin molded body.
  • a valve-acting metal foil such as an aluminum foil having a porous layer such as an etching layer on the surface is prepared, and anodizing is performed on the surface of the porous layer to form a dielectric layer.
  • a solid electrolyte layer is formed on the dielectric layer by screen printing, a carbon layer is subsequently formed on the solid electrolyte layer by screen printing, and a cathode extraction layer is further formed by sheet laminating or screen printing on the carbon layer. ..
  • a capacitor element is obtained by the above process.
  • a plurality of capacitor elements are laminated to form a laminated body, and the periphery of the laminated body is sealed with a sealing resin by a compression mold to obtain a rectangular parallelepiped resin molded body.
  • a first external electrode electrically connected to the anode exposed from the first end face is formed on the first end face of the resin molded body.
  • An electroless Ag plating step or an electroless Cu plating step is performed on the anode exposed from the first end face.
  • the anode exposed from the first end face is subjected to a zincate treatment, followed by an electroless Ag plating step or an electroless Cu plating step. That is, the surface of the aluminum foil of the anode exposed from the first end surface of the resin molded body is etched with an acid containing nitric acid as a main component to remove the oxide film of the anode, and then Zn plating is performed.
  • the zincate treatment preferably involves both the first pickling and the second peeling.
  • an Ag plating layer or a Cu plating layer is formed by performing replacement plating with electroless Ag plating or electroless Cu plating.
  • the plating bath for forming the Ag plating layer is preferably a cyan-containing electroless Ag plating bath, and the pH is preferably 8.0 or more and 9.0 or less (representative value 8.5). ..
  • the plating bath for forming the Cu plating layer is preferably a neutral electroless Cu plating bath, and the pH is preferably 7.0 or more and 8.5 or less (typical value 7.7). ..
  • the thickness of the Ag plating layer or the Cu plating layer can be adjusted by adjusting the conditions (concentration of plating solution, plating time, etc.) of electroless Ag plating or electroless Cu plating.
  • a second external electrode electrically connected to the cathode exposed from the second end surface is formed on the second end surface of the resin molded body.
  • An electroless Ag plating step or an electroless Cu plating step is performed on the cathode exposed from the second surface.
  • the cathode (cathode lead-out layer) exposed from the second end surface may or may not be subjected to the zincate treatment. However, when Al is contained in the cathode extraction layer, it is preferable to perform a zincate treatment.
  • An Ag plating layer or a Cu plating layer is formed by performing a non-electrolytic Ag plating step or a non-electrolytic Cu plating step on the cathode (cathode lead-out layer) exposed from the second end surface.
  • the conditions of the zincate treatment and the conditions of the plating bath can be the same as those in which the electroless Ag plating step or the electroless Cu plating step is performed on the first end surface of the resin molded body.
  • a resin electrode layer is formed on the first end surface and the second end surface of the resin molded body.
  • the resin electrode layer may be formed by screen printing of the electrode paste, or by immersing the resin molded body in the electrode paste.
  • the first external electrode is formed by applying the electrode paste to the first end face of the resin molded product and then heat-curing it.
  • the second external electrode is formed by applying the electrode paste to the second end surface of the resin molded product and then heat-curing it. It is preferable to form the resin electrode layer by screen printing of the electrode paste because the resin electrode layer having high adhesion to the resin molded body and high film thickness uniformity can be formed.
  • the electrode paste contains a conductive component and a resin component.
  • the electrode paste preferably contains 67% by weight or more and 97% by weight or less of the conductive component, and preferably contains 3% by weight or more and 33% by weight or less of the resin component. Further, it is more preferable to contain the conductive component in an amount of 72% by weight or more and 95% by weight or less, and more preferably to contain the resin component in an amount of 5% by weight or more and 28% by weight or less. Further, it is more preferable to contain the conductive component in an amount of 78% by weight or more and 95% by weight or less, and further preferably to contain the resin component in an amount of 5% by weight or more and 22% by weight or less.
  • the conductive component is contained in an amount of 79% by weight or more and 89% by weight or less, and it is particularly preferable that the resin component is contained in an amount of 11% by weight or more and 21% by weight or less.
  • the electrode paste may contain an organic solvent, and it is preferable to use a glycol ether-based solvent as the organic solvent.
  • a glycol ether-based solvent for example, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether and the like can be mentioned.
  • the amount of the additive added is preferably less than 5% by weight based on the weight of the electrode paste.
  • an outer plating layer As the outer layer plating layer, it is preferable to form a Ni plating layer which is a first outer layer plating layer and a Sn plating layer which is a second outer layer plating layer.
  • the outer layer plating layer is formed on the resin electrode layer as the first external electrode and the second external electrode.
  • the laminate including the capacitor element preferably includes a plurality of capacitor elements, but may have one capacitor element.
  • an electrolytic capacitor of the present invention In the method for manufacturing an electrolytic capacitor of the present invention according to the above procedure, only one layer of an electroless Ag plating layer or one layer of an electroless Cu plating layer is formed as an inner plating layer. In this method, the number of steps is smaller than in the case where the Ag plating layer is formed after the Ni plating layer is provided as the inner plating layer, so that the manufacturing cost can be reduced.
  • Examples 1 to 10 The laminate having the constitution shown in FIGS. 1 and 2 was sealed with a sealing resin containing an epoxy resin and silica particles to obtain a resin molded product. Then, the first end face and the second end face of the resin molded product were etched with an acid containing nitric acid as a main component to form a Zn film, thereby performing a zincate treatment. Next, electroless Ag plating or electroless Cu plating was performed. The treatment time of electroless Ag plating or electroless Cu plating was changed to change the film thickness of the electroless plating layer as shown in Table 1.
  • an electrode paste containing Ag is applied to the end faces (first end face and second end face) of the resin molded product by screen printing, and thermosetting at a drying temperature of 150 ° C. or higher and 200 ° C. or lower to form a resin electrode layer.
  • a Ni plating layer and a Sn plating layer which are outer layer plating layers, were formed on the surface of the resin electrode layer to prepare an electrolytic capacitor.
  • the composition of the electrode paste was 50% by weight of Ag powder, 17% by weight of phenol resin, 6% by weight of additives, 20% by weight of diethylene glycol monobutyl ether as a solvent, and 7% by weight of diethylene glycol monophenyl ether as a solvent.
  • Example 3 (Comparative Examples 1 to 3)
  • electroless Ni plating was performed instead of electroless Ag plating.
  • the treatment time of the electroless Ni plating was changed to change the film thickness of the electroless plating layer as shown in Table 1.
  • An electrolytic capacitor was produced in the same manner as in Example 1 except for the above.
  • Example 4 (Comparative Example 4)
  • electroless Ni plating was performed instead of electroless Ag plating, and electroless Ag plating was further performed to provide two layers, a Ni plating layer and an Ag plating layer, as inner layer plating layers.
  • An electrolytic capacitor was produced in the same manner as in Example 1 except for the above.
  • Table 1 shows the total processing time of electroless Ni plating and electrolytic Ag plating.
  • the thickness of the inner plating layer is shown in Table 1 by summing the thicknesses of the two layers.
  • FIG. 3 is a graph showing the relationship between the film thickness of the electroless Ag plating layer and ESR in Examples 1 to 5.
  • FIG. 4 is a graph showing the relationship between the film thickness of the electroless Cu plating layer and ESR in Examples 6 to 10.
  • FIG. 5 is a graph showing the relationship between the film thickness of the electroless Ni plating layer and ESR in Comparative Examples 1 to 3.
  • Electrode Capacitor 3 Electrode 3a Valve Acting Metal Foil 5 Electrode Layer 7 Electrode 7a Solid Electrode Layer 7b Conductive Layer 7c Electrode Drawer Layer 8 Encapsulating Resin 9 Resin Mold 9a First End Face 9b of Resin Mold End face 9c Bottom surface of resin molded body 9d Top surface of resin molded body 9e First side surface of resin molded body 9f Second side surface of resin molded body 11 First external electrodes 11a, 13a Ag plating layer or Cu plating layer 11b, 13b Resin electrode layer 11c, 13c Outer layer Plating layer 13 Second external electrode 20 Capacitor element 30 Laminated body

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
PCT/JP2020/037411 2019-10-04 2020-10-01 電解コンデンサ及び電解コンデンサの製造方法 Ceased WO2021066091A1 (ja)

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