WO2022131020A1 - Élément de condensateur électrolytique solide, condensateur électrolytique solide, procédé de production d'élément de condensateur électrolytique solide et procédé de production de condensateur électrolytique solide - Google Patents

Élément de condensateur électrolytique solide, condensateur électrolytique solide, procédé de production d'élément de condensateur électrolytique solide et procédé de production de condensateur électrolytique solide Download PDF

Info

Publication number
WO2022131020A1
WO2022131020A1 PCT/JP2021/044442 JP2021044442W WO2022131020A1 WO 2022131020 A1 WO2022131020 A1 WO 2022131020A1 JP 2021044442 W JP2021044442 W JP 2021044442W WO 2022131020 A1 WO2022131020 A1 WO 2022131020A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
electrolytic capacitor
metal substrate
solid electrolytic
acting metal
Prior art date
Application number
PCT/JP2021/044442
Other languages
English (en)
Japanese (ja)
Inventor
康浩 玉谷
和哉 楠田
Original Assignee
株式会社村田製作所
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 株式会社村田製作所 filed Critical 株式会社村田製作所
Publication of WO2022131020A1 publication Critical patent/WO2022131020A1/fr

Links

Images

Classifications

    • 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
    • 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
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • 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
    • H01G9/08—Housing; Encapsulation
    • H01G9/10—Sealing, e.g. of lead-in wires

Definitions

  • the present invention relates to a method for manufacturing a solid electrolytic capacitor element, a solid electrolytic capacitor, a solid electrolytic capacitor element, and a method for manufacturing a solid electrolytic capacitor.
  • the solid electrolytic capacitor includes a valve acting metal substrate having a dielectric layer on the surface of a substrate made of a valve acting metal such as aluminum, and a cathode layer including a solid electrolyte layer provided on the dielectric layer.
  • Patent Document 1 prepares a first sheet having (A) a valve acting metal substrate having a dielectric layer formed on its surface and a solid electrolyte layer provided on the dielectric layer, and having a plurality of element regions. Steps, (B) a step of preparing a second sheet made of a metal foil and having a plurality of element regions, and (C) a first end portion and a second end of each element region of the first sheet. A step of covering the portion with the first side portion and the second side portion with an insulating material, (D) a step of forming a conductor layer on the solid electrolyte layer of the first sheet, and (E) a first sheet.
  • a step of laminating the second sheet to produce a laminated sheet (F) a step of filling a through hole of the laminated sheet with a sealing material to produce a laminated block body, and (G) cutting the laminated block body.
  • Patent Document 1 for example, a treatment liquid containing a monomer or a dispersion liquid of a polymer is applied onto a dielectric layer by sponge transfer, screen printing, dispenser, inkjet printing, or the like to form a solid electrolyte layer in a predetermined region. It is stated that it can be done. Further, in Patent Document 1, a mask material made of an insulating material such as an insulating resin is applied to the surface of a valve acting metal substrate and solidified or cured by heating or the like to obtain an edge of each element region of the first sheet. It is described that it is preferable to form a mask layer that covers the portion and the side portion, and to form a solid electrolyte layer in the region surrounded by the mask layer.
  • Patent Document 2 discloses a solid electrolytic capacitor in which the thickness of the solid electrolyte formed in the cut end portion and the masking portion of the valve acting metal porous substrate is larger than that in the other portions.
  • the bias in the thickness of the solid electrolyte layer differs depending on the solid electrolyte formation conditions such as the number of operations of immersing the organic polymer in the monomer-containing liquid and the oxidant-containing liquid on the valve acting metal substrate. It is stated that.
  • Patent Document 3 discloses a solid electrolytic capacitor having a masking structure capable of reliably insulating an anode portion and a cathode portion, and a method for manufacturing the same.
  • the masking layer permeates into the dielectric film and is formed on the permeated portion, and the solid electrolyte permeating into the dielectric film is contained in the dielectric film permeated by the masking material. Shows a structure that cannot penetrate and is completely masked by a masking layer formed on the permeated portion.
  • Patent Document 2 and Patent Document 3 describe that masking is applied to insulate the anode portion and the cathode portion of the solid electrolytic capacitor.
  • a masking layer is formed by applying a masking material in a circumferential shape on a valve acting metal substrate so as to separate an anode portion and a cathode portion, and then in a region to be a cathode portion.
  • a solid electrolyte layer is formed by a dipping method (also referred to as a dip method).
  • a plurality of solid electrolytic capacitor elements can be efficiently manufactured from a large-sized valve acting metal substrate.
  • the solid electrolyte layer is formed by the dipping method described in Patent Document 2 and Patent Document 3, the solid electrolyte layer can be formed on both sides of each element region at the same time, which further simplifies the manufacturing process. It will be possible to do.
  • Patent Document 2 and Patent Document 3 do not disclose any method for forming a solid electrolyte layer in the device region described in Patent Document 1. Therefore, by improving the impregnation property of the solid electrolyte layer in the entire element region, there is room for improvement in improving the capacitance appearance rate, which is one of the capacitance characteristics of the obtained solid electrolytic capacitor element.
  • the present invention has been made to solve the above problems, and to provide a solid electrolytic capacitor element having a high impregnation property of a solid electrolyte layer formed by a dipping method and a high capacitance appearance rate as a capacitance characteristic. With the goal. It is also an object of the present invention to provide a solid electrolytic capacitor including the solid electrolytic capacitor element, a method for manufacturing the solid electrolytic capacitor element, and a method for manufacturing the solid electrolytic capacitor.
  • the solid electrolytic capacitor element of the present invention has a dielectric layer on at least one main surface, a valve acting metal substrate having a rectangular shape when viewed in a plan view from the thickness direction, and the valve on the dielectric layer. It includes an insulating mask layer provided so as to cover four sides around the main surface of the working metal substrate, and a cathode layer provided on the dielectric layer.
  • the cathode layer includes a solid electrolyte layer provided in a region on the dielectric layer surrounded by the insulating mask layer.
  • the solid electrolyte layer has an end portion that has penetrated into a part of the insulating mask layer on at least one side of the outer peripheral portion of the region surrounded by the insulating mask layer.
  • the solid electrolytic capacitor of the present invention includes a solid electrolytic capacitor element, an exterior body, a first external electrode, and a second external electrode.
  • the solid electrolytic capacitor element has a dielectric layer on at least one main surface, a valve acting metal substrate having a rectangular shape when viewed in a plan view from the thickness direction, and the valve acting metal on the dielectric layer. It includes an insulating mask layer provided so as to cover four sides around the main surface of the substrate, and a cathode layer provided on the dielectric layer.
  • the exterior body seals the solid electrolytic capacitor element.
  • the first external electrode is electrically connected to the cathode layer of the solid electrolytic capacitor element exposed from the exterior body.
  • the second external electrode is electrically connected to the valve acting metal substrate of the solid electrolytic capacitor element exposed from the exterior body.
  • the cathode layer includes a solid electrolyte layer provided in a region on the dielectric layer surrounded by the insulating mask layer.
  • the solid electrolyte layer has an end portion that has penetrated into a part of the insulating mask layer on at least one side of the outer peripheral portion of the region surrounded by the insulating mask layer.
  • a valve acting metal substrate having a dielectric layer on at least one main surface is divided into a plurality of element regions having a rectangular shape when viewed from the thickness direction. This comprises a step of forming an insulating mask layer on the dielectric layer of the valve acting metal substrate and a step of forming a cathode layer on the dielectric layer.
  • the step of forming the cathode layer includes a step of forming a solid electrolyte layer in the region surrounded by the insulating mask layer on the dielectric layer.
  • the step of forming the solid electrolyte layer is a step of immersing the valve acting metal substrate in a direction orthogonal to the first side of the element region with respect to the treatment liquid containing the solid electrolyte, and then pulling it out of the treatment liquid. including.
  • a valve working metal substrate having a dielectric layer on at least one main surface is partitioned into a plurality of element regions having a rectangular shape when viewed in plan from the thickness direction. Therefore, a step of forming an insulating mask layer on the dielectric layer of the valve acting metal substrate, a step of forming a cathode layer on the dielectric layer, and a step of forming the insulating mask layer and the cathode layer were formed.
  • the step of forming the first external electrode electrically connected to the cathode layer of the exposed solid electrolytic capacitor element and the valve acting metal substrate of the solid electrolytic capacitor element exposed from the exterior body are electrically connected.
  • a step of forming a second external electrode to be formed is provided.
  • the step of forming the cathode layer includes a step of forming a solid electrolyte layer in the region surrounded by the insulating mask layer on the dielectric layer.
  • the step of forming the solid electrolyte layer is a step of immersing the valve acting metal substrate in a direction orthogonal to the first side of the element region with respect to the treatment liquid containing the solid electrolyte, and then pulling it out of the treatment liquid. including.
  • a solid electrolytic capacitor element having a high impregnation property of a solid electrolyte layer formed by a dipping method and a high capacitance appearance rate as a capacitance characteristic.
  • FIG. 1 is a perspective view schematically showing an example of the solid electrolytic capacitor of the present invention.
  • FIG. 2 is a cross-sectional view taken along the line II-II of the solid electrolytic capacitor shown in FIG.
  • FIG. 3 is an enlarged cross-sectional view of part III of the solid electrolytic capacitor shown in FIG.
  • FIG. 4 is a plan view schematically showing an example of a solid electrolytic capacitor element according to the first embodiment of the present invention.
  • FIG. 5 is a cross-sectional view taken along the line VV of the solid electrolytic capacitor element shown in FIG.
  • FIG. 6 is a plan view schematically showing an example of the solid electrolytic capacitor element according to the second embodiment of the present invention.
  • FIG. 1 is a perspective view schematically showing an example of the solid electrolytic capacitor of the present invention.
  • FIG. 2 is a cross-sectional view taken along the line II-II of the solid electrolytic capacitor shown in FIG.
  • FIG. 3 is an enlarged cross-sectional view of part III of the solid
  • FIG. 7 is a cross-sectional view taken along the line VII-VII of the solid electrolytic capacitor element shown in FIG.
  • FIG. 8 is a perspective view schematically showing an example of a valve acting metal substrate on which an insulating mask layer is formed.
  • FIG. 9 is an enlarged perspective view of a part of the valve acting metal substrate shown in FIG.
  • FIG. 10 is a schematic view showing an example of a step of holding the valve acting metal substrate in the immersion treatment apparatus in the first direction in the first embodiment of the present invention.
  • FIG. 11 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the first short side of the element region is orthogonal to each other in the first embodiment of the present invention.
  • FIG. 12 is a schematic view showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG.
  • FIG. 13 is a schematic view showing an example of a step of holding the valve acting metal substrate in the dipping treatment apparatus in the second direction in the first embodiment of the present invention.
  • FIG. 14 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the second short side of the element region is orthogonal to each other in the first embodiment of the present invention.
  • FIG. 15 is a schematic view showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG. FIG.
  • FIG. 16 is a schematic diagram showing an example of an element region after being immersed and dried a plurality of times in the first embodiment of the present invention.
  • FIG. 17 is a schematic view showing an example of a step of holding the valve acting metal substrate in the dipping treatment apparatus in the first direction in the second embodiment of the present invention.
  • FIG. 18 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the first long side of the element region is orthogonal to each other in the second embodiment of the present invention.
  • FIG. 19 is a schematic view showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG. FIG.
  • FIG. 20 is a schematic view showing an example of a step of holding the valve acting metal substrate in the dipping treatment apparatus in the second direction in the second embodiment of the present invention.
  • FIG. 21 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the second long side of the element region is orthogonal to each other in the second embodiment of the present invention.
  • FIG. 22 is a schematic view showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG. 21.
  • FIG. 23 is a schematic diagram showing an example of an element region after being immersed and dried a plurality of times in the second embodiment of the present invention.
  • FIG. 24 is a perspective view schematically showing an example of a metal foil.
  • FIG. 25 is an enlarged perspective view of a part of the metal leaf shown in FIG. 24.
  • FIG. 26 is a perspective view schematically showing an example of a state before the valve acting metal substrate and the metal foil are laminated.
  • FIG. 27 is a perspective view schematically showing an example of a state in which a valve acting metal substrate and a metal foil are laminated.
  • FIG. 28 is a plan view schematically showing an example of a valve acting metal substrate filled with a sealing material.
  • FIG. 29 is a plan view schematically showing an example of a metal foil filled with a sealing material.
  • FIG. 30 is a perspective view schematically showing an example of a laminated sheet in which a through hole is filled with a sealing material.
  • FIG. 31 is a perspective view schematically showing an example of an element encapsulating body viewed from the first end face side.
  • FIG. 32 is a perspective view schematically showing an example of an element encapsulating body viewed from the second end face side.
  • FIG. 33 is a mapping image of the Si element and the S element on the first long side of the capacitor element of the second embodiment.
  • FIG. 34 is a graph showing the capacitance appearance rate of the capacitor element in Example 1, Example 2, Example 3, and Comparative Example 1.
  • FIG. 35 is a graph showing the leakage current of the capacitor element in Example 1, Example 2, Example 3, and Comparative Example 1.
  • the present invention is not limited to the following configuration, 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 of the individual desirable configurations described below is also the present invention.
  • Solid electrolytic capacitor element and solid electrolytic capacitor an example of the solid electrolytic capacitor element of the present invention and an example of the solid electrolytic capacitor including the solid electrolytic capacitor element of the present invention will be described.
  • the solid electrolytic capacitor element of the present invention may be included in a solid electrolytic capacitor having another configuration.
  • the lead frame may be used as an external electrode.
  • FIG. 1 is a perspective view schematically showing an example of the solid electrolytic capacitor of the present invention.
  • FIG. 2 is a cross-sectional view taken along the line II-II of the solid electrolytic capacitor shown in FIG.
  • FIG. 3 is an enlarged cross-sectional view of part III of the solid electrolytic capacitor shown in FIG.
  • the length direction of the solid electrolytic capacitor 1 and the exterior body 10 is L
  • the width direction is W
  • the height direction is T.
  • the length direction L, the width direction W, and the height direction T are orthogonal to each other.
  • the solid electrolytic capacitor 1 has a substantially rectangular parallelepiped outer shape.
  • the solid electrolytic capacitor 1 includes an exterior body 10, a first external electrode 20, a second external electrode 30, and a plurality of capacitor elements 70.
  • the capacitor element 70 is an example of the solid electrolytic capacitor element of the present invention.
  • the exterior body 10 seals a plurality of capacitor elements 70. That is, a plurality of capacitor elements 70 are embedded in the exterior body 10.
  • the exterior body 10 may seal one capacitor element 70. That is, one capacitor element 70 may be embedded inside the exterior body 10.
  • the exterior body 10 has a substantially rectangular parallelepiped outer shape.
  • the exterior body 10 has a first main surface 10a and a second main surface 10b facing each other in the height direction T, a first side surface 10c and a second side surface 10d facing each other in the width direction W, and a second side surface facing each other in the length direction L. It has one end face 10e and a second end face 10f.
  • the exterior body 10 has a substantially rectangular parallelepiped outer shape, but it is preferable that the corners and ridges are rounded.
  • the corner portion is a portion where the three surfaces of the exterior body 10 intersect, and the ridge portion is a portion where the two surfaces of the exterior body 10 intersect.
  • the exterior body 10 is composed of, for example, a substrate 11 and a mold portion 12 provided on the substrate 11.
  • the exterior body 10 may be composed of only the mold portion 12.
  • the substrate 11 is an insulating resin substrate such as a glass epoxy substrate.
  • the bottom surface of the substrate 11 constitutes the second main surface 10b of the exterior body 10.
  • the thickness of the substrate 11 is, for example, 100 ⁇ m.
  • the mold portion 12 is made of an insulating resin such as an epoxy resin. It is preferable that the insulating resin is dispersed and mixed with an oxide of glass or Si as a filler.
  • the mold portion 12 is provided on the substrate 11 so as to cover the plurality of capacitor elements 70.
  • Each of the plurality of capacitor elements 70 includes a valve acting metal substrate 40 having a dielectric layer 50 on its surface, an insulating mask layer 51, and a cathode layer 60.
  • the plurality of capacitor elements 70 are laminated on the substrate 11 in the height direction T.
  • the extending direction of each of the plurality of capacitor elements 70 is substantially parallel to the main surface of the substrate 11.
  • the shape of the valve acting metal substrate 40 viewed in a plan view from the thickness direction is a square shape, preferably a rectangular shape having a long side and a short side. As shown in FIG. 3, a plurality of recesses are provided on the main surface of the valve acting metal substrate 40. Therefore, the main surface of the valve acting metal substrate 40 is porous. Since the main surface of the valve-acting metal substrate 40 is porous, the surface area of the valve-acting metal substrate 40 is large. It should be noted that the case is not limited to the case where both the front surface and the back surface of the valve acting metal substrate 40 are porous, and only one of the front surface and the back surface of the valve acting metal substrate 40 may be porous.
  • the valve acting metal substrate 40 is composed of, for example, a simple substance such as aluminum, tantalum, niobium, titanium, zirconium, or a valve acting metal such as an alloy containing any of these metals as a main component.
  • An oxide film can be formed on the surface of the valve acting metal.
  • the valve acting metal substrate 40 may be composed of a core portion and a porous portion provided on at least one main surface of the core portion, and the surface of the metal foil may be etched or the surface of the metal foil. It is possible to appropriately adopt a material obtained by forming a porous fine powder sintered body.
  • the dielectric layer 50 is provided on at least one main surface of the valve acting metal substrate 40.
  • the dielectric layer 50 is preferably composed of an oxide film provided on the surface of the valve acting metal.
  • the dielectric layer 50 is made of an oxide of aluminum.
  • the aluminum oxide is formed by anodizing the surface of the valve acting metal substrate 40.
  • an insulating mask layer 51 having a composition different from that of the exterior body 10 is provided on the dielectric layer 50.
  • the insulating mask layer 51 is provided so as to cover the four peripheral sides of the main surface of the valve acting metal substrate 40.
  • the insulating mask layer 51 is preferably provided so as to fill a plurality of pores (recesses) of the valve acting metal substrate 40. However, it is sufficient that the insulating mask layer 51 covers a part of the outer surface of the dielectric layer 50, and there are pores (recesses) in the valve acting metal substrate 40 that are not filled by the insulating mask layer 51. May be good.
  • the insulating mask layer 51 is formed by applying a mask material such as a composition containing an insulating resin, for example.
  • a mask material such as a composition containing an insulating resin
  • the insulating resin include polyphenylsulfone (PPS), polyethersulfone (PES), cyanate ester resin, fluororesin (tetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, etc.), and soluble polyimide.
  • PPS polyphenylsulfone
  • PES polyethersulfone
  • cyanate ester resin fluororesin (tetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, etc.)
  • fluororesin tetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, etc.
  • soluble polyimide
  • the cathode layer 60 is provided on the dielectric layer 50. As shown in FIG. 2, the cathode layer 60 includes a solid electrolyte layer 61, and preferably further includes a conductor layer 62 and a cathode extraction layer 63.
  • the solid electrolyte layer 61 is provided in a region on the dielectric layer 50 surrounded by the insulating mask layer 51. Therefore, the solid electrolyte layer 61 is not provided on the outer surface of the dielectric layer 50 provided on the main surface of the valve acting metal substrate 40 located closer to the second end surface 10f.
  • the solid electrolyte layer 61 is provided so as to fill a plurality of pores (recesses) of the valve acting metal substrate 40. However, it is sufficient that the solid electrolyte layer 61 covers a part of the outer surface of the dielectric layer 50, and there are pores (recesses) of the valve acting metal substrate 40 that are not filled by the solid electrolyte layer 61. May be good.
  • the material constituting the solid electrolyte layer 61 for example, conductive polymers such as polypyrroles, polythiophenes, and polyanilines are used. Among these, polythiophenes are preferable, and poly (3,4-ethylenedioxythiophene) called PEDOT is particularly preferable. Further, the conductive polymer may contain a dopant such as polystyrene sulfonic acid (PSS).
  • PSS polystyrene sulfonic acid
  • a liquid containing a polymerizable monomer such as 3,4-ethylenedioxythiophene is used, and the surface of the dielectric layer 50 is made conductive such as poly (3,4-ethylenedioxythiophene). It is formed by a method of forming a polymer polymer film, a method of applying a dispersion liquid of a conductive polymer such as poly (3,4-ethylenedioxythiophene) to the surface of the dielectric layer 50 and drying it. .. It is preferable to form an inner layer that fills the pores (recesses) of the valve acting metal substrate 40, and then form an outer layer that covers the entire dielectric layer 50.
  • the conductor layer 62 is provided on the outer surface of the solid electrolyte layer 61.
  • the conductor layer 62 includes, for example, a carbon layer or a silver layer. Further, the conductor layer 62 may be a composite layer in which a silver layer is provided on the outer surface of the carbon layer, or a mixed layer containing carbon and silver.
  • the cathode extraction layer 63 is provided on the outer surface of the conductor layer 62.
  • the conductor layers 62 of the capacitor elements 70 adjacent to each other in the stacking direction are electrically connected to each other by the cathode extraction layer 63.
  • the width of the cathode extraction layer 63 in the width direction W is, for example, the same as the width of the valve acting metal substrate 40 in the width direction W.
  • the cathode lead-out layer 63 can be formed of a metal foil or a printed electrode layer. With the above configuration, the capacitor element 70, which is an example of the solid electrolytic capacitor element of the present invention, is formed.
  • a metal foil it is preferably made of at least one metal selected from the group consisting of Al, Cu, Ag and an alloy containing any of these metals as a main component.
  • 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. Above all, it is preferable to use carbon-coated aluminum foil.
  • the cathode extraction layer can be formed in a predetermined area by forming the electrode paste on the conductor 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 cathode extraction layer can be made thinner than when a metal foil is used.
  • the first external electrode 20 is provided on the first end surface 10e of the exterior body 10.
  • the first external electrode 20 is provided from the first end surface 10e of the exterior body 10 to each of the first main surface 10a, the second main surface 10b, the first side surface 10c, and the second side surface 10d. There is.
  • the first external electrode 20 is electrically connected to the cathode layer 60 of the capacitor element 70 exposed from the exterior body 10.
  • the first external electrode 20 is directly or indirectly connected to the cathode extraction layer 63 at the first end surface 10e of the exterior body 10.
  • the first external electrode 20 is composed of, for example, at least one plating layer provided on the first end surface 10e of the exterior body 10.
  • the first external electrode 20 has a Cu plating layer provided on the first end surface 10e of the exterior body 10, a Ni plating layer provided on the Cu plating layer, and Sn plating provided on the Ni plating layer. Consists of layers.
  • the second external electrode 30 is provided on the second end surface 10f of the exterior body 10.
  • the second external electrode 30 is provided from the second end surface 10f of the exterior body 10 to each of the first main surface 10a, the second main surface 10b, the first side surface 10c, and the second side surface 10d. There is.
  • the second external electrode 30 is electrically connected to the valve acting metal substrate 40 of the capacitor element 70 exposed from the exterior body 10.
  • the second external electrode 30 is composed of, for example, at least one plating layer provided on the second end surface 10f of the exterior body 10.
  • the second external electrode 30 has a Cu plating layer provided on the second end surface 10f of the exterior body 10, a Ni plating layer provided on the Cu plating layer, and Sn plating provided on the Ni plating layer. Consists of layers.
  • the solid electrolyte layer is an end that has entered a part of the insulating mask layer at at least one side of the outer peripheral portion of the region surrounded by the insulating mask layer. Has a part.
  • FIG. 4 is a plan view schematically showing an example of a solid electrolytic capacitor element according to the first embodiment of the present invention.
  • FIG. 5 is a cross-sectional view taken along the line VV of the solid electrolytic capacitor element shown in FIG.
  • the shape of the valve acting metal substrate 40 viewed in a plan view from the thickness direction is a rectangular shape having a long side and a short side.
  • an insulating mask layer 51 is provided so as to cover the four peripheral sides of the main surface of the valve acting metal substrate 40.
  • a solid electrolyte layer 61 is provided in a region on the dielectric layer (not shown) surrounded by the insulating mask layer 51.
  • the solid electrolyte layer 61 is a thick film having a larger film thickness on the dielectric layer than the other portions on the opposite short sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51. It is preferable to have parts 61a and 61b. As shown in FIG. 4, it is preferable that the thick film portion 61a provided on one short side is connected to the thick film portion 61b provided on the other short side facing the other.
  • the maximum thickness of the thick film portion 61a may be the same as or different from the maximum thickness of the thick film portion 61b.
  • the solid electrolyte layer 61 does not have a thick film portion on the opposite long side of the outer peripheral portion of the region surrounded by the insulating mask layer 51, but at least one of the opposite long sides. May have a thick film portion. In that case, the maximum thickness of each thick film portion may be the same or different.
  • the solid electrolyte layer 61 has an end portion 61x that has penetrated into a part of the insulating mask layer 51 at the first short side of the outer peripheral portion of the region surrounded by the insulating mask layer 51. ..
  • the end portion 61x of the solid electrolyte layer 61 may be in contact with the insulating mask layer 51 or may be separated from the insulating mask layer 51.
  • the solid electrolyte layer 61 may have an end portion 61x that has penetrated into a part of the insulating mask layer 51 in the whole of the first short side, or the insulating mask layer 51 in a part of the first short side. It may have an end portion 61x that penetrates a part of.
  • the solid electrolyte layer 61 is further formed on the outer peripheral portion of the region surrounded by the insulating mask layer 51 on the second short side facing the first short side. It is preferable to have an end portion 61x that penetrates a part. In this case, the end portion 61x of the solid electrolyte layer 61 may be in contact with the insulating mask layer 51 or may be separated from the insulating mask layer 51.
  • the solid electrolyte layer 61 may have an end portion 61x that penetrates a part of the insulating mask layer 51 in the whole of the second short side, or the insulating mask layer 51 in a part of the second short side. It may have an end portion 61x that penetrates a part of.
  • the distance at which the end portion 61x of the solid electrolyte layer 61 enters a part of the insulating mask layer 51 may be the same or different between the first short side and the second short side.
  • the solid electrolyte layer 61 may have an end portion that has penetrated into a part of the insulating mask layer 51 on at least one of the opposite long sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51. good. In that case, the distance at which the end portion enters a part of the insulating mask layer 51 on each side may be the same or different.
  • FIG. 6 is a plan view schematically showing an example of the solid electrolytic capacitor element according to the second embodiment of the present invention.
  • FIG. 7 is a cross-sectional view taken along the line VII-VII of the solid electrolytic capacitor element shown in FIG.
  • the structure shown in FIG. 6 is the same as the structure shown in FIG. 4, except that the positions of the thick film portions are different.
  • the shape of the valve acting metal substrate 40 viewed in a plan view from the thickness direction is a rectangular shape having a long side and a short side.
  • an insulating mask layer 51 is provided so as to cover the four peripheral sides of the main surface of the valve acting metal substrate 40.
  • a solid electrolyte layer 61 is provided in a region on the dielectric layer (not shown) surrounded by the insulating mask layer 51.
  • the solid electrolyte layer 61 is a thick film having a larger film thickness on the dielectric layer than the other portions on the opposite long sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51. It is preferable to have parts 61c and 61d. As shown in FIG. 6, it is preferable that the thick film portion 61c provided on one long side is connected to the thick film portion 61d provided on the other long side facing the other. The maximum thickness of the thick film portion 61c may be the same as or different from the maximum thickness of the thick film portion 61d.
  • the solid electrolyte layer 61 does not have a thick film portion on the opposite short side of the outer peripheral portion of the region surrounded by the insulating mask layer 51, but at least one side of the facing short sides. May have a thick film portion. In that case, the maximum thickness of each thick film portion may be the same or different.
  • the solid electrolyte layer 61 has an end portion 61y that has penetrated into a part of the insulating mask layer 51 on the first long side of the outer peripheral portion of the region surrounded by the insulating mask layer 51. ..
  • the end portion 61y of the solid electrolyte layer 61 may be in contact with the insulating mask layer 51 or may be separated from the insulating mask layer 51.
  • the solid electrolyte layer 61 may have an end portion 61y that has penetrated into a part of the insulating mask layer 51 in the whole of the first long side, or the insulating mask layer 51 in a part of the first long side. It may have an end portion 61y that penetrates a part of the above.
  • the solid electrolyte layer 61 is further formed on the outer peripheral portion of the region surrounded by the insulating mask layer 51 on the second long side facing the first long side of the insulating mask layer 51. It is preferable to have an end portion 61y that penetrates a part. In this case, the end portion 61y of the solid electrolyte layer 61 may be in contact with the insulating mask layer 51 or may be separated from the insulating mask layer 51.
  • the solid electrolyte layer 61 may have an end portion 61y that has penetrated into a part of the insulating mask layer 51 in the whole of the second long side, or the insulating mask layer 51 in a part of the second long side.
  • the distance at which the end portion 61y of the solid electrolyte layer 61 enters a part of the insulating mask layer 51 may be the same or different between the first long side and the second long side.
  • the solid electrolyte layer 61 may have an end portion that has penetrated into a part of the insulating mask layer 51 on at least one of the opposite short sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51. good. In that case, the distance at which the end portion enters a part of the insulating mask layer 51 on each side may be the same or different.
  • the shape of the valve acting metal substrate in a plan view from the thickness direction may be a rectangular shape other than a rectangular shape.
  • the solid electrolyte layer may have an end portion that penetrates a part of the insulation mask layer on at least one side of the outer peripheral portion of the region surrounded by the insulation mask layer, but the solid electrolyte layer is insulated. It is preferable that at least two sides of the outer peripheral portion of the region surrounded by the mask layer have an end portion that has penetrated into a part of the insulating mask layer, and the outer peripheral portion of the region surrounded by the insulating mask layer. It is more preferable to have an end portion that penetrates into a part of the insulating mask layer on the two opposite sides. The distance at which the edges penetrate a portion of the insulating mask layer on each side may be the same or different.
  • the solid electrolyte layer has an end portion that has entered a part of the insulating mask layer on three sides of the outer peripheral portion of the region surrounded by the insulating mask layer. It may have an end portion which has penetrated into a part of the insulating mask layer on four sides. The distance at which the edges penetrate a portion of the insulating mask layer on each side may be the same or different.
  • the solid electrolyte layer does not have to have a thick film portion at the side where the end portion that has entered a part of the insulating mask layer is located. , It is preferable to have a thick film portion.
  • a side having a thick film portion and a side having no thick film portion may be mixed.
  • the solid electrolyte layer when the solid electrolyte layer has a thick film portion, the solid electrolyte layer is formed on at least one side of the outer peripheral portion of the region surrounded by the insulating mask layer. It suffices to have a thick film portion, but it is preferable to have a thick film portion on at least two sides of the outer peripheral portion of the region surrounded by the insulating mask layer, and the outer peripheral portion of the region surrounded by the insulating mask layer is preferable. It is more preferable to have a thick film portion on two opposite sides of the film.
  • the thick film portion provided on one side is provided on the other side facing each other. It does not have to be connected to the thick film portion, but it is preferable that it is connected.
  • the maximum thickness of each thick film portion may be the same or different.
  • the solid electrolyte layer when the solid electrolyte layer has a thick film portion, the solid electrolyte layer is thick on three sides of the outer peripheral portion of the region surrounded by the insulating mask layer. It may have a film portion or may have a thick film portion on four sides. In that case, the thick film portion provided on one side may not be connected to the thick film portion provided on the other side facing the other side, but it is preferable that the thick film portion is connected.
  • the maximum thickness of each thick film portion may be the same or different.
  • the thick film portion of the solid electrolyte layer is an inner layer that fills the pores (recesses) of the valve acting metal substrate. It is preferable to contain the same material as. For example, PEDOT / PSS is preferable.
  • the thick film portion of the solid electrolyte layer is the same as the outer layer and the portion containing the same material as the inner layer in order from the dielectric layer. It may include a portion containing a material.
  • the solid electrolyte layer may be provided on the insulating mask layer over the outside of the region surrounded by the insulating mask layer.
  • the insulating mask layer is provided on the entire four sides around the main surface of the valve acting metal substrate on the dielectric layer. There may be a portion where the insulating mask layer is not provided on a part of the four peripheral sides.
  • the method for manufacturing a solid electrolytic capacitor element of the present invention may include at least the following steps ST1 and ST2.
  • a plurality of solid electrolytic capacitor elements may be manufactured at the same time using a large-sized valve acting metal substrate, and one valve acting metal substrate is used. Solid electrolytic capacitor elements may be manufactured.
  • Step ST1 Step of forming an insulating mask layer
  • the dielectric of a valve acting metal substrate is divided into a plurality of element regions with respect to the valve acting metal substrate having a dielectric layer on at least one main surface.
  • An insulating mask layer is formed on the body layer.
  • FIG. 8 is a perspective view schematically showing an example of a valve acting metal substrate on which an insulating mask layer is formed.
  • FIG. 9 is an enlarged perspective view of a part of the valve acting metal substrate shown in FIG.
  • a valve acting metal substrate 140 having a porous portion on the surface is prepared, and a dielectric layer 50 is formed on the surface of the porous portion.
  • an aluminum foil as a valve acting metal substrate 140 is immersed in an aqueous solution of ammonium adipate and anodized to form an oxide of aluminum to be a dielectric layer 50.
  • the valve acting metal substrate 140 after cutting is used to form the aluminum oxide on the cut surface. Is immersed again in an aqueous solution of ammonium adipate and anodized.
  • the dielectric of the valve acting metal substrate 140 is divided into a plurality of element regions R11 (hereinafter referred to as a first element region R11) and a plurality of element regions R12 (hereinafter referred to as a second element region R12).
  • the insulating mask layer 51 is formed on the layer 50.
  • the insulating mask layer 51 is formed, for example, by applying the above-mentioned mask material to the surface of the valve acting metal substrate 140 and solidifying or curing it by heating or the like.
  • the mask material is preferably applied by screen printing, dispenser, inkjet printing or the like.
  • the shape of the first element region R11 viewed in a plan view from the thickness direction is a square shape, preferably a rectangular shape having a long side and a short side.
  • the first element region R11 includes a first end portion E11 and a second end portion E12 facing each other in the length direction L, and a first side portion S11 and a second side portion S12 facing each other in the width direction W. It is partitioned by.
  • the dimension of the first element region R11 in the length direction L is larger than the dimension in the width direction W.
  • one first through hole H1 is formed so as to straddle the first end portion E11 of the first element region R11 in the length direction L, and the second element region R11 has a second through hole H1.
  • a plurality of second through holes H2 are formed so as to straddle the end portion E12 in the length direction L.
  • the first through hole H1 is preferably composed of one elongated hole having a width equal to or larger than the width of the first element region R11, and the second through hole H2 is larger than the width of the first element region R11. It preferably consists of a plurality of substantially round holes having a small width.
  • the shape of the second element region R12 viewed in a plan view from the thickness direction is a square shape, preferably a rectangular shape having a long side and a short side.
  • the second element region R12 has the same shape as the first element region R11, but the orientations of the first end portion E11 and the second end portion E12 are opposite to those of the first element region R11. be.
  • the first element region R11 and the second element region R12 are alternately arranged in the length direction L. That is, as shown in FIG. 9, the first element region R11 shares the first end E11 with the adjacent second element region R12, and is second with the other adjacent second element regions R12. It is preferable to share the end E12 of the.
  • the first element region R11 and the second element region R12 are alternately arranged in the width direction W. That is, as shown in FIG. 9, the first element region R11 shares the first side portion S11 with the adjacent second element region R12, and is second with the other adjacent second element regions R12. It is preferable to share the side portion S12 of.
  • the first through hole H1 is not unevenly distributed in the width direction W of the valve acting metal substrate 140, so that the strength of the valve acting metal substrate 140 Is less likely to decrease.
  • the first element region R11 and the second element region R12 are alternately arranged in the length direction L, as shown in FIG. 9, the first element region R11 is an adjacent second element region. It is preferable to share the first end E11 and the first through hole H1 with R12, and share the second end E12 and the second through hole H2 with another adjacent second element region R12. .. In this case, the number of cuts for dividing the element region and the portion to be discarded can be reduced.
  • the first through hole H1 and the second through hole H2 are formed by, for example, laser processing, etching processing, punching processing, or the like.
  • the first through hole H1 and the second through hole H2 may be formed before forming the insulating mask layer 51, or may be formed after forming the solid electrolyte layer 61 described later.
  • the shape of the first through hole H1 is not particularly limited as long as it has a width equal to or larger than the width of the element region.
  • the shape, number, arrangement, and the like of the second through hole H2 are not particularly limited as long as they have a width smaller than the width of the element region, but two or more of the second through holes H2 are formed in the width direction W in each element region. Is preferable. When two or more second through holes H2 are formed, it is preferable that these through holes are formed at equal intervals.
  • the thickness of the valve acting metal substrate 140 is not particularly limited, but the thickness of the portion excluding the porous portion is preferably 5 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the porous portion (thickness of one side) is preferably 5 ⁇ m or more and 200 ⁇ m or less.
  • the size of the entire valve acting metal substrate 140 is determined by the size, shape, number, arrangement, production capacity, etc. of the first element region R11 and the second element region R12, and is not particularly limited.
  • Step ST2 Step of forming a cathode layer
  • a cathode layer is formed on a dielectric layer.
  • the step ST2 for forming the cathode layer includes the step ST21 for forming the solid electrolyte layer in the region surrounded by the insulating mask layer on the dielectric layer.
  • a solid electrolyte layer 61 (see FIG. 2) is formed inside the first element region R11 and inside the second element region R12 on the dielectric layer 50 shown in FIGS. 8 and 9.
  • the solid electrolyte layer 61 in a predetermined region by applying the treatment liquid containing the solid electrolyte on the dielectric layer 50 by the dipping method (dip method).
  • the treatment liquid containing the solid electrolyte for example, a liquid in which particles of the conductive polymer are dispersed in a solvent is used.
  • a conductive polymer film can be formed by adhering the dispersion liquid of the conductive polymer to the outer surface of the dielectric layer 50 and drying it.
  • a liquid containing a polymerizable monomer for example, 3,4-ethylenedioxythiophene and an oxidizing agent may be used.
  • a liquid containing the polymerizable monomer can be attached to the outer surface of the dielectric layer 50 to form a conductive polymer film by chemical polymerization. This conductive polymer film becomes the solid electrolyte layer 61.
  • the maximum thickness of the solid electrolyte layer 61 may be the same as the maximum thickness of the insulating mask layer 51, may be larger than the maximum thickness of the insulating mask layer 51, or may be smaller than the maximum thickness of the insulating mask layer 51.
  • the step ST21 for forming the solid electrolyte layer is a step ST21A of immersing the valve acting metal substrate in the direction in which the first side of the element region is orthogonal to the treatment liquid containing the solid electrolyte and then pulling it out of the treatment liquid.
  • the valve acting metal substrate in addition to the step ST21A, is immersed in the treatment liquid in the direction orthogonal to the second side of the element region, and then pulled up from the treatment liquid. It is preferable to include the step ST21B.
  • step ST21 for forming the solid electrolyte layer it is preferable to repeat the steps ST21A and ST21B in order to form the solid electrolyte layer having a predetermined thickness.
  • the shape of the element region viewed in a plan view from the thickness direction is a rectangular shape having a long side and a short side, and the first side and the second side of the element region are opposite short sides.
  • FIG. 10 is a schematic view showing an example of a step of holding the valve acting metal substrate in the immersion treatment apparatus in the first direction in the first embodiment of the present invention.
  • the immersion processing device 200 shown in FIG. 10 includes a support plate 210, which is also called a temporary bar, and a processing tank 220.
  • the support plate 210 has a seat holding portion 211 and can move in the vertical direction as shown by the white arrow in FIG.
  • a supply valve 221 and a discharge valve 222 are connected to the processing tank 220.
  • the valve acting metal substrate 140 (see FIGS. 8 and 9) in which the insulating mask layer 51 is formed in a grid pattern is held by the sheet holding portion 211 of the support plate 210.
  • the valve acting metal substrate 140 is held so that the length direction L of the element region is parallel to the vertical direction.
  • the treatment liquid 230 containing the solid electrolyte for example, a dispersion liquid of the conductive polymer is supplied to the treatment tank 220.
  • FIG. 11 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the first short side of the element region is orthogonal to each other in the first embodiment of the present invention.
  • the valve acting metal substrate 140 is immersed in the treatment liquid 230 in the direction in which the first short side of the element region is orthogonal to each other. That is, the valve acting metal substrate 140 is immersed in the treatment liquid 230 along the length direction L of the element region. As a result, the dispersion liquid of the conductive polymer is impregnated into the porous portion of the valve acting metal substrate 140.
  • the immersion speed may be any speed, but is preferably 0.5 mm / s or more and 5 mm / s or less.
  • the sheet holding portion 211 holds the end portion of the valve acting metal substrate 140, but a frame may be provided so as to surround the four sides of the valve acting metal substrate 140 to hold the seat holding portion 211.
  • FIG. 12 is a schematic diagram showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG.
  • the valve acting metal substrate 140 is pulled up from the treatment liquid 230.
  • a semi-circular liquid pool A1 is formed in the lower part of the element region after immersion.
  • the liquid pool A1 is a surplus of the dispersion liquid of the conductive polymer that could not be impregnated and hung down at the bottom.
  • the immersion time is preferably 1 second or more and 10 seconds or less.
  • the pulling speed may be any speed, but is preferably 0.01 mm / s or more and 5 mm / s or less. It is more preferably 0.1 mm / s or more and 3 mm or less from the viewpoint of the stability of the amount of liquid pool and the productivity due to the lead time.
  • FIG. 13 is a schematic view showing an example of a step of holding the valve acting metal substrate in the dipping treatment apparatus in the second direction in the first embodiment of the present invention.
  • valve acting metal substrate 140 is inverted 180 degrees and held by the sheet holding portion 211 of the support plate 210.
  • FIG. 14 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the second short side of the element region is orthogonal to each other in the first embodiment of the present invention.
  • valve acting metal substrate 140 is immersed in the treatment liquid 230 in the same direction as in FIG.
  • FIG. 15 is a schematic diagram showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG.
  • the valve acting metal substrate 140 is pulled up from the treatment liquid 230. Similar to FIG. 12, a semicircular liquid pool A2 is formed in the lower part of the element region after immersion.
  • the liquid pool A2 has a shape that is substantially vertically symmetrical with the liquid pool A1 before inversion.
  • FIG. 16 is a schematic diagram showing an example of an element region after being immersed and dried a plurality of times in the first embodiment of the present invention.
  • the solid electrolyte layer 61 is placed on the dielectric layer on the opposite short sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • Has thick film portions 61a and 61b whose film thickness is larger than that of other portions.
  • the solid electrolyte layer 61 has an end portion 61x (see FIG. 5) that has entered a part of the insulating mask layer 51 on the opposite short side of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the solid electrolyte layer 61 may not have the thick film portions 61a and 61b on the opposite short sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the step ST21A of immersing the valve acting metal substrate 140 in the treatment liquid 230 in the direction orthogonal to the first short side and then pulling it up from the treatment liquid 230 is repeated without inverting the valve acting metal substrate 140.
  • the solid electrolyte layer 61 has an end portion 61x that has penetrated into a part of the insulating mask layer 51 at the first short side of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the solid electrolyte layer 61 may not have the thick film portion 61a on the first short side of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the shape of the element region viewed in a plan view from the thickness direction is a rectangular shape having a long side and a short side, and the first side and the second side of the element region are opposite long sides. be.
  • the direction in which the valve acting metal substrate is immersed in the treatment liquid is different from that in the first embodiment.
  • FIG. 17 is a schematic view showing an example of a step of holding the valve acting metal substrate in the dipping treatment apparatus in the first direction in the second embodiment of the present invention.
  • the valve acting metal substrate 140 (see FIGS. 8 and 9) in which the insulating mask layer 51 is formed in a grid pattern is held by the sheet holding portion 211 of the support plate 210.
  • the valve acting metal substrate 140 is held so that the width direction W of the element region is parallel to the vertical direction.
  • the treatment liquid 230 containing the solid electrolyte for example, a dispersion liquid of the conductive polymer is supplied to the treatment tank 220.
  • FIG. 18 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the first long side of the element region is orthogonal to each other in the second embodiment of the present invention.
  • the valve acting metal substrate 140 is immersed in the treatment liquid 230 in the direction in which the first long side of the element region is orthogonal to each other. That is, the valve acting metal substrate 140 is immersed in the treatment liquid 230 along the width direction W of the element region. As a result, the dispersion liquid of the conductive polymer is impregnated into the porous portion of the valve acting metal substrate 140.
  • the immersion speed may be any speed, but is preferably 0.5 mm / s or more and 5 mm / s or less.
  • the sheet holding portion 211 holds the end portion of the valve acting metal substrate 140, but a frame may be provided and held so as to surround the four sides of the valve acting metal substrate 140.
  • FIG. 19 is a schematic diagram showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG.
  • the valve acting metal substrate 140 is pulled up from the treatment liquid 230.
  • a semicircular liquid pool A3 is formed at the lower part.
  • the liquid pool A3 is laterally spread and dispersed. Therefore, the height of the liquid pool A3 is smaller than that of the liquid pool A1 of the first embodiment.
  • the immersion time is preferably 1 second or more and 10 seconds or less.
  • the pulling speed may be any speed, but is preferably 0.01 mm / s or more and 5 mm / s or less. It is more preferably 0.1 mm / s or more and 3 mm / s or less from the viewpoint of the stability of the amount of liquid pool and the productivity due to the lead time.
  • FIG. 20 is a schematic view showing an example of a step of holding the valve acting metal substrate in the dipping treatment apparatus in the second direction in the second embodiment of the present invention.
  • valve acting metal substrate 140 is inverted 180 degrees and held by the sheet holding portion 211 of the support plate 210.
  • FIG. 21 is a schematic view showing an example of a step of immersing a valve acting metal substrate in a treatment liquid in a direction in which the second long side of the element region is orthogonal to each other in the second embodiment of the present invention.
  • valve acting metal substrate 140 is immersed in the treatment liquid 230 in the same direction as in FIG.
  • FIG. 22 is a schematic diagram showing an example of a step of pulling up the valve acting metal substrate from the treatment liquid after the step shown in FIG. 21.
  • the valve acting metal substrate 140 is pulled up from the treatment liquid 230. Similar to FIG. 19, a semicircular liquid pool A4 is formed in the lower part of the element region after immersion.
  • the liquid pool A4 has a shape that is substantially vertically symmetrical with the liquid pool A3 before inversion.
  • FIG. 23 is a schematic diagram showing an example of an element region after being immersed and dried a plurality of times in the second embodiment of the present invention.
  • the solid electrolyte layer 61 is placed on the dielectric layer on the opposite long sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • Has thick film portions 61c and 61d whose film thickness is larger than that of other portions.
  • the area of the thick film portions 61c and 61d of the second embodiment is smaller than that of the thick film portions 61a and 61b of the first embodiment.
  • the solid electrolyte layer 61 has an end portion 61y (see FIG. 7) that has entered a part of the insulating mask layer 51 on the opposite long sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the solid electrolyte layer 61 may not have the thick film portions 61c and 61d on the opposite long sides of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the step ST21A of immersing the valve acting metal substrate 140 in the treatment liquid 230 in the direction orthogonal to the first long side and then pulling it up from the treatment liquid 230 is repeated without inverting the valve acting metal substrate 140.
  • the solid electrolyte layer 61 has an end portion 61y that has penetrated into a part of the insulating mask layer 51 at the first long side of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the solid electrolyte layer 61 does not have to have the thick film portion 61c on the first long side of the outer peripheral portion of the region surrounded by the insulating mask layer 51.
  • the shape of the element region viewed from the thickness direction in a plan view may be a rectangular shape other than a rectangular shape.
  • a region surrounded by an insulating mask layer by immersing the valve acting metal substrate in the direction in which the first side of the element region is orthogonal to the treatment liquid containing the solid electrolyte and then pulling it out of the treatment liquid.
  • the end portion of the solid electrolyte layer can be inserted into a part of the insulating mask layer.
  • the valve acting metal substrate is immersed in the treatment liquid containing the solid electrolyte in the direction in which the first side of the element region is orthogonal to the treatment liquid, and then the treatment liquid is used.
  • the treatment liquid is used.
  • the second side of the element region may be a side different from the first side, but is preferably a side facing the first side.
  • the thick film portion is formed on the first side and the second side facing each other, the thick film portion provided on one side is not connected to the thick film portion provided on the other side facing each other. It may be good, but it is preferable that it is connected.
  • the step ST21 for forming the solid electrolyte layer is a step of immersing the valve acting metal substrate in the direction in which the third side of the element region is orthogonal to the treatment liquid containing the solid electrolyte, and then pulling it out of the treatment liquid.
  • ST21C may be included.
  • the valve acting metal substrate is further immersed in the treatment liquid containing the solid electrolyte in the direction in which the third side of the element region is orthogonal to the treatment liquid, and then the treatment liquid is used.
  • the step ST21C for pulling up may be included, and the step ST21D for pulling up from the treatment liquid after immersing the valve acting metal substrate in the direction in which the fourth side of the element region is orthogonal to the treatment liquid may be included.
  • step ST21 for forming the solid electrolyte layer it is preferable to repeatedly perform the step ST21A, the step ST21B, the step ST21C, and the step ST21D in order to form the solid electrolyte layer having a predetermined thickness.
  • the step ST21A and the step ST21B using the dipping method may be performed to form the inner layer, and then the step for forming the outer layer may be further performed.
  • the outer layer can be formed by, for example, a dipping method, sponge transfer, screen printing, a dispenser, inkjet printing, or the like.
  • the solid electrolyte layer may also be formed on the insulating mask layer over the outside of the region surrounded by the insulating mask layer. ..
  • the insulating mask layer is formed on the entire four sides around the element region on the dielectric layer. There may be a portion where the insulating mask layer is not provided on a part of the four peripheral sides.
  • the step ST2 for forming the cathode layer includes the step ST22 for forming the conductor layer on the outer surface of the solid electrolyte layer.
  • the conductor layer 62 is formed by applying the carbon paste to the outer surface of the solid electrolyte layer 61 to form the carbon layer, and then applying the silver paste to the outer surface of the carbon layer to form the silver layer. be able to.
  • the step ST2 for forming the cathode layer includes the step ST23 for forming the cathode extraction layer on the outer surface of the conductor layer.
  • the step ST21, the step ST22, and the step ST23 form a cathode layer 60 including a solid electrolyte layer 61, a conductor layer 62, and a cathode extraction layer 63.
  • FIG. 24 is a perspective view schematically showing an example of a metal foil.
  • FIG. 25 is an enlarged perspective view of a part of the metal leaf shown in FIG. 24.
  • the metal foil 163 shown in FIGS. 24 and 25 has a plurality of element regions R21 (hereinafter referred to as a first element region) and a plurality of element regions R22 (hereinafter referred to as a second element region). There is.
  • the shape of the first element region R21 viewed in a plan view from the thickness direction is a square shape, preferably a rectangular shape having a long side and a short side.
  • the first element region R21 includes a first end portion E21 and a second end portion E22 facing each other in the length direction L, and a first side portion S21 and a second side portion S22 facing each other in the width direction W. It is partitioned by.
  • the dimension of the first element region R21 in the length direction L is larger than the dimension in the width direction W.
  • a plurality of third through holes H3 (three in FIG. 25) are formed so as to straddle the first end E21 of the first element region R21 in the length direction L, and the first one.
  • One fourth through hole H4 is formed so as to straddle the second end E22 of the element region R21 in the length direction L.
  • the third through hole H3 is preferably composed of a plurality of substantially round holes having a width smaller than the width of the first element region R21, and the fourth through hole H4 is the width of the first element region R21. It is preferably composed of one elongated hole having the above width.
  • the shape of the second element region R22 viewed in a plan view from the thickness direction is a square shape, preferably a rectangular shape having a long side and a short side.
  • the second element region R22 has the same shape as the first element region R21, but the directions of the first end portion E21 and the second end portion E22 are opposite to those of the first element region R21. be.
  • the first element region R21 and the second element region R22 are alternately arranged in the length direction L. That is, as shown in FIG. 25, the first element region R21 shares the first end E21 with the adjacent second element region R22, and is second with the other adjacent second element regions R22. It is preferable to share the end E22 of the.
  • the first element region R21 and the second element region R22 are alternately arranged in the width direction W. That is, as shown in FIG. 25, the first element region R21 shares the first side portion S21 with the adjacent second element region R22, and is second to the other adjacent second element region R22. It is preferable to share the side portion S22 of the.
  • the fourth through hole H4 is not unevenly distributed in the width direction W of the metal foil 163, so that the strength of the metal foil 163 is unlikely to decrease. Become.
  • the first element region R21 and the second element region R22 are alternately arranged in the length direction L, as shown in FIG. 25, the first element region R21 is an adjacent second element region. It is preferable to share the first end E21 and the third through hole H3 with R22, and share the second end E22 and the fourth through hole H4 with another adjacent second element region R22. .. In this case, the number of cuts for dividing the element region and the portion to be discarded can be reduced.
  • the third through hole H3 and the fourth through hole H4 are formed by, for example, laser processing, etching processing, punching processing, or the like.
  • the shape, number, arrangement, and the like of the third through hole H3 are not particularly limited as long as they have a width smaller than the width of the element region, but two or more of the third through holes H3 are formed in the width direction W in each element region. Is preferable. When two or more third through holes H3 are formed, it is preferable that these through holes are formed at equal intervals.
  • each of the third through holes H3 is too small, it becomes difficult to fill the sealing material in the step described later.
  • the ratio of the total width of the third through hole H3 to the width of the element region is too large, the ratio of the cathode layer 60 exposed from the exterior body 10 becomes small, so that the ESR tends to increase.
  • the shape of the fourth through hole H4 is not particularly limited as long as it has a width equal to or larger than the width of the element region.
  • the thickness of the metal foil 163 is not particularly limited, but is preferably 5 ⁇ m or more and 100 ⁇ m or less from the viewpoint of reducing ESR.
  • the size of the entire metal foil 163 is not particularly limited, but it is preferably the same as the size of the entire valve acting metal substrate 140.
  • the shape, number and arrangement of the first element region R21 and the second element region R22 are preferably the same as the shape, number and arrangement of the first element region R11 and the second element region R12.
  • Step ST3 Step of sealing the valve acting metal substrate on which the insulating mask layer and the cathode layer are formed
  • at least one valve acting metal substrate on which the insulating mask layer and the cathode layer are formed is sealed by the exterior body. do.
  • valve-acting metal substrate 140 In the example of using the valve-acting metal substrate 140 and the metal foil 163, first, the valve-acting metal substrate 140 formed up to the conductor layer 62 and the metal foil 163 are laminated.
  • FIG. 26 is a perspective view schematically showing an example of a state before the valve acting metal substrate and the metal foil are laminated.
  • FIG. 27 is a perspective view schematically showing an example of a state in which a valve acting metal substrate and a metal foil are laminated.
  • valve acting metal substrate 140 on which the insulating mask layer 51 and the conductor layer 62 are formed on the surface and the metal foil 163 are alternately laminated. At this time, the valve acting metal substrate 140 and the metal foil 163 are laminated so that the first ends and the second ends of each element region face each other.
  • the laminated sheet 170 shown in FIG. 27 can be obtained.
  • the laminated sheet 170 becomes a capacitor element 70 after cutting.
  • the laminated sheet 170 has a first main surface 170a and a second main surface 170b facing each other in the height direction T.
  • the insulating mask layer 51, the conductor layer 62, and the like formed on the surface of the valve acting metal substrate 140 are omitted (the same applies hereinafter).
  • valve-acting metal substrates 140 and five metal foils 163 are laminated, and the metal foil 163 is on the first main surface 170a and the valve-acting metal substrate 140 is on the second main surface 170b of the laminated sheet 170.
  • the number of sheets in which the valve acting metal substrate 140 and the metal foil 163 are laminated is not particularly limited.
  • the number of valve-acting metal substrates 140 and metal foil 163 to be laminated may be one at a time. Further, the number of valve acting metal substrates 140 and the number of metal foils 163 may be the same or different.
  • valve acting metal substrate 140 or the metal leaf 163 may be arranged on the first main surface 170a and the second main surface 170b of the laminated sheet 170. Further, when the laminated sheet 170 is produced, the valve acting metal substrate 140 and the metal foil 163 may be laminated on a substrate such as a glass epoxy substrate. Such a substrate constitutes the substrate 11 of the exterior body 10 described with reference to FIG.
  • the first through hole H1 (see FIG. 9) of the valve acting metal substrate 140
  • the third through hole H3 of the metal leaf 163 (see FIG. 25)
  • the valve acting metal substrate 140 The second through hole H2 (see FIG. 9) and the fourth through hole H4 (see FIG. 25) of the metal foil 163 are communicated with each other in the height direction T.
  • the second through hole H2 and the third through hole H3 communicate linearly from the first main surface 170a to the second main surface 170b of the laminated sheet 170, respectively.
  • the first through hole H1 and the third through hole H3, and the second through hole H2 and the fourth through hole H4 are communicated with each other in the height direction T, respectively. Therefore, from at least one of the first main surface 170a and the second main surface 170b of the laminated sheet 170, the first through hole H1, the third through hole H3, and the second through hole H2. And the fourth through hole H4 can be filled with a sealing material, respectively.
  • FIG. 28 is a plan view schematically showing an example of a valve acting metal substrate filled with a sealing material.
  • the first sealing portion 111 is formed by filling the first through hole H1 with a sealing material, and the second through hole H2 is formed.
  • the second sealing portion 112 is formed by filling the sealing material.
  • FIG. 29 is a plan view schematically showing an example of a metal foil filled with a sealing material.
  • the first sealing portion 111 is formed by filling the third through hole H3 with a sealing material, and the metal foil 163 is sealed in the fourth through hole H4. By filling the material, the second sealing portion 112 is formed.
  • FIG. 30 is a perspective view schematically showing an example of a laminated sheet in which a through hole is filled with a sealing material.
  • the laminated block body 180 is formed with a third sealing portion 113 that covers the first main surface 170a and the second main surface 170b of the laminated sheet 170.
  • the third sealing portion 113 is provided so as to cover both the first main surface 170a and the second main surface 170b of the laminated sheet 170, but the first main surface 170a of the laminated sheet 170 is provided. And may be provided so as to cover either one of the second main surface 170b.
  • the first sealing portion 111, the second sealing portion 112, and the third sealing portion 113 constitute the mold portion 12 of the exterior body 10 described with reference to FIG. Therefore, as the sealing material, a material constituting the mold portion 12 is used.
  • the maximum diameter of the filler is preferably smaller than the minimum diameter of the second through hole H2 and the third through hole H3 from the viewpoint of ensuring the filling property of the encapsulant.
  • the diameter of the through hole means the diameter when the cross-sectional shape is circular, and the maximum length passing through the center of the cross-section when the cross-sectional shape is not circular.
  • the maximum diameter of the filler is preferably smaller than the minimum thickness of the valve acting metal substrate 140 from the viewpoint of ensuring the filling property of the encapsulant, and the minimum thickness of the metal foil 163. It is preferably smaller than.
  • the encapsulant can be filled by, for example, a molding resin molding method.
  • a molding resin molding method in addition to the first sealing portion 111 and the second sealing portion 112, at least one of the first main surface 170a and the second main surface 170b of the laminated sheet 170 is covered with the first main surface.
  • the sealing portion 113 of 3 can be formed at the same time.
  • Step ST4 Step of cutting the exterior body and separating it into individual solid electrolytic capacitor elements
  • the exterior body is cut so as to divide the element region and separated into individual solid electrolytic capacitor elements.
  • the laminated sheet 170 is separated into individual capacitor elements 70.
  • the valve-acting metal substrate 140 becomes the valve-acting metal substrate 40
  • the metal foil 163 becomes the cathode drawer layer 63.
  • valve acting metal substrate 140 included in the laminated block body 180 is filled with a first through hole H1 straddling the first end E11 of each element region.
  • a second sealing portion 112 is formed to fill the stop portion 111 and the second through hole H2 straddling the second end portion E12 of each element region.
  • the valve acting metal substrate 140 so as to separate the first sealing portion 111 and the second sealing portion 112 on both sides at the positions of the first end portion E11 and the second end portion E12 of each element region.
  • the metal substrate 140 is cut by dicing or the like, the first sealing portion 111 is exposed on the cut surface on the first end portion E11 side, and the valve acting metal substrate 140 is not exposed.
  • the valve acting metal substrate 140 and the second sealing portion 112 are exposed on the cut surface on the second end portion E12 side.
  • valve acting metal substrate 140 is cut at the positions of the first side portion S11 and the second side portion S12 of each element region by dicing or the like, the valve acting metal substrate 140 is exposed on both cut surfaces.
  • the metal foil 163 included in the laminated block body 180 is filled with a third through hole H3 straddling the first end portion E21 of each element region.
  • a second sealing portion 112 is formed to fill the stop portion 111 and the fourth through hole H4 straddling the second end portion E22 of each element region.
  • the metal leaf 163 is diced so as to separate the first sealing portion 111 and the second sealing portion 112 on both sides at the positions of the first end portion E21 and the second end portion E22 of each element region.
  • the metal leaf 163 and the first sealing portion 111 are cut on the cut surface on the first end portion E21 side, the metal leaf 163 and the first sealing portion 111 are exposed.
  • the second sealing portion 112 is exposed on the cut surface on the second end portion E22 side, and the metal foil 163 is not exposed.
  • the metal foil 163 is cut at the positions of the first side portion S21 and the second side portion S22 of each element region, the metal foil 163 is exposed on both cut surfaces.
  • the metal foil 163 and the second end are formed on the cut surface on the first end side.
  • the sealing portion 111 of 1 can be exposed, and the valve acting metal substrate 140 and the second sealing portion 112 can be exposed on the cut surface on the second end side.
  • both the metal foil 163 and the valve acting metal substrate 140 are exposed on the cut surface obtained by cutting the laminated block body 180 at the positions of the first side portion and the second side portion of each element region. do. Therefore, it is preferable to cover these cut surfaces with a sealing material. As described above, an element-sealed body in which the capacitor element 70 is sealed by the exterior body 10 is manufactured.
  • FIG. 31 is a perspective view schematically showing an example of an element encapsulating body viewed from the first end face side.
  • FIG. 32 is a perspective view schematically showing an example of an element encapsulating body viewed from the second end face side.
  • a plurality of capacitor elements 70 are sealed by the exterior body 10. Similar to FIG. 2, the plurality of capacitor elements 70 are stacked along the height direction T. Considering weather resistance such as moisture resistance or heat resistance, the cathode drawer layer 63, which is the metal leaf 163 after cutting, is located on the outermost layers (excluding the third sealing portion 113) facing each other in the height direction T. Is preferable.
  • the cathode extraction layer 63 and the first sealing portion 111 are exposed on the first end surface 10e of the exterior body 10.
  • the valve acting metal substrate 40 and the second sealing portion 112 are exposed on the second end surface 10f of the exterior body 10.
  • the element sealing body 110 includes a third sealing portion 113 that covers the first main surface 10a and the second main surface 10b of the exterior body 10, and the first side surface 10c and the second side surface 10d of the exterior body 10.
  • a fourth sealing portion 114 for covering the above is further provided.
  • the exterior body 10 is composed of the first sealing portion 111, the second sealing portion 112, the third sealing portion 113, and the fourth sealing portion 114.
  • the sum ⁇ 1 of the distances per layer in which the cathode extraction layer 63 is exposed to the first end surface 10e of the exterior body 10 in the width direction W is smaller than the maximum width ⁇ 1 of the cathode extraction layer 63.
  • the sum ⁇ 2 of the distances per layer in which the valve acting metal substrate 40 is exposed on the second end surface 10f of the exterior body 10 is smaller than the maximum width ⁇ 2 of the valve acting metal substrate 40.
  • the wider the width of the second through hole H2 and the third through hole H3 is, the better. Since the ratio and the ratio of the valve acting metal substrate 40 exposed on the second end surface 10f of the exterior body 10 become small, the ESR increases.
  • the value of ⁇ 1 / ⁇ 1 is preferably 0.1 or more, 0.9 or less, and more preferably 0.5 or more.
  • the value of ⁇ 2 / ⁇ 2 is preferably 0.1 or more, 0.9 or less, and more preferably 0.5 or more.
  • the value of ⁇ 1 may be the same as or different from the value of ⁇ 2. Similarly, the value of ⁇ 1 may be the same as or different from the value of ⁇ 2. Therefore, the value of ⁇ 1 / ⁇ 1 may be the same as or different from the value of ⁇ 2 / ⁇ 2.
  • the device encapsulation body 110 is preferably manufactured by the same method as the method for manufacturing the device laminate described in Japanese Patent Application Laid-Open No. 2019-79866. The following is a brief description.
  • the laminated block body 180 is cut along the first side portion and the second side portion of each element region.
  • a method such as dicing using a dicer is applied.
  • a gap along the first side portion and the second side portion was formed.
  • a laminated block body is produced.
  • the metal foil 163 and the valve acting metal substrate 140 are exposed on the cut side surface exposed by the cut.
  • the thickness of the exposed portion of the metal foil 163 and the valve acting metal substrate 140 is larger than the thickness of the unexposed internal metal foil 163 and the valve acting metal substrate 140, and is larger in the thickness direction. It spreads in a tapered shape above and below.
  • the gap formed in the laminated block body 180 is filled with a sealing material.
  • a sealing material for example, a sealing material for forming the first sealing portion 111, the second sealing portion 112, and the third sealing portion 113 can be used.
  • the laminated block body 180 is cut so as to separate the first sealing portion 111 and the second sealing portion 112 on both sides at the positions of the first end portion and the second end portion of each element region.
  • the fourth sealing portion 114 is cut so as to be separated on both sides at the positions of the first side portion and the second side portion of each element region.
  • the first side portion and the second side portion can be separated into an element encapsulation body insulated by the encapsulation portion.
  • methods such as dicing using a dicer, cutting using a cutting blade, laser processing, and scribe are applied.
  • valve acting metal substrate 140 and the metal foil 163 are laminated on a substrate such as a glass epoxy substrate, it is preferable to cut the substrate to a position where the substrate is half-cut in order to reliably cut the metal foil 163.
  • a stepped shape is created from the first side portion and the second side portion of each element region to the substrate, and this stepped shape is filled with a part of the fourth sealing portion 114. Will be.
  • Step ST5 Step of Forming the First External Electrode
  • the first external electrode electrically connected to the cathode layer of the solid electrolytic capacitor element exposed from the exterior body is formed.
  • the first external electrode 20 is formed on the first end surface 10e of the exterior body 10 and is connected to the cathode extraction layer 63 exposed on the first end surface 10e of the exterior body 10.
  • the first external electrode 20 can be formed by, for example, plating, sputtering, dip coating, printing, or the like.
  • Step ST6 Step of Forming the Second External Electrode
  • the second external electrode electrically connected to the valve acting metal substrate of the solid electrolytic capacitor element exposed from the exterior body is formed.
  • a second external electrode 30 is formed on the second end surface 10f of the exterior body 10 and is connected to the valve acting metal substrate 40 exposed on the second end surface 10f of the exterior body 10. .
  • the second external electrode 30 can be formed by, for example, plating, sputtering, dip coating, printing, or the like.
  • the solid electrolytic capacitor element and the solid electrolytic capacitor of the present invention can be manufactured.
  • the valve acting metal substrate 140 serving as an anode portion and the metal leaf 163 serving as a cathode portion are formed into an element. It can be exposed on each end face of the sealant 110. Therefore, the step of polishing the end face in order to expose the valve acting metal substrate 140 and the metal leaf 163 becomes unnecessary. Therefore, the solid electrolytic capacitor can be efficiently manufactured.
  • the method for manufacturing a solid electrolytic capacitor element, a solid electrolytic capacitor, and a solid electrolytic capacitor element of the present invention, and a method for manufacturing a solid electrolytic capacitor are not limited to the above embodiments, and the solid electrolytic capacitor element and the solid electrolytic capacitor can be manufactured.
  • Various applications and modifications can be added within the scope of the present invention regarding the configuration, manufacturing conditions, and the like.
  • the valve action metal substrate 40 and the cathode extraction layer 63 are connected via, for example, a conductor layer 62 provided on the solid electrolyte layer 61.
  • the valve acting metal substrate 40 and the cathode extraction layer 63 may be connected via a conductive adhesive layer provided on the conductor layer 62.
  • the conductor layer 62 may not be provided on the solid electrolyte layer 61.
  • the valve acting metal substrate 40 and the cathode extraction layer 63 may be connected via the solid electrolyte layer 61, or the valve acting metal substrate may be connected via the conductive adhesive layer provided on the solid electrolyte layer 61. 40 and the cathode extraction layer 63 may be connected.
  • the manufacturing method is not particularly limited as long as the configuration of the solid electrolytic capacitor element and the solid electrolytic capacitor of the present invention can be obtained.
  • a laminated sheet by laminating a valve acting metal substrate 140 having a first through hole H1 and a second through hole H2 and a metal foil 163 having a third through hole H3 and a fourth through hole H4.
  • the laminated sheet 170 may be produced by laminating the valve acting metal substrate 140 having the first through hole H1 without using the metal foil 163.
  • the method for producing the laminated sheet 170 is not particularly limited.
  • the laminated sheet 170 may be produced by laminating the valve acting metal substrate 140 having the first through hole H1 and the metal foil 163 having the fourth through hole H4, or the metal foil 163 may be used.
  • the laminated sheet 170 may be produced by laminating the valve acting metal substrate 140 having the first through hole H1 and the second through hole H2.
  • the laminated block body 180 in which the through hole is filled with the sealing material is manufactured as needed.
  • the laminated sheet 170 is cut, while when the laminated block body 180 is produced, the laminated block body 180 is cut to produce a plurality of element encapsulation bodies 110. do.
  • a sealing material may be provided at a required position on the end face of the element sealing body 110.
  • the method of cutting the laminated sheet 170 or the laminated block body 180 and the method of forming the first external electrode 20 and the second external electrode 30 are not particularly limited.
  • a valve acting metal substrate partitioned into a rectangular element region by an insulating mask layer was prepared.
  • the dimension of the capacitance portion in one element region is set to a predetermined dimension between the dimension L in the length direction: 2.8 mm or more and 3.4 mm or less and the dimension W in the width direction: 2.0 mm or more and 2.6 mm or less.
  • An insulating mask layer was formed on the surface.
  • a treatment liquid containing a solid electrolyte a dispersion liquid of poly (3,4-ethylenedioxythiophene), which is a conductive polymer, was used.
  • Example 1 Based on the method described in the first embodiment of [Method for manufacturing solid electrolytic capacitor element and method for manufacturing solid electrolytic capacitor], the valve acting metal substrate is immersed in the treatment liquid in the direction in which the first short side of the element region is orthogonal to each other. After that, the step of pulling up from the treatment liquid and the step of immersing the valve acting metal substrate in the treatment liquid in the direction in which the second short side of the element region is orthogonal to each other and then pulling up from the treatment liquid were repeated to form a solid electrolyte layer. Immersion from the first short side was performed a total of 4 times, and immersion from the second short side was performed a total of 4 times. In addition, the drying treatment was performed every time it was pulled up from the treatment liquid.
  • Example 1 After forming the solid electrolyte layer as described above, the carbon layer and the silver layer were formed by the dipping method. Through the above steps, the capacitor element of Example 1 was manufactured. A five-level capacitor element was manufactured under the conditions of Example 1.
  • Example 2 Based on the method described in the second embodiment of [Method for manufacturing solid electrolytic capacitor element and method for manufacturing solid electrolytic capacitor], the valve acting metal substrate is immersed in the treatment liquid in the direction in which the first long side of the element region is orthogonal to each other. After that, the step of pulling up from the treatment liquid and the step of immersing the valve acting metal substrate in the treatment liquid in the direction in which the second long side of the element region is orthogonal to each other and then pulling up from the treatment liquid were repeated to form a solid electrolyte layer. Immersion from the first long side was performed a total of 4 times, and immersion from the second long side was performed a total of 4 times. In addition, the drying treatment was performed every time it was pulled up from the treatment liquid.
  • Example 2 After forming the solid electrolyte layer as described above, the carbon layer and the silver layer were formed by the dipping method. Through the above steps, the capacitor element of Example 2 was manufactured. A five-level capacitor element was manufactured under the conditions of Example 2.
  • FIG. 33 is a mapping image of the Si element and the S element on the first long side of the capacitor element of the second embodiment.
  • FIG. 33 shows a cross section of the solid electrolytic capacitor shown in FIG. 6 along the VII-VII line.
  • the insulating mask layer 51 containing Si can be confirmed, and from the mapping image of the S element, the solid electrolyte layer 61 containing S can be confirmed. In the region indicated by X in FIG. 33, it can be confirmed that the end portion of the solid electrolyte layer 61 has entered a part of the insulating mask layer 51.
  • Example 3 After immersing the valve acting metal substrate in the treatment liquid in the direction in which the first short side of the element region is orthogonal to each other, the step of pulling up from the treatment liquid was repeated to form a solid electrolyte layer. Immersion from the first short side was performed a total of 8 times. In addition, the drying treatment was performed every time it was pulled up from the treatment liquid.
  • Example 3 After forming the solid electrolyte layer as described above, the carbon layer and the silver layer were formed by the dipping method. Through the above steps, the capacitor element of Example 3 was manufactured. A five-level capacitor element was manufactured under the conditions of Example 3.
  • Comparative Example 1 A treatment liquid was applied to the device region by a dispenser to form a solid electrolyte layer, and then a carbon layer and a silver layer were formed by an immersion method. Through the above steps, the capacitor element of Comparative Example 1 was manufactured. A five-level capacitor element was manufactured under the conditions of Comparative Example 1.
  • Capacity appearance rate The capacitance appearance rate was evaluated as the capacitance characteristic of the capacitor element in Example 1, Example 2, Example 3, and Comparative Example 1.
  • FIG. 34 is a graph showing the capacitance appearance rate of the capacitor element in Example 1, Example 2, Example 3, and Comparative Example 1.
  • FIG. 35 is a graph showing the leakage current of the capacitor element in Example 1, Example 2, Example 3, and Comparative Example 1.
  • Example 1 and 2 in which the dipping direction in the treatment liquid is reversed, the capacity appearance rate is higher than in Example 3 in which the dipping direction in the treatment liquid is not reversed. It is considered that this is because the impregnation property of the solid electrolyte layer in the entire device region is improved by reversing the dipping direction in the treatment liquid.
  • Example 2 in which the long side of the element region is immersed in the treatment liquid, the capacity appearance rate is higher than in Example 1 in which the short side of the element region is immersed in the treatment liquid. It is considered that this is because, in Example 2, the liquid pool is dispersed along the long side as compared with Example 1, so that the area of the liquid pool is reduced, and as a result, the impregnation property is improved.
  • Example 1 Example 2 and Example 3 in which the solid electrolyte layer was formed by the dipping method, compared with Comparative Example 1 in which the solid electrolyte layer was formed by the dispenser.
  • Leakage current is small. It is considered that this is because the end portion of the solid electrolyte layer enters a part of the insulating mask layer, so that the leakage current due to the contact between the conductor layer such as carbon and silver and the solid electrolyte layer is suppressed.
  • Solid electrolytic capacitor 10 Exterior body 10a First main surface of exterior body 10b Second main surface of exterior body 10c First side surface of exterior body 10d Second side surface of exterior body 10e First end surface of exterior body 10f Second surface of exterior body End face 11 Substrate 12 Molded part 20 First external electrode 30 Second external electrode 40, 140 Valve acting metal substrate 50 Dielectric layer 51 Insulation mask layer 60 Cathode layer 61 Solid electrolyte layer 61a, 61b, 61c, 61d Thick film part 61x, 61y End part that has penetrated into a part of the insulation mask layer 62 Conductor layer 63 Cathode extraction layer 70 Condenser element 110 Element encapsulant 111 First encapsulation part 112 Second encapsulation part 113 Third encapsulation part 114 4th sealing part 163 Metal foil 170 Laminated sheet 170a First main surface of laminated sheet 170b Second main surface of laminated sheet 180 Laminated block body 200 Immersion processing device 210 Support plate 211 Sheet holding part 220

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

Un élément de condensateur 70, qui est un exemple d'un élément de condensateur électrolytique solide selon la présente invention, comprend : un substrat métallique d'action de soupape 40, dont la forme telle que vue dans une vue en plan à partir de la direction de l'épaisseur est carrée ; une couche de masque isolant 51 disposée sur une couche diélectrique 50 de façon à recouvrir les quatre côtés le long de la périphérie de la surface principale du substrat métallique d'action de soupape 40 ; et une couche de cathode 60 disposée sur la couche diélectrique 50. La couche de cathode 60 comprend une couche d'électrolyte solide 61 disposée sur la couche diélectrique 50 dans une région entourée par la couche de masque isolant 51. La couche d'électrolyte solide 61 comprend une section d'extrémité 61x qui pénètre dans une partie de la couche de masque isolant 51 le long d'au moins un côté de la section périphérique externe de la région entourée par la couche de masque isolant 51.
PCT/JP2021/044442 2020-12-16 2021-12-03 Élément de condensateur électrolytique solide, condensateur électrolytique solide, procédé de production d'élément de condensateur électrolytique solide et procédé de production de condensateur électrolytique solide WO2022131020A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-208652 2020-12-16
JP2020208652 2020-12-16

Publications (1)

Publication Number Publication Date
WO2022131020A1 true WO2022131020A1 (fr) 2022-06-23

Family

ID=82057627

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/044442 WO2022131020A1 (fr) 2020-12-16 2021-12-03 Élément de condensateur électrolytique solide, condensateur électrolytique solide, procédé de production d'élément de condensateur électrolytique solide et procédé de production de condensateur électrolytique solide

Country Status (1)

Country Link
WO (1) WO2022131020A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05190394A (ja) * 1992-01-17 1993-07-30 Elna Co Ltd 固体電解コンデンサの製造方法
WO2008143234A1 (fr) * 2007-05-21 2008-11-27 Showa Denko K. K. Procédé et appareil de fabrication d'un condensateur électrolytique solide
JP2011109024A (ja) * 2009-11-20 2011-06-02 Sanyo Electric Co Ltd 固体電解コンデンサの製造方法
JP2019079866A (ja) * 2017-10-20 2019-05-23 株式会社村田製作所 固体電解コンデンサの製造方法、及び、固体電解コンデンサ
WO2020153451A1 (fr) * 2019-01-24 2020-07-30 パナソニックＩｐマネジメント株式会社 Condensateur à électrolyte solide et son procédé de fabrication

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05190394A (ja) * 1992-01-17 1993-07-30 Elna Co Ltd 固体電解コンデンサの製造方法
WO2008143234A1 (fr) * 2007-05-21 2008-11-27 Showa Denko K. K. Procédé et appareil de fabrication d'un condensateur électrolytique solide
JP2011109024A (ja) * 2009-11-20 2011-06-02 Sanyo Electric Co Ltd 固体電解コンデンサの製造方法
JP2019079866A (ja) * 2017-10-20 2019-05-23 株式会社村田製作所 固体電解コンデンサの製造方法、及び、固体電解コンデンサ
WO2020153451A1 (fr) * 2019-01-24 2020-07-30 パナソニックＩｐマネジメント株式会社 Condensateur à électrolyte solide et son procédé de fabrication

Similar Documents

Publication Publication Date Title
CN113012942B (zh) 固体电解电容器
CN109791844B (zh) 固体电解电容器
JP6819691B2 (ja) 固体電解コンデンサ及び固体電解コンデンサの製造方法
JP7408288B2 (ja) 固体電解コンデンサ
JP7067512B2 (ja) 固体電解コンデンサ
US11011317B2 (en) Solid electrolytic capacitor
JP6747512B2 (ja) 固体電解コンデンサ
JP7020504B2 (ja) 固体電解コンデンサ
JP2018032768A (ja) 固体電解コンデンサ素子、固体電解コンデンサ、固体電解コンデンサ素子の製造方法、及び、固体電解コンデンサの製造方法
JP7063301B2 (ja) 固体電解コンデンサの製造方法
WO2022131020A1 (fr) Élément de condensateur électrolytique solide, condensateur électrolytique solide, procédé de production d'élément de condensateur électrolytique solide et procédé de production de condensateur électrolytique solide
JP7435433B2 (ja) 固体電解コンデンサ素子の製造方法、及び、固体電解コンデンサの製造方法
JP7226081B2 (ja) 固体電解コンデンサの製造方法、及び、固体電解コンデンサ
JP2018032769A (ja) 固体電解コンデンサ素子、固体電解コンデンサ、固体電解コンデンサ素子の製造方法、及び、固体電解コンデンサの製造方法
WO2023276695A1 (fr) Condensateur électrolytique solide et procédé de fabrication de condensateur électrolytique solide
JP2020145276A (ja) 固体電解コンデンサ
WO2023090141A1 (fr) Élément condensateur électrolytique
WO2023153432A1 (fr) Élément condensateur électrolytique
WO2022264794A1 (fr) Élément condensateur électrolytique solide et condensateur électrolytique solide
JP7375710B2 (ja) 固体電解コンデンサ、及び、固体電解コンデンサの製造方法
WO2024014469A1 (fr) Élément de condensateur électrolytique solide, condensateur électrolytique solide et procédé de fabrication d'élément de condensateur électrolytique solide
WO2023190050A1 (fr) Condensateur électrolytique solide
JP2023067561A (ja) 固体電解コンデンサ素子、固体電解コンデンサ及び固体電解コンデンサ素子の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21906383

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21906383

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP