WO2024143173A1 - 固体電解コンデンサ - Google Patents

固体電解コンデンサ Download PDF

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Publication number
WO2024143173A1
WO2024143173A1 PCT/JP2023/046019 JP2023046019W WO2024143173A1 WO 2024143173 A1 WO2024143173 A1 WO 2024143173A1 JP 2023046019 W JP2023046019 W JP 2023046019W WO 2024143173 A1 WO2024143173 A1 WO 2024143173A1
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WIPO (PCT)
Prior art keywords
layer
solid electrolytic
electrolytic capacitor
substrate
insulating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
PCT/JP2023/046019
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English (en)
French (fr)
Japanese (ja)
Inventor
明子 松居
淳一 栗田
尾野　誠
さおり 上田
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202380088697.XA priority Critical patent/CN120418911A/zh
Priority to JP2024567724A priority patent/JPWO2024143173A1/ja
Publication of WO2024143173A1 publication Critical patent/WO2024143173A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors

Definitions

  • One aspect of the present disclosure is a capacitor comprising at least one capacitor element including an anode portion and a cathode portion; A substrate supporting the capacitor element; a sealant that seals the capacitor element; a plurality of external electrodes electrically connected to the anode portion and the cathode portion,
  • the substrate relates to a solid electrolytic capacitor including at least one insulating layer and at least one metal layer.
  • FIG. 1 is a schematic cross-sectional view of a solid electrolytic capacitor according to an embodiment of the present disclosure.
  • FIG. 4 is a schematic cross-sectional view of a solid electrolytic capacitor according to another embodiment of the present disclosure.
  • the substrate may have two insulating layers, and the metal layer may be interposed between the two insulating layers and adhered to each of the opposing main surfaces of the two insulating layers.
  • the metal layer may be interposed between the two insulating layers and adhered to each of the opposing main surfaces of the two insulating layers.
  • Such a substrate can be easily obtained from readily available commercially available substrates, and is cost-effective.
  • the water vapor permeability of the substrate can be kept low, and the fluctuation in ESR of the solid electrolytic capacitor when exposed to high temperatures can be reduced, and the variation in the ESR fluctuation range between individual capacitors can be reduced.
  • the metal layer may be at least one selected from the group consisting of copper foil and copper alloy foil.
  • a substrate can be easily obtained from a commercially available substrate that is easily available, and is advantageous in terms of cost.
  • the metal layer may not be in contact with any of the multiple external electrodes. This can prevent short circuits between external electrodes with different polarities through the metal layer.
  • the insulating layer may contain at least one selected from the group consisting of epoxy resin and polyimide resin, and glass fiber.
  • the substrate is easily available and relatively inexpensive, it is possible to reduce the fluctuation in ESR of the solid electrolytic capacitor when exposed to high temperatures, and to suppress the variation in the fluctuation range between individual capacitors.
  • the content of the metal layer in the entire substrate may be 1% by mass or more and 55% by mass or less. In this case, the intrusion of moisture into the solid electrolytic capacitor can be further suppressed, and the fluctuation of the ESR of the solid electrolytic capacitor when exposed to high temperatures can be further reduced.
  • Solid electrolytic capacitor The present disclosure relates to a solid electrolytic capacitor that includes at least one capacitor element, a substrate that supports the capacitor element, a seal that seals the capacitor element, and a plurality of external electrodes.
  • the capacitor element includes an anode portion and a cathode portion.
  • the plurality of external electrodes are electrically connected to the anode portion and the cathode portion, respectively.
  • the substrate In a solid electrolytic capacitor, the substrate includes at least one insulating layer and at least one metal layer.
  • the substrate may have multiple insulating layers.
  • the substrate may have one or multiple metal layers.
  • the substrate may have two insulating layers with a metal layer interposed between the two insulating layers.
  • the metal layer covers each of the opposing main surfaces of the two insulating layers.
  • the insulating layer includes, for example, an insulating resin.
  • the insulating layer may further include an additive (such as a filler).
  • Insulating resins include epoxy resins, polyimide resins, fluororesins, polyamide resins, polyamideimide resins, phenolic resins, aromatic polyester resins, silicone resins, and rubber-like polymers. These resins may be modified resins.
  • the coating may contain one of these insulating resins, or may contain two or more in combination.
  • the insulating resin may be a thermoplastic resin or a curable resin (such as a thermosetting resin or a photocurable resin).
  • the insulating resin may contain additives such as a catalyst, a curing agent, a crosslinking agent, a polymerization initiator, and a curing accelerator in addition to a resin or a precursor of a resin (such as a curable compound (monomer, oligomer, etc.)).
  • a thermoplastic resin or a composition thereof
  • the formed insulating layer contains a thermoplastic resin (or a composition thereof).
  • a curable resin (or a composition thereof) is used to form an insulating layer, the formed insulating layer contains a cured product of the curable resin (or a composition thereof).
  • the filler examples include insulating particles and insulating fibers.
  • the insulating material constituting the filler include insulating compounds such as silica and alumina (oxides (including ceramics)), glass, and mineral materials (talc, mica, clay, etc.).
  • the coating may contain one type of filler or a combination of two or more types. Fibrous fillers may be contained in the form of, for example, a nonwoven fabric.
  • the insulating layer contains at least a fibrous filler.
  • the fibrous filler is preferably glass fiber.
  • the glass fiber may be contained in the form of a nonwoven fabric (for example, as glass cloth, etc.).
  • the insulating layer may further include a particulate filler. Ceramic particles are preferable as the particulate filler. In this case, the intrusion of moisture through the substrate is further suppressed, and the fluctuation of ESR when exposed to high temperatures can be further reduced. In addition, the variation in the amount of ESR fluctuation between individual units can be reduced.
  • Substrates having an insulating layer containing epoxy resin, polyimide resin, etc. are relatively inexpensive and easy to obtain.
  • the insulating layer may contain at least one selected from the group consisting of epoxy resin and polyimide resin, and glass fiber (e.g., glass cloth).
  • the insulating layer may further contain ceramic particles.
  • the metal layer may be at least one selected from the group consisting of metal foil and metal alloy foil.
  • the metal layer may be a single layer or a laminate of multiple layers.
  • the type of metal constituting the metal layer is not particularly limited. Examples of metals include aluminum, iron, copper, and alloys of these metals. From the viewpoint of easy availability of the substrate and cost advantage, it is preferable that the metal layer is at least one selected from the group consisting of copper foil and copper alloy foil.
  • the cathode part and the metal layer of the capacitor element are bonded via a conductive adhesive layer and the metal layer is in contact with the external electrode, if the metal layer contains copper, the electrical connectivity between the cathode part and the external electrode is improved, and the electrical connectivity between the external electrode and the capacitor element can be further improved.
  • the thickness of the metal layer may be 5 ⁇ m or more and 100 ⁇ m or less, 5 ⁇ m or more and 70 ⁇ m or less, or 10 ⁇ m or more and 30 ⁇ m or less.
  • the thickness of the metal layer is in such a range, it is possible to further reduce the intrusion of moisture through the substrate, and it is advantageous from the viewpoint of miniaturization and cost reduction of the solid electrolytic capacitor.
  • the thickness of the insulating layer and the metal layer is determined by measuring the thickness at five or more randomly selected locations on each of the insulating layer and the metal layer based on a cross-sectional image that includes at least the substrate, and averaging the measured thicknesses.
  • the content of the metal layer in the entire substrate may be 1% by mass or more and 55% by mass or less, 10% by mass or more and 50% by mass or less, 20% by mass or more and 50% by mass or less, or 35% by mass or more and 50% by mass or less. If the content of the metal layer is in such a range, it is possible to further reduce the intrusion of moisture through the substrate, and it is advantageous from the viewpoint of reducing the cost of the solid electrolytic capacitor.
  • the metal layer is arranged to cover the main surface of the insulating layer.
  • the area of the main surface of the insulating layer covered by the metal layer may be 50 area% or more, 70 area% or more, 75 area% or more, or 80 area% or more, 85 area% or more.
  • the area of the main surface of the insulating layer covered by the metal layer is the area ratio of the part covered by the metal layer when the area of the entire main surface with which the metal layer is in contact is 100 area%.
  • this area ratio may be referred to as the coverage rate or the coverage rate by the metal layer.
  • the coverage rate by the metal layer may be less than 100 area% and less than 95 area%.
  • the coverage may be, for example, 50 area% or more and less than 100 area%, 70 area% or more and less than 100 area%, or 80 area% or more and less than 100 area%.
  • the substrate has a low water vapor permeability by having a metal layer.
  • the water vapor permeability of the substrate may be 10 g/m 2 ⁇ day or less, 9.0 g/m 2 ⁇ day or less, or 8.5 g/m 2 ⁇ day or less.
  • the water vapor permeability of the substrate is the water vapor permeability of the entire substrate including the insulating layer and the metal layer.
  • the lower limit of the water vapor permeability of the substrate is preferably as low as possible, but it is difficult to make it completely 0 g/m 2 ⁇ day, and may be, for example, 0.1 g/m 2 ⁇ day or more.
  • the water vapor permeability of the substrate can be measured in accordance with JIS Z 0208:1976 "Test method for moisture permeability of moisture-proof packaging materials (cup method)". The test is carried out under temperature and humidity conditions of 85°C and 85% relative humidity. The substrate before the formation of the solid electrolytic capacitor (substrate in a wide state) is used as the measurement sample.
  • the moisture absorption amount of the solid electrolytic capacitor may be 155 ⁇ g/ cm2 or less, or may be 154 ⁇ g/ cm2 or less per unit surface area of one solid electrolytic capacitor.
  • the water vapor permeability of the substrate (and the moisture absorption amount of the solid electrolytic capacitor) can be adjusted, for example, by the coverage rate of the metal layer, the thickness of the metal layer, the mass ratio of the metal layer to the substrate, the components contained in the insulating layer and their contents, the thickness of the insulating layer, etc.
  • the metal layer can reduce the water vapor permeability of the substrate and the moisture absorption amount of the solid electrolytic capacitor, so that the fluctuation of ESR when the solid electrolytic capacitor is exposed to high temperatures can be suppressed.
  • the capacitor element placed on the substrate includes an anode portion and a cathode portion.
  • An insulating separation layer may be provided to electrically separate the anode portion and the cathode portion.
  • the solid electrolytic capacitor includes at least one capacitor element, and may include two or more capacitor elements. The two or more capacitor elements may be, for example, stacked.
  • an anode foil When an anode foil is used as an anode body, a porous portion is usually formed on the surface of at least the second portion of the anode foil in order to increase the surface area.
  • Such an anode foil has a core and a porous portion formed on the surface of the core.
  • the porous portion is formed, for example, by forming irregularities on the surface of the anode foil.
  • An anode foil having a porous portion may be formed, for example, by roughening the surface of at least the second portion of the anode foil by etching (electrolytic etching, etc.). It is also possible to perform a roughening process such as an etching process after placing a predetermined masking member on the surface of the first portion.
  • anode foil is obtained that does not have a porous portion on the surface of the first portion and has a porous portion on the surface of the second portion.
  • a porous portion is formed on the surface of the first portion in addition to the surface of the second portion.
  • etching process a known method may be used, for example, electrolytic etching.
  • the masking member is not particularly limited and may be a conductor containing a conductive material, but an insulator such as a resin is preferable. The masking material is removed before the solid electrolyte layer is formed.
  • the surface of the first portion has a porous portion.
  • at least a portion of the porous portion formed in the first portion may be removed in advance or compressed to crush the pores of the porous portion. This makes it possible to prevent a decrease in the reliability of the solid electrolytic capacitor due to air entering the solid electrolytic capacitor.
  • the dielectric layer is formed, for example, by anodizing the valve metal on at least the surface of the second portion of the anode body by chemical conversion treatment or the like.
  • the dielectric layer contains an oxide of the valve metal.
  • the dielectric layer contains aluminum oxide.
  • the dielectric layer is formed along at least the surface of the second portion in which the porous portion is formed (including the inner wall surface of the hole of the porous portion). Note that the method of forming the dielectric layer is not limited to this, and it is sufficient if an insulating layer that functions as a dielectric can be formed on the surface of the second portion.
  • the dielectric layer may also be formed on the surface of the first portion (for example, the porous portion on the surface of the first portion).
  • the chemical conversion treatment can be carried out, for example, by immersing the anode body in a chemical conversion solution, thereby impregnating the surface of the anode body with the chemical conversion solution, and applying a voltage between the anode body as the anode and a cathode immersed in the chemical conversion solution. If the surface of the anode body has a porous portion, the dielectric layer is formed to conform to the uneven shape of the surface of the porous portion.
  • the cathode part is formed on the second part of the anode body having the dielectric layer, and may cover the surface of the separation layer facing the second part.
  • the cathode portion includes, for example, a solid electrolyte layer that covers at least a portion of the dielectric layer, and a cathode lead layer that covers at least a portion of the solid electrolyte layer.
  • the cathode portion is formed by forming a solid electrolyte so as to cover at least a portion of the dielectric layer, and by forming a cathode lead layer so as to cover at least a portion of the solid electrolyte layer.
  • a capacitor element is obtained by forming the cathode portion on a portion of an anode body having a dielectric layer.
  • the cathode extraction layer may include, for example, a conductive layer in contact with the solid electrolyte layer and covering at least a portion of the solid electrolyte layer.
  • the cathode extraction layer includes at least a first layer covering at least a portion of the solid electrolyte layer.
  • the cathode extraction layer may include the first layer covering at least a portion of the solid electrolyte layer and a second layer covering at least a portion of the first layer.
  • the metal foil may be a sintered foil, a vapor-deposited foil, or a coated foil in which the surface of the metal foil (for example, Al foil, Cu foil) is covered with a conductive film by vapor deposition or coating.
  • the vapor-deposited foil may be an Al foil with Ni vapor-deposited on the surface.
  • Examples of the conductive film include Ti, TiC, TiO, and C (carbon) films.
  • the conductive film may be a carbon coating.
  • the conductive carbon contained in the carbon layer serving as the first layer can be, for example, graphite (artificial graphite, natural graphite, etc.).
  • the layer containing metal powder as the second layer can be formed, for example, by laminating a composition containing metal powder onto the surface of the first layer.
  • a composition containing metal powder onto the surface of the first layer.
  • An example of such a second layer is a metal paste layer formed using a composition containing metal powder and a resin (binder resin).
  • An example of the metal paste layer is a silver paste layer containing silver particles and a resin.
  • a thermoplastic resin can be used as the resin, it is preferable to use a thermosetting resin such as an imide resin or an epoxy resin.
  • Examples of the metal foil for the second layer include the metal foils exemplified for the first layer.
  • the separation layer is formed before the cathode portion is formed.
  • the separation layer may be provided in the vicinity of the cathode portion so as to cover at least a part of the surface of the first portion. From the viewpoint of suppressing the intrusion of air into the inside of the solid electrolytic capacitor, the separation layer may be in close contact with the first portion and the sealing body.
  • the separation layer may be disposed on the first portion via a dielectric layer. Such a separation layer is provided after the dielectric layer is formed. This is not limited to this case, and may be provided before the dielectric layer is formed, as necessary.
  • the separation layer may contain, for example, a resin, and may be one of the examples of the sealing body described below.
  • the dielectric layer formed in the porous portion of the first part may be compressed and densified to provide insulation.
  • the separation layer may be provided, for example, by attaching a sheet-like insulating member (such as a resin tape) to the first portion.
  • a sheet-like insulating member such as a resin tape
  • the sheet-like insulating member has an adhesive layer on the surface that is attached to the first portion.
  • a liquid resin may be applied to or impregnated into at least a part of the first part to form an insulating member that adheres to the first part.
  • the insulating member may be formed so as to fill in the unevenness of at least the surface layer of the porous part of the first part. In this case, the liquid resin easily penetrates into the recesses in the surface layer of the porous part, and the insulating member can be easily formed in the recesses as well.
  • the insulating member since the porous part of the surface layer of the anode body is protected by the insulating member, the collapse of the porous part of the anode body is suppressed when the end of the anode body is partially removed together with the sealing body to form the outer surface of the sealing body and the end face of the anode body is exposed from the outer surface of the sealing body. Since the surface layer of the porous part of the anode body and the insulating member are firmly adhered to each other, the insulating member is suppressed from peeling off from the surface of the porous part of the anode body when the end of the anode body is partially removed together with the sealing body.
  • liquid resin for example, a curable resin composition exemplified for the sealing body described later may be used, or a solution in which the resin is dissolved in a solvent may be used. Also, a sheet-like insulating material may be used in addition to coating or impregnation with the liquid resin.
  • Each capacitor element 10 includes an anode body 3 constituting an anode portion, and a cathode portion 6.
  • the anode body 3 is, for example, an anode foil.
  • the anode body 3 has a core portion 4 and a porous portion 5 formed on the surface of the core portion 4 (the surface layer of the anode body 3).
  • a dielectric layer (not shown) is formed on at least a portion of the surface of the porous portion 5.
  • the cathode portion 6 covers at least a portion of the dielectric layer.
  • the cathode portion 6 includes a solid electrolyte layer 7 and a cathode lead layer.
  • the sealing body 14 has a substantially rectangular parallelepiped outer shape, and the solid electrolytic capacitor 100 also has a substantially rectangular parallelepiped outer shape.
  • the sealing body 14 has a first outer surface 14a and a second outer surface 14b opposite the first outer surface 14a.
  • the end face 1a of the first end of the anode body 3, which is the anode portion of each capacitor element 10, is exposed at the first outer surface 14a.
  • the end face 20a of the metal foil 20 constituting the cathode portion 6 is exposed from the sealing body at the second outer surface 14b.
  • each of the end faces 1a exposed from the sealing body 14 at the first ends of the multiple anode bodies 3 and the first outer surface 14a are covered with a first external electrode 21.
  • a contact layer 15 is formed on the end face 1a of the anode body 3 so as to cover the end face 1a.
  • the end face of the separation layer 12 is also exposed from the first outer surface 14a of the sealing body 14, and this exposed end face is also covered with a first external electrode 21.
  • the first external electrode 21 is electrically connected to the end face 1a of the anode body 3 via the contact layer 15.
  • FIG. 2 is a cross-sectional view showing a schematic structure of a solid electrolytic capacitor according to another embodiment of the present disclosure.
  • the solid electrolytic capacitor in FIG. 2 differs from FIG. 1 only in the layer configuration of the substrate 17, and is otherwise the same as FIG. 1, so the explanation for FIG. 1 can be referred to.
  • the substrate 17 has two insulating layers 17a and a metal layer 17b interposed between them.
  • the metal layer 17b is in contact with the second external electrode 22, but not with the first external electrode 21.
  • the average thickness of the insulating layer was approximately 100 ⁇ m per insulating layer, and the average thickness of the copper foil was 18 ⁇ m.
  • each component in each board is shown in Table 1. However, the total content of the components does not exceed 100% by mass.
  • the sealing body 14 was cut so that the end surface 1a of the anode body 3 of each capacitor element 10 and the insulating layer 17a of the substrate 17 were exposed from the first outer surface 14a, and the end surface 20a of the metal foil 20 and the metal layer 17b and insulating layer 17a of the substrate 17 were exposed from the second outer surface 14b.
  • a precursor was obtained in which end face 1a and insulating layer 17a of anode body 3 were exposed from first outer surface 14a, and end face 20a, insulating layer 17a, and metal layer 17b of metal foil 20 constituting cathode portion 6 were exposed from second outer surface 14b.
  • First outer surface 14a and second outer surface 14b of sealing body 14, and the end face of separation layer 12 exposed from first outer surface 14a were subjected to a cleaning treatment and a hydrophilization treatment.
  • the first external electrode 21 and the second external electrode 22 were formed so as to cover the contact layer 15 formed in (7) above and the first outer surface 14a and the second outer surface 14b, respectively.
  • a conductive paste containing silver particles and resin was applied to the contact layer 15 and the outer surface of the sealing body, and heated and dried to form conductive paste layers 21A and 22A, respectively.
  • an electrolytic Ni plating layer and an electrolytic Sn plating layer were formed to cover the conductive paste layers 21A and 22A, respectively.
  • Ni/Sn plating layers 21B and 22B, respectively were formed.
  • the surfaces of the plating layers were washed with water and dried to obtain solid electrolytic capacitors having a first external electrode 21 and a second external electrode 22. A total of 20 solid electrolytic capacitors were produced for each example using the same procedure.
  • the solid electrolytic capacitor was left in a thermostatic chamber at 30°C and 60% RH for 192 hours.
  • the solid electrolytic capacitor removed from the thermostatic chamber was cooled to 25°C.
  • the solid electrolytic capacitor was subjected to a reflow treatment in accordance with IPC/JEDEC J-STD-020D. Specifically, the solid electrolytic capacitor was preheated at a holding temperature of 150°C to 200°C and a holding time of 180 seconds or less.
  • the solid electrolytic capacitor after preheating was heated at a temperature of 255°C or more (maximum temperature 260°C) for 30 seconds.
  • the heating at the maximum temperature of 260°C was limited to 10 seconds or less.
  • the solid electrolytic capacitor was cooled to 25°C over 10 minutes, and this heating and cooling were repeated two more times (i.e., a total of three times).
  • the ESR of the solid electrolytic capacitor was measured at 20°C using the same procedure as above.
  • the amount of change in ESR due to the moisture absorption reflow test was determined by subtracting the initial ESR from the ESR after the moisture absorption reflow test, and the average value (m ⁇ ) of 20 pieces was calculated.
  • the solid electrolytic capacitor according to the present disclosure can prevent moisture from penetrating into the interior through a substrate including an insulating layer, and can suppress fluctuations in ESR when exposed to high temperatures such as during reflow processing. Therefore, the solid electrolytic capacitor according to the present disclosure can be used in a variety of applications requiring high reliability, and is also useful in applications requiring high heat resistance and applications in high humidity environments. However, the applications of the solid electrolytic capacitor are not limited to these.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
PCT/JP2023/046019 2022-12-26 2023-12-21 固体電解コンデンサ Ceased WO2024143173A1 (ja)

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CN202380088697.XA CN120418911A (zh) 2022-12-26 2023-12-21 固体电解电容器
JP2024567724A JPWO2024143173A1 (https=) 2022-12-26 2023-12-21

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018198298A (ja) * 2016-06-15 2018-12-13 株式会社村田製作所 固体電解コンデンサ
WO2022059459A1 (ja) * 2020-09-17 2022-03-24 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018198298A (ja) * 2016-06-15 2018-12-13 株式会社村田製作所 固体電解コンデンサ
WO2022059459A1 (ja) * 2020-09-17 2022-03-24 パナソニックＩｐマネジメント株式会社 固体電解コンデンサ

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