WO2024190596A1 - 固体電解コンデンサ用陽極箔、固体電解コンデンサ及び固体電解コンデンサ用陽極箔の製造方法 - Google Patents

固体電解コンデンサ用陽極箔、固体電解コンデンサ及び固体電解コンデンサ用陽極箔の製造方法 Download PDF

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Publication number
WO2024190596A1
WO2024190596A1 PCT/JP2024/008766 JP2024008766W WO2024190596A1 WO 2024190596 A1 WO2024190596 A1 WO 2024190596A1 JP 2024008766 W JP2024008766 W JP 2024008766W WO 2024190596 A1 WO2024190596 A1 WO 2024190596A1
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Prior art keywords
etching
solid electrolytic
electrolytic capacitor
anode foil
forming
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PCT/JP2024/008766
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English (en)
French (fr)
Japanese (ja)
Inventor
純一 佐藤
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2025506771A priority Critical patent/JPWO2024190596A1/ja
Priority to CN202480017813.3A priority patent/CN120937100A/zh
Publication of WO2024190596A1 publication Critical patent/WO2024190596A1/ja
Priority to US19/317,822 priority patent/US20260038744A1/en
Anticipated expiration legal-status Critical
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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
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • 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
    • H01G9/0029—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • 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

  • the present invention relates to an anode foil for a solid electrolytic capacitor, a solid electrolytic capacitor, and a method for manufacturing an anode foil for a solid electrolytic capacitor.
  • Patent Document 1 describes an anode substrate obtained by forming through-type tunnel pits in valve metal foil and then roughening the surface to form spongy pits using cubic pits formed by AC etching.
  • Patent document 2 describes a technology for creating tunnel-shaped pits and fine pits in aluminum foil.
  • the through-type tunnel pits described in Patent Documents 1 and 2 tend to connect adjacent tunnels like a cut line, which can easily lead to a decrease in the strength of the core metal.
  • tunnel pits have a small expansion rate of the specific surface area, making it difficult to balance the specific surface area and strength.
  • the present invention has been made to solve the above problems, and aims to provide an anode foil for solid electrolytic capacitors that has an excellent balance between specific surface area and strength for the anode foil as a whole, a solid electrolytic capacitor, and a method for manufacturing an anode foil for solid electrolytic capacitors.
  • the anode foil for a solid electrolytic capacitor of the present invention comprises a metal core, a sponge-like porous layer provided on the metal core, and a sponge-like through hole provided in a portion of the surface of the metal core and penetrating the metal core.
  • the solid electrolytic capacitor of the present invention is equipped with the anode foil for a solid electrolytic capacitor of the present invention.
  • the method for manufacturing an anode foil for a solid electrolytic capacitor of the present invention is a method for manufacturing an anode foil for a solid electrolytic capacitor having a porous layer on the surface thereof, and includes the steps of etching the surface of a substrate to form a spongy porous layer, and etching a part of the surface of the core metal of the substrate to form a spongy through hole penetrating the core metal.
  • the present invention provides an anode foil for a solid electrolytic capacitor that has an excellent balance between specific surface area and strength for the anode foil as a whole, a solid electrolytic capacitor, and a method for manufacturing an anode foil for a solid electrolytic capacitor.
  • FIG. 1 is a cross-sectional view that typically illustrates an anode foil for a solid electrolytic capacitor according to an embodiment of the present invention.
  • FIG. 2 is a perspective view that typically shows pits that constitute sponge-like through-holes in an anode foil for a solid electrolytic capacitor according to an embodiment of the present invention.
  • Fig. 3A is a schematic diagram showing an example of an initial substrate surface on which pits are formed by etching.
  • Fig. 3B is a schematic diagram showing an example of a substrate surface on which a protective film is formed after etching.
  • Fig. 3C is a schematic diagram showing an example of a substrate surface on which pits are again formed by etching after the formation of a protective film.
  • Fig. 3A is a schematic diagram showing an example of an initial substrate surface on which pits are formed by etching.
  • Fig. 3B is a schematic diagram showing an example of a substrate surface on which a protective film is formed after etching.
  • FIG. 3D is a schematic diagram showing an example of a substrate surface on which pit formation by etching has progressed without the formation of a protective film.
  • FIG. 4 is a cross-sectional view that illustrates a schematic configuration of a solid electrolytic capacitor according to an embodiment of the present invention.
  • FIG. 5 is an enlarged cross-sectional view of a portion II in FIG. 6 is a cross-sectional view of the solid electrolytic capacitor of FIG. 4 as viewed from the direction of the arrows indicated by the line III-III.
  • the anode foil for a solid electrolytic capacitor, the solid electrolytic capacitor, and the method for producing the anode foil for a solid electrolytic capacitor of the present invention will be described below.
  • the present invention is not limited to the following configurations, and can be modified and applied as appropriate within the scope of the present invention. Note that the present invention also includes a combination of two or more of the individual desirable configurations described below.
  • FIG. 1 is a cross-sectional view showing a schematic diagram of an anode foil for a solid electrolytic capacitor according to an embodiment of the present invention.
  • the anode foil 10 for a solid electrolytic capacitor shown in FIG. 1 is an electrode foil for an anode of a solid electrolytic capacitor made of a valve metal, and includes a metal core 12, a pair of porous layers 14, and a number of through holes 16.
  • valve metals examples include aluminum, tantalum, niobium, titanium, zirconium, magnesium, silicon, and other metals, or alloys containing these metals. Among these, aluminum or aluminum alloys are preferred.
  • the core metal 12 is a foil-shaped portion located at the center of the thickness of the anode foil 10.
  • the thickness of the core metal 12 is preferably 5 ⁇ m or more and 100 ⁇ m or less, more preferably 10 ⁇ m or more and 80 ⁇ m or less, and even more preferably 15 ⁇ m or more and 40 ⁇ m or less.
  • the porous layer 14 is sponge-like and is preferably an etched layer that has been electrolytically etched with hydrochloric acid or the like.
  • the porous layer 14 is provided on both main surfaces of the core metal 12, but may be provided on only one of the main surfaces of the core metal 12.
  • the thickness of the porous layer 14 is preferably 5 ⁇ m or more and 200 ⁇ m or less per layer on one side, more preferably 10 ⁇ m or more and 100 ⁇ m or less, and even more preferably 20 ⁇ m or more and 70 ⁇ m or less.
  • the through holes 16 are sponge-like through holes that are provided in a portion of the surface of the metal core 12 and penetrate the metal core 12. By providing a path that penetrates the metal core 12 in this way, a path is created for gas to escape to the opposite side of the conductive polymer filling from the surface of the anode foil 10, making it easier for gas-liquid exchange to occur. This improves the filling (impregnation) of the conductive polymer deep into the porous layer 14, and increases the capacity expression rate of the solid electrolytic capacitor.
  • the through holes 16 are sponge-like, that is, the sponge structure penetrates the core metal 12, the metal remnants are present three-dimensionally in the through holes 16. Therefore, structurally, the through holes 16 are unlikely to be connected like cut lines (less likely to cause a decrease in the strength of the core metal 12), and are also likely to contribute to increasing the specific surface area. Therefore, it is possible to achieve a balance between the specific surface area and strength of the anode foil 10 as a whole. Furthermore, by providing the sponge-like through holes 16, the surface expansion ratio of the porous layer 14 can also be reduced compared to when the sponge-like through holes 16 are not provided in the core metal 12.
  • the sponge-like through holes 16 are provided in a dispersed manner within the surface of the core metal 12.
  • the area ratio of the through holes 16 within the surface of the core metal 12 is not particularly limited, but the larger the ratio, the more the impregnation of the conductive polymer is improved, but if the ratio is too large, there is a risk that the strength of the core metal 12 cannot be sufficiently ensured. From this viewpoint, specifically, the area ratio of the through holes 16 within the surface of the core metal 12 is preferably 10% or more and 90% or less, and more preferably 20% or more and 60% or less.
  • the area ratio of the through holes 16 to the surface of the core metal 12 can be calculated as the ratio (percentage) of the area of the through holes to the observation area by, for example, scraping off the core metal portion by a method such as mechanical polishing, processing an observation image obtained by observation with a scanning electron microscope (SEM) or the like into a binary image, and analyzing the binary image. Since the brightness of the core metal portion and the through hole portion in the observation image is clearly different, the two regions can be distinguished by binarization.
  • the area occupied by the sponge-like through holes 16 is preferably 0.025 ⁇ m 2 or more and 1 ⁇ m 2 or less per one through hole 16, and more preferably 0.05 ⁇ m 2 or more and 0.5 ⁇ m 2 or less.
  • the area occupied by the sponge-like through holes 16 can be calculated, for example, by analyzing an observation image obtained by SEM observation or the like as described above, measuring the areas of at least 50 through holes, and taking the average value (arithmetic mean).
  • the pit structure that constitutes the sponge-like through-holes 16 may be the same as the pit structure that constitutes the porous layer 14, but it is preferable that it is different.
  • a pit refers to a single cavity (cluster) of a uniform shape, and examples of the pit structure include the shape and dimensions (e.g., diameter) of the pit, and the arrangement of multiple pits.
  • the pits 14a constituting the sponge-like porous layer 14 and the pits 16a constituting the sponge-like through-holes 16 are cubic with the same dimensions, but the dimensions and shapes of the pits 14a and 16a are not particularly limited.
  • the shapes of the pits 14a and 16a may be different from each other, and the pits 14a constituting the porous layer 14 may be cubic while the pits 16a constituting the through-holes 16 may be spherical.
  • Such spherical pits can be obtained, for example, by forming cubic pits by electrolytic etching and then chemically dissolving the surfaces of the pits. It should be noted that cubic pits can be formed by electrolytic etching using an alternating current, as described below.
  • FIG. 2 is a perspective view showing a schematic diagram of pits that form sponge-like through-holes in an anode foil for a solid electrolytic capacitor according to an embodiment of the present invention.
  • the area of the overlapping portion (communicating portion) 16b of adjacent cubic pits 16a of the through hole 16 can be enlarged as necessary by chemical dissolution after electrolytic etching. This can further increase the impregnation of the conductive polymer.
  • the method for manufacturing an anode foil for a solid electrolytic capacitor according to this embodiment is a method for manufacturing an anode electrode foil for a solid electrolytic capacitor having a porous layer on its surface, and is suitable for manufacturing the anode foil for a solid electrolytic capacitor according to the embodiment described above.
  • a substrate is prepared.
  • a first etching process is performed to etch the surface of the substrate to form spongy pits
  • a first intermediate process is performed to form a protective film on the surface of the pits formed by the first etching process.
  • the first etching process and the first intermediate process are usually performed alternately multiple times.
  • the dispersion state of the etching pits and the degree of progress of the etching process in the depth direction can be changed, making it easier to obtain the desired etching state. This is also true when a sine wave AC current is applied.
  • the first etching process and the first intermediate process for forming this porous layer may be carried out in the same manner as the etching process and intermediate process for forming a conventional sponge-like porous layer.
  • a second etching process is performed in which a portion of the surface of the core metal is etched to form sponge-like pits, and a second intermediate process is performed in which a protective film is formed on the surface of the pits formed by the second etching process.
  • the second etching process and the second intermediate process are usually performed alternately multiple times.
  • the etched substrate is immersed in a treatment liquid, for example, an aqueous solution of phosphate, to form a coating that is a complex containing phosphate ions and aluminum on the etched substrate surface, which acts as a protective film.
  • a treatment liquid for example, an aqueous solution of phosphate
  • the pits may fuse together to form large holes, reducing the surface area.
  • the intermediate treatment during the etching process to form a protective film the progress of local etching of the already formed pits is suppressed, improving (suppressing) the fusion of the pits.
  • examples of the protective film formed in the first and second intermediate treatments include aluminum hydrate.
  • the first and second intermediate processes satisfy at least one of the following conditions (1) to (3).
  • (1) The number of times the second intermediate process is performed is less than the number of times the first intermediate process is performed.
  • (2) The time for the second intermediate processing is shorter than the time for the first intermediate processing.
  • (3) The concentration of the processing liquid used in the second intermediate processing is lower than the concentration of the processing liquid used in the first intermediate processing.
  • a porous layer is formed while dispersing pits in the in-plane direction and the depth direction in the first etching process accompanied by the first intermediate process, and then, in the second etching process accompanied by the second intermediate process, etching proceeds in the depth direction from both main surfaces of the substrate in a part of the in-plane direction to connect the pits, and sponge-like through holes can be easily formed.
  • the second etching treatment is performed by at least one of (4) a second AC etching in which a positive current and a negative current are alternately passed through the substrate, and (5) an etching in which only a positive current is intermittently passed through the substrate, and it is preferable that (4) the second AC etching satisfies at least one of the following conditions (4A) and (4B).
  • (4A) The absolute value of the negative current is smaller than the absolute value of the positive current.
  • (4B) The time during which the negative current is passed is shorter than the time during which the positive current is passed.
  • etching is performed with an AC waveform that reduces the negative current (conditions (4A) and (4B) above) and/or etching is performed without passing a negative current (condition (5) above), so that the sponge-like through holes can be easily formed.
  • the second AC etching in (4) above may be performed, for example, by passing a square wave AC current with a bias voltage applied in the direction in which the positive current flows. This allows the formation of sponge-like through-holes composed of cubic pits.
  • the second AC etching in (4) above may be performed by passing a sinusoidal AC current with a bias voltage applied in the direction in which the positive current flows.
  • the etching in (5) above is preferably performed with a waveform similar to a half-wave of a square AC wave. This also makes it possible to form sponge-like through-holes composed of cubic pits. Alternatively, the etching in (5) above may be performed with a waveform similar to a half-wave of a sine AC wave.
  • the first half of the etching process to form the sponge-like porous layer i.e., the first etching process
  • the capacitance of the solid electrolytic capacitor will decrease. Therefore, in the first etching process, it is preferable to perform AC etching by passing a positive current and a negative current alternately through the substrate as described above to prevent a decrease in capacitance.
  • FIG. 3A is a schematic diagram showing an example of an initial substrate surface on which pits have been formed by etching.
  • FIG. 3B is a schematic diagram showing an example of a substrate surface on which a protective film has been formed after etching.
  • FIG. 3C is a schematic diagram showing an example of a substrate surface on which pits have been formed again by etching after the formation of a protective film.
  • FIG. 3D is a schematic diagram showing an example of a substrate surface on which pit formation by etching has progressed without the formation of a protective film.
  • etching is performed while a protective film is sufficiently formed, thereby forming pits dispersed within the substrate surface, whereas in the through hole formation process, etching is performed while the protective film is not sufficiently formed (including the case where a protective film is not formed), thereby forming pits locally within the substrate surface and allowing them to grow in the depth direction.
  • Solid electrolytic capacitor Next, a solid electrolytic capacitor according to an embodiment of the present invention will be described.
  • FIG. 4 is a cross-sectional view showing a schematic configuration of a solid electrolytic capacitor according to an embodiment of the present invention.
  • FIG. 5 is a cross-sectional view showing an enlarged view of part II in FIG. 4.
  • FIG. 6 is a cross-sectional view of the solid electrolytic capacitor in FIG. 4 as viewed from the direction of the arrows III-III.
  • L the length direction of the insulating resin body described below
  • T the height direction of the insulating resin body
  • W width direction of the insulating resin body by W.
  • the height direction T is perpendicular to the length direction L
  • the width direction W is perpendicular to both the length direction L and the height direction T.
  • the solid electrolytic capacitor 100 shown in Figures 4 to 6 has a generally rectangular parallelepiped shape.
  • the external dimensions of the solid electrolytic capacitor 100 are, for example, 7.3 mm in the length direction L, 4.3 mm in the width direction W, and 1.9 mm in the height direction T.
  • the solid electrolytic capacitor 100 comprises three or more capacitor elements 180, an insulating resin body 110, a first terminal 120, and a second terminal 130.
  • the insulating resin body 110 has a substantially rectangular parallelepiped outer shape.
  • the insulating resin body 110 has a first main surface 110a and a second main surface 110b that face each other in the height direction T, a first side surface 110c and a second side surface 110d that face each other in the width direction W, and a first end surface 110e and a second end surface 110f that face each other in the length direction L.
  • the insulating resin body 110 has a substantially rectangular parallelepiped outer shape, but the corners and ridges may be rounded.
  • the corners are the parts where three faces of the insulating resin body 110 intersect, and the ridges are the parts where two faces of the insulating resin body 110 intersect.
  • At least one of the first main surface 110a, the second main surface 110b, the first side surface 110c, the second side surface 110d, the first end surface 110e, and the second end surface 110f may have irregularities.
  • the insulating resin body 110 is composed of an insulating resin such as epoxy resin in which glass or silicon oxide is dispersed and mixed as a filler.
  • Each of the three or more capacitor elements 180 includes an anode portion 140, a dielectric layer 150, and a cathode portion 160.
  • the three or more capacitor elements 180 are stacked on top of each other in the height direction T.
  • the anode section 140 is made of the anode foil 10 for a solid electrolytic capacitor described above.
  • the dielectric layer 150 is provided on the outer surface of the anode foil 10.
  • the dielectric layer 150 is made of an oxide of aluminum.
  • the dielectric layer 150 is made of an oxide of aluminum formed by anodizing the outer surface of the anode foil 10.
  • the cathode section 160 has a solid electrolyte layer 161 and a current collector layer.
  • the solid electrolyte layer 161 is provided on a part of the outer surface of the dielectric layer 150.
  • the solid electrolyte layer 161 is not provided on the outer surface of the dielectric layer 150 provided on the outer surface near the second end face 110f of the anode foil 10, located on the opposite side to the cathode section 160.
  • the part adjacent to the part where the solid electrolyte layer 161 is provided has its outer surface covered with an insulating resin layer 151 described below.
  • the solid electrolyte layer 161 is provided so as to fill multiple recesses in the anode foil 10. However, it is sufficient that the solid electrolyte layer 161 covers the above-mentioned part of the outer surface of the dielectric layer 150, and there may be recesses in the anode foil 10 that are not filled with the solid electrolyte layer 161.
  • the solid electrolyte layer 161 is composed of a polymer that includes a conductive polymer such as poly(3,4-ethylenedioxythiophene).
  • the current collector layer is provided on the outer surface of the solid electrolyte layer 161.
  • the current collector layer is composed of a first current collector layer 162 provided on the outer surface of the solid electrolyte layer 161, and a second accumulation layer 163 provided on the outer surface of the first current collector layer 162.
  • the first current collector layer 162 contains carbon.
  • the second accumulation layer 163 contains silver.
  • the portion adjacent to the portion where the solid electrolyte layer 161 is provided has its outer surface covered with an insulating resin layer 151 having a composition different from that of the insulating resin body 110.
  • the insulating resin layer 151 is provided so as to fill multiple recesses in the outer surface of the anode foil 10 in a portion adjacent to the portion where the solid electrolyte layer 161 is provided.
  • the insulating resin layer 151 contains an insulating resin such as a polyimide resin or a polyamide-imide resin.
  • the collector layers of adjacent capacitor elements 180 in the stacking direction are electrically connected to each other by a connecting conductor layer 190.
  • the width of the connecting conductor layer 190 in the width direction W is equal to the width of the anode foil 10 in the width direction W.
  • the connecting conductor layer 190 contains silver.
  • the ends of the anode foils 10 of the capacitor elements 180 adjacent to each other in the stacking direction that are close to the second end faces 110f are electrically connected to each other by resistance welding or the like.
  • the first terminal 120 is a lead frame.
  • the first terminal 120 is electrically connected to the cathode portion 160 of each of the three or more capacitor elements 180, and is drawn out to the outside of the insulating resin body 110.
  • a portion located inside the insulating resin body 110 faces each of the current collector layers of two capacitor elements 180 adjacent to each other in the stacking direction, and is connected to each of the current collector layers by a connecting conductor layer 190.
  • a portion located outside the insulating resin body 110 is bent along the first end surface 110e and the second main surface 110b of the insulating resin body 110.
  • the second terminal 130 is a lead frame.
  • the second terminal 130 is electrically connected to the anode parts 140 of the three or more capacitor elements 180 and is drawn out to the outside of the insulating resin body 110.
  • the part of the second terminal 130 located inside the insulating resin body 110 is sandwiched between the ends of the anode foils 10 of the two capacitor elements 180 adjacent to each other in the stacking direction, close to the second end faces 110f, and is connected to each of the anode foils 10 by resistance welding or the like.
  • the part of the second terminal 130 located outside the insulating resin body 110 is bent along the second end face 110f and the second main surface 110b of the insulating resin body 110.
  • a pair of lead frames drawn out from a pair of end faces are used as a pair of terminals (external electrodes) electrically connected to the anode and cathode portions of each capacitor element, respectively.
  • a pair of electrode layers formed on a pair of end faces may also be used as a pair of terminals (external electrodes).
  • the solid electrolytic capacitor of the present invention may be used by being embedded in a package substrate included in a semiconductor device.
  • the semiconductor device is a semiconductor composite device in which a voltage regulator (voltage control device) and a load are mounted on a package substrate.
  • ⁇ 2> The anode foil for a solid electrolytic capacitor according to ⁇ 1>, wherein a pit structure constituting the through-holes is different from a pit structure constituting the porous layer.
  • a solid electrolytic capacitor comprising the anode foil for a solid electrolytic capacitor according to ⁇ 1> or ⁇ 2>.
  • a method for producing an anode foil for a solid electrolytic capacitor having a porous layer on a surface thereof comprising the steps of: Etching the surface of the substrate to form a sponge-like porous layer; and a step of etching a portion of the surface of the metal core of the substrate to form a sponge-like through hole penetrating the metal core.
  • the step of forming the porous layer includes a first etching process for etching a surface of the base material to form spongy pits, and a first intermediate process for forming a protective film on surfaces of the pits formed by the first etching process;
  • the step of forming the through hole includes a second etching process for etching a part of the surface of the core metal to form a spongy pit, and a second intermediate process for forming a protective film on a surface of the pit formed by the second etching process;
  • the time period for the second intermediate treatment carried out in the step of forming the through holes is shorter than the time period for the first intermediate treatment carried out in the step of forming the porous layer.
  • the concentration of the treatment liquid used in the second intermediate treatment carried out in the step of forming the through holes is lower than the concentration of the treatment liquid used in the first intermediate treatment carried out in the step of forming the porous layer.
  • the step of forming the porous layer includes a first etching treatment for etching a surface of the substrate to form spongy pits; the step of forming the through hole includes a second etching process for etching a part of the surface of the core metal to form a spongy pit;
  • the first etching process is performed by first AC etching in which a positive current and a negative current are alternately applied to the substrate;
  • the second etching process is performed by at least one of (4) a second AC etching process in which a positive current and a negative current are alternately applied to the substrate, and (5) an etching process in which only a positive current is intermittently applied to the substrate,

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PCT/JP2024/008766 2023-03-10 2024-03-07 固体電解コンデンサ用陽極箔、固体電解コンデンサ及び固体電解コンデンサ用陽極箔の製造方法 Ceased WO2024190596A1 (ja)

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JP2025506771A JPWO2024190596A1 (https=) 2023-03-10 2024-03-07
CN202480017813.3A CN120937100A (zh) 2023-03-10 2024-03-07 固体电解电容器用阳极箔、固体电解电容器以及固体电解电容器用阳极箔的制造方法
US19/317,822 US20260038744A1 (en) 2023-03-10 2025-09-03 Anode foil for solid electrolytic capacitor, solid electrolytic capacitor, and method for manufacturing anode foil for solid electrolytic capacitor

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JP2023-037911 2023-03-10

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