WO2006008970A1 - Film d'électrode pour condensateur et procédé de fabrication de celui-ci - Google Patents

Film d'électrode pour condensateur et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2006008970A1
WO2006008970A1 PCT/JP2005/012520 JP2005012520W WO2006008970A1 WO 2006008970 A1 WO2006008970 A1 WO 2006008970A1 JP 2005012520 W JP2005012520 W JP 2005012520W WO 2006008970 A1 WO2006008970 A1 WO 2006008970A1
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yes
metal
aluminum
foil
fluorine
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PCT/JP2005/012520
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Japanese (ja)
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Hiromasa Shoji
Tsutomu Sugiura
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Nippon Steel Corporation
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium

Definitions

  • the present invention relates to an electrode foil for a capacitor and a method for manufacturing the same, and particularly relates to an increase in capacitance.
  • an aluminum electrode foil constituting an electrolytic capacitor is subjected to electrolytic etching by applying a DC voltage or an AC voltage to the aluminum foil in an acid water solution, and a large number of pitches are formed on the foil surface to increase the surface area. After that, it is anodized in a chemical conversion solution to form an aluminum oxide film on the foil surface and used as an electrode material.
  • Increasing the capacitance includes increasing the surface area of the foil and thinning the oxide film, which is a dielectric, and various studies have been conducted.
  • increasing the dielectric constant of the oxide film is another way to increase the electrostatic capacity, and higher capacity is being studied by forming a titanium oxide film with a high dielectric constant and a composite oxide film of titanium oxide and aluminum oxide.
  • the current situation is that the capacity has not been increased sufficiently.
  • Japanese Patent Laid-Open No. 2003-4036 a CVD method, a sputtering method, a sol-gel method, a sol-gel electrophoresis electrodeposition method, etc. are studied for forming a titanium oxide film. Since film formation on A1 foil is extremely difficult, sufficient electrostatic capacity cannot be obtained, and leakage current increases. In the sol-gel method, since it is difficult to form a dense oxide film by the sol-gel electrokinetic electrodeposition method, a sufficient electrostatic capacity cannot be obtained, and the leakage current also increases. Therefore, Japanese Patent Application Laid-Open No. 2003-257796 has improved the sol-gel method and examined the inclusion of a valve metal oxide polymer-aromatic compound solvent complex having a high degree of polymerization.
  • JP-A-5-3 15 197 an oxide film is formed by thermal decomposition after applying a metal salt or an organic metal salt, and in the same manner as described above, by reducing the density due to volatile components at that time. As a result, sufficient capacitance cannot be obtained, and the leakage current cannot be improved sufficiently. Disclosure of the invention
  • an electrode foil for a capacitor characterized in that it is an aluminum foil having at least a fluorine-containing film mainly composed of a metal oxide composed of a valve action metal excluding aluminum. Depending on the dielectric constant of the valve metal And found that the capacitance increases. Furthermore, an electrode foil for a capacitor, which is an aluminum foil having at least a film mainly composed of aluminum oxide and a film containing fluorine mainly composed of a metal oxide composed of a valve action metal excluding aluminum.
  • a film mainly composed of aluminum oxide and a valve action excluding aluminum and aluminum A film containing fluorine mainly composed of one or both of a composite oxide of metal and a mixed oxide and a valve action excluding aluminum
  • Capacitor electrode foil which is an aluminum foil having at least a fluorine-containing coating composed mainly of metal oxides composed of metal, has a higher capacitance depending on the dielectric constant of the valve metal. Found to increase.
  • the gist of the present invention is as follows.
  • An electrode foil for capacitors characterized in that it is an aluminum foil having at least a coating film containing fluorine, the main component of which is a metal oxide composed of a valve action metal excluding aluminum.
  • An aluminum foil having at least a film mainly composed of aluminum oxide and a film containing fluorine mainly composed of a metal oxide composed of a valve metal excluding aluminum. Capacitor electrode foil.
  • An electrode foil for a capacitor characterized in that it is an aluminum foil having at least a coating film containing fluorine mainly composed of a metal oxide composed of a valve action metal excluding aluminum.
  • aqueous solution in which a valve action metal ion excluding aluminum and a fluorine ion in a molar ratio of 6 times or more with respect to the ion, or a valve action metal excluding aluminum and a mole ratio of 6 times or more with respect to the metal.
  • An aluminum foil is brought into contact with a treatment liquid mainly composed of one or both of an aqueous solution containing complexions composed of fluorine in a specific ratio, a metal oxide film is formed on the surface of the foil, and then anodized and heat-treated.
  • Capacitor electrode foil characterized by comprising
  • valve metal is one or more of titanium, tantalum, and niobium.
  • a valve action metal ion excluding aluminum and a fluorine ion in a molar ratio of 6 times or more with respect to the ion coexists, or a valve action metal excluding aluminum and the metal more than 6 times with respect to the metal.
  • An aluminum foil is brought into contact with a treatment liquid containing as a main component one or both of an aqueous solution containing complexions of fluorine having a molar ratio of, and an anodizing treatment is performed after forming a metal oxide film on the surface of the foil.
  • An aluminum foil is brought into contact with a treatment liquid mainly composed of one or both of an aqueous solution containing complex ions composed of fluorine having a molar ratio of, and after forming a metal oxide film on the surface of the foil, anodizing is performed.
  • valve metal is one or more of titanium, tantalum, and niobium.
  • a valve metal means a metal oxide whose current flows only in one direction and is very difficult to flow in the opposite direction. Specific examples include tantalum, niobium, zirconium, and titanium. If it has the above-mentioned action, it is not limited to these metals.
  • Fluorine-containing film composed mainly of metal oxides composed of valve action metals excluding aluminum, and one or both of complex oxides or mixed oxides of valve action metals excluding aluminum and aluminum.
  • coatings containing fluorine or coatings composed mainly of aluminum oxide the smaller the film thickness, the larger the capacity. Further, it may further contain a coating or a component that does not inhibit the action of these three types of coating.
  • the mechanism of the effect of fluorine present in the coating is thought to be contributing to the catalytic action and stabilization of the oxide coating, but is not clear.
  • the fluorine-containing concentration in the coating is preferably 0.1 atomic% to 60 atomic%. 0. Less than 1 atomic%, the effect is not fully manifested, and over 60 atomic%, the leakage current may increase.
  • Valve action metal ions excluding aluminum and an aqueous solution in which fluorine ions with a molar ratio of 6 times or more with respect to the ions are present, or aluminum
  • an aqueous solution containing a valve action metal except for and a complex ion composed of fluorine at a molar ratio of 6 times or more with respect to the metal an equilibrium reaction between the metal ion and the oxide occurs.
  • Fluorine ions include hydrofluoric acid or salts thereof, such as ammonium salt, potassium salt, sodium salt, etc., and there are no restrictions on these.
  • Complex ions comprising a metal and the metal in a molar ratio of 6 times or more include hexafluorotitanic acid, hexafluoroniobic acid, hexafluorotantalic acid, hexafluorozirconium. Acids, etc., or salts thereof, such as ammonium salt, potassium salt, sodium salt, etc. can be used, and there are no particular restrictions on these. Furthermore, elements other than metals and fluorine may be contained in the complex ions. When using a salt, the saturation solubility differs depending on the cation species, so it may be necessary to select the salt concentration range. When the molar ratio of metal ions to fluorine ions in the treatment liquid was less than 6 times, a sound film was formed, but a sufficient increase in capacity was not confirmed.
  • the treatment solution pH is preferably 4-7. More preferably, it is 5-6.
  • the treatment solution pH is less than 4, although a healthy film was formed, a sufficient increase in volume was not confirmed. The reason for this is not clear.
  • the liquid is unstable, and agglomerated material may be deposited, which is not suitable for forming a thinner film.
  • the treatment solution pH may be adjusted by a known method. Other conditions for the precipitation reaction of the present invention are not particularly limited. What is necessary is just to set reaction temperature and reaction time suitably.
  • Examples of film formation include immersion, spraying, and spraying.
  • the method is not limited as long as the aluminum foil is in contact with the treatment liquid.
  • Examples of the electrolytic solution for anodizing treatment may include ammonium borate, phosphoric acid, adipic acid, oxalic acid, sulfuric acid, sebacic acid, or a solution containing one or more of these ammonium salts. But not limited. Further, the anodizing conditions may be any known conditions and are not particularly limited.
  • the heat treatment temperature after anodization is preferably 400 ° C or lower, more preferably 200 to 400 ° C. If the temperature is less than 200 ° C, the effect of heat treatment may not be fully confirmed. If the temperature exceeds 400 ° C, a decrease in capacitance is confirmed.
  • the atmosphere during the heat treatment is preferably in a vacuum or in an inert gas such as nitrogen or argon. In making the vacuum, the pressure may be reduced from the atmosphere, or may be reduced after the atmosphere is replaced with an inert gas.
  • Examples of the aluminum foil used include high-purity aluminum foil used for capacitors such as 1 N99 and 1N90.
  • an aluminum sintered body may be used. Etching does not depend on the degree of roughening.
  • An aluminum foil with a coating may be used as the anode to form a capacitor.
  • the electrolyte and the cathode are not limited and may be appropriately selected and used.
  • the processing solutions, processing conditions and results are shown in Tables 1 and 2 (continued in Table 1).
  • the base material was unformed A1 foil (1N99) that was not etched.
  • a 12% ammonium adipate aqueous solution was applied at a temperature of 80 ° C. and a voltage of 50 V for 60 minutes.
  • the capacitance was measured at 120 Hz using an LCR meter using a 12% aqueous ammonium adipate solution.
  • the leakage current was measured by applying 5V. Evaluation was performed according to the following criteria in comparison with Experiment No. 46, which is a comparative example below.
  • Capacitance X Lower than No. 46
  • the treatment liquid is a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ion to fluorine ion of 1: 5.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment liquid is a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ion to fluorine ion of 1: 6.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. In the film The amount of fluorine was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution is a 0.1M titanium chloride / ammonium fluoride mixed aqueous solution with a molar ratio of titanium ions to fluorine ions of 1: 6.
  • the pH is adjusted to 4, 5, 6, 7 with hydrofluoric acid or ammonia water. It was adjusted.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. Anodization was performed. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ions to fluorine ions of 1: 6, and the pH was adjusted to 5 with hydrofluoric acid or ammonia water.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C.
  • the heat treatment atmosphere was vacuum, nitrogen, and vacuum containing less than 1% nitrogen.
  • the amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ions to fluoride ions of 1: 6, and the pH was adjusted to 6 and 7 with hydrofluoric acid and ammonia water.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atoms.
  • the treatment solution uses a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ions to fluorine ions of 1: 6.
  • the pH was adjusted to 4, 5, and 6 with aqueous ammonia.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 90 ° C and about 450 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment liquid is a 0.1M titanium chloride / ammonium hydrogen fluoride aqueous solution with a molar ratio of titanium ions to fluoride ions of 1:12.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was 0.1M hexafluorotitanic acid aqueous solution, and the pH was adjusted to 3, 4, 5, 6, 7, 8 with hydrofluoric acid or ammonia water.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy, and it was confirmed that it was 0.1 to 60 atomic% / _ o
  • the treatment solution was 0.1M ammonium hexatitanate aqueous solution, and the pH was adjusted to 3, 4, 5, 6, 7, 8 with hydrofluoric acid or ammonia water.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%. [Experiment No. 46]
  • the substrate was anodized and then heat treated at about 300 ° C in vacuum.
  • Example 10 6 1-1- ⁇ to ⁇ ⁇
  • Example 13 A1 foil flat 4 Yes 1 ⁇ ⁇ ⁇ ⁇ ⁇
  • Example 28 Titanium ion, fluorine ion 3 Yes-Yes 1 ⁇ ⁇
  • the processing solutions, processing conditions and results are shown in Table 3 and Table 4 (continued in Table 3).
  • the base material was an unformed A1 foil (1N99) that was etched with direct current so as to have a surface area about 20 times larger than that of an etching solution mainly composed of hydrochloric acid.
  • a 12% ammonium adipate aqueous solution was used and applied at a temperature of 80 ° C and a voltage of 50 V for 60 minutes.
  • Capacitance was measured at ⁇ using LCR method using 12% ammonium adipate aqueous solution. The leakage current was measured by applying 5V. Evaluation was performed according to the following criteria in comparison with Experiment No. 92, which is a comparative example below.
  • Capacitance X Lower than No. 92
  • the treatment liquid is a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ion to fluorine ion of 1: 5.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%. P2005 / 012520 approved.
  • the treatment liquid is a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ions to fluorine ions of 1: 6.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution is a 0.1M titanium chloride / ammonium fluoride mixed aqueous solution with a molar ratio of titanium ions to fluorine ions of 1: 6.
  • the pH is adjusted to 4, 5, 6, 7 with hydrofluoric acid or ammonia water. It was adjusted.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. Anodization was performed. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ions to fluorine ions of 1: 6, and the pH was adjusted to 5 with hydrofluoric acid or ammonia water.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C.
  • the heat treatment atmosphere was vacuum, nitrogen, and vacuum containing less than 1% nitrogen.
  • the amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M titanium chloride and ammonium fluoride with a molar ratio of titanium ion to fluorine ion of 1: 6, and the pH was adjusted to 6 and 7 with hydrofluoric acid and ammonia water. Immerse the film at room temperature for 5 minutes. After film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution used was a 0.1M titanium chloride and ammonium hydrogen fluoride aqueous solution with a molar ratio of titanium ions to fluoride ions of 1: 6, and the pH was adjusted to 4, 5, or 6 with hydrofluoric acid or ammonia water. .
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 90 ° C and about 450 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment liquid is a 0.1M titanium chloride and ammonium hydrogen fluoride aqueous solution with a molar ratio of titanium ions to fluoride ions of 1: 9.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was 0.1M hexafluorotitanic acid aqueous solution, and the pH was adjusted to 3, 4, 5, 6, 7, 8 with hydrofluoric acid or ammonia water.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was 0.1M ammonium hexatitanate aqueous solution, and the pH was adjusted to 3, 4, 5, 6, 7, 8 with hydrofluoric acid or ammonia water.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the substrate was anodized and then heat treated at about 300 ° C in vacuum.
  • Example 57 7 1 1-1 ⁇ ⁇ ⁇ ⁇ ⁇
  • Example 75 Mixed aqueous solution 4 Yes 1 Yes 1 ⁇ ⁇
  • Treatment liquid, treatment conditions and results are shown in Table 5 and Table 6 (continued in Table 5).
  • the base material used was an unformed A1 foil (1N99) that was etched with a direct current so as to have a surface area approximately 20 times as large as an etching solution mainly composed of hydrochloric acid.
  • a 12% ammonium adipate aqueous solution was used and applied at a temperature of 80 ° C. and a voltage of 50 V for 60 minutes.
  • the capacitance was measured at 120 Hz using an LCR meter using a 12% aqueous ammonium adipate solution.
  • the leakage current was measured by applying 5V. Evaluation was performed according to the following criteria in comparison with Experiment No. 92, which is a comparative example below.
  • Capacitance X Lower than No. 92
  • the treatment liquid is a mixed aqueous solution of 0.1M tantalum chloride and ammonium fluoride with a molar specific power of tantalum ion and fluorine ion of 5, and pH is 3, 4, 5, 6, 7, with hydrofluoric acid or ammonia water. Adjusted to 8. Film formation was performed by immersing for 5 minutes at room temperature, and after film formation, it was washed with water and air-dried. After the anode oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%. [Experiment No. 99-104]
  • the treatment solution is a 0.1M tantalum chloride / ammonium hydrogen fluoride aqueous solution with a molar ratio of tantalum ion to fluorine ion of 1: 6, and the pH is adjusted to 4, 5, 6, 7 with hydrofluoric acid or ammonia water. did.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. Anodization was performed. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M tantalum chloride and ammonium fluoride having a molar ratio of tantalum ions to fluoride ions of 1: 6, and the pH was adjusted to 5 with hydrofluoric acid or ammonia water.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After the anodic oxidation, heat treatment was performed at about 300 ° C.
  • the heat treatment atmosphere was vacuum, nitrogen, and vacuum containing less than 1% nitrogen.
  • the amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution used was a mixed aqueous solution of 0.1M tantalum chloride and ammonium fluoride having a molar ratio of tantalum ions to fluoride ions of 1: 6, and the pH was adjusted to 6 and 7 with hydrofluoric acid and ammonia water.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodizing, Heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M tantalum chloride and ammonium fluoride having a molar ratio of tantalum ions to fluorine ions of 1: 6, and the pH was adjusted to 4, 5, and 6 with hydrofluoric acid and ammonia water.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 90 ° C and about 450 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution is a 0.1M tantalum chloride / ammonium hydrogen fluoride aqueous solution with a molar ratio of tantalum ions to fluoride ions of 1: 7.
  • the pH is 3, 4, 5, 6, 7 with hydrofluoric acid or ammonia water. , Adjusted to 8.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After the anode oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was 0.1M hexafluorotantalic acid aqueous solution, and the pH was adjusted to 3, 4, 5, 6, 7, and 8 with hydrofluoric acid and ammonia water.
  • the film formation was performed by immersing at room temperature for 5 minutes. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • Treatment solution is 0.1M hexafluorotantalic acid aqueous solution.
  • the pH was adjusted to 3, 4, 5, 6, 7, 8 with hydrofluoric acid or aqueous ammonia.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • Example 1 1 1 5 Yes-Yes 1 ⁇ ⁇ Vacuum + inert power 'Example 112 6 Yes-Yes- ⁇ ⁇
  • Example 121 Mixed aqueous solution 4 Yes 1 Yes 1 ⁇ ⁇
  • Example 135 Aqueous potassium solution 6 Yes 1 Yes 1 ⁇ ⁇
  • the processing solutions, processing conditions and results are shown in Tables 7 and 8 (continued in Table 7).
  • the base material used was an unformed A1 foil (1N99) that was etched with a direct current so as to have a surface area approximately 20 times as large as an etching solution mainly composed of hydrochloric acid.
  • 1% ammonium adipate aqueous solution was applied at a temperature of 80 ° C and a voltage of 50V for 60 minutes.
  • the capacitance was measured at 120 Hz using a 12% ammonium adipate aqueous solution and an LCR standard.
  • the leakage current was measured by applying 5V. Evaluation was performed according to the following criteria in comparison with Experiment No. 92, which is a comparative example below.
  • Capacitance X Lower than No. 92
  • the treatment solution is a mixed aqueous solution of 0.1M niobium chloride and ammonium fluoride with a molar ratio of niobium ions to fluoride ions of 1: 5.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%. [Experiment No. 144-149]
  • the treatment solution is a mixed aqueous solution of 0.1M niobium chloride and ammonium fluoride with a molar ratio of niobium ions to fluoride ions of 1: 6.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment liquid is a 0.1M niobium chloride / ammonium fluoride mixed aqueous solution with a molar ratio of niobium ions to fluoride ions of 1: 6.
  • the pH is adjusted to 4, 5, 6, 7 with hydrofluoric acid or ammonia water. It was adjusted.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. Anodization was performed. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M niobium chloride and ammonium fluoride having a molar ratio of niobium ions to fluoride ions of 1: 6, and the pH was adjusted to 5 with hydrofluoric acid or aqueous ammonia.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C.
  • the heat treatment atmosphere was vacuum, nitrogen, and vacuum containing less than 1% nitrogen.
  • the amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a mixed aqueous solution of 0.1M niobium chloride and ammonium fluoride having a molar ratio of niobium ions to fluoride ions of 1: 6, and the pH was adjusted to 6 and 7 with hydrofluoric acid and ammonia water.
  • Film formation was carried out by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, vacuum Inside, it was heat-treated at about 300 ° C. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was a 0.1M niobium chloride / ammonium fluoride mixed aqueous solution with a molar ratio of niobium ions to fluoride ions of 1: 6, and the pH was adjusted to 4, 5, or 6 with hydrofluoric acid or ammonia water. .
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, it was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 90 ° C and about 450 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution is a 0.1M niobium chloride / ammonium fluoride mixed aqueous solution with a molar ratio of niobium ions to fluoride ions of 1: 7.
  • the pH is adjusted to 3, 4, 5, 6, with hydrofluoric acid or ammonia water. Adjusted to 7 and 8.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution was 0.1 M hexafluoroniobic acid aqueous solution, and the pH was adjusted to 3, 4, 5, 6, 7, 8 with hydrofluoric acid or ammonia water.
  • the film formation was performed by immersing for 5 minutes at room temperature. After film formation, the film was washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the film was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • the treatment solution is 0.1M hexafluoroniobic acid aqueous solution
  • the pH was adjusted to 3, 4, 5, 6, 7, and 8 with hydrofluoric acid and aqueous ammonia.
  • Film formation was performed by immersing at room temperature for 5 minutes, and after film formation, washed with water and air-dried. After anodic oxidation, heat treatment was performed at about 300 ° C in vacuum. The amount of fluorine in the coating was measured by X-ray photoelectron spectroscopy and confirmed to be 0.1 to 60 atomic%.
  • Example 151 5 Exist 1 ⁇ ⁇ ⁇
  • Example 166 Mixed aqueous solution 4 Yes ⁇ Yes ⁇ ⁇ ⁇
  • Hexafluo D Off 'acid aqueous solution 1 6 ⁇ ⁇
  • the electrode foil of the present invention showed excellent characteristics as compared with the comparative material, and the effect was confirmed.
  • a capacitor electrode foil and a capacitor that can be increased in capacity if they are the same size as conventional electrolytic capacitors, and can be further reduced in size if they are the same capacity as conventional electrolytic capacitors. It will be possible.

Abstract

L'invention porte sur un film d'électrode pour condensateurs grande capacité et sur un procédé de fabrication d'un tel film d'électrode. Il est divulgué spécifiquement un film d'électrode pour condensateurs caractérisé qu'il est sous forme d'un film d'aluminium possédant un film de revêtement contenant du fluor composé principalement d'un oxyde d'un métal valve autre que l'aluminium.
PCT/JP2005/012520 2004-07-23 2005-06-30 Film d'électrode pour condensateur et procédé de fabrication de celui-ci WO2006008970A1 (fr)

Applications Claiming Priority (2)

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JP2004215911A JP2006041030A (ja) 2004-07-23 2004-07-23 コンデンサ用電極箔及びその製造方法
JP2004-215911 2004-07-23

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WO2006008970A1 true WO2006008970A1 (fr) 2006-01-26

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TW (1) TWI282103B (fr)
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN110380055A (zh) * 2018-04-13 2019-10-25 丰田自动车株式会社 正极、非水电解质二次电池以及正极的制造方法
CN114446667A (zh) * 2022-01-17 2022-05-06 南通海星电子股份有限公司 一种高介电常数电极箔的制备方法

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
JP4844973B2 (ja) * 2006-03-29 2011-12-28 パナソニック株式会社 電極箔の製造方法
JP4835488B2 (ja) * 2006-03-29 2011-12-14 パナソニック株式会社 電解コンデンサおよび電解コンデンサの製造方法
JP4753809B2 (ja) * 2006-07-27 2011-08-24 三洋電機株式会社 電解コンデンサの製造方法

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JPH07169656A (ja) * 1993-12-15 1995-07-04 Mitsubishi Alum Co Ltd アルミニウム電解コンデンサ陽極用箔
JP2003055796A (ja) * 2001-08-09 2003-02-26 Showa Denko Kk アルミニウム材およびその製造方法、ならびに電子写真用感光体および電解コンデンサ電極用アルミニウム材料

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Publication number Priority date Publication date Assignee Title
JP2003257796A (ja) * 2002-03-06 2003-09-12 Japan Carlit Co Ltd:The 電解コンデンサ用アルミニウム陽極箔

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Publication number Priority date Publication date Assignee Title
JPH07169656A (ja) * 1993-12-15 1995-07-04 Mitsubishi Alum Co Ltd アルミニウム電解コンデンサ陽極用箔
JP2003055796A (ja) * 2001-08-09 2003-02-26 Showa Denko Kk アルミニウム材およびその製造方法、ならびに電子写真用感光体および電解コンデンサ電極用アルミニウム材料

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110380055A (zh) * 2018-04-13 2019-10-25 丰田自动车株式会社 正极、非水电解质二次电池以及正极的制造方法
CN110380055B (zh) * 2018-04-13 2022-08-12 丰田自动车株式会社 正极、非水电解质二次电池以及正极的制造方法
CN114446667A (zh) * 2022-01-17 2022-05-06 南通海星电子股份有限公司 一种高介电常数电极箔的制备方法
CN114446667B (zh) * 2022-01-17 2023-09-08 南通海星电子股份有限公司 一种高介电常数电极箔的制备方法

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