Electrode foil for aluminum electrolytic capacitor and...

Electricity: electrical systems and devices – Electrolytic systems or devices – Liquid electrolytic capacitor

Reexamination Certificate

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C361S509000, C361S528000, C361S529000

Reexamination Certificate

active

06611422

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to an electrode foil used for an aluminum electrolytic capacitor, and particularly concerns an electrode foil for an aluminum electrolytic capacitor for a high and medium voltage and a method of manufacturing the same.
BACKGROUND OF THE INVENTION
In recent years, as electronic equipment has become smaller with higher reliability, users have strongly demanded smaller aluminum electrolytic capacitors. Thus, electrode foil used for aluminum electrolytic capacitors needs to be larger in electrostatic capacitance per unit area than the conventional art.
A typical aluminum electrolytic capacitor is configured such that a capacitor element is composed of an anode foil and a cathode foil that are wound via a separator, the capacitor element is dipped into an electrolytic solution for driving, and the capacitor element is sealed into a metallic case. The anode foil has a dielectric oxide film formed by performing anodic oxidation on a surface of aluminum foil, which has an effective surface area increased by etching. The cathode foil includes aluminum foil whose effective surface area is increased by etching.
Regarding such an aluminum electrolytic capacitor, in order to have a larger electrostatic capacitance or a smaller size, it has been necessary to increase an effective surface area of the anode foil and an electrostatic capacitance per unit area. Thus, etching technique for increasing the effective surface area of the anode foil has been developed in earnest.
The above method of etching the anode foil is performed chemically or electrochemically in a solution of hydrochloric acid, in which acid such as sulfuric acid, nitric acid, phosphoric acid, and oxalic acid for forming a film is added. A method of etching the anode foil used for a medium and high voltage basically includes a first etching step of generating main pits and a final etching step of increasing the main pits in a diameter suitable for a used voltage of an aluminum electrolytic capacitor. An important point is how to generate a large number of main pits and to efficiently increase the main pits in size.
For example, as disclosed in JP7-272983A, a technique for increasing an effective surface area of the anode foil includes a first etching step of electrochemically performing etching using a direct current in a solution of hydrochloric acid or the like, an middle etching step of performing etching using a direct current in a solution of neutral salt such as sodium chloride, and a final etching step of performing electrical etching in a solution of nitric acid, sulfuric acid, or mixed acid thereof. With the above manufacturing method, a large number of main pits can be formed from a surface and an effective surface area on aluminum foil can be increased by forming branched sub pits at the midpoints or the ends of the main pits.
Further, a technique disclosed in JP60-36700A includes a first preliminary corrosion step using acid and a second anodizing step of treatment using a direct current with a high current density. Aluminum foil is subjected to an alternating current (AC) treatment and is corroded in the first preliminary corrosion step, and the aluminum foil is subjected to a direct current (DC) treatment in the second anodizing step, so that the aluminum foil is increased in electrostatic capacitance and mechanical strength.
However, according to the above-mentioned technique disclosed in JP7-272983A, in the middle etching step, an etching solution is used which includes at least one of a solution of neutral salt and a solution of acid salt solution. The solution of neutral salt contains at least one of three kinds of chlorine ions including sodium chloride, ammonium chloride, and potassium chloride. When DC etching is performed by using direct current in such an etching solution, in the case where direct current is simply supplied for a fixed time, a large amount of aluminum hydroxide gel is generated around the front ends of etching pits, and sub pits are formed in a vertical direction only on surfaces of the main pits formed in the first etching step. Hence, the above method hardly increases an effective surface area of aluminum foil.
Further, according to the technique disclosed in JP60-36700A, after aluminum foil is subjected to alternating current (AC) treatment and is corroded in the first preliminary corrosion step, the aluminum foil is subjected to a direct current (DC) treatment in the second anodizing step. In this case, although corrosion is surely accelerated, etching pits generated by the direct current treatment have uneven shapes. Thus, it is not possible to obtain a satisfactory electrostatic capacitance and mechanical strength.
Furthermore, according to the conventional technique for increasing an effective surface area of anode foil, in the middle etching step of forming the sub pits, which are branched from the surface layer to the ends of the main pits, on the main pits formed in the first etching step, as shown in
FIG. 9
, although a surface of aluminum foil
63
is not melted, many sub pits
62
branched from main pits
61
are formed on a surface layer of the aluminum foil
63
. Thus, the anode foil cannot be increased in electrostatic capacitance. Here,
FIG. 9
is a schematic diagram showing a cross section of etching pits formed by etching on the conventional aluminum foil
63
.
DISCLOSURE OF THE INVENTION
The present invention is achieved to solve the above-mentioned conventional problems and has as its object the provision of an electrode foil for an aluminum electrolytic capacitor and a method of manufacturing the same, by which sub pits branched on a surface layer of an aluminum foil can be reduced with high mechanical strength and large electrostatic capacitance.
In order to attain the above object, the electrode foil for an aluminum electrolytic capacitor of the present invention is configured such that a large number of main pits are formed by etching from a surface of aluminum foil in a thickness direction on both surfaces of aluminum foil, and sub pits are branched from the vicinity of a surface layer other than the surface layer on the main pits to the ends of the main pits. With this configuration, sub pits branched on the surface layer of aluminum foil are not formed in the present invention, thereby increasing an electrostatic capacitance of the electrode foil for an aluminum electrolytic capacitor.
Further, in the electrode foil for an aluminum electrolytic capacitor of the present invention, the sub pits are shorter than the main pits. Such a configuration can increase mechanical strength of the electrode foil for an aluminum electrolytic capacitor of the present invention.
The method of manufacturing the electrode foil for an aluminum electrolytic capacitor of the present invention comprises a first etching step in which aluminum foil is dipped into an etching solution of an acidic aqueous solution containing hydrochloric acid and sulfuric acid and/or nitric acid and a direct current is supplied to form main pits, an middle etching step in which the direct current is supplied and etching is performed in an etching solution of neutral salt containing an additive therein to effectively form the sub pits branched from the midpoints or the ends of the main pits other than the surface layer on the main pits, and a final etching step of increasing the main pits and the sub pits in diameter. With this method, since the surface of the aluminum foil is covered with an oxide film, a large number of sub pits are formed in a depth direction of the main pits without forming the sub pits branched into the surface layer of the aluminum foil. Thus, it is possible to produce electrode foil for an aluminum electrolytic capacitor with high mechanical strength and a large electrostatic capacitance in a stable manner.
According to a method of manufacturing the electrode foil for an aluminum electrolytic capacitor of the present invention, in the above-mentioned manufacturing method, at least one or more additives are selected from oxali

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