JP3443927B2 - Electrolytic capacitor and method for manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic capacitor and a method for manufacturing the same, and a conductive material is provided on either or both of an anode foil and a cathode foil made of a valve metal having a dielectric oxide film formed on the surface. A conductive layer is formed to form a layer, or a conductive layer is formed on either surface of the anode foil and the cathode foil without a separator, and both electrode foils are wound or laminated. The present invention relates to an electrolytic capacitor and its manufacturing method.

[0002]

2. Description of the Related Art Hitherto, as a means for lowering the impedance of an electrolytic capacitor, many attempts have been made to lower the impedance by improving the electric conductivity of an electrolytic solution.

However, since an electrolytic solution having a high electric conductivity has high activity and causes corrosion of the electrodes and leakage of the liquid, there is a limit to improving the electric conductivity of the electrolytic solution, and the performance is still sufficient. The electrolytic capacitor was not realized.

On the other hand, what has been examined as an alternative means for solving the problem is a constitution in which a conductive composite obtained by making a sheet-shaped insulator such as paper, cloth, non-woven fabric or polymer film conductive is used as a separator. .

As such a structure, for example, one in which fibers or particles such as metal or carbon are woven or mixed, and one in which a conductive polymer is formed on the surface by chemical polymerization from a polymerizable monomer such as pyrrole or aniline ( Synthetic Metals, Volume 28 C, 8
23 (1989)) has been proposed.

On the other hand, in a wound type aluminum electrolytic capacitor, in order to improve frequency characteristics and loss characteristics, separator thickness is reduced, density is reduced, opening diameter is made uniform, and material is changed from paper to polymer non-woven fabric. Studies such as changes have been made in the past.

It has also been reported that an aluminum electrolytic capacitor using a separator compounded with graphite powder not only improves the frequency characteristics of impedance but also improves the distortion of sound quality (Funkscha).
u, No. 8, p. 40 (1984)).

Further, a structure using a separator made conductive with a conductive polymer has also been disclosed (JP-A-64-9).
No. 0517).

[0009]

However, among such conventional constitutions, a conductive composite obtained by weaving or mixing fibers or particles such as metal or carbon to make the insulator conductive is used as a separator. In this case, since the electrical conductivity is low and it is difficult to form a low density material, it is necessary to increase the addition amount in order to obtain high electrical conductivity.

Further, in the case where a conductive polymer is formed on the surface by chemical polymerization from a polymerizable monomer such as pyrrole or aniline, there is little or no chemical conversion, so that leakage current and short-circuit failure occur. There was a problem such as an increase.

Further, in the case of an electrolytic capacitor using a separator composited with graphite powder, it is unavoidable that the graphite powder comes off and is dispersed in the electrolytic solution, so that there is a problem that short-circuit defects increase. .

An object of the present invention is to solve the above problems and provide an electrolytic capacitor having excellent frequency characteristics and loss characteristics.

[0013]

In order to solve the above problems, the present invention provides an anode foil formed of a valve metal having a dielectric oxide film formed on its surface, a cathode foil formed of the valve metal, and A conductive layer formed on the surface of either or both of the anode foil and the cathode foil, a conductive separator provided between the cathode foil and the anode foil, and the cathode via the conductive separator. An electrolytic capacitor having a foil and an electrolyte provided between the anode foil.

Alternatively, instead of providing a conductive separator, the electrolytic capacitor uses a conductive layer formed on the surface of one or both of the anode foil and the cathode foil as a substantial separator.

This conductive separator may have a structure having a base material and a composite conductive layer containing a conductive polymer obtained from a polymerizable monomer formed on the surface of the base material and manganese oxide. Good.

Alternatively, the conductive separator includes a base material,
It may be configured to have a composite conductive layer containing a conductive polymer formed from a polymerizable monomer formed on the surface of the substrate and graphite particles.

Alternatively, the conductive separator includes a base material,
It may be a composite conductive layer containing a conductive polymer obtained from a polymerizable monomer formed on the surface of the base material, manganese oxide, and graphite particles.

Alternatively, the conductive separator may have a constitution having a carbonized base material and a conductive polymer layer obtained from a polymerizable monomer formed on the surface of the base material. Alternatively, the conductive separator is a structure having a carbonized base material and a composite conductive layer containing a conductive polymer obtained from a polymerizable monomer formed on the surface of the base material and manganese oxide. May be.

On the other hand, the conductive layer formed on the surface of either or both of the anode foil and the cathode foil is a conductive polymer layer obtained from a polymerizable monomer or a conductive polymer obtained from a polymerizable monomer. It is a structure of a composite conductive layer containing a metal oxide and manganese oxide.

Alternatively, in the method of manufacturing an electrolytic capacitor according to the present invention, a step of forming a dielectric oxide film on the surface of the first valve metal and preparing it as an anode foil, and preparing a second valve metal as a cathode foil. Step, a step of forming a conductor layer on the surface of either or both of the anode foil and the cathode foil, the dielectric oxide film or the conductor layer of the anode foil and the surface of the cathode foil or the conductivity A step of installing a conductive separator between the body layer, a step of providing an electrolyte between the anode foil and the cathode foil via the conductive separator, and a step of winding or laminating both electrode foils. However, instead of providing a conductive separator, since it is also possible to use the conductor layer formed on the surface of either or both of the anode foil and the cathode foil as a substantial separator, the conductive separator Set up It is also possible to omit the step of.

This conductive separator has a step of preparing a base material and a step of forming a composite conductive layer containing a conductive polymer obtained from a polymerizable monomer and manganese oxide on the surface of the base material. It can be formed by a conductive separator forming step.

Alternatively, this conductive separator includes a step of preparing a base material and a step of forming a composite conductive layer containing a conductive polymer obtained from a polymerizable monomer and graphite particles on the surface of the base material. It can be formed by the conductive separator forming step.

Alternatively, in this conductive separator, a step of preparing a base material and a composite conductive layer containing a conductive polymer obtained from a polymerizable monomer, manganese oxide and graphite particles are formed on the surface of the base material. Can be formed by a conductive separator forming step including a step.

Alternatively, in this conductive separator, a step of preparing a base material, a step of carbonizing the base material, and a step of forming a conductive polymer layer obtained from a polymerizable monomer on the surface of the base material. And a conductive separator forming step including. Alternatively, the conductive separator includes a step of preparing a base material, a step of carbonizing the base material, and a composite conductive material containing a conductive polymer obtained from a polymerizable monomer and a manganese oxide on the surface of the base material. It can be formed by a conductive separator forming step including a step of forming a layer.

On the other hand, the conductive polymer layer obtained from the polymerizable monomer on the surface of the anode foil and / or the cathode foil can be formed by an electrolytic polymerization process.

Alternatively, the conductive polymer layer obtained from the polymerizable monomer on the surface of the anode foil and / or the cathode foil may be formed by a chemical polymerization process.

Alternatively, the conductive polymer layer obtained from the polymerizable monomer on the surface of the anode foil and / or the cathode foil is a solution or dispersion of the conductive polymer on the surface of the anode foil and / or the cathode foil. It may be formed by impregnation or coating.

Alternatively, on the surface of the anode foil and / or the cathode foil,
A composite conductive layer containing a conductive polymer obtained from a polymerizable monomer and manganese oxide may be formed by a chemical reaction. Furthermore, a conductive polymer obtained from the polymerizable monomer of the conductor layer formed on the surface of the anode foil and / or the cathode foil, and a conductive polymer obtained from the polymerizable monomer of the composite conductive layer of the conductive separator. May be formed substantially simultaneously or separately.

The electrolyte is an impregnated liquid or solid, and the electrolytic capacitor of the present invention may be a wound type or a laminated type.

[0030]

In the electrolytic capacitor according to the present invention, the impedance is reduced by using the conductive separator, and further, the impedance is further reduced by forming the conductor layer on one or both surfaces of the electrode foil.

When a composite conductive layer composed of a conductive polymer and manganese oxide is used, the impedance is reduced, and at the same time, the leakage current increases and the short circuit is caused by the high oxide metal film repairing power of the manganese oxide. It also prevents the occurrence of defects.

When a composite conductive layer composed of a conductive polymer and graphite particles is used, the impedance can be further reduced, and at the same time, the graphite particles are covered with the conductive polymer, so that the graphite particles fall off. It also prevents dispersion in the electrolyte.

Further, when the separator is carbonized to form a conductive polymer layer on the surface, the carbonization treatment renders the separator conductive and further forms a conductive polymer layer on the surface of the carbonized separator. Therefore, the impedance is further reduced.

Further, a conductor is provided on either surface of the electrode foil.
By forming an electrolytic capacitor by forming a layer without using a separator and impregnating an electrolytic solution, the impedance component generated at the separator and the interface between the separator and the electrolytic solution is reduced, and thus the separator is used. The loss factor and impedance are greatly reduced compared to electrolytic capacitors.

[0035]

EXAMPLES Examples of the present invention will be described in detail below.

(Embodiment 1) Hereinafter, a first embodiment of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a partial sectional view of an electrolytic capacitor according to this embodiment. In FIG. 1, 1 is an anode foil, 2 is a cathode foil, 3 is a dielectric oxide film, 4 is a conductor layer, 5 is an electrolyte, and 6 is a conductive separator.

That is, in this embodiment, the conductive separator 6 is sandwiched between the anode foil 1 having the dielectric oxide film 3 formed on its surface and the cathode foil 2 having no dielectric oxide film 3 on its surface. An electrolytic solution as an electrolyte 5 is impregnated between the dielectric oxide film 3 and the conductive polymer layer 4 via the electrolyte.

Hereinafter, a method of manufacturing the electrolytic capacitor of this embodiment
The method will be described in detail. Specifically, Manila hemp
Low density separator paper for capacitors (0.03 g / cm ²)
Is immersed in an aqueous solution of potassium permanganate (0.30M)
Immediately after, add pyrrole monomer (5M) sulfuric acid (0.2M)
Soak in ethanol solution containing potassium permanganate and
Surface (dipped by chemical reaction of pyrrole monomer
(Surface) is a composite conductor consisting of a conductive polymer and manganese oxide
Obtaining a conductive separator 6 which is a conductive composite having layers
It was

Next, the cathode foil 2 made of an etched aluminum foil was treated with pyrrole monomer (0.25M) and sodium triisopropylnaphthalene sulfonate (0.10M).
M) and water were placed in a polymerization liquid, a constant voltage of 5 V was applied to carry out an electrolytic polymerization reaction, and after washing and drying, a conductive polymer layer was formed as a conductor layer 4.

On the other hand, by applying a constant voltage in an aqueous solution of ammonium adipate (3 parts by weight) at about 70 ° C., the dielectric oxide film 3 is formed on the surface of the anode foil 1 made of an etched aluminum foil by anodizing. did.

Next, a cathode foil 2 having a conductive polymer layer formed on the surface and an anode foil 1 having a dielectric oxide film 3 on the surface are wound with a conductive separator 6 made of a conductive composite interposed therebetween. After turning, re-formation was performed to repair the dielectric oxide film 3 formed on the surface of the anode foil 1.

Incidentally, FIG. 1 typically shows a portion which can be approximated to a flat plate shape in a sectional view of an electrolytic capacitor formed by winding in this way.

After that, washing and drying are performed, and an electrolytic solution containing γ-butyrolactone as a solvent and containing monomethyltriethylammonium phthalate (20 parts by weight) is impregnated under reduced pressure as an electrolyte 5, and an exterior is applied to perform electrolysis with a rating of 16 V and 10 μF. Completed the capacitor.

In this embodiment, the number of fabrication is five.
120 Hz and 1 for these obtained capacitors
The capacitance and loss factor at kHz and the impedance at 400 kHz were measured.

The average value of these measured values is shown in (Table 1). Further, for comparison, as Comparative Example 1, a conductor is provided on the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the surface of the cathode foil 2 through a separator paper having no composite conductive layer on the surface. Five electrolytic capacitors were completed and measured in the same manner as in Example 1 except that both electrode foils were wound without forming the layer 4.

The average value of these measured values is also shown in (Table 1). For comparison, as Comparative Example 2, the conductor layer 4 was wound without forming the conductor layer 4 on both the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the surface of the cathode foil 2. Except for the above, five electrolytic capacitors were completed and measured in the same manner as in Example 1.

The average value of these measured values is also shown in (Table 1).

[0049]

[Table 1]

As is clear from this (Table 1), a conductive polymer layer was formed as the conductor layer 4 on the surface of the cathode foil 2 according to this example, and the conductive polymer and manganese oxide were formed on the surface of the separator paper. An electrolytic capacitor configured by using a conductive separator 6 having a composite conductive layer made of is composed of a conductive polymer layer formed as a conductive layer 4 on the surface of the cathode foil 2 and a resistance component due to the effect of the conductive separator. It can be seen that the electrolytic coefficient is reduced, and as a result, the loss coefficient and impedance in the high frequency range are greatly reduced, and the electrolytic capacitor having excellent frequency characteristics and loss characteristics is obtained.

Since manganese oxide has a high ability to repair the oxide film of the valve metal, it is possible to prevent deterioration of the leakage current characteristics.

In this example, a step of immersing the separator paper in the aqueous solution of potassium permanganate as permanganate, and a step of immersing the separator paper in a solution containing a polymerizable monomer and an anion serving as a dopant. According to the method, a conductive separator is obtained by forming a composite conductive layer containing a conductive polymer and manganese oxide on the surface of the separator paper by a step of chemically reacting a polymerizable monomer and permanganate, Other permanganates can be similarly used as long as they can chemically react with a polymerizable monomer to form a composite conductive layer composed of a conductive polymer and manganese oxide.

In this embodiment, the conductive polymer layer is formed on the surface of the cathode foil 2, but the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 instead of the cathode foil 2. Alternatively, even if the conductive polymer layer is formed on both the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the surface of the cathode foil 2, the electrolytic capacitor has the conductive polymer layer. The equivalent series resistance is reduced, which makes it possible to reduce the impedance.

Further, this embodiment describes the case where the conductive polymer layer is formed on the surface of the electrode foil by the electrolytic polymerization method using the polymerization liquid containing the polymerizable monomer and the anion serving as the dopant. Is a chemical polymerization method having a step of immersing the electrode foil in a solution containing a polymerizable monomer and a step of immersing the electrode foil in a solution containing an oxidant and an anion serving as a dopant, or conductivity to the surface of the electrode foil. The conductive polymer layer can be formed on the surface of the electrode foil also by impregnation or coating of a polymer solution or dispersion.

As described above, according to this embodiment, the conductive polymer layer is formed on either or both surfaces of the electrode foil, and the composite conductive layer composed of the conductive polymer and manganese oxide is formed on the surface. Since the conductive separator having the above is used, it is possible to reduce the loss coefficient and the impedance of the electrolytic capacitor in the high frequency range.

(Second Embodiment) The second embodiment of the present invention will be described in detail below.

In this example, first, ammonium adipate (3 parts by weight) at about 70 ° C. was passed through a low-density separator paper (0.03 g / cm ² ) for capacitors made from Manila hemp.
An anode foil 1 made of an etched aluminum foil and a cathode foil 2 made of an etched aluminum foil provided with a dielectric oxide film 3 prepared by an anodizing method in which a constant voltage is applied in an aqueous solution were wound. After winding, re-formation is performed and anode foil 1
The dielectric oxide film 3 formed on the surface of was repaired.

Next, after re-formation, it was dipped in an aqueous solution of potassium permanganate (0.30M) and then dipped in an ethanol solution containing pyrrole monomer (0.5M) sulfuric acid (0.2M) to obtain permanganate. A conductive separator 6 which is a conductive composite having a composite conductive layer made of a conductive polymer and manganese oxide on the surface of the separator is obtained by a chemical reaction of potassium and a pyrrole monomer, and at the same time, the anode foil 1
A composite conductive layer composed of a conductive polymer and manganese oxide was also formed as the conductive layer 4 on the surface of the dielectric oxide film 3 and the surface of the cathode foil 2 formed on the surface of the.

Thereafter, as in Example 1, the electrolytic solution was replaced with the electrolyte 5.
Was impregnated under reduced pressure to complete 5 capacitors and measured.

The average value of these measured values is shown in the above (Table 1). As is clear from this (Table 1), a conductive separator 6 having a composite conductive layer composed of a conductive polymer and manganese oxide on the surface of the separator paper according to this example was used to form on the surface of the anode foil 1. The electrolytic capacitor formed by forming a composite conductive layer composed of a conductive polymer and manganese oxide as the conductor layer 4 on the surface of the dielectric oxide film 3 and the surface of the cathode foil 2 is the surface of the anode foil 1. The resistance component in the composite conductive layer and the conductive separator formed on the surface of the dielectric oxide film 3 and the surface of the cathode foil 2 formed on the substrate is reduced, and as a result, the loss coefficient and impedance in the high frequency range are greatly reduced. However, it can be seen that an electrolytic capacitor having excellent frequency characteristics and loss characteristics is obtained.

Further, since manganese oxide has a high ability to repair the oxide film of the valve metal, it is possible to prevent deterioration of the leakage current characteristics.

In the present embodiment, an electrolytic capacitor element formed by winding the anode foil 1 and the cathode foil 2 having the dielectric oxide film 3 via the separator paper is used as a permanganate salt of permanganate. A surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 by a step of immersing in an aqueous solution of potassium and a step of immersing the electrolytic capacitor element in a solution containing a polymerizable monomer and an anion serving as a dopant; A composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the cathode foil 2 by a chemical reaction between a polymerizable monomer and permanganate, and at the same time, a conductive polymer and manganese oxide are formed on the surface. There is obtained a conductive separator having a composite conductive layer containing a substance, but other permanganates also chemically react with a polymerizable monomer to form a conductive polymer and man As long as it can form a composite conductive layer comprising a phosphorylated product can be used as well.

A composite conductive layer composed of a conductive polymer and manganese oxide is formed on either the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 or the surface of the cathode foil 2. However, the composite conductive layer reduces the equivalent series resistance of the electrolytic capacitor, thereby reducing the impedance.

Further, a composite conductive film made of a conductive polymer and manganese oxide formed on either or both of the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the surface of the cathode foil 2. The layer and the composite conductive layer containing a conductive polymer and manganese oxide formed on the surface of the conductive separator can be formed at different times.

As described above, according to this embodiment, the anode foil 1
A composite conductive layer composed of a conductive polymer and manganese oxide is formed as a conductive layer 4 on the surface of the dielectric oxide film 3 and the surface of the cathode foil 2, which are formed on the surface of the conductive polymer. Since the conductive separator having the composite conductive layer made of manganese oxide is used, the loss coefficient and impedance of the electrolytic capacitor in the high frequency range can be reduced.

(Embodiment 3) The third embodiment of the present invention will be described in detail below.

In this embodiment, separator paper is coated with water-dispersed colloidal graphite, dried, and immediately immersed in the undiluted solution of pyrrole. Immediately thereafter, sodium triisopropylnaphthalene sulfonate (0.10M) and ammonium persulfate (0.30M) are prepared. ) An electrolytic capacitor similar to Example 1 except that the conductive separator 6 which is a conductive composite having a composite conductive layer containing a conductive polymer obtained by a chemical polymerization method and graphite particles, which was immersed in an aqueous solution, was used. Completed 5 pieces.

Then, measurement was carried out in the same manner as in Example 1, and the average value of these measured values is shown in (Table 1) above.

For comparison, as Comparative Example 3, the conductor layer 4 was not formed on both the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the surface of the cathode foil 2. Five electrolytic capacitors were completed and measured in the same manner as in Example 3 except that they were wound.

The average value of these measured values is shown in (Table 1). As is clear from this (Table 1), according to the present embodiment,
An electrolytic capacitor formed by forming a conductive polymer layer as a conductor layer 4 on the cathode foil and having a composite conductive layer having a conductive polymer and graphite particles on the surface of separator paper is Due to the effect of the conductive polymer layer formed on the foil and the conductive separator, the equivalent series resistance of the electrolytic capacitor is reduced, and as a result, the loss coefficient and impedance in the high frequency range are greatly reduced, resulting in frequency characteristics and loss. It can be seen that an electrolytic capacitor having excellent characteristics is obtained.

In particular, by forming the composite conductive layer containing graphite particles and the conductive polymer on the surface of the separator, the electric conductivity is higher than that when only the conductive polymer layer is formed on the surface of the separator. A conductive separator is obtained, and since graphite particles are wrapped in a conductive polymer, it is possible to effectively prevent the graphite particles from falling out of the separator and being dispersed in the electrolytic solution, which also deteriorates the leakage current characteristics. It is prevented.

In this example, after the step of impregnating the surface of the separator paper with colloidal graphite, the step of immersing the separator paper in a solution containing a polymerizable monomer and the separator paper containing an oxidant and anion serving as a dopant. A conductive polymer obtained from a polymerizable monomer was compounded with graphite particles by a chemical polymerization method including a step of immersing in a solution, and electrolytic polymerization was performed using a polymerization solution containing the polymerizable monomer and an anion serving as a dopant. It is also possible to compound a conductive polymer obtained from a polymerizable monomer by a legal method with graphite particles, or a conductive polymer with a graphite particle by impregnation or coating of a solution or dispersion of a conductive polymer. .

Further, in the present embodiment, the conductive polymer layer is formed as the conductor layer 4 on the surface of the cathode foil 2, but the dielectric formed on the surface of the anode foil 1 instead of the cathode foil 2. Even if the conductive polymer layer is formed on the surface of the oxide film 3 or on both the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the surface of the cathode foil 2, the conductive polymer layer is formed. The layers reduce the equivalent series resistance of the electrolytic capacitor,
As a result, the impedance can be reduced.

If necessary, the conductive polymer layer or the composite conductive layer in the present embodiment may be combined with the conductive polymer layer or the composite conductive layer in Example 1 or 2 to form the cathode foil 2.
Oxide film 3 formed on the surface of the anode and the surface of the anode foil 1.
It can also be formed on the surface of, or on the surface of the separator paper.

Further, in this embodiment, the case where the conductive polymer layer is formed on the surface of the electrode foil by the electrolytic polymerization method using the polymerization liquid containing the polymerizable monomer and the anion serving as the dopant is described. Is a chemical polymerization method having a step of immersing the electrode foil in a solution containing a polymerizable monomer and a step of immersing the electrode foil in a solution containing an oxidant and an anion serving as a dopant, or conductivity to the surface of the electrode foil. The conductive polymer layer can be formed on the surface of the electrode foil also by impregnation or coating of a polymer solution or dispersion.

As described above, according to the present embodiment, the conductive polymer layer is formed on either or both surfaces of the electrode foil, and the conductive layer has the composite conductive layer composed of the conductive polymer and the graphite particles. Since the separator is used, the loss coefficient and impedance of the electrolytic capacitor in the high frequency range can be reduced.

(Embodiment 4) The fourth embodiment of the present invention will be described in detail below.

In this example, separator paper was coated with water-dispersed colloidal graphite, dried, and immersed in an aqueous solution of potassium permanganate (0.30M), followed by pyrrole monomer (5M) sulfuric acid (0.2M). Conductive composite having a composite conductive layer in which a conductive polymer, manganese oxide and graphite particles are composited on the surface of the separator by a chemical reaction of potassium permanganate and a pyrrole monomer by immersing in an ethanol solution containing Five capacitors were completed and measured in the same manner as in Example 3 except that the separator 6 was used.

The average value of these measured values is shown in the above (Table 1).
Shown in. As is clear from this (Table 1), a conductive polymer layer was formed as the conductor layer 4 on the cathode foil 2 according to this example, and the conductive polymer, manganese oxide, and graphite particles were formed on the surface of the separator paper. The electrolytic capacitor configured by using the conductive separator 6 having the composite conductive layer
Due to the effect of the conductive polymer layer formed on the cathode foil 2 and the conductive separator 6, the equivalent series resistance of the electrolytic capacitor is reduced, and as a result, the loss coefficient and impedance in the high frequency range are greatly reduced, It can be seen that an electrolytic capacitor having excellent characteristics and loss characteristics is obtained.

In particular, by forming a composite conductive layer containing graphite particles, a conductive polymer and manganese oxide on the surface of the separator, compared to the case where only the conductive polymer layer is formed on the surface of the separator, the electric conductivity is improved. A conductive separator having high conductivity is obtained, and since graphite particles are wrapped in a conductive polymer, it is possible to effectively prevent the graphite particles from falling out of the separator and being dispersed in the electrolytic solution, and manganese oxide. With the high valve metal oxide film repair ability, deterioration of leakage current characteristics can also be prevented.

In this example, after the step of impregnating the surface of the separator paper with colloidal graphite, the step of immersing the separator paper in the aqueous solution of potassium permanganate as permanganate, and the step of separating the separator paper with the polymerizable monomer. And a manganese oxide obtained by the step of chemically reacting the polymerizable monomer with the permanganate by a step of immersing in a solution containing an anion serving as a dopant and a manganese oxide were complexed with graphite particles. Although obtaining a conductive separator having a composite conductive layer formed on the surface,
Similar to Example 3, any other permanganate may be used as long as it can chemically react with a polymerizable monomer to form a composite conductive layer composed of a conductive polymer and manganese oxide. be able to.

Also in this embodiment, the conductive polymer layer is formed as the conductor layer 4 on the surface of the cathode foil 2, but the dielectric formed on the surface of the anode foil 1 instead of the cathode foil 2. Even if the conductive polymer layer is formed on the surface of the oxide film 3 or on both the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the surface of the cathode foil 2, the conductive polymer layer is formed. The layers reduce the equivalent series resistance of the electrolytic capacitor,
As a result, the impedance can be reduced.

Further, in this embodiment, the conductive polymer layer is formed on the surface of the electrode foil by the electrolytic polymerization method using the polymerization liquid containing the polymerizable monomer and the anion serving as the dopant. Similarly, a chemical polymerization method having a step of immersing the electrode foil in a solution containing a polymerizable monomer and a step of immersing the electrode foil in a solution containing an oxidant and an anion serving as a dopant, or to the surface of the electrode foil. The conductive polymer layer can be formed on the surface of the electrode foil also by impregnating or coating the solution or dispersion of the conductive polymer.

As described above, according to this embodiment, the conductive polymer layer is formed on either or both surfaces of the electrode foil, and the composite conductive layer is formed of the conductive polymer, manganese oxide and graphite particles. Since the conductive separator having the above is used, it is possible to reduce the loss coefficient and the impedance of the electrolytic capacitor in the high frequency range.

(Embodiment 5) The fifth embodiment of the present invention will be described in detail below.

In this embodiment, the cathode foil 2 made of an etched aluminum foil was not subjected to any treatment, and the anode foil 1 made of an etched aluminum foil having a dielectric oxide film 3 formed on its surface was replaced with potassium permanganate. Pyrrole monomer (5M) sulfuric acid (0.2M) after immersion in (0.30M) aqueous solution
It is soaked in an ethanol solution containing, and a conductive polymer and manganese oxide are formed as a conductor layer 4 on the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 by a chemical reaction between potassium permanganate and a pyrrole monomer. An electrolytic capacitor was prepared in the same manner as in Example 3 except that a composite conductive layer made of a material was formed.
Individual pieces were completed and measurements were performed.

The average value of these measured values is shown in the above (Table 1).
Shown in. As is clear from this (Table 1), a composite conductive material containing a conductive polymer and manganese oxide as the conductive layer 4 on the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 according to this example. The electrolytic capacitor formed by forming a layer and having a composite conductive layer having a conductive polymer and graphite particles on the surface of the separator paper is a dielectric oxide film formed on the surface of the anode foil 1. By the effect of the composite conductive layer formed on the surface of 3 and the conductive separator, the equivalent series resistance of the electrolytic capacitor is reduced, and as a result, the loss coefficient and impedance in the high frequency range are greatly reduced, and the frequency characteristics and loss are reduced. It can be seen that an electrolytic capacitor having excellent characteristics is obtained.

In particular, by forming the composite conductive layer containing graphite particles and the conductive polymer on the surface of the separator, the electric conductivity is higher than that when only the conductive polymer layer is formed on the surface of the separator. A conductive separator is obtained, and since graphite particles are wrapped in a conductive polymer, it is possible to effectively prevent the graphite particles from falling out of the separator and being dispersed in the electrolytic solution, which also deteriorates the leakage current characteristics. It is prevented.

In this example, after the step of impregnating the surface of the separator paper with colloidal graphite, the step of immersing the separator paper in a solution containing a polymerizable monomer and the separator paper containing an oxidant and an anion serving as a dopant. A conductive polymer obtained from a polymerizable monomer was compounded with graphite particles by a chemical polymerization method including a step of immersing in a solution, and as in Example 3, a polymerization liquid containing a polymerizable monomer and an anion serving as a dopant. A composite of a conductive polymer obtained from a polymerizable monomer and a graphite particle by an electrolytic polymerization method carried out using, or a conductive polymer and a graphite particle by impregnation or coating of a solution or dispersion of the conductive polymer It is also possible to combine

Further, in this embodiment, the step of immersing the anode foil 1 provided with the dielectric oxide film 3 in an aqueous solution of potassium permanganate as permanganate, and the dielectric oxide film 3 are used.
By immersing the anode foil 1 provided with a solution containing a polymerizable monomer and an anion serving as a dopant,
A composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 by a step of chemically reacting a polymerizable monomer and permanganate. However, similarly, other permanganates can be similarly used as long as they can chemically react with a polymerizable monomer to form a composite conductive layer composed of a conductive polymer and manganese oxide. You can

Further, instead of the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1, the surface of the cathode foil 2 or the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the cathode. Even if a composite conductive layer is formed both on the surface of the foil 2
The composite conductive layer reduces the equivalent series resistance of the electrolytic capacitor, which allows the impedance to be reduced.

As described above, according to this embodiment, a composite conductive layer containing a conductive polymer and manganese oxide is formed on one or both surfaces of the electrode foil, and the conductive polymer and the graphite particles are used. Since the conductive separator having the composite conductive layer is used, the loss coefficient and impedance in the high frequency range of the electrolytic capacitor can be reduced.

(Embodiment 6) The sixth embodiment of the present invention will be described in detail below.

In this embodiment, water-dispersible colloidal graphite is applied to the separator paper and dried, and the separator paper is treated with potassium permanganate (0.30).
M) After being dipped in an aqueous solution, it is dipped in an ethanol solution containing pyrrole monomer (5M) sulfuric acid (0.2M), and a conductive polymer and manganese oxide are formed on the surface of the separator by a chemical reaction between potassium permanganate and the pyrrole monomer. Five capacitors were completed and measured in the same manner as in Example 5, except that the separator 6, which was a conductive composite having a composite conductive layer in which graphite particles were composited, was used.

The average value of these measured values is shown in the above (Table 1).
Shown in. As is clear from this (Table 1), a composite conductive material containing a conductive polymer and manganese oxide as the conductive layer 4 on the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 according to this example. An electrolytic capacitor formed by forming a layer and using a conductive separator 6 having a composite conductive layer composed of a conductive polymer, manganese oxide and graphite particles on the surface of the separator paper is formed on the surface of the anode foil 1. By the effect of the composite conductive layer containing the conductive polymer and manganese oxide formed on the surface of the dielectric oxide film 3 and the conductive separator 6, the equivalent series resistance of the electrolytic capacitor is reduced. It can be seen that the loss coefficient and impedance in the high frequency range are greatly reduced, and an electrolytic capacitor having excellent frequency characteristics and loss characteristics is obtained.

In particular, by forming a composite conductive layer containing graphite particles, a conductive polymer and manganese oxide on the surface of the separator, compared to the case where only the conductive polymer layer is formed on the surface of the separator, the electric conductivity is improved. A conductive separator having high conductivity is obtained, and since graphite particles are wrapped in a conductive polymer, it is possible to effectively prevent the graphite particles from falling out of the separator and being dispersed in the electrolytic solution, and manganese oxide. With the high valve metal oxide film repair ability, deterioration of leakage current characteristics can also be prevented.

In this example, after the step of impregnating the surface of the separator paper with colloidal graphite, the step of immersing the separator paper in the aqueous solution of potassium permanganate as permanganate, and the step of separating the separator paper with the polymerizable monomer. And a manganese oxide obtained by the step of chemically reacting the polymerizable monomer with the permanganate by a step of immersing in a solution containing an anion serving as a dopant and a manganese oxide were complexed with graphite particles. Although obtaining a conductive separator having a composite conductive layer formed on the surface,
Similarly, other permanganates can be similarly used as long as they can chemically react with a polymerizable monomer to form a composite conductive layer composed of a conductive polymer and manganese oxide.

Further, in this embodiment, the step of immersing the anode foil 1 provided with the dielectric oxide film 3 in an aqueous solution of potassium permanganate as permanganate, and the dielectric oxide film 3 are used.
By immersing the anode foil 1 provided with a solution containing a polymerizable monomer and an anion serving as a dopant,
A composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 by a step of chemically reacting a polymerizable monomer and permanganate. However, similarly, other permanganates can be similarly used as long as they can chemically react with a polymerizable monomer to form a composite conductive layer composed of a conductive polymer and manganese oxide. You can

Further, instead of the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1, the surface of the cathode foil 2 or the surface of the dielectric oxide film 3 formed on the surface of the anode foil 1 and the cathode. Even if a composite conductive layer is formed both on the surface of the foil 2
The composite conductive layer reduces the equivalent series resistance of the electrolytic capacitor, which allows the impedance to be reduced.

As described above, according to this embodiment, the anode foil 1
Surface of the dielectric oxide film 3 formed on the surface of the cathode and the cathode foil 2
A conductive separator having a composite conductive layer containing a conductive polymer and manganese oxide on one or both of the surfaces and a composite conductive layer composed of the conductive polymer, manganese oxide and graphite particles. The loss coefficient and the impedance of the electrolytic capacitor in the high frequency range can be reduced because of.

(Embodiment 7) Hereinafter, a seventh embodiment of the present invention will be described in detail with reference to the drawings.

FIG. 2 shows a sectional view of the electrolytic capacitor in this embodiment. In FIG. 2, 11 is an anode foil, 12 is a cathode foil, 13 is a dielectric oxide film, 14 is a conductor layer, 15
Is an electrolyte and 16 is a conductive separator.

That is, the conductive polymer layer is formed on both surfaces of the anode foil 11 having the dielectric oxide film 13 formed on the surface and the cathode foil 12 having no dielectric oxide film 13 formed thereon. The conductive separator 16 is sandwiched between
The electrolyte 15 is impregnated between the conductor layers 14 through this.

The method for producing the electrolytic capacitor of this example will be described in detail below. Specifically, first, low density separator paper (0.03 g / cm) for Manila hemp capacitors.
² ) Anode foil 11 made of an etched aluminum foil provided with a dielectric oxide film 13 produced by an anodizing method in which a constant voltage is applied in an aqueous solution of ammonium adipate (3 parts by weight) at about 70 ° C. An electrolytic capacitor element was prepared by winding the cathode foil 12 made of an etched aluminum foil.

Next, this element was exposed to a high temperature atmosphere of 300 ° C. for 30 minutes to perform carbonization treatment on the separator, re-formation, and then immersed in an undiluted solution of pyrrole, and further hydrogen peroxide (0.
14M) Sulfuric acid (0.10M) aqueous solution, and a conductive polymer layer is formed on the surface of the carbonized separator by a chemical polymerization method to obtain a conductive composite separator 16 and at the same time both electrode foil surfaces As the conductor layer 14, a conductive polymer layer was simultaneously formed by a chemical polymerization method.

After washing and drying, the electrolyte 15 is γ-.
An electrolytic solution containing monomethyltriethylammonium phthalate (20 parts by weight) was impregnated under reduced pressure using butyrolactone as a solvent, and was externally coated to complete five electrolytic capacitors having a rating of 16 V and 10 μF.

FIG. 2 typically shows a portion of the cross-sectional view of the electrolytic capacitor thus wound which can be approximated to a flat plate.

The same measurements as in Example 1 were carried out for these, and the average value of the measured values is shown in (Table 1) above.

For comparison, as Comparative Example 4, five electrolytic capacitors were completed and measured in the same manner as in Example 7 below without performing the chemical polymerization after the carbonization treatment and the re-formation.

The average value of these measured values is shown in (Table 1). As is clear from this (Table 1), according to the present embodiment,
The conductive polymer layer is formed on the surface of the carbonized separator paper to obtain the conductive separator 16, and at the same time, the anode foil 11
The electrolytic capacitor formed by forming a conductive polymer layer on both the surface of the dielectric oxide film 13 formed on the surface of the cathode foil and the surface of the cathode foil 12 is a conductive polymer formed on the electrode foil. The equivalent series resistance of the electrolytic capacitor is reduced by the effect of the layer and the conductive separator, and as a result, the loss coefficient and impedance in the high frequency range are greatly reduced.
It can be seen that an electrolytic capacitor having excellent frequency characteristics and loss characteristics is obtained.

In particular, carbonization of the separator also renders the separator itself conductive, so that the equivalent series resistance of the electrolytic capacitor is reduced and the impedance is reduced.

Further, a conductive polymer layer is formed on the surface of the carbonized separator paper to obtain the conductive separator 16, and at the same time, the surface of the dielectric oxide film 13 formed on the surface of the anode foil 11 and the cathode foil. By forming the conductive polymer layer on both of the surfaces of 12, the equivalent series resistance of the electrolytic capacitor is further reduced and the impedance is reduced.

In this example, after the step of carbonizing the separator paper provided between the surface of the dielectric oxide film 13 formed on the surface of the anode foil 11 and the surface of the cathode foil 12, the carbonization was performed. A step of immersing the treated separator paper and the anode foil 11 having the dielectric oxide film 13 on the surface and the cathode foil 12 in a solution containing a polymerizable monomer; and the dielectric oxide film on the separator paper and the surface. A conductive separator 16 having a conductive polymer layer formed on the surface thereof by a chemical polymerization method including a step of immersing the anode foil 11 having 13 and the cathode foil 12 in a solution containing an anion serving as an oxidant and a dopant. At the same time as obtaining the anode foil 11
Although the conductive polymer layer is formed on both the surface of the dielectric oxide film 13 formed on the surface of the cathode foil 12 and the surface of the cathode foil 12, the dielectric oxide film 13 formed on the surface of the anode foil 11 is formed.
After the step of carbonizing the separator paper installed between the surface of the cathode foil and the surface of the cathode foil 12, the anode foil 11 and the cathode having the carbon dioxide-treated separator paper and the dielectric oxide film 13 on the surface. Also by the method of impregnating the foil 12 with a solution or dispersion of a conductive polymer, the conductive separator 16 having the conductive polymer layer formed on the surface thereof is obtained, and at the same time, the dielectric oxide film formed on the surface of the anode foil 11. The conductive polymer layer can be formed on both the surface of 13 and the surface of the cathode foil 12.

If necessary, the conductor layers formed on the surfaces of the separator paper, the anode foil 11 and the cathode foil 12 can be manufactured in separate steps.

As described above, according to this example, a conductive separator in which a conductive polymer layer was formed on the surface of separator paper which was made conductive by carbonization was obtained, and at the same time the dielectric formed on the surface of the anode foil was obtained. By forming the conductive polymer layer on both the surface of the body oxide film and the surface of the cathode foil, the loss coefficient and impedance in the high frequency range of the electrolytic capacitor can be further reduced.

(Embodiment 8) The eighth embodiment of the present invention will be described in detail below.

In the present embodiment, the separator paper which is placed between the surface of the dielectric oxide film 13 formed on the surface of the anode foil 11 and the surface of the cathode foil 12 and carbonized, and the dielectric oxide film on the surface. The anode foil 11 having 13 and the cathode foil 12 are immersed in an aqueous solution of potassium permanganate (0.30M) and then immersed in an ethanol solution containing pyrrole monomer (0.5M) sulfuric acid (0.2M) to obtain potassium permanganate. 1. A conductive separator which is a conductive composite having a composite conductive layer in which a conductive polymer and manganese oxide are composited on the surface of the separator by a chemical reaction of a pyrrole monomer.
6 at the same time, the chemicals of potassium permanganate and pyrrole monomer as conductor layers 14 are formed on both the surface of the dielectric oxide film 13 formed on the surface of the anode foil 11 and the surface of the cathode foil 12. To form a composite conductive layer that is a composite of a conductive polymer and manganese oxide by a dynamic reaction,
Thereafter, in the same manner as in Example 7 , five electrolytic capacitors were completed and measurements were performed.

The average value of these measured values is shown in (Table 1). As is clear from this (Table 1), according to the present embodiment,
A composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the carbonized separator paper to obtain the conductive separator 16, and at the same time, the dielectric oxide film 13 formed on the surface of the anode foil 11 is formed. An electrolytic capacitor configured by forming a composite conductive layer containing a conductive polymer and manganese oxide on both the surface and the surface of the cathode foil 12 is electrically conductive with the composite conductive layer formed on the electrode foil. It can be seen that the equivalent series resistance of the electrolytic capacitor is reduced by the effect of the separator, and as a result, the loss coefficient and impedance in the high frequency range are significantly reduced, and an electrolytic capacitor having excellent frequency characteristics and loss characteristics is obtained.

In particular, carbonization of the separator also renders the separator itself conductive, so that the equivalent series resistance of the electrolytic capacitor is reduced and the impedance is reduced.

Further, a composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the carbonized separator paper to obtain the conductive separator 16, and at the same time, the dielectric oxide formed on the surface of the anode foil 11 is oxidized. Surface of coating 13 and cathode foil 12
By forming a composite conductive layer containing a conductive polymer and manganese oxide both on the surface of the capacitor, the equivalent series resistance of the electrolytic capacitor can be further reduced and the impedance can be reduced.

Furthermore, since manganese oxide has a high ability to repair the oxide film of the valve metal, it is possible to prevent deterioration of the leakage current characteristics.

In the present embodiment, after the step of carbonizing the separator paper provided between the surface of the dielectric oxide film 13 formed on the surface of the anode foil 11 and the surface of the cathode foil 12, the carbonization is performed. Immersing the treated separator paper and the anode foil 11 and the cathode foil 12 having the dielectric oxide film 13 on the surface in an aqueous solution of potassium permanganate as permanganate, the separator paper and the A step of immersing the anode foil 11 and the cathode foil 12 in a solution containing a polymerizable monomer and an anion serving as a dopant, and the surface of the dielectric oxide film 13 formed on the surface of the anode foil 11 and the cathode. A composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the foil 12 by a step of chemically reacting a polymerizable monomer and permanganate, and at the same time, The conductive separator 16 having the composite conductive layer containing a conductive polymer and manganese oxide on the surface thereof is obtained, but other permanganate also chemically reacts with the polymerizable monomer to achieve conductivity. Any material that can form a composite conductive layer composed of a polymer and manganese oxide can be similarly used.

As described above, according to this embodiment, at the same time as the conductive separator having the composite conductive layer containing the conductive polymer and the manganese oxide formed on the surface of the separator paper which has been made conductive by the carbonization treatment, By forming a composite conductive layer containing a conductive polymer and manganese oxide on both the surface of the dielectric oxide film formed on the surface of the anode foil and the surface of the cathode foil, in the high frequency range of the electrolytic capacitor. It is possible to further reduce the loss coefficient and the impedance.

(Ninth Embodiment) A ninth embodiment of the present invention will be described in detail below with reference to the drawings.

FIG. 3 shows a sectional view of the electrolytic capacitor of this embodiment. In FIG. 3, 21 is an anode foil, 22 is a cathode foil, 23 is a dielectric oxide film, 24 is a conductor layer, 25
Is an electrolyte.

In other words, in this embodiment, the electrolyte 25 is interposed between the anode foil 21 having the dielectric oxide film 23 formed on its surface and the cathode foil 22 having no dielectric oxide film 23 on its surface without a separator. Is the dielectric oxide film 23 and the conductor layer 2
4 has an impregnated structure.

The method of manufacturing the electrolytic capacitor according to this embodiment is as follows. The cathode foil 22 made of an etched aluminum foil is used for polymerization using pyrrole (0.25M), sodium triisopropylnaphthalene sulfonate (0.10M) and water . After being placed in the liquid , a constant voltage of 5 V was applied to carry out electrolytic polymerization reaction, and after washing and drying, a conductive polymer layer was formed as the conductor layer 24.

On the other hand, by applying a constant voltage in an aqueous solution of ammonium adipate (3 parts by weight) at about 70 ° C., the dielectric oxide film 23 is formed on the surface of the anode foil 21 made of an etched aluminum foil by anodizing. did.

Next, the cathode foil 22 having the conductive polymer layer 24 formed on the surface and the anode foil 21 having the dielectric oxide film 23 on the surface are wound without a separator and then re-formed. Then, the dielectric oxide film 23 formed on the surface of the anode foil 21 was repaired.

After washing and drying, the electrolyte 25 is γ-.
An electrolytic solution containing monomethyltriethylammonium phthalate (20 parts by weight) was impregnated under reduced pressure using butyrolactone as a solvent, and was externally coated to complete five electrolytic capacitors having a rating of 16 V and 10 μF.

Incidentally, FIG. 3 typically shows a portion which can be approximated to a flat plate shape in the cross-sectional view of the electrolytic capacitor thus formed by winding.

Also in this example, the same measurement as in Example 1 was carried out, and the average value of these measured values is shown in the above (Table 1).

As is clear from this (Table 1), by forming a conductive polymer layer on the surface of the cathode foil 22 by electrolytic polymerization according to this example, and forming an electrolytic capacitor without using a separator, It can be seen that the impedance component generated by the separator or the interface between the separator and the electrolytic solution is reduced, and as a result, the loss coefficient and impedance in the high frequency range are significantly reduced, and an electrolytic capacitor having excellent frequency characteristics and loss characteristics can be obtained. .

In this embodiment, the conductive polymer layer itself formed on the surface of the electrode foil is considered as a substitute for the conductive separator, and the conductive separator is not provided.

As described above, by omitting the separator and substituting the conductive polymer layer formed on the surface of the electrode foil, the equivalent series resistance of the electrolytic capacitor is reduced, thereby reducing the impedance. .

Although the conductive polymer layer is formed on the surface of the cathode foil 22 in this embodiment, the dielectric oxide film 23 formed on the surface of the anode foil 21 instead of the cathode foil 22.
Even if a conductive polymer layer is formed on both the surface of the anode foil 21 and the surface of the dielectric oxide film 23 formed on the surface of the anode foil 21 and the surface of the cathode foil 22, an electrolytic capacitor is formed by the conductive polymer layer. The equivalent series resistance possessed by is reduced, which allows the impedance to be reduced.

In this embodiment, the conductive polymer layer is formed on the surface of the electrode foil by the electrolytic polymerization method using the polymerization liquid containing the polymerizable monomer and the anion serving as the dopant. A chemical polymerization method having a step of immersing in a solution containing a polymerizable monomer and a step of immersing the electrode foil in a solution containing an oxidant and an anion serving as a dopant, or a solution of a conductive polymer on the surface of the electrode foil. Alternatively, the conductive polymer layer can be formed on the surface of the electrode foil by impregnation or coating of the dispersion.

As described above, according to the present embodiment, the conductive polymer layer is formed on one surface of the electrode foil, and the electrolytic capacitor is constructed without the separator, whereby the frequency characteristics and the loss characteristics are improved. It is possible to obtain an excellent electrolytic capacitor.

(Tenth Embodiment) The tenth embodiment of the present invention will be described in detail below.

In this example, an anode made of an etched aluminum foil having a dielectric oxide film 23 formed on its surface by applying a constant voltage in an aqueous solution of ammonium adipate (3 parts by weight) at about 70 ° C. The foil 21 was dipped in an aqueous solution of potassium permanganate (0.30M) and then dipped in an ethanol solution containing pyrrole monomer (0.5M) sulfuric acid (0.2M) to oxidize the dielectric formed on the surface of the anode foil 21. On the surface of the film 23, a composite conductive layer in which a conductive polymer and manganese oxide are compounded is formed as a conductive layer 24 by a chemical reaction of potassium permanganate and a pyrrole monomer, and the same as in Example 9 below. 5 electrolytic capacitors
It was completed and measured.

The average value of these measured values is shown in (Table 1). As is clear from this (Table 1), according to the present embodiment,
On the surface of the dielectric oxide film 23 formed on the surface of the anode foil 21, a composite conductive layer in which a conductive polymer and manganese oxide are compounded is formed by a chemical reaction of potassium permanganate and a pyrrole monomer, By configuring the electrolytic capacitor without using the separator, the impedance component generated by the separator or the interface between the separator and the electrolytic solution is reduced, as a result of which the loss coefficient and impedance in the high frequency range are greatly reduced, the frequency characteristic, It can be seen that an electrolytic capacitor having excellent loss characteristics can be obtained.

Also in this example, the composite conductive layer itself, which is a composite of the conductive polymer formed on the surface of the electrode foil and manganese oxide, is considered as an alternative to the conductive separator, and the conductive separator is not used. There is no configuration.

As described above, by omitting the separator and substituting the composite conductive layer in which the conductive polymer formed on the surface of the electrode foil is mixed with the manganese oxide, the equivalent series resistance of the electrolytic capacitor can be improved. This reduces the impedance, thereby reducing the impedance.

Further, since manganese oxide has a high ability to repair the oxide film of the valve metal, it is possible to prevent deterioration of the leakage current characteristic.

In the present embodiment, the dielectric oxide film 23
Immersing the anode foil 21 having the above in an aqueous solution of potassium permanganate as permanganate;
Of a polymerizable monomer and a permanganate on the surface of the dielectric oxide film 23 formed on the surface of the anode foil 21 by immersing the polymer in a solution containing a polymerizable monomer and an anion serving as a dopant. The composite conductive layer containing the conductive polymer and manganese oxide is formed by the step of chemically reacting, but other permanganates also chemically react with the polymerizable monomer to form the conductive polymer and manganese oxide. Any material that can form a composite conductive layer made of a material can be used similarly.

Further, in this embodiment, a composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the dielectric oxide film 23 formed on the surface of the anode foil 21. Dielectric oxide film 23 formed on the surface of foil 21
Instead of the surface of the above, even if the composite conductive layer is formed on the surface of the cathode foil 22, or on both the surface of the dielectric oxide film 23 formed on the surface of the anode foil 21 and the surface of the cathode foil 22, The composite conductive layer reduces the equivalent series resistance of the electrolytic capacitor, thereby reducing the impedance.

As described above, according to this embodiment, the conductive polymer and the manganese oxide are provided on either or both of the surface of the dielectric oxide film formed on the surface of the anode foil and the surface of the cathode foil. By forming the composite conductive layer containing the, the loss coefficient and impedance in the high frequency region of the electrolytic capacitor can be further reduced.

In all of the above examples, only the case where the separator paper made of Manila hemp is used as the material of the separator has been described as a representative, but if the thickness, density and material suitable for the separator are provided, other Paper, cloth, non-woven fabric or polymer film can also be preferably used.

Further, in the above examples, only the case where pyrrole was used as the polymerizable monomer was described, but a monomer such as aniline, thiophene, furan, etc. which can be used as an electrode to obtain a conductive polymer having electric conductivity can be obtained. Other polymerizable monomers can be preferably used as long as they are present.

In the above examples, the triisopropylnaphthalene sulfonic acid anion or the sulfate anion is
Although only the case where it is used as a dopant of a conductive polymer obtained by electrolytic polymerization or chemical polymerization is described, it is sufficient that the anion is contained in the conductive polymer as a dopant, and the anion of the dopant is limited. Instead, several kinds of anions may be combined and used.

Further, in the above embodiments, only the case where the etched aluminum foil is used as the electrode foil has been described, but other valve metals can also be used as the electrode foil.

In the above embodiments, the surface of the dielectric oxide film formed on the surface of the anode foil and the surface of the cathode foil are impregnated with or without a conductive separator. Only the case of using an electrolytic solution as an electrolyte was described, but other substances may be used as long as they have proper electric conductivity as an electrolyte and there is no fear of corroding the electrode foil. Moreover, it can be liquid or solid.

Further, in the above examples, only the case where monomethyltriethylammonium phthalate was used as the ion conductive salt of the electrolytic solution was described, but there is no fear of corroding the electrode foil, and the electrolytic solution is appropriate. Other substances may be used as long as they have good electric conductivity.

Further, in the above examples, only the case where γ-butyrolactone was used as the solvent of the electrolytic solution was described, but the solute of the electrolytic solution is sufficiently dissolved, and the electrolytic solution has an appropriate electric conductivity. Other solvents may be used as long as they are such.

Further, in the above examples, only the electrolytic polymerization using an aqueous solution of a polymerizable monomer and an anion serving as a dopant was described, but a conductive polymer layer having an electric conductivity which can be used as an electrode is formed. If it is obtained, other substances can be used as a solvent for the polymerization solution, and of course, additives can be added to the polymerization solution as needed.

In the above examples, the chemical polymerization was carried out by immersing the electrode foil in the solution of the polymerizable monomer and then in the aqueous solution containing the oxidant and the anion serving as the dopant. It may be immersed in an aqueous solution containing an anion serving as a dopant and then in a solution of a polymerizable monomer.

The polymerizable monomer used in the above examples may be used as a neat liquid, or may be used in either a liquid phase or a gas phase, and has an electric conductivity usable as an electrode. As long as a conductive polymer layer having a is obtained, chemical polymerization may be carried out by other procedures than electrolytic polymerization.

In the above examples, hydrogen peroxide or ammonium persulfate was used only as an oxidizing agent for the oxidative polymerization of conductive polymers.
Other non-metal substances, may be selected from metal salts, as long as a conductive polymer having an electrical conductivity that can be used as an electrode is obtained, is not limited by the type of substance, Several kinds of substances may be combined and used.

Further, in the above examples, the case where potassium permanganate or sodium permanganate was used as the permanganate was described. However, the chemical reaction between the permanganate and the polymerizable monomer causes conductivity. Other permanganates such as sodium permanganate may be used as long as the composite conductive layer of polymer and manganese oxide can be formed.

Further, in the above embodiments, the case where the water-dispersed colloidal graphite is used has been described. However, colloidal graphite dispersed in an organic solvent may be used.

Further, among the above examples, in the examples using the conductive separator having the conductive polymer or the composite conductive layer in which the conductive polymer and manganese oxide are compounded with the graphite particles on the surface, Substantially the conductive polymer contained in the dielectric oxide film formed on the surface of the foil or the conductive layer formed on the surface of the cathode foil and the conductive polymer contained in the composite conductive layer of the conductive separator. Although they are formed separately, it is assumed that both of the conductive polymers are formed at the same time, and when the separator already impregnated with graphite particles and both electrode foils are brought into contact with each other, the graphite particles dropped from the separator are This is because it eliminates the possibility of damaging the dielectric oxide film formed on the surface of the anode foil.

Therefore, in other cases, both of the above conductive polymers can be formed substantially at the same time, and when sufficient impregnation is realized so that the graphite particles do not fall off, the graphite particles are Even if a composite separator is used, it can be formed at the same time.

Further, among the above examples, in the examples using the conductive separator in which the conductive polymer layer or the composite conductive layer containing the conductive polymer and manganese oxide was formed on the surface of the carbonized separator, Since it is difficult to handle the separator that has been brittle and easily damaged by carbonization alone, it is necessary to carbonize the separator paper after the separator paper is previously installed between both electrode foils. The conductive polymer contained in the dielectric oxide film formed on the surface of or the conductive layer formed on the surface of the cathode foil and the conductive polymer contained in the composite conductive layer of the conductive separator are substantially at the same time. Although formed, in other cases, of course, in the case of using a carbonized separator if the flexibility of the carbonized separator is sufficiently secured,
It is also possible to form both conductive polymers substantially separately.

Further, in the above embodiments, the wound type electrolytic capacitor has been described, but it is needless to say that the same constitution can be adopted also in a laminated type electrolytic capacitor laminated in a flat plate shape or the like. In these cases, the cross sectional views of FIGS.

Of course, the present invention is not limited to the compounds and treatment steps described in the above examples, and it goes without saying that substitutable compounds and treatment steps other than the exemplified ones may be used.

[0166]

As described above, the present invention provides an electrolytic capacitor in which a conductor layer is formed on either or both of the anode foil and the cathode foil having a dielectric oxide film formed on the surface. Liquid or solid by winding or laminating both electrode foils via a conductive separator, or without interposing a separator by forming a conductive polymer layer on the surface of either or both of the anode foil and the cathode foil. It is possible to realize an electrolytic capacitor having excellent frequency characteristics and loss characteristics by being impregnated with an electrolyte composed of

[Brief description of drawings]

1 is a partial cross-sectional view of an electrolytic capacitor according to a first, second, third, fourth, fifth or sixth embodiment of the present invention.

FIG. 2 is a partial cross-sectional view of an electrolytic capacitor according to the seventh or eighth embodiment.

FIG. 3 is a partial sectional view of an electrolytic capacitor according to the ninth or tenth embodiment.

[Explanation of symbols]

1 Anode foil 2 cathode foil 3 Dielectric oxide film 4 Conductor layer 5 electrolyte 6 Conductive separator 11 Anode foil 12 Cathode foil 13 Dielectric oxide film 14 Conductor layer 15 Electrolyte 16 Conductive separator 21 Anode foil 22 cathode foil 23 Dielectric oxide film 24 Conductor layer 25 electrolyte

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01G 9/14 H01G 9/04 313 9/24 AC (72) Inventor Mutsuaki Murakami 3-10 Higashimita, Tama-ku, Kawasaki-shi, Kanagawa No. 1 in Matsushita Giken Co., Ltd. (56) Reference JP-A-5-299305 (JP, A) JP-A-61-116816 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) ) H01G 9/02 301 H01G 9/00 H01G 9/028 H01G 9/035 H01G 9/048 H01G 9/14

Claims (40)

(57) [Claims] 1. A valve metal having a dielectric oxide film formed on its surface.
Anode foil formed from, and cathode foil formed from valve metal
And one or both of the anode foil and cathode foil
Conductor layer formed on the surface, the cathode foil and the anode foil
Between the conductive separator and the conductive separator
Provided between the cathode foil and the anode foil via a
Is having an electrolyte, the conductive separator is used, the number a substrate and a composite conductive layer comprising a conductive polymer and manganese oxide obtained from a polymerizable monomer, which is formed on a surface of said substrate It is that electrolytic capacitors. 2. A valve metal having a dielectric oxide film formed on its surface.
Anode foil formed from, and cathode foil formed from valve metal
And one or both of the anode foil and cathode foil
Conductor layer formed on the surface, the cathode foil and the anode foil
Between the conductive separator and the conductive separator
Provided between the cathode foil and the anode foil via a
And the conductive separator has a base material, and a composite conductive layer containing a conductive polymer and graphite particles obtained from a polymerizable monomer formed on the surface of the base material. that electrolytic capacitors. 3. A valve metal having a dielectric oxide film formed on its surface.
Anode foil formed from, and cathode foil formed from valve metal
And one or both of the anode foil and cathode foil
Conductor layer formed on the surface, the cathode foil and the anode foil
Between the conductive separator and the conductive separator
Provided between the cathode foil and the anode foil via a
And a conductive layer having a prepared electrolyte, a substrate, and a composite conductive layer containing a conductive polymer and manganese oxide and graphite particles obtained from a polymerizable monomer formed on the surface of the substrate. that electrolytic capacitors have a. 4. A valve metal having a dielectric oxide film formed on its surface.
Anode foil formed from, and cathode foil formed from valve metal
And one or both of the anode foil and cathode foil
Conductor layer formed on the surface, the cathode foil and the anode foil
Between the conductive separator and the conductive separator
Provided between the cathode foil and the anode foil via a
Is having an electrolyte, the conductive separator carbide treated substrate, a conductive polymer layer and that electrolytic capacitors have a derived from a polymerizable monomer, which is formed on a surface of said substrate . 5. A valve metal having a dielectric oxide film formed on its surface.
Anode foil formed from, and cathode foil formed from valve metal
And one or both of the anode foil and cathode foil
Conductor layer formed on the surface, the cathode foil and the anode foil
Between the conductive separator and the conductive separator
Provided between the cathode foil and the anode foil via a
And a conductive material having a manganese oxide , wherein the conductive separator has a carbonized base material, and a conductive polymer obtained from a polymerizable monomer formed on the surface of the base material and manganese oxide. that electrolytic capacitors have a and layers. 6. The conductive layer formed on one or both surfaces of the anode foil and the cathode foil, according to any of claims 1-5 which is a conductive polymer layer obtained from a polymerizable monomer Electrolytic capacitor. 7. The conductor layer formed on the surface of one or both of the anode foil and the cathode foil is a composite conductive layer containing a conductive polymer obtained from a polymerizable monomer and manganese oxide. electrolytic capacitor according to any one of claims 1 to 5. 8. The polymerizable monomer contained in the conductor layer formed on the surface of one or both of the anode foil and the cathode foil and the conductor layer formed in the conductive separator is pyrrole, thiophene, furan, The electrolytic capacitor according to claim 6 or 7, which is a combination of at least one or a plurality of aniline and derivatives thereof. 9. The electrolytic capacitor according to claim 8 , which is a liquid or a solid impregnated with an electrolyte and is a wound type or a laminated type. 10. A dielectric oxide film on the surface of the first valve metal.
Forming the anode foil and preparing the second valve metal.
Step of preparing as a cathode foil, and the anode foil and cathode foil
Step of forming a conductor layer on either or both surfaces
And the dielectric oxide film or the conductor layer of the anode foil
And a conductive layer between the cathode foil surface or the conductor layer.
The step of installing the palletizer and the conductive separator
Then, an electrolyte is provided between the anode foil and the cathode foil.
And a step of winding or laminating both electrode foils, the conductive separator is a step of preparing a base material, and a conductive material obtained from a polymerizable monomer on the surface of the base material. production process steps and the conductive separator formed Ru electrolytic capacitors are formed by a process having to form a composite conductive layer comprising a polymer and a manganese oxide. 11. The method for producing an electrolytic capacitor according to claim 10 , wherein the composite conductive layer is formed by a step of chemically reacting a polymerizable monomer and permanganate. 12. A composite conductive layer, a substrate, immersing the permanganate solution, according to claim 10 or formed by immersing in a solution containing the anion to be a polymerizable monomer and a dopant 11. The method for producing an electrolytic capacitor as described in 11 . 13. A dielectric oxide film on the surface of the first valve metal.
Forming the anode foil and preparing the second valve metal.
Step of preparing as a cathode foil, and the anode foil and cathode foil
Step of forming a conductor layer on either or both surfaces
And the dielectric oxide film or the conductor layer of the anode foil
And a conductive layer between the cathode foil surface or the conductor layer.
The step of installing the palletizer and the conductive separator
Then, an electrolyte is provided between the anode foil and the cathode foil.
And a step of winding or laminating both electrode foils, the conductive separator is a step of preparing a base material, and a conductive material obtained from a polymerizable monomer on the surface of the base material. production process steps and the conductive separator formed Ru electrolytic capacitors are formed by a process having to form a composite conductive layer comprising a polymer and a graphite particles. 14. The step of impregnating or applying colloidal graphite on the surface of a prepared base material for the composite conductive layer,
14. A method of manufacturing an electrolytic capacitor according to claim 13, which is formed by a step of complexing a conductive polymer with graphite particles by electrolytic polymerization to form a composite conductive layer. 15. The method for producing an electrolytic capacitor according to claim 14 , wherein the electrolytic polymerization step is performed using a polymerization liquid containing a polymerizable monomer and an anion serving as a dopant. 16. The composite conductive layer comprises a step of impregnating or coating colloidal graphite on the surface of a prepared substrate,
The method for producing an electrolytic capacitor according to claim 13, further comprising the step of forming a composite conductive layer by compounding a conductive polymer with graphite particles by chemical polymerization. 17. The chemical polymerization step includes a step of immersing a base material impregnated or coated with colloidal graphite in a solution containing a polymerizable monomer, and a step of immersing it in a solution containing an oxidant and an anion serving as a dopant. Item 17. A method for manufacturing an electrolytic capacitor according to Item 16 . 18. The composite conductive layer comprises a step of impregnating or applying colloidal graphite on the surface of a prepared substrate,
Then claim 1 of a solution or dispersion of the conductive polymer is formed by the steps of impregnating or coating the surface of the substrate
3. The method for manufacturing an electrolytic capacitor as described in 3 . 19. A dielectric oxide film on the surface of the first valve metal.
Forming the anode foil and preparing the second valve metal.
Step of preparing as a cathode foil, and the anode foil and cathode foil
Step of forming a conductor layer on either or both surfaces
And the dielectric oxide film or the conductor layer of the anode foil
And a conductive layer between the cathode foil surface or the conductor layer.
The step of installing the palletizer and the conductive separator
Then, an electrolyte is provided between the anode foil and the cathode foil.
And a step of winding or laminating both electrode foils, the conductive separator has a step of preparing a base material and a conductive material obtained from a polymerizable monomer on the surface of the base material. production process steps and the conductive separator formed Ru electrolytic capacitors are formed by a process having to form a composite conductive layer comprising a polymer and a manganese oxide and graphite particles. 20. A step of impregnating or applying colloidal graphite on the surface of a prepared base material for the composite conductive layer,
Next, a step of chemically reacting a polymerizable monomer and permanganate to form a composite conductive layer by complexing a conductive polymer and manganese oxide with graphite particles. 20. The method for producing an electrolytic capacitor as described in 19 . 21. A step of impregnating or applying colloidal graphite on the surface of a prepared base material for the composite conductive layer,
The method for producing an electrolytic capacitor according to claim 19 or 20, which is formed by a step of immersing in a permanganate aqueous solution and a step of immersing in a solution containing a polymerizable monomer and an anion serving as a dopant. 22. A dielectric oxide film is formed on the surface of the first valve metal.
Forming the anode foil and preparing the second valve metal.
Step of preparing as a cathode foil, and the anode foil and cathode foil
Step of forming a conductor layer on either or both surfaces
And the dielectric oxide film or the conductor layer of the anode foil
And a conductive layer between the cathode foil surface or the conductor layer.
The step of installing the palletizer and the conductive separator
Then, an electrolyte is provided between the anode foil and the cathode foil.
And a step of winding or laminating both electrode foils, the conductive separator has a step of preparing a base material, a step of carbonizing the base material, and a step of forming the base material. method for producing a conductive separator formed electrolytic capacitors Ru is formed by a process including a step of forming a conductive polymer layer obtained from a polymerizable monomer on the surface. 23. The carbonization treatment is performed after a separator is placed between the dielectric oxide film on the anode foil and the surface of the cathode foil, and the carbonization treatment is performed on the dielectric oxide film on the anode foil and the surface of the cathode foil. The method for producing an electrolytic capacitor according to claim 22 , wherein a conductive polymer layer is formed on the surface of the separator by chemical polymerization. 24. The chemical polymerization step comprises a step of immersing a carbonized separator placed between the dielectric oxide film of the anode foil and the surface of the cathode foil in a solution containing a polymerizable monomer, and an oxidizing agent. 24. The process for producing an electrolytic capacitor according to claim 23 , further comprising a step of immersing the carbonized separator provided between the dielectric oxide film of the anode foil and the surface of the cathode foil in a solution containing anion serving as a dopant. Method. 25. The carbonization treatment is performed after a separator is placed between the dielectric oxide film of the anode foil and the surface of the cathode foil, and the carbonization treatment is performed on the dielectric oxide film of the anode foil and the surface of the cathode foil. 23. The method for manufacturing an electrolytic capacitor according to claim 22 , wherein the conductive polymer layer is formed by impregnating the surface of the separator with a solution or dispersion of a conductive polymer. 26. A dielectric oxide film on the surface of the first valve metal
Forming the anode foil and preparing the second valve metal.
Step of preparing as a cathode foil, and the anode foil and cathode foil
Step of forming a conductor layer on either or both surfaces
And the dielectric oxide film or the conductor layer of the anode foil
And a conductive layer between the cathode foil surface or the conductor layer.
The step of installing the palletizer and the conductive separator
Then, an electrolyte is provided between the anode foil and the cathode foil.
And a step of winding or laminating both electrode foils, the conductive separator has a step of preparing a base material, a step of carbonizing the base material, and a step of forming the base material. method for producing a conductive separator formed Ru electrolytic capacitors are formed by a process including a step of forming a composite conductive layer comprising a conductive polymer obtained from a polymerizable monomer and manganese oxide on the surface. 27. The carbonization treatment is performed after a separator is placed between the dielectric oxide film on the anode foil and the surface of the cathode foil, and the carbonization treatment is performed on the dielectric oxide film on the anode foil and the surface of the cathode foil. 27. The method for manufacturing an electrolytic capacitor according to claim 26 , wherein a composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of the separator by a step of chemically reacting a polymerizable monomer and permanganate. 28. In the step of chemically reacting the polymerizable monomer and permanganate, the carbonized separator is placed between the dielectric oxide film of the anode foil and the surface of the cathode foil to give the permanganate. A step of immersing in an aqueous solution, and a step of immersing the carbonized separator installed between the dielectric oxide film of the anode foil and the surface of the cathode foil in a solution containing a polymerizable monomer and an anion serving as a dopant. Claim 2 having
The method for producing an electrolytic capacitor as described in 6 or 27 . 29. The conductive polymer layer obtained from the polymerizable monomer on the surface of the anode foil and / or the cathode foil is formed by an electrolytic polymerization step, and the conductive polymer layer is formed according to any one of claims 10 to 22 , or 26 . Method of manufacturing electrolytic capacitor. 30. The method for producing an electrolytic capacitor according to claim 29 , wherein the electrolytic polymerization step is performed using a polymerization liquid containing a polymerizable monomer and an anion serving as a dopant. 31. The conductive polymer layer obtained from a polymerizable monomer on the surface of the anode foil and / or the cathode foil is formed by a chemical polymerization step, and the conductive polymer layer is formed according to any one of claims 10 to 24 or 26 . Method of manufacturing electrolytic capacitor. 32. The chemical polymerization step comprises a step of immersing the anode foil and / or the cathode foil in a solution containing a polymerizable monomer, and a solution containing the anode foil and / or the cathode foil with an oxidant and an anion serving as a dopant. And a step of immersing in
31. A method for manufacturing an electrolytic capacitor as described in 31 . 33. The conductive polymer layer obtained from a polymerizable monomer on the surface of the anode foil and / or the cathode foil is a solution or dispersion of a conductive polymer on the surface of the anode foil and / or the cathode foil. , claims 10, which is formed by impregnating or coating 2
27. The method for manufacturing an electrolytic capacitor according to claim 2 , or any one of claims 25 and 26 . To 34. anode foil and / or the surface of the cathode foil, it claims 10 to form a composite conductive layer 22 comprising a conductive polymer obtained from a polymerizable monomer and manganese oxide, or wherein Item 29. A method for manufacturing an electrolytic capacitor according to any one of Items 26 to 28 . 35. A composite conductive layer containing a conductive polymer and manganese oxide is formed on the surface of an anode foil and / or a cathode foil by a step of chemically reacting a polymerizable monomer and permanganate. Item 34. A method for manufacturing an electrolytic capacitor according to Item 34 . 36. The step of chemically reacting the polymerizable monomer and permanganate includes a step of immersing the anode foil and / or the cathode foil in an aqueous permanganate solution, and a step of polymerizing the anode foil and / or the cathode foil. 36. The method for producing an electrolytic capacitor according to claim 35 , further comprising a step of immersing in a solution containing a monomer and an anion serving as a dopant. 37. A dielectric oxide film on the surface of the first valve metal.
Forming the anode foil and preparing the second valve metal.
Step of preparing as a cathode foil, and the anode foil and cathode foil
Step of forming a conductor layer on either or both surfaces
And the dielectric oxide film or the conductor layer of the anode foil
And a conductive layer between the cathode foil surface or the conductor layer.
The step of installing the palletizer and the conductive separator
Then, an electrolyte is provided between the anode foil and the cathode foil.
And extent, both electrode foil and a step of winding or stacking, polymerizable monomer of the electrically <br/> conductor layer formed on the <br/> anode foil and / or the surface of the cathode foil A conductive polymer obtained from
The conductive polymer obtained from the polymerizable monomer of the composite conductive layer of the conductive separator is formed at substantially the same time.
Method of manufacturing that electrolytic capacitors. 38. A dielectric oxide film on the surface of the first valve metal.
Forming the anode foil and preparing the second valve metal.
Step of preparing as a cathode foil, and the anode foil and cathode foil
Step of forming a conductor layer on either or both surfaces
And the dielectric oxide film or the conductor layer of the anode foil
And a conductive layer between the cathode foil surface or the conductor layer.
The step of installing the palletizer and the conductive separator
Then, an electrolyte is provided between the anode foil and the cathode foil.
And extent, both electrode foil and a step of winding or stacking, polymerizable monomer of the electrically <br/> conductor layer formed on the <br/> anode foil and / or the surface of the cathode foil A conductive polymer obtained from
The conductive polymer obtained from the polymerizable monomer of the composite conductive layer of the conductive separator is formed substantially separately.
Method of manufacturing that electrolytic capacitors. 39. The polymerizable monomer used in the conductor layer formed on the surface of one or both of the anode foil and the cathode foil and the conductor layer formed in the conductive separator,
Pyrrole, thiophene, furan, aniline and at one or method of manufacturing an electrolytic capacitor according to any of claims 10 38 of which is a combination of those derivatives thereof. 40. The electrolyte is impregnated method of manufacturing an electrolytic capacitor according to any of claims 10 is a liquid or solid 39.