JPH06124858A - Capacitor and its manufacture - Google Patents

Abstract

PURPOSE:To provide a capacitor being excellent in capacitor characteristics and, above all, in frequency characteristics and the manufacture of the capacitor, which can be user on an AC circuit and on a circuit where the direction of voltage changes sometimes and in which a polarity need not be discriminated also at the time of mounting. CONSTITUTION:When foil-shaped or plate-shaped valve metal parts 2, in which electrolytes composed of dielectric film and conductive macromolecules are formed successively, are caused to correspond to each other and a plurality of adjacent valve metal parts 3, in which electrolyte layers are not formed, are located in two directions in no manner of overlapping with each other and laminated while having electric junction and respective electrode leads 8 are formed in the parts 3, in which the electrolyte layers are not formed, so that a capacitor is constituted, it is possible to obtain a non-polar solid electrolytic capacitor being excellent in frequency characteristics. Because manganese dioxide acting as intermediary for growing the conductive macromolecular film on the dielectric is formed by the reduction of permanganate, the damage of the dielectric film is small; and because the surface of the conductive macromolecules is cleaned by a surface active agent, the macromolecular film is prevented from separating from a graphite layer so that it is possible to obtain a capacitor being stable in characteristics.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a capacitor having excellent frequency characteristics, loss characteristics and reliability characteristics, and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, with the digitization of electrical equipment,
The capacitors are also required to be small in size and large in capacity and have low impedance in the high frequency region. Conventionally, capacitors used in the high frequency region include plastic capacitors, mica capacitors, and laminated ceramic capacitors, but these capacitors have a large shape and it is difficult to increase the capacity.

On the other hand, as a large-capacity capacitor, there is an electrolytic capacitor such as an aluminum dry electrolytic capacitor or an aluminum or tantalum solid electrolytic capacitor.
In these capacitors, the oxide film that serves as the dielectric is extremely thin, so a large capacity can be realized, but on the other hand, because the oxide film is easily damaged, it is necessary to provide an electrolyte between it and the cathode to repair it. is there.

In the aluminum dry type capacitor, the etched positive and negative electrode aluminum foil is wound around a separator, and the separator is impregnated with a liquid electrolyte. Since this liquid electrolyte is ionic conductive and has a large specific resistance, the loss is large and the impedance frequency characteristics and temperature characteristics are significantly inferior.In addition, liquid leakage, evaporation, etc. are unavoidable, and the capacity decreases and the I had a problem with an increase.

Further, since the manganese dioxide is used as the electrolyte in the tantalum solid electrolytic capacitor, the problems of temperature characteristics and changes with time such as capacity and loss are improved, but since the specific resistance of manganese dioxide is relatively high, the loss and impedance are relatively high. Was inferior in frequency characteristics to the monolithic ceramic capacitor or film capacitor.

In recent years, a frequency characteristic using a conductive polymer containing anion of a supporting electrolyte as a dopant by electrolytically oxidatively polymerizing a heterocyclic monomer such as pyrrole or thiophene using a supporting electrolyte as an electrolyte (true cathode). Also, solid electrolytic capacitors having excellent temperature characteristics have been proposed (JP-A-60-37114 and JP-A-60-244017).

Furthermore, a large-capacity film capacitor has been proposed in which a dielectric made of an electrodeposited polyimide thin film is formed on an etched aluminum foil and then an electrolytically polymerized conductive polymer layer is formed to serve as an electrode (electrochemistry. Pp. 251-252 (1991)).

[0008]

However, in the conventional structure in which the above conductive polymer is used as the electrolyte and the oxide film of the valve metal is used as the dielectric, it is unavoidable that it has polarity.
There is a problem that it cannot be used in a circuit that applies only alternating current and a circuit in which the voltage direction changes from time to time, and that the polarity must be distinguished even in mounting. The above-mentioned film capacitor having an electrodeposited polyimide thin film dielectric on an etched aluminum foil is non-polar, but has a dielectric constant of polyimide of about 3 and one third of aluminum oxide, and nine times that of tantalum oxide. Since it is as small as 1, it cannot be said that the volumetric efficiency is sufficiently high.

Furthermore, when a conductive polymer is formed on the surface of a dielectric by electrolytic polymerization, it is necessary to make it conductive.
Manganese dioxide is suitable for that purpose. Conventionally, manganese nitrate was used at 300 ° C to form this manganese dioxide.
Although a high temperature pyrolysis method was used to some extent, there was a problem that the dielectric film was easily damaged at that time.

Furthermore, since adhesion of low-molecular weight impurities may occur on the surface of the electropolymerized polymer layer, the adhesion between the layer and the colloidal graphite layer for forming a cathode may be improved. There was also a problem of weak peeling and loss factor.

This tendency is remarkable when a phenol-based additive is used in order to improve the electric conductivity of the polypyrrole obtained by electrolytic polymerization.

The present invention solves the above-mentioned problems of the prior art, and can be used in a circuit in which the direction of alternating current or voltage changes from time to time, and has high frequency characteristics and temperature characteristics that do not cause reverse polarity connection during mounting. Another object of the present invention is to provide a small nonpolar solid electrolytic capacitor having excellent reliability characteristics and a manufacturing method thereof. Another object of the present invention is to provide a capacitor excellent in leakage current, loss factor, etc. by improving the damage of the dielectric film during the formation of the manganese dioxide layer and the adhesion between the conductive polymer electrolyte and the graphite layer.

[0013]

In order to achieve this object, the present invention provides an insulating layer for partitioning at a predetermined portion of a foil-shaped or plate-shaped valve metal surface, and one of them is divided by the insulating layer. A dielectric layer and an electrolyte layer mainly composed of a conductive polymer are sequentially provided in a portion, and a plurality of the valve metals are separated by another insulating layer of each adjacent valve metal, and the other portion is not provided with the electrolyte layer. So that they are located in two directions so that they do not overlap each other, the portions provided with the electrolyte layers are correspondingly electrically joined and laminated, and the electrolyte of the valve metal located in the two directions is not provided. The present invention provides a solid electrolytic capacitor having both electrodes formed on a part thereof and a method for manufacturing the same.

Further, an example of a method for manufacturing the present capacitor will be described below. An insulating layer for partitioning is provided on the valve metal foil, a dielectric film is formed on one of the divided parts by anodic oxidation, and then a manganese oxide layer is formed on the surface of the dielectric film, which is used as a polymerizable monomer. Then, the conductive polymer layer is formed by electrolytic polymerization by immersing in a solution containing a supporting electrolyte and a polymerization initiating electrode provided on the surface thereof in proximity or in contact therewith. The element thus obtained is coated and dried with colloidal graphite, the valve metal foil is made to correspond to the conductive polymer forming portion, and the other electrolyte layer of the adjacent valve metal foil is not formed. Do not overlap each other 2
In the same direction, the parts provided with the electrolyte are made to correspond by using silver paint, and the respective electrodes are formed in the parts not provided with the electrolyte of the valve metal located in the same direction. To get Finally, this device is packaged to obtain a capacitor.

In order to prevent damage to the dielectric film during the formation of manganese dioxide, a permanganate reduction method which allows selection of mild conditions for its formation is used.

Impurities attached to the surface of the electropolymerized conductive polymer layer are removed by washing with a surfactant in order to prevent the graphite layer and the conductive polymer layer from peeling off and to improve the loss coefficient.

[0017]

As described above, since the electrolytes that also serve as cathodes are electrically connected to each other, a nonpolar capacitor is formed.
Therefore, it can be used in a circuit that applies only alternating current and a circuit in which the direction of voltage sometimes changes. Also, it is not necessary to distinguish the polarities even when mounting.

Since the electrolyte of this capacitor is made of a conductive polymer having high conductivity, it has excellent impedance and temperature characteristics in the high frequency range. By adopting a non-polar configuration, the capacitance is halved as compared with the case of having a polarity, but when aluminum oxide and tantalum oxide are used as dielectrics, the capacitance of a capacitor configured similarly with polyimide as a dielectric is about the same. 1.5 times and about 4.
Five times the capacity is obtained.

The manufacturing method is also such that individual foil-shaped or plate-shaped elements in which a dielectric and a conductive polymer electrolyte are sequentially formed are laminated by electrically connecting the cathodes to each other and the directions are alternately changed one by one. It is extremely easy to simply pull out both electrodes from the respective valve metals positioned in two directions.

In order to generate pyrolytic manganese dioxide from manganese nitrate, a high temperature of about 250 ° C. or higher is required, and corrosive nitrogen oxides are generated.
The reduction reaction of permanganate easily proceeds by releasing oxygen at about 200 ° C. in air and at about 60 ° C. in solution. Therefore, in the capacitor of the present invention, the degree of damage to the dielectric film is reduced, and the leakage current characteristic is improved.

In the capacitor of the present invention, at least one of the electrodes is a conductive polymer layer formed on the dielectric film by electrolytic polymerization using an electrolytic solution containing at least a supporting electrolyte, a polymerizable monomer and a phenol-based additive. The surface of the above conductive polymer layer is treated with a nonionic surfactant solution, and then a carbon layer and a silver paint layer are provided. By treating with a nonionic surfactant solution as described above, impurities existing on the surface of the conductive polymer layer are removed and the wettability of the water-dispersible colloidal graphite to the conductive polymer layer surface is increased. Therefore, the characteristics of the capacitor can be improved.

[0022]

【Example】

(First Embodiment) A first embodiment of the present invention will be described below with reference to the drawings.

FIG. 1 is a diagram showing the structure of a foil valve metal in one embodiment of the present invention. 1 is a plan view thereof, and FIG. 2 is A
It is sectional drawing in -A '.

As shown in FIG. 1, an insulating layer 1 made of a polyimide tape having a width of 1 mm is provided on both sides so as to divide a 4 × 10 mm aluminum etched foil into 3 mm and 6 mm portions, and a 4 × 6 mm portion 2 is provided. 3% ammonium adipate aqueous solution was applied at 50 ° C. at about 70 ° C. to form the dielectric film 4 by anodic oxidation, and then manganese nitrate 30%
The anode was prepared by immersing in an aqueous solution and further heating at 250 ° C. for 10 minutes to deposit pyrolytic manganese oxide on the surface.

A stainless electrolytic electrode for electrolytic polymerization was brought into contact with this anode foil to prepare a pyrrole monomer (0.25M) and sodium isopropylnaphthalene sulfonate (0.1M).
M) A voltage of 2.5 V was applied between the second electrode for electrolytic polymerization, which was soaked in an electrolytic solution made of water and separated from the electrolytic polymerization electrode, to form an electrolytic polymerization film 5 made of polypyrrole.
The electrolytic polymerization electrode was removed, washed with water, and then air-dried at 105 ° C. Then, colloidal graphite 6 was applied to obtain a valve metal foil having an electrolyte layer formed thereon.

FIG. 2 is a sectional view showing the structure. As shown in FIG. 3, the valve metal foil was alternately separated by 180 ° at each of the portions 3 separated by an insulating layer and having no electrolyte layer formed thereon.
Toward different directions, four portions are laminated using the silver paint 7 so as to correspond to the portion 2 on which the electrolyte layer is formed, and further the electrode leads 8 are attached to the portion 3 on which the electrolyte layer is not formed by welding. A capacitor element was obtained. FIG. 3 is a side view showing the capacitor element configured as described above.

Polypyrrole was deposited in the same manner as above except that the anode was replaced with a 20 mm × 30 mm nickel plate from an aluminum foil formed with a dielectric and manganese oxide, and its electrical conductivity was measured by the 4-terminal method. 25S
/ Cm was obtained. This is an order of magnitude larger than the salt solutions of organic acids or electrolytes such as manganese dioxide that have been used in conventional electrolytic capacitors.

The above capacitor element was sealed with epoxy resin to complete 10 capacitors. These were applied with an alternating current of 50 Hz and 13 V, but were found to function as nonpolar capacitors. The initial capacity and loss at 120 Hz and the impedance at 400 kHz are shown (Table 1). For comparison, 10 capacitors were prepared in the same manner as above except that a counter lead was not provided on the silver paint and no lamination was performed, and the same evaluation as above was performed. The results are shown in Table 1 as Comparative Example 1.

[0029]

[Table 1]

From these comparisons, the non-polar solid electrolytic having substantially the same characteristics as the solid electrolytic capacitor prepared by providing the cathode on the electrolyte forming portion of one sheet of valve metal foil before lamination and having extremely excellent characteristics. It can be seen that a capacitor was obtained.

(Example 2) 10 instead of aluminum foil
% Capacitor was prepared in the same manner as in Example 1 except that a tantalum foil formed at 90 ° C. using a phosphoric acid aqueous solution was used, and the same evaluation as in Example 1 was performed. Was shown to work as.
The initial capacity and loss at 120Hz is 400
The impedance at kHz is shown (Table 1).

These are almost the same characteristics as a solid electrolytic capacitor produced by providing a cathode on the electrolyte forming portion of one sheet of valve metal foil before lamination, and a non-polar solid electrolytic capacitor having extremely excellent characteristics is obtained. Was obtained.

(Example 3) Instead of the pyrrole of Example 1, pyrrole 0.15M and N-methylpyrrole 0.15 were used.
Ten capacitors were produced in the same manner as in Example 1 except that M was mixed and used, and the same evaluation as in Example 1 was performed. It was shown that the capacitor functions as a nonpolar solid electrolytic capacitor.

(Example 4) Instead of thermal decomposition of manganese nitrate, 0.2M potassium permanganate solution was attached, and 2
Example 1 except that the electrode lead was pulled out of the silver paint layer instead of heating for 30 minutes in air at 00 ° C to form manganese dioxide by reduction and then a non-polar construction.
Ten capacitors were prepared in the same manner as in, and the same evaluation as in Example 1 was performed. The results are shown in (Table 1). It has been found that even when manganese dioxide obtained by reduction from potassium permanganate is used, a capacitor having excellent characteristics can be obtained.

Example 5 A capacitor was prepared in the same manner as in Example 4 except that the foil was immersed for 30 minutes in a 0.2 M potassium permanganate solution acidified with nitric acid at 60 ° C. instead of heating at 200 ° C. Individual pieces were produced and evaluated in the same manner as in Example 1. The results are shown in (Table 1). It has been found that even when manganese dioxide obtained by reduction from potassium permanganate is used, a capacitor having excellent characteristics can be obtained.

(Embodiment 6) 7 g in length with anode lead ×
Aluminum etched foil 1 having a width of 10 g is applied with a 3% ammonium adipate aqueous solution at about 70 ° C. and an applied voltage of 70 V.
The dielectric film 2 was formed on the surface of the etched foil by performing anodic oxidation for 40 minutes under the conditions of. Then, it was dipped in a 30% manganese nitrate aqueous solution and air-dried, then at 3O 0 C for 3
A thermal decomposition treatment was performed by heating for 0 minutes to form a conductive layer of the manganese oxide layer 3 on the dielectric film. Next, the etched foil provided with the conductive layer was treated with pyrrole (0.25 mol / l) and sodium triisopropylnaphthalene sulfonate (0.
10 mol / l), m-hydroxybenzoic acid (0.15 mol / l) and p-nitrophenol (0.01 m) as additives.
ol / l), placed in an electrolytic polymerization liquid consisting of water, the polymerization initiation electrode is brought close to the conductive layer, and a constant voltage of 1.5 V is applied to the polymerization initiation electrode for 50 minutes to carry out an electrolytic polymerization reaction, An electropolymerized polypyrrole layer 4 was formed.

The etched foil having the electrolytically polymerized polypyrrole layer formed thereon was washed with water for 10 minutes, and the concentrated nonionic surfactant polyethylene glycol alkyl ether concentrated solution was immersed in a solution diluted 20 times with water for 5 minutes to form an electrolytically polymerized polypyrrole layer. The surface was treated, washed with water for another 10 minutes, and dried at 105 ° C. for 5 minutes. Next, water-dispersible colloidal graphite is applied onto the electrolytically polymerized polypyrrole layer to form a carbon layer 5
And a silver paint layer 6 were further provided to obtain a capacitor. The number of manufactured pieces is 10.

The obtained capacitor was kept at 10 V for 1 hour, and
After aging at 6.3 V for 1 hour, the initial capacity and loss factor at 120 Hz were measured. The average value of the measured values is shown in (Table 1).

For comparison, pyrrole (0.25 mol /
l), sodium triisopropylnaphthalene sulfonate (0.10 mol / l), electrolytic polymerization of m-hydroxybenzoic acid (0.15 mol / l) and p-nitrophenol (0.03 mol / l) as additives, and water 1.5 in liquid
A constant voltage of V is applied for 40 minutes to carry out an electrolytic polymerization reaction, and 1
Immediately after washing with water for 0 minutes without treatment with a surfactant, 105 ° C
Repeat the procedure as above except that the capacitors were dried for 5 minutes.
Individual pieces were prepared and the same measurement was performed. The average value of the measured values is shown in Table 1 as Comparative Example 2.

In Comparative Example 2, the data of the capacitor not treated with the surfactant is shown, but in comparison with this, in Example 6, the deposit was removed by the treatment with the surfactant,
The wettability of water-dispersible colloidal graphite is also increased, and as a result, the loss coefficient is greatly reduced. The capacities of Example 6 and Comparative Example 1 are almost the same. From this, there is no fear that the capacity will decrease even if the treatment is performed with a surfactant.

The initial capacity and loss at 120 Hz and impedance at 400 kHz are shown in Table 1.
Show. Note that these are almost the same characteristics as the solid electrolytic capacitor produced by providing the cathode on the electrolyte forming portion of one valve metal foil before lamination, and a nonpolar solid electrolytic capacitor having extremely excellent characteristics was obtained. . In the example,
Although only the case where the insulating layer of the partition is formed by pasting a polymer film is described, it can be formed by applying a polymer substance that is cured by heating or a substance that is solidified by volatilization of a solvent, and the formation means can The present invention is not limited.

In the embodiment, only the case where four valve metal foils having an electrolyte layer are laminated is described, but any other number may be laminated as long as it is two or more.
The number of stacked layers can be selected according to the required capacity. From the concept of a non-polar capacitor, it is desirable that the capacities of both electrodes are approximately the same, and from that meaning it is desirable that both electrodes be configured in the same shape and the number of laminated layers be the same, but valve metals with different partial areas where the electrolyte layer is formed With foil,
It is also possible to adopt a configuration in which the capacities are made equal without adjusting the number of laminated layers.

In the embodiment, the case where the adjacent portions of the valve metal foil on which the electrolyte is not formed are laminated in different directions by 180 ° has been described. However, the present invention is not limited to that direction.

In the examples, only the case where the silver paint layer is used for laminating the portion where the electrolyte layer is formed is described, but other conductive adhesives can be used.

In the examples, the electrode formation is described only when welding is performed, but the end face may be formed by metal spraying, plating, or silver paint, and the present invention is not limited to this means.

In the examples, only the case where a conductive polymer having pyrrole or N-methylpyrrole as a repeating unit was used for the electrolyte was described, but a conductive polymer obtained from thiophene, aniline or their derivatives was used. Can be used, and the present invention is not limited to the type.

In the examples, only the case where isopropyl naphthalene sulfonate is used as the supporting electrolyte and water is used as the solvent has been described, but other compounds can be used and the present invention is not limited to these types.

In the examples, only the case where polyethylene glycol alkyl ether was used as the surfactant was described, but if it is a nonionic surfactant,
Other surfactants can also be used.

In the examples, only the case where p-nitrophenol and m-hydroxybenzoic acid were added to the electrolytic polymerization solution as additives was described. However, even when other phenol-based additives were added, high conductivity was obtained. The surfactant treatment is effective as a means for removing impurities generated on the surface of the molecular layer.

In the examples, only the case where pyrrole was used as the polymerizable monomer was described, but other polymerizable monomers may be used as long as the conductive polymer has an electric conductivity that can be used as an electrode. it can.

In the examples, only the case where the valve metal aluminum is used as the anode has been described, but as is clear from the gist of the present invention, other substances may be used as long as they have electric conductivity that can be used as the electrode. It is possible.

In the examples, only the case where aluminum oxide is used as the dielectric is described, but other substances that can be used as the dielectric of the capacitor such as electrodeposited polyimide can also be used.

In the examples, only the case where the conductive polymer is used for one electrode has been described, but it is also possible to use the conductive polymer for the other electrode. It is not limited by the number of electrodes using the polymer.

[0054]

INDUSTRIAL APPLICABILITY As described above, the present invention provides an insulating layer for partitioning on a predetermined portion of a foil-shaped or plate-shaped valve metal surface,
An electrolyte layer mainly composed of a dielectric layer and a conductive polymer is sequentially provided on one portion divided by the insulating layer, and a plurality of the valve metals, and an electrolyte layer divided by adjacent insulating layers of each valve metal. The portions provided with the electrolyte layers are electrically bonded to each other and laminated so that the other portions not provided with are placed in the two directions so as not to overlap each other, and are placed in the two directions. Provided are a solid electrolytic capacitor having both electrodes formed on a portion of a valve metal where an electrolyte is not provided, and a method for manufacturing the same. A non-polar solid electrolytic capacitor having excellent frequency characteristics can be easily constructed and manufactured. It was made possible.

Further, the present invention provides a method for producing manganese dioxide, which assists the growth of an electropolymerized conductive polymer, by reducing potassium permanganate. The conditions are mild and corrosive gas is not generated. Therefore, it is possible to obtain a capacitor in which the dielectric foil film is less damaged.

Furthermore, the present invention provides a method for producing the electrolytically polymerized conductive polymer film, which is then washed with a surfactant on the surface thereof to prevent peeling from the graphite layer provided thereon. , A capacitor having a small loss coefficient can be obtained.

[Brief description of drawings]

FIG. 1 is a plan view of a foil valve metal portion in a first embodiment of the present invention.

FIG. 2 is a dielectric film according to the first embodiment of the present invention,
Cross-sectional view of a foil valve metal on which a conductive polyelectrolyte and a graphite layer are sequentially formed.

FIG. 3 is a conceptual diagram showing a configuration of a capacitor element in the first embodiment of the present invention.

[Explanation of symbols]

1 Insulation layer for partitioning a portion where an electrolyte layer is formed and a portion where an electrolyte layer is not formed 2 A portion where an electrolyte layer of a foil or plate valve metal is formed 3 A portion where an electrolyte layer of a foil or plate valve metal is not formed 4 Dielectric Body film layer 5 Conductive polymer electrolyte layer 6 Graphite layer 7 Silver paint layer 8 Electrode lead

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshikuni Kojima 3-10-1 Higashisanda, Tama-ku, Kawasaki-shi, Kanagawa Matsushita Giken Co., Ltd.

Claims (19)

[Claims] 1. An electrolyte mainly composed of a dielectric layer and a conductive polymer in one portion divided by the insulating layer by providing an insulating layer for partitioning on a predetermined portion of the surface of the foil-shaped or plate-shaped valve metal. The layers are sequentially provided, and the plurality of valve metals are divided by the adjacent insulating layers of the respective valve metals, and the other portion where the electrolyte layer is not provided is located in two directions so as not to overlap each other. A capacitor in which parts provided with layers are correspondingly electrically bonded and laminated, and both electrodes are formed in parts where the electrolyte of the valve metal located in the two directions is not provided. 2. The capacitor according to claim 1, wherein the dielectric layer is an oxide of a valve metal. 3. The capacitor according to claim 1, wherein the valve metal is one selected from aluminum and tantalum. 4. The capacitor according to claim 1, wherein the conductive polymer film has a repeating unit of a polymerizable monomer that can be a conjugated double bond polymer. 5. The capacitor according to claim 1, wherein the polymerizable monomer is composed of at least one of pyrrole, thiophene, aniline and their derivatives. 6. The capacitor according to claim 1, wherein a conductive adhesive is used to electrically connect the portions provided with the electrolyte. 7. An electrolyte mainly composed of a dielectric layer and a conductive polymer in one portion divided by the insulating layer by providing an insulating layer for partitioning on a predetermined portion of the surface of the valve-shaped or plate-shaped valve metal. Layers are sequentially provided, and the valve metal consisting of a plurality of sheets is
The portions provided with the electrolyte layers are made to correspond to each other so that the other portion which is divided by the insulating layer and is not provided with the electrolyte layer is adjacent to each other in two directions not in the same direction, and has electrical conduction. A method of manufacturing a capacitor in which both electrodes are formed in such a manner that the two electrodes are formed in a portion where the electrolyte of the valve metal that is positioned in the two directions is not provided. 8. The method of manufacturing a capacitor according to claim 7, wherein the dielectric layer is provided by anodic oxidation of the valve metal. 9. The method for producing a capacitor according to claim 7, wherein the conductive polymer film is formed by electrolytic polymerization in a liquid medium in which at least the polymerizable monomer and the supporting electrolyte are dissolved or dispersed. 10. The method for producing a capacitor according to claim 7, wherein the polymerizable monomer is one selected from pyrrole, thiophene, aniline and derivatives thereof. 11. The method of manufacturing a capacitor according to claim 7, wherein silver paint is used for the laminate having electrical connection. 12. The method according to claim 7, wherein the valve metals positioned in two directions are electrically connected to each other and both electrodes are formed by at least one selected from welding, thermal spraying, metal plating and silver paint. Manufacturing method of capacitors. 13. A method for producing a capacitor, wherein an electroconductive polymer layer electrolyte is formed by electrolytic polymerization through a manganese dioxide layer formed by reduction of permanganate provided on the surface of a dielectric. 14. The method for producing a capacitor according to claim 13, wherein the formation of manganese dioxide on the surface of the dielectric is performed in a permanganate aqueous solution. 15. The method for producing a capacitor according to claim 13, wherein the formation of manganese dioxide on the surface of the dielectric is performed under the condition of heating at 200 ° C. or higher with an aqueous solution of permanganate attached. 16. A method for producing a capacitor, which comprises treating a surface of a conductive polymer layer with a surfactant and then sequentially providing a carbon layer and a silver paint layer. 17. The method for producing a capacitor according to claim 16, wherein the surfactant is a nonionic surfactant. 18. The conductive polymer layer formed on the dielectric film by electrolytic polymerization from an electrolytic solution containing at least a polymerizable monomer, a supporting electrolyte and a phenolic additive is used as an electrode. Method of manufacturing capacitors 19. The method for producing a capacitor according to claim 18, wherein the polymerizable monomer is pyrrole or a derivative thereof, and the supporting electrolyte is naphthalene sulfonate having an alkyl substituent.