JPS61281513A - Electrolytic capacitor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [□Technical Field of the Invention] The present invention relates to an electrolytic capacitor, particularly a 7.7° 8.8-
The subject matter is an electrolytic capacitor that has an organic semiconductor such as tetracyanoquinodimethane salt in the electrolyte. □ [Technical background of the invention and its problems] Generally, electrolytic capacitors are made of aluminum (A1) or tantalum (Ta).
The valve metal is used as an anode, an anodic oxide film (hereinafter referred to as oxide film) formed on its surface is used as a dielectric, and a cathode is arranged facing each other with an electrolyte layer interposed on the oxide film. There is. These electrolytic capacitors are broadly divided into those using a liquid electrolyte (hereinafter referred to as electrolyte) and those using a solid electrolyte. used in circuits.

Important characteristics in evaluating electrolytic capacitors are capacitance fu, tan δ, and leakage current. capacitance C,
Tan δ is generally expressed by the following formula.

C=Kx (S/d)-to-X<S/V)...(1
) tan δ −ω CR=a>C(R+ 10 R2
) -(2) However, K, - is a constant, S is the electrode area,
d is the oxide film thickness, ■ is the oxide film withstand voltage, ω is the angular frequency, R is the equivalent series resistance, R1 is the resistance due to the oxide film,
R2 is resistance caused by the electrolyte, electrodes, etc.

By the way, in order to realize a small, large-capacity electrolytic capacitor, it is necessary to increase the electrode surface taS and make the oxide film withstand voltage V as close to the rated voltage of the capacitor as possible, as is clear from equation (1) above. is necessary. However, the oxide film is not inherently perfect and has many defects within the film, as well as areas where the film is damaged due to mechanical or thermal stress during the capacitor manufacturing process. There is. These defective parts of the oxide film increase the leakage current of the capacitor and cause an undesirable drop in withstand voltage. Therefore, the electrolyte must have the ability to repair defective parts of the oxide film, reduce and stabilize leakage current, and if it does not have this ability, the oxide film will have an excessive withstand voltage compared to the rated voltage. must be used. Further, in order to increase the electrode area S, the surface of the anode body is generally designed to have a WJ structure with fine irregularities. However, if the electrolyte layer does not cover the entire surface of these irregularities, the effective electrode area S cannot be increased and, on the contrary, the characteristics deteriorate.

On the other hand, in order to reduce tan δ, which is the loss of the capacitor, it is necessary to reduce the equivalent series resistance R as shown in equation (2) above. Of the equivalent series resistance R, the resistance R1 due to the oxide film depends on the properties and formation conditions of the oxide film itself, and it is not easy to reduce this resistance. Furthermore, since the equivalent series resistance R in the high frequency range is dominated by the resistance R2 caused by the electrolyte etc., if this resistance R2 can be made small, tan δ can be reduced over a wide frequency range. The resistance R2 naturally depends on the conductivity of the electrolyte, but it is also greatly influenced by the state of formation of the electrolyte.

From the above points of view, the preparation of electrolytes for electrolytic capacitors is
The necessary conditions are as follows.

■Have sufficient anodic oxidation properties to repair and form (reform) the weathered film.

■Low electrolyte resistance, which greatly affects the resistance component of electrolytic capacitors.

(2) The coverage of the entire surface of the oxide film is high, and a dense electrolyte layer that adheres to the oxide film with low resistance can be formed.

Here, a conventional electrolytic capacitor will be explained.

Aluminum electrolytic capacitors are commonly used as capacitors using electrolytes, and the electrolyte used is, for example, an electrolyte solution made of dylene glycol-organic acid salt.

The anode and cathode are made of aluminum foil that has been electrochemically etched to increase the surface area, and the anode foil has an oxide film that has a withstand voltage approximately 1.5 times the rated voltage of the capacitor. has been done. The anode foil and the cathode foil are twisted with a separator (isolating paper) sandwiched between the two parts, and the electrolytic solution is impregnated into the separator by, for example, a vacuum impregnation method, so as to coat the oxide film and the positive electrode.

It is filled between the cathodes. Aluminum like this.

As shown in FIG. 3, the electrolytic solution 4 can be sufficiently impregnated into the fine irregularities of the Sihi film 2 on the highly etched aluminum anode foil 1, and the oxide film 2 can be completely impregnated with the electrolyte 4. Almost the entire surface can be covered with the electrolytic solution 4.

In this way, the coverage of the electrolyte on the oxide film is extremely high at over 90%1, and because the electrolyte has excellent anodic oxidation properties, the oxide film has a withstand voltage exceeding the rated voltage. is unnecessary. Therefore, it is possible to reduce the size and increase the capacity of the capacitor, but the resistance of the 1.mu. distillate is relatively large, and there is a limit to reducing the tan δ of the capacitor. Furthermore, since the conduction mechanism is ion conduction, it has the disadvantage of poor low-temperature characteristics and high-frequency characteristics.

On the other hand, tantalum solid electrolytic capacitors are widely known as capacitors using solid electrolytes, and manganese dioxide (Mn'
02) is used as an isoelectrolyte. For the anode, a porous anode body made by sintering a molded body of tantalum powder is used, and an oxide film having a withstand voltage of about five times the rated voltage is formed on the surface of the anode body. The above Mn 02 solid electrolyte layer was prepared by immersing the anode body in a manganese nitrate solution at approximately 300°C.
is formed by repeating the thermal decomposition process several times or more. A cathode layer made of silver paste and solder is provided.

In the electrolytic capacitor using the solid electrolyte described above, since the electrical resistance of Mno2 is low and electronic conduction is the main feature, a small and reliable capacitor with excellent low temperature characteristics can be obtained. However, damage to the oxide film during the thermal decomposition process during the formation of the MrlO2 layer is unavoidable, and MnO2 has almost no anodic oxidation property. Therefore, in order to prevent an increase in leakage current and a decrease in withstand voltage due to damage to these films or defects existing in the film, even if an oxide film is used that has an excessive withstand voltage relative to the rated voltage, it is necessary to It has the disadvantage that it requires anodic oxidation using an electrolytic solution every time it undergoes thermal decomposition, which requires a complicated process. In addition, the coverage of the oxide film of the Mn02 layer is significantly lower than that of the electrolyte, making it possible to effectively utilize the expensive tantalum porous anode body. This is a drawback.

Furthermore, an attempt to use an organic semiconductor with high T1 conductivity as a solid electrolyte in place of the MnO2 solid electrolyte has been proposed, and 7.
7.8.8-tetracyanoquinodimethane (hereinafter TCNQ)
Research is underway on solid electrolytic capacitors using TCNQ salt, which has an anion of . TCNQ salt is 1
It is a microcrystal in the form of a fine powder that exhibits a low resistance of 0-2 to 101 Ωcm, and it has been the subject of debate until now as to whether it can be formed as a solid electrolyte layer.

Methods for forming solid electrolytes using TC'NQ salts that have been proposed to date can be broadly classified into two types. First, the first method is disclosed in, for example, US Pat. No. 3,214.648, in which TCNQ salt is dissolved in a solvent and the TCNQ
This method forms a solid electrolyte layer made of T C'NQ salt by applying a Q salt solution to an anode body and then removing the solvent by scattering it. The second is Japanese Patent Publication No. 5'7-1'7'392
8 and JP-A-58-17609, the TCNQ salt is heated to a temperature above its melting point.
This is a method in which a solid electrolyte layer made of T'CNQ salt is formed by melting and liquefying the T'CNQ salt at high temperature, impregnating it into an anode body or a wound horizontally wound element, and then cooling and assimilating it.

However, all of the above methods focus only on the high electronic conductivity of TCNQPA as a picture element, and sufficient characteristics have not yet been achieved for the electrolyte A of a capacitor. That is, the important problem is that it is significantly inferior to electrolytes in terms of anodic oxidation properties and oxide film coverage, which are necessary conditions for electrolytes. In particular, requiring an electronically conductive substance to have cationic oxidation properties is a serious problem for Furi Kiri.

The above-mentioned anodic oxidation property and oxidation film coverage will be explained in detail. Regarding anodic oxidation, the oxide film has many internal defects as mentioned above, and the oxide film is also severely damaged during the manufacturing process.
If defects in the film are not repaired after forming the solid electrolyte layer made of salt and before providing the capacitor as a product, the capacitor will become unusable due to a decrease in withstand voltage and an increase in leakage current.

Therefore, in order to reduce and stabilize the leakage current, it is necessary to perform a stabilization treatment generally called aging to repair and form the oxide film (reformation). Aging is performed by applying a DC voltage to the capacitor for an appropriate period of time, but since the above-mentioned 1TCNQ salt is an electronically conductive material and has poor anodic oxidation properties, in many cases conventional solid state using MnO2 is used. Not only does it require an extremely long aging process like electrolytic capacitors, but in order to achieve reliability, it is necessary to use an oxide film that has a withstand voltage that exceeds the rated voltage. .

Regarding the coverage of the oxide film, the method using a solvent as in U.S. Pat. No. 3,214,648,
In order to suppress thermal deterioration of the oxide film, it was necessary to process at a temperature of 125° C. or lower. However, at such temperatures, the TCNQ salt concentration in the TCNQ salt solution is at most 10
It is limited to an extremely low value of %. Therefore, solid electrodes of TCNQ salt can be deposited inside the micropores of highly etched electrodes or porous sintered bodies for electrolytic capacitors. It is completely impossible to form a trading layer. On the other hand, JP-A-57-1
In the melting method as disclosed in Japanese Patent Application Laid-open No. 73928 and Japanese Patent Application Laid-open No. 17609/1980, the viscosity of the TCNQ salt in the 11-solution state is low enough to penetrate into the micropores of the anode body. In addition, TCNQ is
It is necessary to carry out the impregnation treatment in an extremely short period of time to avoid deterioration of the salt. Therefore, when the TCNQ salt solid electrolyte layer 3 is formed on the oxide film 2 on the highly etched aluminum anode foil 1 shown in FIG. A portion 6 remains where the layer 3 is not formed, and a sufficient coverage cannot be obtained. For this reason, the capacitance of the capacitor can only be about 70% of the desired capacitance, and the resistance component of the capacitor increases, making it impossible to obtain a sufficiently low tan δ.

[Objective of the Invention] In view of the above-mentioned points, an object of the present invention is to form an electrolyte layer having high lightning conductivity, excellent anodic oxidation property, and high coverage with respect to an oxide film. Our objective is to provide an excellent, inexpensive, and highly reliable electrolytic capacitor.

[Summary of the Invention] The present invention provides an electrolyte that is interposed between an anode body in which an oxide film is formed on a valve metal such as aluminum or tantalum and a cathode body disposed opposite to the anode body. It is composed of an electrically conductive mixture consisting of a solvent and a solvent. This forms the electrolyte into a solid-liquid mixed state consisting of an organic semiconductor and a solvent.

[Embodiments of the Invention] Examples of the electrolytic capacitor according to the present invention will be described below. In the following embodiments, a case will be described in which the present invention is applied to a capacitor element having a wound structure used in a general aluminum electrolytic capacitor.

First, a first embodiment of the present invention will be described.

First, an aluminum foil is electrochemically etched and anodized in an aqueous phosphate solution to form an oxide film on the surface, and then a lead wire for drawing out the electrode is attached to produce an aluminum anode foil.

On the other hand, after etching the aluminum foil, a lead wire for drawing out the electrode was prepared. , manufacture capacitor elements. In this case, an element with a rating of 25,2.2 .mu.m is manufactured.

On the other hand, the TCNQ salt forming the conductive mixture electrolyte is "(N-n-butylisoquinolinium)" (TCNQ), which is composed of N-n-butylisoquinolinium and TCNQ.
-(TCNQ) salt is used, and γ-butyrolactone is used as the solvent.

The method for obtaining an electrolytic capacitor by forming a conductive mixture consisting of (N-n-butylisoquinolinium) + (TCNQ)-(TCNQ) salt and γ-butyrolactone as an electrolyte layer on the above capacitor element is as follows. .

First, (If-n-butylisoquinolinium) + (TC
Prepare a conductive mixture in which γ-butyrolactone is added to NQ) (TCNQ) salt. In this mixture state, it is very difficult to form an electrolyte that is sufficient for the sensor element, so this implementation was carried out. In the example, these mixtures are heated to a temperature at which they completely dissolve, resulting in a high concentration of TC.
The NQ salt solution is impregnated into a capacitor element and cooled to form a conductive mixture electrolyte consisting of recrystallized TCNQ salt and γ-butyrolactone.

In this case, if the amount of γ-butyrolactone increases, dissolution is possible at a relatively low temperature, and in this example, for example, γ-butyrolactone
-175 for those containing 50% butyrolactone
10% by weight was carried out at 210°C. The impregnation time needs to be adjusted depending on the viscosity of the solution, but it is about 15 seconds or more.
It can be done in 50 seconds.

Subsequently, the capacitor element on which the conductive mixture electrolyte layer was formed was placed in an aluminum case, and the opening was sealed using butyl rubber and epoxy resin to produce an electrolytic capacitor.

FIG. 1 shows an enlarged view of the vicinity of the anode foil after the formation of the conductive mixture electrolyte. As shown in this figure, the conductive mixture electrolyte layer 7 is applied to the oxide film 2 on the highly etched aluminum anode foil 1 as a highly concentrated TCNQ salt solution consisting of TCNQ salt and γ-butyrolactone within the capacitor element. It is formed by impregnating it with water and cooling it. The conductive mixture electrolyte layer 7 is made of recrystallized TCNQ salt 3
The electrolyte layer is composed of a solution 5 consisting of , T CN o t= and γ-butyrolactone, and has electronic conductivity and ionic conductivity. As a result, the viscosity is lower than in the conventional example in which the TCNQ salt is melted alone, and it is possible to impregnate the deep part of the fine etching holes. A monoconductive mixture electrolyte layer 7 is formed which exhibits average conductivity.

In order to compare with the electrolytic capacitor of the first embodiment described above, using the same capacitor element, (N-n-butylisoquinolinium) "(TCNQ)"(TCNQ>salt was used alone at 250℃. After melting and impregnating, a conventional solid electrolytic capacitor was manufactured in the same manner.Furthermore, using the same capacitor element, 78% by weight of ethylene glycol and 1
A conventional aluminum electrolytic capacitor was impregnated with an electrolytic solution consisting of 2% by weight ammonium adipate and 10% by weight water and sealed with an aluminum case and butyl rubber.

Subsequently, the capacitors of this embodiment and the conventional example are subjected to aging in order to repair the oxide film and reduce and stabilize leakage current. The aging time was set to 1 hour, which is the usual condition for aluminum electrolytic capacitors.

As is clear from the above table, the leakage current of the electrolytic capacitor using the conductive mixture of this example is significantly smaller than that of the conventional TCNQ salt solid state electrode.
In this example, (N-n-butylisoquinolinium> +
It has been found that a conductive mixture electrolyte consisting of (TCNQ)-(TCNQ) salt and γ-butyrolactone exhibits excellent anodic oxidation properties comparable to that of an electrolytic solution.

In this way, if the electrolyte has excellent anodic oxidation properties, defects in the oxide film can be repaired instantly, making it possible to bring the FjJ voltage of the oxide film closer to the rated voltage of the oxide film. Therefore, according to the above formula (1), it is possible to realize a smaller capacitor and a larger capacity.

Furthermore, as in the production of conventional solid electrolytic capacitors, each time a solid electrolyte is formed, the oxide film is anodized in an electrolytic solution, or the oxide film is repaired before the solid electrolyte is formed. There is no need to do this, and the process can be simplified to the extent of ■, leading to one reduction in product loss. on the other hand,
Although the same aging was performed, the T of the conventional example
The leakage current of a CNQ salt solid electrolytic capacitor is extremely large, and cannot be put to practical use as it is. Leakage current is a major factor that affects capacitor characteristics, and if the leakage current is large or the stability is lacking, for example, a capacitor of 437. II [I. In order to reduce and stabilize this leakage current in the conventional example, an extremely long aging time of, for example, 48 hours is required.

FIG. 2 shows the relationship between γ-butyrolactone in the lightning conductive mixture electrolyte, capacitance [μF] and tan δ [%] at 20° C. and 120 Hz. The electrolytic capacitor of this example containing γ-butyrolactone has a significantly larger capacitance compared to a solid electrolytic capacitor manufactured by a conventional method using TCNQ salt as a solid electrolyte, and furthermore, γ-butyrolactone contains 40 ffx, m% or less. These have equivalent or better properties in terms of tan δ.

Table 2 shows the electrolytic capacitor of this example and the TC of the conventional example.
Regarding NQ salt solid electrolytic capacitors and aluminum electrolytic capacitors using electrolyte solution, we will explain them by citing the features of 24 monolithic surfaces.

Below is the margin ζ "However, in the table above, (N-n-butylisoquinolinium)"
(TCNQ)” (TCNQ) salt (NnBu IQ)T
It is abbreviated as CNQH, and the equivalent series resistance R is abbreviated as ESR. Capacitance (μF), tanδ (%)
and FSR (Ω) are both measurement results at 20° C. and 120 Hz.

As is clear from Table 2, (N-n-butylisoquinolinium)+(TCNQ)-(TCN'Q) salt 99.5
~30% by weight and γ-butyrolactone 0°5~70% by weight
The electrolytic capacitor according to the embodiment of the present invention has a significant capacitance increase effect of ~30% compared to the conventional solid-state wl capacitor, and in this respect, the conductive mixture electrolyte of the present invention is equivalent to an electrolytic solution. It is a characteristic of

On the other hand, the tan δ and ESR are much better than those of conventional electrolytic capacitors using an electrolytic solution, and exhibit characteristics equal to or better than those of the TCNQ salt solid electrolyte.

Table 3 shows the low temperature characteristics of the typical capacitor of the above embodiment, and Table 4 shows the high frequency characteristics.

However, in the above table, capacitance (μF) and tanδ (%)
indicates the measured value at 20℃ and 120Hz, and the rate of change in capacitance is 2% of the capacitance at -40℃ and 120Hz.
It shows the rate of change in capacity at 0°C and 12011z.

Margins below However, in the table above, capacitance (μF), tan δ (%
) indicates the measured value at 20°C and 10Kl-Lz, and the rate of change in capacitance ΔC (%) is J It shows the rate of change. Also, ESR (Ω) is 20℃.

The equivalent series resistance value at 100KHz is shown.

As is clear from Tables 3 and 4, the electrolytic capacitor according to the embodiment of the present invention using a conductive mixture electrolyte outperforms the conventional electrolytic capacitor using an electrolyte in terms of low temperature characteristics and high frequency characteristics. Depending on the composition of the conductive mixture, it has properties equivalent to or better than the conventional solid electrolyte using TCNQ salt solid electrolyte VR1.

As described above, the electrolytic capacitor of the present invention has (N-n-butylisoquinolinium)"(TCNQ)-(TCNQ)
Because the conductive mixture electrolyte layer is formed by impregnating salt in an extremely highly concentrated solution, a high coverage rate that could not be achieved with conventional solid electrolytic capacitors can be achieved with a single impregnation operation. . Furthermore, this conductive mixture electrolyte exhibits anodic oxidation properties comparable to that of an electrolytic solution, and the resulting electrolytic capacitor of the present invention has low-temperature characteristics and high-frequency characteristics similar to those of solid electrolytic capacitors, and can also be called a solid-liquid electrolytic capacitor. . However, the content of γ-butyrolactone in the conductive mixture electrolyte is 0.5% by weight.
If the amount is extremely low (less than 70% by weight), it is disadvantageous in terms of anodic oxidation properties and coverage, and if it exceeds 70% by weight, as can be seen from FIG. Since the proportion of carbon in the electrolyte increases, ionic conduction becomes dominant, resulting in a decline in low-temperature characteristics and high-frequency characteristics.

Next, an example of an electrolytic capacitor using a conductive mixture electrolyte having a composition different from that of the first example will be described. In this example, an electrolytic capacitor was manufactured in the same manner as in the first example using the same condenser element, and the capacitance (μF), tan δ (%),
Table 5 shows the results of measuring each characteristic of leakage current (μA).

1 Mi 3- However, the above table is the measured value at 20° C. and 120 tlz.

It is clear that the capacitors using the conductive mixture electrolytes shown in Table 5 exhibited characteristics equivalent to those of the first example, and that the electrolytic capacitors of the present invention are extremely superior. In addition, quinolinium (TCN) shown in Table 5
Q) iTCNQ> Because salt does not melt even when heated to high temperatures, or decomposes at the same time as it melts, it is considered difficult to form a solid electrolyte by melting as shown in the comparative conventional example of the first embodiment. However, addition of a solvent enabled electrolyte formation. Furthermore, as shown in Table 5, an effective electrolyte can also be formed using a conductive organic semiconductor using a TCNQ derivative such as 2-methylTCNQ as an acceptor. Note that capacitors using an MS mixture containing a large amount of triethylene glycol as an electrolyte tend to have poor low-temperature characteristics, but this can be easily improved by adjusting the content.

The electrolyte mixture of the present invention only needs to be composed of an organic semiconductor having high conductivity and a solvent, and is not limited to those listed in Examples 1-12.

Moreover, it is also possible to use a mixture of two or more types of organic semiconductors and solvents instead of relying on one type. Furthermore, it is also possible to configure the electrolyte to contain substances other than the organic semiconductor and its solvent. Furthermore, the WJ structure of the capacitor element is not limited to capacitors using an anode body whose surface has been enlarged by etching, but can also be applied to capacitors using a sintered anode body. Further, the anode body is not limited to aluminum, but a configuration using a valve metal such as tantalum is also possible, and the cathode body can also be configured using other metals.
'Furthermore, in the above embodiment, the mixture electrolyte layer is formed by immersing the condenser element in the mixed fragrance solution, but the present invention is not limited to this, and it is possible to apply the mixture solution to the anode body. It may be formed by

[Effects of the Invention] As described above, in the electrolytic capacitor of the present invention, the electrolyte formed between the anode body on which the oxide film is formed and the cathode body disposed opposite thereto is composed of an organic semiconductor and a solvent. Because it is a conductive mixture composed of electrolytes, it is possible to realize compactness and large-scale development due to the extremely high covering properties and remarkable anodic oxidation properties of this electrolyte mixture. Furthermore, in order to maintain the high conductivity of the organic semiconductor, excellent low-temperature characteristics and high-frequency characteristics can be achieved. Therefore, it is possible to provide a highly reliable, superior electrolytic capacitor that has the advantages of both conventional electrolytic capacitors using an electrolytic solution and solid electrolytic capacitors using a solid electrolyte. Furthermore, the amount of organic semiconductors used, such as T'CNQ salts, which are currently very expensive, can be reduced by adding a solvent to improve properties, which is advantageous in terms of cost.

[Brief explanation of drawings]

FIG. 1 is an enlarged sectional view of the vicinity of the anode foil in an electrolytic capacitor showing a first embodiment of the present invention, and FIG.
A graph showing the relationship between capacitance and tan δ with respect to the amount of γ-butyrolactone in Examples, FIG. 3 is an enlarged cross-sectional view showing the state near the anode foil in an electrolytic capacitor using a conventional electrolyte, and FIG. FIG. 2 is an enlarged cross-sectional view showing the state of the vicinity of an anode foil in a conventional solid electrolytic capacitor using a CN'Q salt solid electrolyte. 1... Aluminum anode foil 2... Oxide film 3.
... TGNQ salt 5 ... Solution consisting of TCNQ salt and γ-butyrolactone 7 ... Conductive mixture electrolyte layer 1
Meeting nnl figure 3

Claims (16)

[Claims] (1) An electrolyte interposed between an anode body with an oxide film formed on the metal surface and a cathode body disposed opposite to the anode body,
An electrolytic capacitor characterized in that it is formed of a conductive mixture consisting of at least an organic semiconductor and its solvent. (2) The electrolytic capacitor according to claim 1, wherein the conductive mixture comprises 99.5 to 30% by weight of an organic semiconductor and 0.5 to 70% by weight of a solvent. (3) The electrolytic capacitor according to claim 1 or 2, wherein the organic semiconductor is a salt consisting of 7,7,8,8-tetracyanoquinodimethane or a derivative thereof. (4) The organic semiconductor has quinolinium or quinolinium substituted at the N-position with an n-propyl group as a cation and 7,7,8,8- as an anion. The electrolytic capacitor according to claim 1, 2, or 3, which is a tetracyanoquinodimethane salt. (5) The organic semiconductor has an n-butyl group or is
A patent characterized in that it is a 7,7,8,8-tetracyanoquinodimethane salt having an o-butyl group-substituted isoquinolinium as a cation and 7,7,8,8-tetracyanoquinodimethane as an anion. An electrolytic capacitor according to claim 1, 2, or 3. (6) The organic semiconductor has quinolinium substituted with a methyl group at the N position as a cation, and 2-methyl-7,7,8,
The electrolytic capacitor according to claim 1, 2, or 3, wherein the electrolytic capacitor is a salt having 8-tetracyanoquinodimethane as an anion. (7) The organic semiconductor is a 7,7,8,8-tetraconductor having quinolinium or quinolinium substituted at the N-position with an n-propyl group as a cation and 7,7,8,8-tetracyanoquinodimethane as an anion. cyanoquinodimethane salt,
7,7,8,8-tetracyanoquinodimethane salt in which the N-position is an isoquinolinium substituted with an n-butyl group or an isobutyl group as a cation and 7,7,8,8-tetracyanoquinodimethane as an anion; Using quinolinium substituted with a methyl group at the N position as a cation, 2-methyl-7, 7, 8,
The electrolytic capacitor according to claim 1, 2, or 3, characterized in that it is a mixture of two or more types of salts having 8-tetracyanoquinodimethane as an anion. (8) A patent characterized in that the solvent is one or a mixture of two or more of γ-butyrolactone, diethylene glycol mono-n-butyl ether, benzyl alcohol, triethylene glycol, and glital nitrile. An electrolytic capacitor according to claim 1 or 2. (9) The conductive mixture may contain the organic semiconductor (N-n
-butylisoquinolinium)^+(TCNQ)^-(T
9. The electrolytic capacitor according to claim 1, 2, 3, 5, or 8, wherein the electrolytic capacitor is a mixture of CNQ) salt and γ-butyrolactone as the solvent. (10) The conductive mixture may contain the organic semiconductor (N-
n-butylisoquinolinium)^+(TCNQ)^-(
The electrolytic method according to claim 1, 2, 3, 5, or 8, wherein the electrolytic method is a mixture of TCNQ) salt and diethylene glycol mono-n-butyl ether as the solvent. capacitor. (11) The conductive mixture may contain the organic semiconductor (N-
n-butylisoquinolinium)^+(TCNQ)^-(
9. The electrolytic capacitor according to claim 1, 2, 3, 5, or 8, wherein the electrolytic capacitor is a mixture of TCNQ) salt and glutaronitrile as the solvent. (12) The conductive mixture may contain the organic semiconductor (N-
isobutylisoquinolinium)^+(TCNQ)^-
9. The electrolytic capacitor according to claim 1, 2, 3, 5, or 8, wherein the electrolytic capacitor is a mixture of (TCNQ) salt and triethylene glycol as the solvent. (13) The conductive mixture may contain the organic semiconductor (N-
isobutylisoquinolinium)^+(TCNQ)^-
The electrolytic capacitor according to claim 1, 2, 3, 5, or 8, which is a mixture of (TCNQ) salt and benzyl alcohol as the solvent. (14) The conductive mixture may contain the organic semiconductor (N-
n-propylquinolinium)^+(TCNQ)^-(T
The electrolytic capacitor according to claim 1, 2, 3, 4, or 8, wherein the electrolytic capacitor is a mixture of CNQ) salt and γ-butyrolactone as the solvent. (15) The conductive mixture is a mixture in which the organic semiconductor is a (quinolinium)^+(TCNQ)^-(TCNQ) salt and the solvent is γ-butyrolactone. 8. The electrolytic capacitor according to item 2, item 3, item 4, or item 8. (16) The conductive mixture may contain the organic semiconductor (N-
methylquinolinium)^+(2-methylTCNQ)^-
(2-MethylTCNQ) salt and the solvent is γ-butyrolactone. capacitor.