JP2008153628A - Composition for manufacturing conductive polymer capacitor, and method of manufacturing conductive polymer capacitor using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a conductive polymer capacitor having a high breakdown voltage and a low impedance, as well as a composition for manufacturing the conductive polymer capacitor. <P>SOLUTION: The problem is solved by: the composition for manufacturing the conductive polymer capacitor including conductive polymer monomer (A) and an ionic liquid (B) containing sulfate anion and characterized by a molar ratio of (A) to (B) being (A):(B)=1:0.01 to 1:0.60; and the method of manufacturing the conductive polymer capacitor using the composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition for producing a conductive polymer capacitor and a method for producing a conductive polymer capacitor using the same, and more particularly, to a novel conductive high-capacity polymer using an ionic liquid containing a conductive polymer monomer and an alkyl sulfate anion. It concerns molecular capacitors.

  Conventionally, an electrolytic capacitor using a conductive polymer as a cathode conductive layer is known. In such an electrolytic capacitor, it is known that an electrolytic capacitor with low leakage current and high heat resistance and moisture resistance can be manufactured.

Although the prior patent document discloses a technique aiming at high withstand voltage by drawing out the ability to restore conductive polymer electrolyte by ionic liquid, its important characteristics are low impedance, withstand voltage, and capacity development. There was no disclosure of a technique that should express the rate simultaneously (Patent Documents 1 and 2).
JP 2003-022938 A JP 2006-124615 A

  The present invention has been made to solve the above-described problems, and the object of the present invention is to achieve a high capacity achievement rate and a high breakdown voltage (preferably 70% of the formation voltage without causing an increase in impedance). And a manufacturing method thereof.

  The present inventors have blended a composition composed of a conductive polymer monomer and an ionic liquid composed of a specific anion at a specific ratio, and have found that the conductive polymer capacitor exhibits a withstand voltage and a low resistance.

  That is, the present invention includes a conductive polymer monomer (A) and an ionic liquid (B) containing a sulfate anion, and the molar ratio of (A) :( B) is (A) :( B) = 1: It is related with the composition for electroconductive polymer capacitor manufacture characterized by being 0.01-1: 0.60.

  The (A) of the present invention preferably contains at least one selected from the group consisting of pyrrole, aniline, thiophene, quinone, quinoline, furan and derivatives thereof.

The present invention, the anionic component is _R 1 -OSO ₃ of (B) ^- (wherein, _{R 1} is a monovalent aliphatic hydrocarbon group having a carbon number of 5 to 50, have a branching Or may contain one or more fluorine atoms). One of the reasons why the number of carbon atoms is preferably 5 or more is that the alkyl sulfate anion is generally unstable to hydrolysis when the number of carbon atoms in the alkyl group is small, and the durability of the capacitor when used as a capacitor electrolyte. Is a concern.

The anion component (B) of the present invention is
_{CH 3 - (CH 2) 3} -CH 2 OSO 3 -,
_{CH 3 - (CH 2) 4} -CH 2 OSO 3 -,
_{CH 3 - (CH 2) 5} -CH 2 OSO 3 -,
_{CF 3 - (CF 2) 4} -CH 2 OSO 3 - and _{CF 3 - (CF 2) 5} -CH 2 OSO 3 -,
It is preferable to contain at least one selected from the group consisting of:

  The cationic component of the present invention includes ammonium and its derivatives, imidazolinium and its derivatives, pyridinium and its derivatives, pyrrolidinium and its derivatives, pyrrolinium and its derivatives, pyrazinium and its derivatives, pyrimidinium and its derivatives, triazonium and its derivatives, triazinium and its derivatives Derivatives thereof, triazine derivative cations, quinolinium and derivatives thereof, isoquinolinium and derivatives thereof, indolinium and derivatives thereof, quinoxalinium and derivatives thereof, piperazinium and derivatives thereof, oxazolinium and derivatives thereof, thiazolinium and derivatives thereof, morpholinium and derivatives thereof, And at least one selected from the group consisting of piperazine and its derivatives. It, is preferable.

  It is preferable that the (B) of the present invention has the structure of the following formula (1).

本発明は、導電性高分子モノマー（Ａ）及び硫酸アニオンを含むイオン性液体（Ｂ）を含み、かつ（Ａ）と（Ｂ）のモル比が（Ａ）：（Ｂ）=１：０．０１〜１：０．６０である事を特徴とする導電性高分子コンデンサ製造用組成物を用いて製造することを特徴とする導電性高分子コンデンサの製造方法であること、が好ましい。

The present invention includes an ionic liquid (B) containing a conductive polymer monomer (A) and a sulfate anion, and the molar ratio of (A) to (B) is (A) :( B) = 1: 0. It is preferably a method for producing a conductive polymer capacitor, characterized in that it is produced using a composition for producing a conductive polymer capacitor, characterized in that the ratio is from 01 to 1: 0.60.

  The present invention is preferably a method for producing a conductive polymer capacitor, wherein the conductive polymer is formed by chemical polymerization.

  The present invention is preferably a method for producing a conductive polymer capacitor, wherein the conductive polymer is formed by electrolytic polymerization.

  A homogeneous electrode structure can be easily formed, and a low-impedance, high withstand voltage, large-capacity conductive polymer capacitor can be obtained, contributing to improvement in performance.

  Conventionally, it has been known that a conductive polymer capacitor to which an ionic liquid is added improves the withstand voltage as the amount added increases, but the resistance increases and cannot be put to practical use. However, when the anionic component of the ionic liquid is an alkyl sulfate anion, it has been found that the performance as a capacitor is dramatically improved by blending in a small proportion with respect to the conductive polymer monomer.

  In other words, as described in the prior art, this technique is known to be effective in improving the withstand voltage when an ionic liquid is added, but in terms of impedance, the ionic liquid can be increased. It was common knowledge of those skilled in the art that the higher the level, the higher.

  However, as a result of diligent investigations, the present inventors have discovered that the resistance is low, contrary to conventional common sense, only when a specific ionic liquid having an alkylsulfate anion having been discovered by the present inventors is added at a specific ratio. In addition, the present invention is characterized in that it has an effect of solving the trade-off relationship of improving the withstand voltage.

  That is, as shown in FIG. 1, this effect is obtained by changing the molar ratio of ionic liquid-1 (ILs-1) or ionic liquid-2 (ILs-2) and the conductive polymer monomer to a specific molar ratio. Of 0.1 to 0.60, the impedance obtained from the ESR value is 70% or more with respect to the formation voltage while maintaining a state lower than the impedance of the ionic liquid having no alkylsulfate anion. It can be seen that a high withstand voltage can be shown. Such knowledge has never been found before, and it is important to discover that both high withstand voltage and low impedance can be achieved.

  A method for producing a conductive polymer capacitor including an electrolyte and an electrode according to the present invention is not particularly limited. For example, a valve metal in which a dielectric oxide film is formed on a surface of a wound-type conductive polymer aluminum electrolytic capacitor. And a capacitor element constructed by winding a cathode foil with a separator interposed between the anode foil and the anode foil. The capacitor element is composed of a conductive polymer and an ionic liquid between the anode foil and the cathode foil. After providing an electrolyte and housing the element in, for example, a bottomed cylindrical aluminum case, a conductive polymer capacitor can be configured by sealing the opening of the aluminum case with a sealing agent.

  In the present invention, the electrolyte is obtained by adding an oxidizing agent to a solution containing the conductive polymer monomer and the ionic liquid (chemical polymerization method). The chemical polymerization method is a method of polymerizing and synthesizing raw material monomers such as pyrrole by oxidative dehydration in the presence of an oxidant described later.

  As the oxidizing agent, persulfates, hydrogen peroxide, diazonium salts, halogens and halides, or transition metal salts such as iron, copper, and manganese can be used. Since the conductive polymer synthesized by chemical polymerization is also incorporated into the polymer in the polymerization process as an anion of the oxidizing agent as a dopant, a conductive polymer can be obtained by a one-step reaction. When chemical polymerization is carried out in an ionic liquid, the anionic component of the ionic liquid may be incorporated into the conductive polymer as a dopant, which is particularly preferable for the purpose of the present invention.

  In the case of the polymerization, it is preferable to add an oxidizing agent to the solution containing the conductive polymer monomer (A) and the ionic liquid (B). In this case, the viscosity and concentration may be adjusted by adding a solvent. The polymerization solvent used in the polymerization may be a known solvent such as water, alcohol, ether, nitrile, ketone, amide, carbonate, ester, lactone, sulfur-containing solvent, halogenated hydrocarbon. And hydrocarbon solvents, and two or more of these solvents may be used.

  The polymerization conditions may be known polymerization conditions, and the polymerization is preferably performed in the temperature range of −100 ° C. to 200 ° C. for 1 minute to 120 hours. The polymerization is particularly preferably carried out in the temperature range of 0 ° C. to 150 ° C. for 1 minute to 60 minutes. The polymerization may be repeated a plurality of times.

  Next, a method for forming an electrolyte by electrolytic polymerization will be described. The electrolytic polymerization method is a method in which a conductive polymer is dissolved in a solvent and anodized to dehydrogenate the conductive polymer. Electropolymerization is, for example, a method in which a pyrrole monomer is dissolved in a solvent together with a supporting electrolyte and subjected to dehydrogenation polymerization by anodic oxidation, whereby polypyrrole, which is a conductive polymer, can be deposited on the anode. In general, since the oxidation-reduction potential of a polymer is lower than that of a monomer, the oxidation of the polymer skeleton proceeds further in the polymerization process, and accordingly, the anion of the supporting electrolyte is incorporated into the polymer as a dopant. In electropolymerization, such a mechanism has an advantage that a polymer having conductivity can be obtained without adding a dopant later. In addition, when electrolytic polymerization is performed in an ionic liquid, the anionic component of the ionic liquid may be incorporated into the conductive polymer as a dopant, which is particularly preferable for the purpose of the present invention. When synthesizing a conductive polymer by electrolytic polymerization, the oxide film on the valve metal is a dielectric, so a conductive film is formed on the dielectric beforehand to make it conductive, Electropolymerization is performed by applying a voltage. As the conductive film used for such a purpose, a conductive polymer synthesized by chemical polymerization, pyrolytic manganese dioxide, or the like can be used.

  When the electrolyte is used as a conductive polymer capacitor, it is particularly preferable that the conductive polymer electrolyte contains an ionic liquid (composites). This is because an ideal capacitor electrolyte can be realized by adding the excellent anodic oxidation property of the ionic liquid and the excellent electronic conductivity of the conductive polymer electrolyte. In other words, by utilizing the high conductivity of the conductive polymer, it is possible to significantly reduce the resistance between the electrodes in the conductive portion, and as a result, an electrolytic capacitor having excellent impedance characteristics can be easily obtained, and at the same time, By interposing together the ionic liquid having the ability to repair the dielectric oxide film of the working metal, an electrolytic capacitor having a high withstand voltage and a low leakage current can be obtained.

  The conductive polymer monomer is not particularly limited, but has high conductivity at the time of polymer formation and is stable in the air. Therefore, thiophene or a derivative thereof, pyrrole or a derivative thereof, aniline or a derivative thereof, It is preferably selected from quinone or a derivative thereof, quinoline or a derivative thereof, furan or a derivative thereof.

  For example, as derivatives of thiophene, 1,4-dioxythiophene, 3,4-dioxythiophene, 3,4-ethylenedioxythiophene, 3-alkylthiophene (alkyl groups include butyl, hexyl, octyl Group, dodecyl group, etc.), fluorophenylthiophene, allylthiophene and the like, but are not limited thereto.

  Examples of pyrrole derivatives include, but are not limited to, those having a pyrrole skeleton and having substituents such as a hydroxyl group, a carboxyl group, and an alkyl group. Examples of aniline derivatives include, but are not limited to, those having an aniline skeleton having an alkyl group, a cyano group, a sulfone group, or a carboxyl group. Examples of the quinone derivative include, but are not limited to, benzoquinone having a substituent, naphthoquinone having a substituent, and anthraquinone having a substituent. Polyquinone derivatives include polybenzoquinone derivatives synthesized from substituted benzoquinone monomers, polynaphthoquinone derivatives synthesized from substituted naphthoquinone monomers, polyanthraquinone derivatives synthesized from substituted anthraquinone monomers, etc. However, it is not limited to these. Examples of furan derivatives include, but are not limited to, those having a furan skeleton and having substituents such as a hydroxyl group, a carboxyl group, and an alkyl group.

  In particular, a conductive polymer composed of poly- (2,3-dihydrothieno- [3,4-b] -1,4 dioxin) or polypyrrole is preferably used in terms of conductivity and heat resistance.

  The ionic liquid contained in the electrolyte of the present invention is also called a room temperature molten salt, and refers to a liquid that is liquid at room temperature despite being composed only of ions. A combination of a cation such as imidazolinium and an appropriate anion Consists of. The ionic liquid is not partially ionized and dissociated like a normal organic solvent, but is considered to be formed from only ions and 100% ionized. As described above, the ionic liquid is usually a liquid at room temperature, but the ionic liquid used in the present invention does not necessarily need to be a liquid at room temperature, and becomes a liquid during the aging process or heat treatment of the capacitor. Any material can be used as long as it spreads throughout the electrolyte and becomes liquid by the Joule heat generated when the oxide film is repaired. Among these, imidazolinium or a derivative thereof, ammonium or a derivative thereof, pyridinium or a derivative thereof can be preferably used for this purpose.

In the ionic liquid used in the present invention, the anion component is an alkyl sulfate anion. If this ionic liquid used as a capacitor element, the other anionic components (anion PF ₆ ^-, etc.) than the withstand voltage not only is high, it is that is superior resistance is small.

  Moreover, the effect as a capacitor | condenser is improved dramatically by adding a specific ratio with respect to a conductive polymer monomer. The molar ratio of the conductive polymer monomer (A) and the ionic liquid (B) in the present invention is preferably (A) :( from the viewpoint of withstand voltage and low resistance in the conductive polymer capacitor produced after polymerization. B) = 1: 0.01 to 1: 0.60, more preferably (A) :( B) = 1: 0.10 to 1: 0.50. When (B) is 0.01 or more, the withstand voltage is excellent, and when it is 0.60 or less, the low resistance is excellent. That is, the ratio of (B) / (A) is preferably 0.01 or more, more preferably 0.10 or more from the viewpoint of withstand voltage, and preferably 0.60 or less from the viewpoint of low resistance. More preferably, it is 0.50 or less. If it is less than that, the effect is lowered, and if it is more than the range, the resistance is increased, which is not preferable.

  The electrolytic capacitor of the present invention is formed using an electrolyte layer provided with a high ion conductivity region, and includes at least an electrolyte layer, and an anode and a cathode disposed so as to face each other with the electrolyte layer interposed therebetween. The electrolytic capacitor of the present invention can be formed in either a chip type or a wound type. A chip-type electrolytic capacitor typically has a capacitor element in which an electrolyte layer and a cathode are laminated in this order on the dielectric film of an anode made of an anode metal having a dielectric film formed on the surface thereof. A connection terminal electrically connected to the capacitor element is provided. On the other hand, a wound-type electrolytic capacitor typically has an electrolyte layer, a separator, a cathode, and a separator on the dielectric film of an anode made of an anode metal having a dielectric film formed on the surface thereof from the radially inner side. Are arranged so as to be arranged in this order, and the capacitor element is laminated and wound, and a connection terminal electrically connected to the capacitor element. In the separator, usually, a separator material made of, for example, polyolefin or cellulose fiber and a conductive polymer are combined.

  As the anode of the electrolytic capacitor of the present invention, conventionally known electrolytic capacitors can be preferably used. For example, as the anode metal, the surface of an electrode foil such as aluminum is etched to form etching holes, tantalum or the like. An anode composed of an anode metal and a dielectric film can be formed by combining a dielectric film composed of an oxide film formed by a method such as anodic oxidation on the surface of the anode metal. The above anodic oxidation can be performed by immersing the anode metal in, for example, an aqueous solution of ammonium adipate and applying a chemical voltage.

  As the cathode, for example, carbon paste and silver paste can be formed by a conventionally known method. The anode and cathode are each connected to a terminal. Thus, an electrolytic capacitor including at least an anode, an electrolyte membrane, and a cathode can be formed.

  Hereinafter, an example of a typical manufacturing method of the electrolytic capacitor of the present invention will be described. The components of the capacitor not specifically mentioned in the electrolytic capacitor of the present invention are not particularly limited, and conventionally known components can be appropriately applied. In the following description, a case where a chip-type electrolytic capacitor is formed using an anode provided with an etching hole will be described as an example. However, the present invention is not limited to this.

  In the present embodiment, a case where an electrolyte layer is formed by an ionic liquid immersion process and a chemical polymerization process will be described. An electrolytic capacitor manufacturing method according to the present embodiment includes an anode forming step of forming an anode composed of an anode metal and a dielectric film, an electrolyte layer forming step of forming an electrolyte layer in contact with the dielectric film, and an electrolyte layer A cathode forming step of forming a cathode on the surface. The electrolyte layer forming step includes an ionic liquid dipping step in which the anode is immersed in an ionic liquid, a chemical polymerization composition after the anode is immersed in a chemical polymerization composition including at least the ionic liquid and the polymerizable material. And a chemical polymerization step of forming a complex including an ionic liquid and a conductive polymer by polymerization by a polymerization method. The chemical polymerization process can be performed only once or can be repeated multiple times.

  In addition, the polymerization process can be repeated several times while changing the mass ratio between the ionic liquid and the polymerizable substance in the polymerization composition, and any method that can be assumed by general knowledge of those skilled in the art is possible. It is.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples, In the range which does not change the summary, it can change suitably.

<Ionic liquid: ILs>
First, a method for synthesizing and obtaining an ionic liquid used as an example will be described.
(ILs-1)

ＷＯ２００５−１０５７５６Ａ１記載に準拠して調製した。
（ＩＬｓ−２）

Prepared according to the description in WO2005-105756A1.
(ILs-2)

ソルベントイノベーション社より購入。
（ＩＬｓ−３）

Purchased from Solvent Innovation.
(ILs-3)

ＷＯ２００５−１０５７５６Ａ１記載に準拠して調製した。
（ＩＬｓ−４）

Prepared according to the description in WO2005-105756A1.
(ILs-4)

ＷＯ２００５−１０５７５６Ａ１記載に準拠して調製した。
（ＩＬｓ−５）

Prepared according to the description in WO2005-105756A1.
(ILs-5)

ＷＯ２００５−１０５７５６Ａ１記載に準拠して調製した。
（ＩＬｓ−６）

Prepared according to the description in WO2005-105756A1.
(ILs-6)

ＷＯ２００５−１０５７５６Ａ１記載に準拠して調製した。
（ＩＬｓ−７）
（１−ｎＣ_４Ｈ_９−３−ＣＨ_３−Ｉｍ）^＋（ＰＦ_６）⁻
関東化学（株）より購入。
（ＩＬｓ−８）
（１−Ｃ_２Ｈ_５−３−ＣＨ_３−Ｉｍ）^＋（（ＣＦ_３ＳＯ_２）_２Ｎ）⁻
関東化学（株）より購入。

Prepared according to the description in WO2005-105756A1.
(ILs-7)
_{(1-nC 4 H 9 -3} -CH 3 -Im) + (PF 6) -
Purchased from Kanto Chemical Co., Ltd.
(ILs-8)
^{_{(1-C 2 H 5 -3}} -CH 3 -Im) + ((CF 3 SO 2) 2 N) -
Purchased from Kanto Chemical Co., Ltd.

(Measurement of liquid capacity of restoration chemical conversion aluminum foil)
The volume in the liquid was calculated from the slope of the graph obtained in a constant current charge / discharge test of 50 μA between 0 and 4 V using solartron, model number “1480” manufactured by Toyo Technica.

(Measurement of initial capacity of electrode)
The foil thus obtained was used as a sample, and after aging at 20 V for 1 hour, the initial capacity was measured using the mercury cell shown in FIG.
A solartron manufactured by Toyo Technica, model number “1480” was used as the apparatus, a constant current charge / discharge test of 50 μA was performed in the range of 0 to 4 V, and the capacity was calculated from the slope of the obtained graph.

(Volume expression rate)
(Volume in liquid / initial volume) × 100 was defined as “capacity expression rate”, and the variation in liquid capacity of the repaired and formed aluminum foil used was normalized.

(Impedance measurement)
After the initial capacity measurement, impedance was measured using the mercury cell shown in FIG.
As a device, solartron manufactured by Toyo Technica, model number “1480” was used, and measurement was performed in the range of 1 Hz to 1 MHz under the conditions of DC Potential = 0V and AC Amplitude 100V. The impedance value of 100 kHz was defined as the electrode impedance.

(Withstand voltage measurement)
After measuring the impedance, the withstand voltage (V) was measured using the mercury cell shown in FIG.
As a device, model number “TR6143” manufactured by Advantest Corporation was used and measured by increasing the voltage at a speed of 20 mV / sec. The withstand voltage value was defined as the voltage at which a current of 10 mA flowed.

(Example 1)
A conductive polymer aluminum electrolytic capacitor was produced by forming a conductive polymer obtained by chemical polymerization of 3,4-ethylenedioxythiophene on an aluminum oxide film.

  That is, an aluminum etched foil having an effective area of 10 mm × 10 mm is dipped in a 1% ammonium adipate aqueous solution, first raised from 0 to 45 V at a rate of 20 mV / sec, and then a constant voltage of 45 V is applied for 40 minutes, A dielectric film was formed on the surface of the aluminum etched foil. Next, this foil was washed with running deionized water for 3 minutes and then dried at 120 ° C. for 1 hour. The volume of the aluminum etched foil obtained at this time was 25 μF. Next, the chemical polymerization composition used for electrolyte formation was prepared with the following compounding ratio. As a conductive polymer monomer, from 0.1 g of 3,4-ethylenedioxythiophene (hereinafter abbreviated as EDOT, manufactured by HC Starck-V TECH) and 0.16 g of ionic liquid (ILs-1). A 1-butanol (0.30 g) solution of 0.20 g of iron paratoluenesulfonate was added to the composition as an oxidizing agent and mixed in a well-dried beaker. These compounds are monomer: oxidizer: ionic liquid = 1: 0.5: 0.5. Next, the aluminum etched foil was immersed in the polymerization solution in the polymerization solution, and after being pulled up, heat treatment was performed at 120 ° C for 1 hour. The same treatment was repeated four times so that the surface of the foil was uniformly covered with the electrolyte. The initial capacity of the foil thus obtained was measured using the mercury cell shown in FIG. Moreover, impedance and withstand voltage (V) were measured. Table 1 shows the characteristics of the obtained electrode. The results in Table 1 are average values for 10 electrodes.

(Example 2)
A capacitor of the present invention was produced in the same manner as in Example 1 except that the ionic liquid was ILs-1 and the blending ratio was monomer: oxidant: ionic liquid = 1: 0.5: 0.1. Table 1 shows the characteristics of the obtained capacitor.

(Example 3)
A capacitor of the present invention was produced in the same manner as in Example 1 except that the ionic liquid was ILs-2. Table 1 shows the characteristics of the obtained capacitor.

Example 4
A capacitor of the present invention was produced in the same manner as in Example 1 except that the ionic liquid was ILs-2 and the mixing ratio was monomer: oxidant: ionic liquid = 1: 0.5: 0.1. Table 1 shows the characteristics of the obtained capacitor.

(Examples 5 to 8)
A capacitor of the present invention was produced in the same manner as in Example 1 except that the ionic liquid was changed to ILs-3 to 6. Table 1 shows the characteristics of the obtained capacitor.

(Comparative Example 1)
A capacitor of the present invention was produced in the same manner as in Example 1 except that the ionic liquid was ILs-7. Table 1 shows the characteristics of the obtained capacitor of the present invention.

(Comparative Example 2)
A capacitor of the present invention was produced in the same manner as in Example 1 except that the ionic liquid was ILs-8. Table 1 shows the characteristics of the obtained capacitor of the present invention.

(Comparative Example 3)
A capacitor of the present invention was produced in the same manner as in Example 1 except that the ionic liquid was ILs-1 and the mixing ratio was monomer: oxidant: ionic liquid = 1: 0.5: 1.0. Table 1 shows the characteristics of the obtained capacitor of the present invention.

(Comparative Example 4)
A capacitor of the present invention was produced and obtained in the same manner as in Example 1 except that the ionic liquid was not used and the blending ratio was changed to monomer: oxidant: ionic liquid = 1: 0.5: 0. Table 1 shows the characteristics of the capacitors.

この結果から捲回型アルミ電解コンデンサにおいても重合溶媒にイオン性液体を添加し、これを用いて電解質形成を行う事によりすぐれた耐圧特性を有するコンデンサが作製できる事が分かった。

From this result, it was found that a wound type aluminum electrolytic capacitor can also be produced by adding an ionic liquid to a polymerization solvent and forming an electrolyte using the ionic liquid.

  As described above, the method for manufacturing a conductive polymer capacitor according to the present invention achieves a high capacity achievement rate and a high breakdown voltage (preferably 70% or more of the formation voltage) without causing an increase in ESR (ESR). It becomes possible to provide a capacitor having the same and a method for manufacturing the same, which is useful.

Relationship between monomer / ionic liquid molar ratio and initial capacitor characteristics Mercury cell for measuring electrodes

Claims (10)

  The conductive polymer monomer (A) and an ionic liquid (B) containing an alkylsulfate anion are included, and the molar ratio of (A) to (B) is (A) :( B) = 1: 0.01-1 : A composition for producing a conductive polymer capacitor, which is 0.60.   2. The composition for producing a conductive polymer capacitor according to claim 1, wherein (A) includes at least one selected from the group consisting of pyrrole, aniline, thiophene, quinone, quinoline, furan, and derivatives thereof. object. The anionic component of (B) is R ₁ -OSO ₃ ^-
(Here, R ₁ is a monovalent aliphatic hydrocarbon group having 5 to 50 carbon atoms, may be branched, and may contain one or more fluorine atoms.)
The composition for producing a conductive polymer capacitor according to claim 1, wherein the composition is for manufacturing a conductive polymer capacitor. The anion component of (B) is
_{CH 3 - (CH 2) 3} -CH 2 OSO 3 -,
_{CH 3 - (CH 2) 4} -CH 2 OSO 3 -,
_{CH 3 - (CH 2) 5} -CH 2 OSO 3 -,
_{CF 3 - (CF 2) 4} -CH 2 OSO 3 - and _{CF 3 - (CF 2) 5} -CH 2 OSO 3 -,
The composition for producing a conductive polymer capacitor according to claim 1, comprising at least one selected from the group consisting of:   The cationic component of (B) is ammonium and derivatives thereof, imidazolinium and derivatives thereof, pyridinium and derivatives thereof, pyrrolidinium and derivatives thereof, pyrrolinium and derivatives thereof, pyrazinium and derivatives thereof, pyrimidinium and derivatives thereof, triazonium and derivatives, Triazinium and its derivatives, triazine derivative cations, quinolinium and its derivatives, isoquinolinium and its derivatives, indolinium and its derivatives, quinoxalinium and its derivatives, piperazinium and its derivatives, oxazolinium and its derivatives, thiazolinium and its derivatives, morpholinium and its derivatives Derivatives and at least one selected from the group consisting of piperazine and derivatives thereof Characterized in that it comprises a conductive polymer capacitor prepared composition according to any one of claims 1 to 4. The composition for producing a conductive polymer capacitor according to claim 1 or 2, wherein (B) has a structure represented by the following formula (1).

  It manufactures using the composition for conductive polymer capacitor manufacture of any one of Claims 1-6, The manufacturing method of the conductive polymer capacitor characterized by the above-mentioned.   The method of manufacturing a conductive polymer capacitor according to claim 7, wherein the conductive polymer capacitor is formed by chemical polymerization.   The electrolyte is formed by mixing and polymerizing the composition for producing a conductive polymer capacitor according to any one of claims 1 to 6 and an oxidizing agent. The manufacturing method of the electroconductive polymer capacitor of description.   The method for producing a conductive polymer capacitor according to claim 7, wherein the conductive polymer capacitor is formed by electrolytic polymerization.

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