KR102486550B1 - 3,4-ethylenedioxythiophene copolymer, solid electrolyte including the same, solid electrolytic capacitor including the same and method for preparing the same - Google Patents

Abstract

상기 화학식 1에서, n 및 m은 1 내지 8의 서로 다른 정수이고, 상기 a 및 b는 상기 화학식 1의 공중합체를 구성하는 전체 반복단위에 대한 각각의 반복단위의 몰%로서, 각각 10 내지 90 몰%이다.Disclosed are a 3,4-ethylenedioxythiophene copolymer having high withstand voltage and low equivalent series resistance, a solid electrolyte including the same, a solid electrolyte capacitor including the same, and a manufacturing method thereof. The 3,4-ethylenedioxythiophene copolymer is represented by Formula 1 below.
[Formula 1]

In Formula 1, n and m are different integers from 1 to 8, and a and b are mol% of each repeating unit with respect to all repeating units constituting the copolymer of Formula 1, respectively, from 10 to 90 is mol%.

Description

3,4-ethylenedioxythiophene copolymer, solid electrolyte including the same, solid electrolyte capacitor including the same, and method for manufacturing the same preparing the same}

The present invention relates to a 3,4-ethylenedioxythiophene copolymer, a solid electrolyte containing the same, a solid electrolytic capacitor containing the same, and a manufacturing method thereof, and more particularly, to a 3,4-ethylenedioxythiophene copolymer having high withstand voltage and low equivalent series resistance. - It relates to an ethylenedioxythiophene copolymer and a solid electrolyte containing the same, a solid electrolyte capacitor including the same, and a manufacturing method thereof.

There is a solid electrolytic capacitor (capacitor, condenser) formed by forming a solid electrolyte containing a conductive polymer in a capacitor formed through winding (meaning wrapping in a circle) or lamination by separating the anode electrode layer and the cathode electrode layer having an oxide film. . As solid electrolyte forming materials used in the solid electrolytic capacitor, inorganic conductive materials represented by manganese dioxide and organic conductive materials such as 8,8-tetracyanoquinodimethane (TCNQ) complex are known. In addition, solid electrolytic capacitors having as a solid electrolyte a conductive polymer material having more excellent electrical properties than these solid electrolyte-forming materials are widely used. As the conductive polymer material, a conductive polymer prepared by polymerization of 3,4-Ethylenedioxythiophene (EDOT) monomers is widely known. The 3,4-ethylenedioxythiophene is used as a useful material for forming a solid electrolyte layer of a solid electrolytic capacitor because the polymerization rate is slow and a conductive polymer layer having good adhesion to the dielectric oxide film of the anode is formed.

However, recent electronic devices need to save more power and operate at higher frequencies, and solid electrolytic capacitors used in these electronic devices also need to improve electrical characteristics, for example, miniaturization, high capacity and low Equivalent Series Resistance (ESR) is required. In the conventionally synthesized 3,4-ethylenedioxythiophene monomer, the carbon to which the substituent of the 6-ring structure is bonded is 1-substituted on the tertiary carbon, or in the case of the 7-ring structure, the carbon to which the substituent is bonded is 1-substituted on the tertiary carbon. It is shown in Korean Patent Publication No. 2012-0113701 (hereinafter referred to as the 701 patent) that is substituted or disubstituted on a quaternary carbon to form a symmetrical form.

As described above, electrical characteristics such as capacitance, equivalent series resistance (ESR), and withstand voltage (Volt) appear differently depending on the position of the substituent or the number of carbon atoms in the bonded substituent. Although the 701 patent has improved withstand voltage, the higher the withstand voltage It is difficult to use because the equivalent series resistance increases. Therefore, there is a need to develop a 3,4-ethylenedioxythiophene copolymer capable of reducing equivalent series resistance while improving withstand voltage.

Accordingly, an object of the present invention is to provide a 3,4-ethylenedioxythiophene copolymer having improved withstand voltage and low equivalent series resistance, a solid electrolyte including the same, a solid electrolyte capacitor including the same, and a manufacturing method thereof.

In order to achieve the above object, the present invention provides a 3,4-ethylenedioxythiophene copolymer represented by Formula 1 below.

[Formula 1]

In Formula 1, n and m are different integers from 1 to 8, and a and b are mol% of each repeating unit with respect to all repeating units constituting the copolymer of Formula 1, respectively, from 10 to 90 is mol%.

In addition, the present invention is an anode electrode layer having an oxide film; a cathode electrode layer; and a separator positioned between the anode electrode layer and the cathode electrode layer. and a solid electrolyte, wherein the solid electrolyte is a 3,4-ethylenedioxythiophene copolymer represented by Formula 1 below.

[Formula 1]

In Formula 1, n and m are different integers from 1 to 8, and a and b are mol% of each repeating unit with respect to all repeating units constituting the copolymer of Formula 1, respectively, from 10 to 90 is mol%.

The 3,4-ethylenedioxythiophene copolymer according to the present invention is not a single polymerization of a monomeric compound in which the tertiary carbon substituent bonding portion is substituted in the 6-ring structure of the 3,4-ethylenedioxythiophene monomer, but rather When two or more compounds are polymerized into a copolymer and used as a solid electrolyte, the withstand voltage is improved and the equivalent series resistance is low.

1 is a perspective view of a solid electrolytic capacitor as an example of a capacitor according to the present invention.
2 is an enlarged cross-sectional view of a solid electrolyte layer produced according to the present invention.

Hereinafter, the present invention will be described in detail.

The solid electrolyte according to the present invention includes a 3,4-ethylenedioxythiophene copolymer represented by Formula 1 below.

[Formula 1]

In Formula 1, n and m are different integers from 1 to 8. Specifically, the difference between n and m is 1 to 7, specifically 4 or more. In addition, n is an integer of 1 to 4, and m is an integer of 5 to 8. If the range of n and m and the difference between n and m are out of the above range, the effect of improving the withstand voltage and lowering the value of the equivalent series resistance may be insufficient. In addition, when n and m exceed 8, the polymerization reactivity of the compound is lowered, making it difficult for the polymerization reaction to occur. The 3,4-ethylenedioxythiophene copolymer according to the present invention has a withstand voltage and equivalent series resistance value of a polymer formed by polymerization of a monomer having n of 1 and a withstand voltage and equivalent of a polymer formed by polymerization of a monomer having m of 8. It is characterized by having a lower equivalent series resistance value and higher withstand voltage characteristics than the withstand voltage and equivalent series resistance value predicted from the series resistance value. The weight average molecular weight of the 3,4-ethylenedioxythiophene copolymer is 100 to 5,000, specifically 200 to 1,000. If the weight average molecular weight of the 3,4-ethylenedioxythiophene copolymer is too small, the dielectric oxide film layer cannot produce sufficient withstand voltage characteristics and leakage current may increase, and if it is too large, 3,4-ethylenedioxythiophene air Since the coalescence is not completely dissolved, a dense and uniform solid electrolyte layer cannot be formed, and thus low ESR value and withstand voltage characteristics cannot be realized.

In addition, the a and b are mol% of each repeating unit with respect to the total repeating units constituting the copolymer of Formula 1, respectively 10 to 90 mol%, specifically 20 to 80 mol%, more specifically 30 to 70 mol%, and may be, for example, 50 mol%. Here, if the a and b are out of the above ranges, there is a concern that the effect of lowering the equivalent series resistance value and the effect of increasing the withstand voltage characteristic may be insufficient.

As shown in Reaction Scheme 1 below, the 3,4-ethylenedioxythiophene copolymer is a copolymer of two or more monomers including a monomer represented by the following Chemical Formula 2 and a monomer represented by the following Chemical Formula 3, specifically, a random copolymer. it is a composite

[Scheme 1]

[Formula 2]

[Formula 3]

In Reaction Scheme 1 and Formulas 2 and 3, n, m, a and b are as described above in Formula 1 above.

,

,

,

,

,

,

,

등을 예시할 수 있다. 상기 화학식 2로 표시되는 3,4-에틸렌디옥시티오펜 모노머는 하기 반응식 2에 나타낸 바와 같이, 디올(diol) 화합물과 화합물 c로 표시되는 3,4-디메톡시티오펜(3,4-dimethoxythiophen)을 반응시켜 합성된다.Specific examples of the monomers represented by Formulas 2 and 3 include,

,

,

,

,

,

,

,

etc. can be exemplified. As shown in Scheme 2 below, the 3,4-ethylenedioxythiophene monomer represented by Formula 2 is a diol compound and 3,4-dimethoxythiophene represented by compound c synthesized by reacting

[Scheme 2]

In Scheme 2, n is an integer from 1 to 8.

In addition, the 3,4-ethylenedioxythiophene monomer represented by Formula 3 is synthesized in the same reaction except that n is changed to m in Scheme 2 above. Said m is an integer of 1-8.

The 3,4-ethylenedioxythiophene copolymer may be formed by either chemical oxidation polymerization or electrolytic oxidation polymerization, but is specifically prepared by chemical oxidation polymerization. For example, a solution in which the 3,4-ethylenedioxythiophene monomer represented by Chemical Formulas 2 and 3 and an oxidizing agent are dissolved is mixed and then heated to polymerize. Specifically, the 3,4-ethylenedioxythiophene copolymer is prepared by mixing the 3,4-ethylenedioxythiophene monomer with a solution in which an oxidizing agent is dissolved in a weight ratio of 1:2.5, and then mixing the 3,4-ethylenedioxythiophene copolymer at 40 to 50 °C, specifically 45 A first heating step of heating at 1 to 3 hours, specifically 2 hours at ° C, a second heating step of heating at 100 to 110 ° C, specifically 105 ° C for 30 to 40 minutes, specifically 35 minutes, and 120 to 130° C., specifically 125° C. for 30 to 90 minutes, specifically 1 hour, through a third heating step to polymerize.

Organic sulfonic acid iron (III) may be used as the oxidizing agent. Specifically, as the organic sulfonic acid iron (III), ferric salts of p-toluenesulfonic acid, ferric benzenesulfonic acid salts, ferric naphthalenesulfonic acid salts, and mixtures thereof may be used. In addition, n-butanol, ethanol, toluene, etc. may be used as a solvent in which the oxidizing agent is dissolved, and the solution is 20 to 90% by weight, specifically 30 to 80% by weight, more specifically 40 to 70% by weight The oxidizing agent of is dissolved in an alcohol type solvent.

The solid electrolyte according to the present invention is characterized in that the equivalent series resistance value is reduced and withstand voltage characteristics are improved by copolymerizing a monomer having a short substituted alkyl chain and a monomer having a long substituted alkyl chain.

Next, a solid electrolytic capacitor (capacitor, condenser) according to the present invention will be described. A solid electrolytic capacitor according to the present invention includes an anode electrode layer having an oxide film; a cathode electrode layer; and a separator and a solid electrolyte positioned between the positive electrode layer and the negative electrode layer. The solid electrolyte is a polymer of two or more monomers including a monomer represented by Formula 1 below and a monomer represented by Formula 2 below. The separator is divided into cellulose type with good impregnation and acrylic type with good pressure resistance. In the case of using the 3,4-ethylenedioxythiophene copolymer of the present invention, it is preferable to use a nylon type that does not require a carbonization process due to its low density. , but is not limited to nylons. In addition, the thickness of the separator is 10 to 100 μm, specifically 30 to 50 μm, more specifically 35 to 40 μm, and the density is 0.1 to 0.8 g/cm ³ , specifically 0.3 to 0.6 g/cm ³ , more specifically from 0.5 to 0.55 g/cm ³ . If the thickness of the separator is too thin, the strength of the slitted separator is lowered, it cannot be wound well in the winding process, the defect rate in the processing process is high, and in the process of manufacturing a capacitor element, the gap between electrodes must be sufficiently maintained. Therefore, a lot of insulation defects may occur in the capacitor element. In addition, if the thickness of the separator is too thick, the thickness when winding the cathode foil, the anode foil, and the separator becomes excessively thick, making it impossible to obtain a small product useful as an electronic component, as well as having a regulated size. Compared to capacitor parts, only a capacitor with a small capacity per unit volume can be manufactured after being relatively wound.

In order to manufacture the solid electrolytic capacitor according to the present invention, first, a separator is placed between an anode electrode layer and a cathode electrode layer made of metal such as aluminum and having an oxide film on the surface. Next, two or more monomers including the monomer represented by Formula 1 and the monomer represented by Formula 2 and an oxidizing agent are impregnated between the anode electrode layer and the cathode electrode layer, and the monomers are heated to form a 3,4- A solid electrolyte comprising the ethylenedioxythiophene copolymer is formed. The impregnation may be performed for 120 seconds. Next, the capacitor case is manufactured by using epoxy resin on the formed capacitor element, and a voltage of 4 V is applied to the anode, followed by aging to manufacture a solid electrolytic capacitor.

1 is a perspective view of a solid electrolytic capacitor that is an example of a capacitor according to the present invention, and FIG. 2 is an enlarged cross-sectional view of a solid electrolyte layer produced according to the present invention. As shown in Figs. 1 and 2, the solid electrolytic capacitor according to the present invention can be manufactured in the following way. First, a separator 5 is placed between the anode electrode layer 1 and the cathode electrode layer 2 having the oxide film 6, and wound to form a capacitor element. Next, the capacitor element is impregnated with two or more monomers including the monomer represented by Chemical Formula 1 and the monomer represented by Chemical Formula 2, and an oxidizing agent, and an oxidative polymerization reaction in the capacitor element causes the air represented by Chemical Formula 3 to occur. A solid electrolyte layer made of the composite is formed. The solid electrolyte layer is maintained as a separator (5). An aluminum winding type solid electrolytic capacitor may be manufactured by sealing the capacitor case using an epoxy resin and aging the solid electrolyte layer by applying a voltage to the anodes according to a conventional method. The anode electrode layer 1 is made of metal such as aluminum, and a plurality of etching pits are formed on its surface by etching treatment to increase the specific target, and a commonly used chemical conversion liquid, for example, ammonium borate , an oxide film 6 serving as a dielectric is formed by applying a voltage in an aqueous solution such as ammonium adipate. Like the cathode electrode layer 1, the cathode electrode layer 2 is made of a metal such as aluminum, and only an etching process is performed on the surface.

Lead wires 3 and 4 for connecting the respective electrodes to the outside are connected to the positive electrode layer 1 and the negative electrode layer 2 in a conventional manner, for example, by means of stitching, ultrasonic welding, etc. there is. The lead wires 3 and 4 are made of aluminum, etc., and constitute an external connection part responsible for electrical connection between the connection part of the anode electrode layer 1 and the cathode electrode layer 2 and the outside, and the ends of the wound capacitor element It protrudes from the side.

Since the solid electrolytic capacitor according to the present invention has high withstand voltage and low equivalent series resistance, it can be used in circuits using capacitors such as various electronic components, for example, central processing circuits and power supply circuits, and the circuits can be used in computers. , servers, cameras, game machines, DVD devices, AV devices and various digital devices such as mobile phones, and various electronic devices such as power supplies.

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited by the following examples.

[Preparation Example 1] Synthesis of 2-Propyl-2,3-dihydrothieno[3,4-b][1,4]dioxine

As shown in Scheme 3 below, 3,4-dimethoxythiophene (1) 30.00 g (208.06 mmol), 1,2-pentanediol (1,2-pentanediol, ( 2)) 43.34 g (416.12 mmol), 3.96 g (20.81 mmol) of p -toluenesulfonic acid and 300 mL of toluene were mixed and reacted at 110 ° C. for 9 hours with stirring. The reaction solution was completely dissolved by adding ethyl acetate, extracted with water, and the organic layer was dried over sodium sulfate (NaSO ₄ ), and the remaining organic layer was concentrated. The concentrated organic layer was developed with a silicon dioxide (SiO ₂ ) column chromatography with a mixed solution of hexane : ethyl acetate = 10 : 1 (volume ratio), column purification was performed, and 25.00 g of compound (3) was obtained. (Yield: 65 to 70%, ¹ H-NMR (CDCl ₃ , Varian 400 MHz): δ 0.88 (3H, t, J = 12 Hz), 1.31-1.70 (4H, m), 3.86 (1H, dd, J = 8.0, 3.2 Hz), 4.10–4.16 (2H, m), 6.30 (2H, s).

[Scheme 3]

[Production Example 2] Synthesis of 2-Butyl-2,3-dihydrothieno[3,4-b][1,4]dioxine

As shown in Scheme 4 below, 3,4-dimethoxythiophene (3,4-dimethoxythiophene, (1)) 30.00 g (208.06 mmol), 1,2-hexenediol (1,2-hexanediol, ( 4)) 49.18 g (416.12 mmol), 3.96 g (20.81 mmol) of p -toluenesulfonic acid, and 300 mL of toluene were mixed and reacted at 110 ° C. for 9 hours with stirring. The reaction solution was completely dissolved by adding ethyl acetate, extracted with water, and the organic layer was dried over sodium sulfate (NaSO ₄ ), and the remaining organic layer was concentrated. The concentrated organic layer was developed with a silicon dioxide (SiO ₂ ) column chromatography with a mixed solution of hexane : ethyl acetate = 10 : 1 (volume ratio), column purification was performed, and 34.90 g of compound (5) was obtained. (Yield: 65 to 85%, ¹ H-NMR (CDCl ₃ , Varian 400 MHz): δ 0.93 (3H, t, J = 12 Hz), 1.35-1.70 (6H, m), 3.86 (1H, dd, J = 8.0, 3.2 Hz), 4.08–4.16 (2H, m), 6.30 (2H, s).

[Scheme 4]

[Preparation Example 3] Synthesis of 2-Hexyl-2,3-dihydrothieno[3,4-b][1,4]dioxine

As shown in Scheme 5 below, 20.00 g (138.71 mmol) of 3,4-dimethoxythiophene (1), 1,2-octanediol (1,2-octanediol, ( 6)) 40.57 g (277.42 mmol), p -toluenesulfonic acid (p-toluenesulfonic acid) 2.64 g (13.87 mmol) and 200 mL of toluene were mixed and reacted at 110 ° C. for 9 hours with stirring. The reaction solution was completely dissolved by adding ethyl acetate, extracted with water, and the organic layer was dried over sodium sulfate (NaSO ₄ ), and the remaining organic layer was concentrated. The concentrated organic layer was developed with silicon dioxide (SiO ₂ ) column chromatography with a mixed solution of hexane : ethyl acetate = 10 : 1 (volume ratio), column purification was carried out, and 24.00 g of compound (7) was obtained. (Yield: 65 to 88%, ¹ H-NMR (CDCl ₃ , Varian 400 MHz): δ 0.88 (3H, t, J = 12 Hz), 1.31-1.69 (10H, m), 3.86 (1H, dd, J = 8.0, 3.2 Hz), 4.08–4.16 (2H, m), 6.30 (2H, s).

[Scheme 5]

[Preparation Example 4] Synthesis of 2-Octyl-2,3-dihydrothieno[3,4-b][1,4]dioxine

As shown in Scheme 6 below, 50.00 g (346.76 mmol) of 3,4-dimethoxythiophene (1), 1,2-decanediol (1,2-octanediol, ( 8)) 120.87 g (693.52 mmol), p -toluenesulfonic acid (p-toluenesulfonic acid) 6.60 g (34.68 mmol) and toluene 500 mL were mixed and reacted while stirring at 110 ° C. for 9 hours. The reaction solution was completely dissolved by adding ethyl acetate, extracted with water, and the organic layer was dried over sodium sulfate (NaSO ₄ ), and the remaining organic layer was concentrated. The concentrated organic layer was developed with a silicon dioxide (SiO ₂ ) column chromatography with a mixed solution of hexane : ethyl acetate = 10 : 1 (volume ratio), followed by column purification to obtain 57.0 g of compound (9). (Yield: 65 to 70%, ¹ H-NMR (CDCl ₃ , Varian 400 MHz): δ 0.88 (3H, t, J = 12 Hz), 1.27-1.71 (14H, m), 3.86 (1H, dd, J = 8.0, 3.2 Hz), 4.07–4.15 (2H, m), 6.29 (2H, s).

[Scheme 6]

[Production Example 5] Synthesis of 2-Decyl-2,3-dihydrothieno[3,4-b][1,4]dioxine

As shown in Scheme 7 below, 3,4-dimethoxythiophene (3,4-dimethoxythiophene, (1)) 30.00 g (208.06 mmol), 1,2-dodecanediol (1,2-dodecanediol, ( 10) 42.07 g (416.12 mmol), 3.96 g (20.81 mmol) of p-toluenesulfonic acid and 300 mL of toluene were mixed and reacted with stirring at 110 ° C. for 9 hours. , The reaction solution was completely dissolved, extracted with water, and the organic layer was dried with sodium sulfate (NaSO ₄ ), and the remaining organic layer was concentrated The concentrated organic layer was subjected to silicon dioxide (SiO ₂ ) column chromatography to obtain hexane: ethyl acetate = 10 : 1 (volume ratio) 38.20 g of compound (9) was obtained by column purification while developing the mixed solution.(Yield: 65 to 70%, ¹ H-NMR (CDCl ₃ , Varian 400 MHz): δ 0.88 (3H, t , J = 12 Hz), 1.27–1.71 (18H, m), 3.86 (1H, dd, J = 8.0, 3.2 Hz), 4.07–4.15 (2H, m), 6.29 (2H, s).

[Scheme 7]

[Comparative Example 1] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly mono - propyl EDOT) and preparation of solid electrolytic capacitor

After the surface of the aluminum foil is etched, a chemical conversion treatment is performed to form a dielectric layer made of an oxide film on the surface of the aluminum foil, and lead terminals are attached to the anode and the cathode made of the aluminum foil, and the lead terminals are attached. A capacitor element was fabricated by winding an anode and a cathode through a nylon separator.

3,4-ethylenedioxythiophene monomer and (2-propyl 2,3-dihydrocyeno) dioxin monomer solution prepared in Preparation Example 1 (molar ratio: respectively 50%: 50%, 1:1) were mixed. After preparing by mixing, a conductive polymer electrolyte solution was prepared by mixing 50% p-toluenesulfonic acid ferric salt/n-butanol solution as an oxidizing agent at a ratio of 1:2.5 (weight ratio). The capacitor element was immersed in the conductive polymer electrolyte solution, taken out, and sequentially heated at 45° C. for 2 hours, 105° C. for 35 minutes, and 125° C. for 1 hour to perform oxidative polymerization, thereby forming a solid made of a conductive polymer. An electrolyte layer was formed. The capacitor case was sealed using an epoxy resin, and aging was performed by applying a voltage of 4 V to the anode and the cathode, thereby manufacturing an aluminum wound solid electrolytic capacitor.

[Comparative Example 2] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly mono-butyl EDOT ) and preparation of solid electrolytic capacitor

A pre-treated capacitor was prepared in the same manner as in Comparative Example 1, and the polymerization compound 3,4-ethylenedioxythiophene monomer used in Comparative Example 1 and (2-butyl 2,3-di An aluminum winding type solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that hydrocyeno)dioxin monomers were mixed at a molar ratio of 50% (1:1), respectively.

[Example 1] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly propyl - octyl EDOT) and the manufacture of solid electrolytic capacitors

A pre-processed condenser was prepared in the same manner as in Comparative Example 1, and the (2-propyl 2,3-dihydrocyeno) dioxin monomer and (2-octyl 2,3-dihydrogenol) prepared in Preparation Examples 1 and 4 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 1:9.

[Example 2] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - octyl EDOT) and preparation of solid electrolytic capacitor

A pre-treated capacitor was prepared in the same manner as in Comparative Example 1, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-octyl 2,3-di An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 1:9.

[Example 3] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( poly butyl - decyl EDOT) and preparation of solid electrolytic capacitor

A capacitor preliminarily treated in the same manner as in Comparative Example 1 was prepared, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-decyl 2,3-dihydrogenol) prepared in Preparation Examples 2 and 5 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 1:9.

[Example 4] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly propyl - octyl EDOT) and the manufacture of solid electrolytic capacitors

A pre-processed condenser was prepared in the same manner as in Comparative Example 1, and the (2-propyl 2,3-dihydrocyeno) dioxin monomer and (2-octyl 2,3-dihydrogenol) prepared in Preparation Examples 1 and 4 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 2:8.

[Example 5] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( poly butyl - octyl EDOT) and preparation of solid electrolytic capacitor

A pre-treated capacitor was prepared in the same manner as in Comparative Example 1, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-octyl 2,3-di An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 2:8.

[Example 6] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - decyl EDOT) and preparation of solid electrolytic capacitor

A capacitor preliminarily treated in the same manner as in Comparative Example 1 was prepared, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-decyl 2,3-dihydrogenol) prepared in Preparation Examples 2 and 5 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 2:8.

[Example 7] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly propyl - octyl EDOT) and the manufacture of solid electrolytic capacitors

A pre-processed condenser was prepared in the same manner as in Comparative Example 1, and the (2-propyl 2,3-dihydrocyeno) dioxin monomer and (2-octyl 2,3-dihydrogenol) prepared in Preparation Examples 1 and 4 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 3:7.

[Example 8] Preparation of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - octyl EDOT)

A pre-treated capacitor was prepared in the same manner as in Comparative Example 1, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-octyl 2,3-di An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 3:7.

[Example 9] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - decyl EDOT) and preparation of solid electrolytic capacitor

A capacitor preliminarily treated in the same manner as in Comparative Example 1 was prepared, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-decyl 2,3-dihydrogenol) prepared in Preparation Examples 2 and 5 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 3:7.

[Example 10] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly hexyl - decyl EDOT ) and the manufacture of solid electrolytic capacitors

A pretreated condenser was prepared in the same manner as in Comparative Example 1, and the (2-hexyl 2,3-dihydrocyeno) dioxin monomer and (2-decyl 2,3 prepared in Preparation Examples 3 and 5 were prepared). An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the dihydroxeno)dioxin monomers were mixed in a molar ratio of 3:7.

[Example 11] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly propyl - octyl EDOT) and the manufacture of solid electrolytic capacitors

A pre-processed condenser was prepared in the same manner as in Comparative Example 1, and the (2-propyl 2,3-dihydrocyeno) dioxin monomer and (2-octyl 2,3-dihydrogenol) prepared in Preparation Examples 1 and 4 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 5:5.

[Example 12] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( poly butyl - octyl EDOT) and preparation of solid electrolytic capacitor

A pre-treated capacitor was prepared in the same manner as in Comparative Example 1, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-octyl 2,3-di An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 5:5.

[Example 13] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( poly butyl - decyl EDOT) and preparation of solid electrolytic capacitor

A capacitor preliminarily treated in the same manner as in Comparative Example 1 was prepared, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-decyl 2,3-dihydrogenol) prepared in Preparation Examples 2 and 5 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed in a molar ratio of 5:5.

[Example 14] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly manufacture of hexyl - decyl EDOT) and solid electrolytic capacitors

A pretreated condenser was prepared in the same manner as in Comparative Example 1, and the (2-hexyl 2,3-dihydrocyeno) dioxin monomer and (2-decyl 2,3 prepared in Preparation Examples 3 and 5 were prepared). An aluminum winding type solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that dihydroxeno)dioxin monomers were mixed in a molar ratio of 5:5.

[Example 15] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly propyl - octyl EDOT) and the manufacture of solid electrolytic capacitors

A pre-processed condenser was prepared in the same manner as in Comparative Example 1, and the (2-propyl 2,3-dihydrocyeno) dioxin monomer and (2-octyl 2,3-dihydrogenol) prepared in Preparation Examples 1 and 4 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 6:4.

[Example 16] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - octyl EDOT) and preparation of solid electrolytic capacitor

A pre-treated capacitor was prepared in the same manner as in Comparative Example 1, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-octyl 2,3-di An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 6:4.

[Example 17] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - decyl EDOT) and preparation of solid electrolytic capacitor

A capacitor preliminarily treated in the same manner as in Comparative Example 1 was prepared, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-decyl 2,3-dihydrogenol) prepared in Preparation Examples 2 and 5 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 6:4.

[Example 18] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly propyl - octyl EDOT) and the manufacture of solid electrolytic capacitors

A pre-processed condenser was prepared in the same manner as in Comparative Example 1, and the (2-propyl 2,3-dihydrocyeno) dioxin monomer and (2-octyl 2,3-dihydrogenol) prepared in Preparation Examples 1 and 4 were prepared. An aluminum winding type solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that hydrocyeno)dioxin monomers were mixed in a molar ratio of 7:3.

[Example 19] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - octyl EDOT) and preparation of solid electrolytic capacitor

A pre-treated capacitor was prepared in the same manner as in Comparative Example 1, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-octyl 2,3-di An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 7:3.

[Example 20] Polymerization of 3,4 -ethylenedioxythiophene copolymer ( Poly butyl - decyl EDOT) and preparation of solid electrolytic capacitor

A capacitor preliminarily treated in the same manner as in Comparative Example 1 was prepared, and the (2-butyl 2,3-dihydroxieno) dioxin monomer and (2-decyl 2,3-dihydrogenol) prepared in Preparation Examples 2 and 5 were prepared. An aluminum wound solid electrolytic capacitor was manufactured in the same manner as in Comparative Example 1, except that the hydrocyeno)dioxin monomers were mixed at a molar ratio of 7:3.

[Experimental Example 1] Evaluation of aluminum wound solid electrolytic capacitor

ESR at 100 kHz and capacitance at 120 Hz were measured for the wound aluminum solid electrolytic capacitors prepared in Comparative Examples 1 and 2 and Examples 1 to 18 using an LCR meter (4284A) from HEWLETTPACKARD under conditions of 25 ° C. The breakdown voltage was measured using PRk 650-2.5 manufactured by Matsusada Precision Zone under conditions of 25° C. by raising the voltage at a rate of 1 V/min to measure the voltage, and the results are shown in Table 1 below. In Table 1 below, the values of ESR, capacitance, and breakdown voltage are obtained by averaging 30 values each, ESR and capacitance are values shown by rounding to the second decimal place, and breakdown voltage values to less than a decimal point (8 x element size of 9, operating voltage: 80 V, capacitance: 22 μF).

Capacity change rate (%) ESR (mΩ) Leakage current (㎂) Breakdown voltage (V) Comparative Example 1 -1.1 17.3 25.5 35 Comparative Example 2 -2.1 22.1 26.5 35 Example 1 -12.0 32.2 42.5 55 Example 2 -9.9 43.4 55.4 60 Example 3 -14.8 60.4 62.5 65 Example 4 -14.6 20.5 22.8 55 Example 5 -12.1 28.6 64.5 58 Example 6 -19.7 68.2 48.3 70 Example 7 -20.8 34.6 53.4 75 Example 8 -11.9 26.7 21.0 80 Example 9 -26.8 73.5 35.6 75 Example 10 -27.9 81.5 45.5 70 Example 11 -7.0 15.2 48.7 70 Example 12 -22.0 32.1 20.9 50 Example 13 -12.8 41.8 25.4 65 Example 14 -17.6 73.5 35.6 70 Example 15 -18.6 29.1 28.4 55 Example 16 -12.0 38.8 22.4 60 Example 17 -22.2 52.3 20.2 63 Example 18 -14.3 38.2 43.4 40 Example 19 -17.8 45.6 48.5 44 Example 20 -28.7 54.5 55.4 60

As shown in Table 1, the wound type aluminum solid electrolytic capacitors prepared in Examples 1 to 18 have a lower rate of change in capacitance than the wound type aluminum solid electrolytic capacitors prepared in Comparative Examples 1 and 2, and are important for capacitors. In the case of ESR (equivalent series resistance) and breakdown voltage, which are characteristics, the ESR was formed in a range of 15 to 82, respectively, and the breakdown voltage was 40 to 80 V, compared to the wound aluminum solid electrolytic capacitor of Comparative Examples 1 and 2. It can be seen that it has a high breakdown voltage and a low ESR value, in particular, the ESR of the wound type aluminum electrolytic capacitors of Examples 4, 5, 8, 11 and 15 is as high as 20 mΩ, and satisfies the target ESR of 30 mΩ or less, It can be seen that the breakdown voltage is 1.5 times higher than that of the wound type aluminum electrolytic capacitors of Comparative Examples 1 and 2, and the withstand voltage and ESR characteristics are excellent.

Claims (11)

A 3,4-ethylenedioxythiophene copolymer represented by Formula 1 below.
[Formula 1]

In Formula 1, n is an integer of 1 to 4, m is an integer of 5 to 8, and a and b are mole% of each repeating unit with respect to all repeating units constituting the copolymer of Formula 1. , 10 to 90 mol%, respectively. The 3,4-ethylene according to claim 1, wherein the 3,4-ethylenedioxythiophene copolymer is a copolymer of two or more monomers including a monomer represented by Formula 2 below and a monomer represented by Formula 3 below. Deoxythiophene Copolymer.
[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is an integer from 1 to 4, and m is an integer from 5 to 8. The 3,4-ethylenedioxythiophene copolymer according to claim 1, wherein a is 10 to 60 mol% and b is 40 to 90 mol%. The 3,4-ethylenedioxythiophene copolymer according to claim 1, wherein the difference between n and m is 4 or more. The 3,4-ethylenedioxythiophene copolymer according to claim 1, wherein n is an integer of 1 to 2 and m is 8. The 3,4-ethylenedioxythiophene copolymer according to claim 1, wherein the 3,4-ethylenedioxythiophene copolymer has a weight average molecular weight of 100 to 5,000. A solid electrolyte comprising the copolymer according to any one of claims 1 to 6. an anode electrode layer having an oxide film;
a cathode electrode layer; and
a separator positioned between the anode electrode layer and the cathode electrode layer; and a solid electrolyte;
The solid electrolyte is a 3,4-ethylenedioxythiophene copolymer represented by Formula 1 below, a solid electrolyte capacitor.
[Formula 1]

In Formula 1, n is an integer of 1 to 4, m is an integer of 5 to 8, and a and b are mole% of each repeating unit with respect to all repeating units constituting the copolymer of Formula 1. , 10 to 90 mol%, respectively. 9. The solid electrolytic capacitor according to claim 8, wherein n is an integer from 1 to 2, m is 8, and the equivalent series resistance (ESR) is 30 mΩ or less. 9. The solid electrolytic capacitor according to claim 8, wherein the positive electrode layer, the negative electrode layer and the separator are wound. An electronic component comprising the capacitor according to any one of claims 8 to 10.

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