TWI492981B - Electrolyte, method and composition for preparing the same, and capacitor employing the same - Google Patents

Description

Electrolyte and method of producing the same, composition for forming an electrolyte, and inclusion Capacitor

The present invention relates to an electrolyte, a method of producing the same, a composition for forming an electrolyte, and a capacitor comprising the same.

Capacitors are electronic components that are widely used in various electronic products. With the development of technology, electronic products tend to be smaller and lighter. The capacitors used in them are miniaturized, large-capacity, and used at high frequencies. Characteristics such as lower low impedance.

Capacitors can be divided into traditional liquid capacitors and newly developed solid capacitors depending on the electrolyte type. Although the conventional liquid capacitor satisfies the demand for large capacity at a low cost, since the electrolyte used is a liquid, there are disadvantages such as low conductivity and high temperature resistance. Although liquid electrolytes can be added with hydrogen absorbing agents to reduce the possibility of explosion, they do not solve the problem at all.

The solid electrolyte is composed of a conductive polymer, and the conductive polymer has higher conductivity than the liquid electrolyte used in the conventional electrolytic capacitor, and has moderate high-temperature insulation characteristics. In the current manufacture of solid capacitors, reactive monomers (such as 3,4-ethylenedioxythiophene (EDOT)) and iron salt oxidants (such as iron (to) (Iron(III)) are generally used. P-toluenesulfonate, FePTS) is polymerized to obtain Conductive polymer. However, the conductivity of the conductive polymer obtained by the polymerization using the conventional iron salt oxidant is not high, and the solid capacitor including the same has a high energy consumption coefficient (DF) and equivalent series resistance (equivalent series). Resistance, ESR).

Based on the above, the development of a novel solid electrolyte to solve the problems encountered in the prior art is an important subject of the current solid state electrical technology.

The invention provides an electrolyte comprising: a conductive polymer, an iron ion, an auxiliary metal ion, and a pair of toluenesulfonic acid anion dispersion, wherein the auxiliary metal ion is cobalt ion, nickel ion, copper ion, zinc ion a calcium ion, a manganese ion, or a combination thereof; and the conductive polymer is polymerized from a monomer having a structure represented by the formula (I) , wherein X ¹ and X ² are independently O or S; Y is ,or And each R is independently hydrogen or a C _1-6 alkyl group.

According to another embodiment of the present invention, the present invention also provides a composition for forming the above electrolyte, comprising: a pair of iron salt of toluenesulfonic acid; a metal salt of auxiliary p-toluenesulfonic acid, wherein the auxiliary p-toluenesulfonic acid metal salt system Cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate, manganese p-toluenesulfonate, or a combination thereof; (I) monomer of the structure shown

Wherein, X ¹ and X ² are independently O or S; Y is , or And each R is independently hydrogen or a C _1-6 alkyl group.

According to another embodiment of the present invention, the present invention also provides a method for producing an electrolyte, comprising: mixing a pair of toluenesulfonic acid iron salt, an auxiliary p-toluenesulfonic acid metal salt, and a monomer, and performing a polymerization reaction, The auxiliary p-toluenesulfonic acid metal salt is a p-toluenesulfonic acid cobalt salt, a p-toluenesulfonic acid nickel salt, a toluenesulfonate copper salt, a p-toluenesulfonic acid zinc salt, a p-toluenesulfonic acid calcium salt, a p-toluenesulfonic acid manganese salt. Or a combination thereof; and the monomer has the structure represented by the formula (I)

Wherein, X ¹ and X ² are independently O or S; Y is , or And each R is independently hydrogen or a C _1-6 alkyl group.

According to another embodiment of the present invention, the present invention also provides a capacitor, which may include a capacitor element; and an electrolyte formed on the capacitor element, wherein the electrolyte is coated on the capacitor element by the composition for forming an electrolyte described above. Formed on it.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

Fig. 1 is a UV absorption spectrum of a p-toluenesulfonic acid metal salt, EDOT, and PEDOT obtained in Preparation Examples 1-8 of the present invention.

Fig. 2 is a graph showing the absorbance of UV light having a wavelength of 350 nm versus time for a p-toluenesulfonic acid metal salt solution of Comparative Example 1-8 of the present invention.

Fig. 3 is a graph showing the absorbance of UV light having a wavelength of 350 nm versus time for a p-toluenesulfonic acid metal salt solution of Comparative Example 1 and Example 1-4 of the present invention.

Fig. 4 is a graph showing the absorbance of UV light having a wavelength of 350 nm versus time for the p-toluenesulfonic acid metal salt solutions of Comparative Examples 1 and 9 and Examples 2 and 5-9 of the present invention.

Fig. 5 is a graph showing the absorbance of UV light having a wavelength of 350 nm versus time for a p-toluenesulfonic acid metal salt solution of Comparative Example 1 and Examples 10-14 of the present invention.

The present invention discloses an electrolyte, a composition for forming the same, and uses thereof. The electrolyte is characterized by oxidative polymerization of a monomer (for example, 3,4-ethylenedioxythiophene, EDOT) using a specific oxidizing agent. Since the specific oxidizing agent contains an organic sulfonic acid metal in addition to the organic sulfonic acid iron salt The salt can assist in catalyzing the oxidative polymerization of the monomer in the iron ion, thereby increasing the reactivity of the monomer and increasing the degree of polymerization of the obtained conductive polymer. The above electrolytes are well suited for use in solid electrolytic capacitors, which increase the capacitance value and reduce the dissipation factor (DF) and equivalent series resistance (ESR).

The electrolyte of the present invention may be a solid electrolyte comprising a conductive polymer, a ferric ion, an auxiliary metal ion, and a pair of toluenesulfonic acid anions. Wherein, the auxiliary metal ion is cobalt ion, nickel ion, copper ion, zinc ion, calcium ion, manganese ion, or a combination thereof; and the conductive polymer is a monomer having a structure represented by formula (I) Aggregate , wherein X ¹ and X ² are independently O or S; Y is , or And each R is independently hydrogen or a C _1-6 alkyl group. According to other embodiments of the invention, the p-toluenesulfonic acid anion may be substituted with other suitable organic sulfonic acid anions.

Further, according to an embodiment of the present invention, in addition to the iron ions, the auxiliary metal ions, and the p-toluenesulfonic acid anion, the electrolyte may further comprise an aluminum ion.

Furthermore, according to other embodiments of the present invention, the monomer having the structure shown in the formula (I) may be ,or .

An embodiment of the invention also provides a composition for forming the electrolyte described above. The composition may comprise the following components: a solvent; a pair of toluenesulfonic acid iron salts; a secondary p-toluenesulfonic acid metal salt, wherein the auxiliary p-toluenesulfonic acid metal salt is a p-toluenesulfonic acid cobalt salt, a p-toluenesulfonic acid nickel salt Salt, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate, manganese p-toluenesulfonate, or a combination thereof; and a monomer having the structure shown in formula (I)

Wherein, X ¹ and X ² are independently O or S; Y is , or And each R is independently hydrogen or a C _1-6 alkyl group.

The solvent can be, for example, an alcohol solvent such as methanol, ethanol, butanol, or a combination thereof. The monomer having the structure represented by the formula (I) may be , or .

According to an embodiment of the invention, the composition may further comprise a pair of aluminum tosinates.

It is worth noting that the solid content of the composition for forming an electrolyte may be between 20% and 70%. If the solid content is too low, the number of equivalents is insufficient to completely react with EDOT, and the voids in the capacitor are too large. To reduce the reliability of the capacitor, if the solid content is too high, the viscosity of the solution is too high to penetrate into the hole of the aluminum foil, resulting in a decrease in capacitance. In the composition, the p-toluenesulfonic acid metal salt (for example comprising iron p-toluenesulfonate and auxiliary p-toluenesulfonic acid metal salt, or p-toluenesulfonic acid iron salt, auxiliary p-toluenesulfonic acid metal salt, and p-toluene The weight ratio of the aluminum sulfonate salt to the monomer may be between 0.4 and 2, such as between 0.4 and 1.8, between 0.5 and 1.8, or between 0.6 and 1.6. In addition, the weight ratio of the p-toluenesulfonic acid iron salt to the auxiliary p-toluenesulfonic acid metal salt (or auxiliary p-toluenesulfonic acid metal salt and p-toluenesulfonic acid aluminum salt) may be between 19,000 and 190, if the weight ratio is higher than The effect of 19000 auxiliary p-toluenesulfonic acid metal salt and p-toluenesulfonic acid aluminum salt is not obvious. On the contrary, if the weight ratio is less than 190, the p-toluenesulfonic acid iron salt concentration is insufficient, and the reactivity of the p-toluenesulfonic acid metal salt composition is lowered. .

Since the electrical characteristics of the capacitor (such as capacitance value, energy consumption coefficient, and equivalent series resistance) are mainly determined by the degree of polymerization of the conductive polymer (polymerized by the monomer), the factors mainly affect the polymerization degree of the conductive polymer. It is the choice of oxidant. When a monomer (such as EDOT) is reacted with an oxidant of a different formulation, a conductive polymer of a different molecular weight (for example, ploy(3,4-ethylenedioxythiophene), PEDOT) is obtained.

In the present invention, at least two kinds of organic sulfonic acid metal salts (one of which is an organic sulfonic acid iron salt) are used to enhance the reactivity of the oxidizing agent to increase the degree of polymerization of the conductive polymer. When the monomer is polymerized, it is more susceptible to electrons released by a monomer (for example, EDOT) due to the presence of a metal ion other than iron ions (M ⁽ⁿ⁺¹⁾⁺ , n is an integer of 1 or more). At the same time, the metal ion can further promote the transfer of electrons to the iron ions, assisting and catalyzing the oxidative polymerization of the monomer (for example, EDOT) in the iron ions.

The above reaction mechanism can be expressed by the chemical reaction formula: EDOT+M ⁿ⁺ → PEDOT+Mn ⁽ⁿ⁺¹⁾⁺

Fe ³⁺ +M ⁽ⁿ⁺¹⁾⁺ → Fe ²⁺ +M ⁿ⁺

The total reaction formula is: EDOT+Fe ³⁺ → PEDOT+Fe ²⁺

When iron ions are used for oxidative polymerization of EDOT, electrons of EDOT are transferred to iron ions. However, EDOT and iron ions differ greatly in energy level, and electron transfer from each other is not easy. Therefore, if a suitable metal ion can be provided, the electron energy of the EDOT can be easily transferred to the metal ion, and the electron between the metal ion and the iron ion can be easily transferred, thereby reducing the activation energy of the reaction and improving the EDOT. Reactivity.

Based on the above, the present invention mainly utilizes an organic sulfonic acid iron salt and an organic sulfonic acid metal salt as an oxidizing agent, and is used for oxidative polymerization of a monomer to enhance the reactivity of the monomer (reducing the amount of unreacted monomers) , a conductive polymer having a higher degree of polymerization is obtained. As a result, electrical characteristics (for example, capacitance value, energy consumption coefficient, and equivalent series resistance) of the capacitor using the above-mentioned high polymerization degree conductive polymer as an electrolyte can be improved.

According to other embodiments of the present invention, the present invention also provides a capacitor, which may include a capacitor element; and an electrolyte formed on the capacitor element Above, wherein the electrolyte is formed by coating the above-mentioned composition for forming an electrolyte on the crypto-ene. Here, the capacitor element refers to a semi-finished product of a capacitor, that is, a capacitor that has not been coated with an electrolyte. The manufacturing method of the capacitor element can be, for example, nailing an anode metal foil (for example, aluminum foil) and a cathode metal foil (for example, aluminum foil) to a guide pin, separating the two electrodes by a separator paper, and winding the two electrodes and the separator paper. Wrap it and finally fix it with tape. The capacitor element can be further oxidized by applying a voltage of 20 V to a 10% aqueous solution of diammonium adipate to form a dielectric layer on the surface and washed with pure water. It was then dried at 120 ° C for 30 minutes, and the separator paper was carbonized at 250 ° C, and cooled for use.

The above-described and other objects, features, and advantages of the present invention will become more apparent and understood. Capacitor.

Synthesis of p-toluenesulfonic acid metal salt

Preparation Example 1: Synthesis of iron p-toluenesulfonate

FeO(OH) 8.89 g was taken, 57 g of p-toluenesulfonic acid and 200 g of water were added, and the temperature was slowly raised to 90 ° C, and stirred at this temperature for 4 hours. After the reaction was completed, the temperature was lowered to 60 ° C, and insoluble materials were collected. Next, the insoluble matter was washed with 25 g of pure water at 60 °C. The filtrate was collected and some of the water (100 g) was removed by concentration under reduced pressure. Next, the precipitated crystals were heated and dissolved, and then allowed to stand to obtain yellow flaky crystals. Finally, the collected yellow flaky crystals were dried at 120 ° C to give an orange solid in a yield of 51.6%.

Preparation Example 2: Synthesis of cobalt p-toluenesulfonate

This was carried out as described in Preparation 1, except that FeO(OH) was replaced by cobalt hydroxide (9.3 g), and the addition of p-toluenesulfonic acid was changed from 57 g to 38 g. After crystallization An orange-red flaky crystal was obtained, which was dried to give a yellow solid (yield: 75.4%).

Preparation Example 3: Synthesis of nickel p-toluenesulfonate

This was carried out as described in Preparation Example 1, except that FeO(OH) was replaced by nickel hydroxide (9.3 g), and the addition of p-toluenesulfonic acid was changed from 57 g to 38 g. After crystallization, green flake crystals were obtained, which were dried to give a pink solid, yield: 82.1%.

Preparation Example 4: Synthesis of copper p-toluenesulfonate

This was carried out as described in Preparation 1, except that FeO(OH) was replaced by copper hydroxide (9.8 g), and the addition of p-toluenesulfonic acid was changed from 57 g to 38 g. After crystallization, blue needle-like crystals were obtained, which were dried to give a green solid, yield 85.5%.

Preparation Example 5: Synthesis of zinc p-toluenesulfonate

This was carried out as described in Preparation 1, except that FeO(OH) was replaced by zinc hydroxide (9.9 g), and the addition of p-toluenesulfonic acid was changed from 57 g to 38 g. After crystallization, white flake crystals were obtained, which were dried to give a white solid.

Preparation Example 6: Synthesis of calcium p-toluenesulfonate

7.4 g of calcium hydroxide was slowly added to 10-20 ° C of pure water (200 g) and stirred uniformly. Thereafter, 38 g of p-toluenesulfonic acid was slowly added to control the temperature of the reaction solution to be lower than 40 °C. After the p-toluenesulfonic acid was completely added, it was heated to 80 ° C, stirred for 2 hours, and then cooled to 60 ° C to collect insoluble matters. Next, the insoluble matter was washed with 25 g of pure water at 60 °C. The filtrate was collected and some of the water (100 g) was removed by concentration under reduced pressure. After the precipitated crystals were heated and dissolved, the white needle crystals were allowed to stand. Finally, the collected white needle crystals were dried at 120 ° C to give a white solid in a yield of 70.0%.

Preparation Example 7: Synthesis of aluminum p-toluenesulfonate

Take 13.3 grams of aluminum chloride, add 100 grams of water, stir to dissolve, cool down to After 15 ° C, 1 N NaOH was slowly added to about 100 mL, and the pH was controlled between 5-9, at which time a white solid was produced. The solid was precipitated at the bottom by a centrifuge, and after the clarified liquid was poured out, an equal amount of pure water was added. The impurities were repeatedly removed by centrifugation and pure water was added 10 times. Only 50 g of water was added at the last time, and 57 g of p-toluenesulfonic acid was added, and heated to 80 ° C, and uniformly stirred for 4 hours. After the completion of the reaction, the mixture was filtered while hot, and about 30 g of water was removed under reduced pressure, and the crystals were allowed to stand to obtain white needle crystals. Finally, the white needle crystals were dried at 120 ° C to give a white powder solid in a yield of 52%.

Preparation Example 8: Synthesis of manganese p-toluenesulfonate

8.7 g of MnO2 was taken, 50 mL of water and 10 mL of 37% hydrochloric acid were added, and the mixture was heated to 60 ° C and stirred for 2 hours until MnO _{2 was} dissolved. After dissolution, 1 M aqueous NaOH was added and the pH was adjusted between 5 and 9 to give a brown solid. The solid was precipitated at the bottom by a centrifuge, and after the clarified liquid was poured out, an equal amount of pure water was added. The impurities were repeatedly removed by centrifugation and pure water was added 10 times. The last time 200 g of water was added, and 76 g of p-toluenesulfonic acid was added, and heated to 80 ° C, and uniformly stirred for 4 hours. After the completion of the reaction, the mixture was filtered while hot, and an appropriate amount of water was removed under reduced pressure, and the crystals were allowed to stand to obtain white needle crystals. The white needle crystals were dried at 120 ° C to give a white powder solid, yield 56%.

UV absorption of p-toluenesulfonic acid metal salt, EDOT, and PEDOT

The p-toluenesulfonic acid metal salt (0.1 g) obtained in Preparation Example 1-8, 0.1 g EDOT (3,4-ethylenedioxythiophene), and 0.1 g PEDOT (poly 3, 4) -Ethylene dioxythiophene (poly-3,4-ethylenedioxythiophene) was dissolved in 1 kg of acetonitrile, uniformly mixed and stirred, and then placed in a 100 ppm acetonitrile solution, and the UV absorption spectrum of the solutions was measured by an ultraviolet spectrometer. , please refer to the first result Figure.

It can be seen from Fig. 1 that at a wavelength of 350 nm, only PEDOT has significant UV absorption. Therefore, the detection wavelength of different p-toluenesulfonic acid metal salt composition and EDOT will be detected at 350 nm as the detection wavelength.

PEDOT polymerization degree assessment

Preparation Example 9: Preparation of EDOT solution

First, 1 g of EDOT (3,4-ethylenedioxythiophene) was dissolved in 99 g of methanol to prepare a 1% EDOT methanol solution.

Preparation Example 10: Preparation of iron p-toluenesulfonic acid solution

2 g of iron p-toluenesulfonate (obtained from Preparation Example 1) was added to 18 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain p-toluenesulfonic acid. Iron methanol solution.

Preparation 11: Preparation of a cobalt p-toluenesulfonate solution

0.2 g of cobalt p-toluenesulfonate (obtained from Preparation 2) was added to 19.8 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain 1% p-toluene. Cobalt sulfonate methanol solution.

Preparation Example 12: Preparation of a nickel p-toluenesulfonate solution

0.2 g of nickel p-toluenesulfonate (obtained from Preparation 3) was added to 19.8 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain 1% p-toluene. Nickel sulfonate methanol solution.

Preparation Example 13: Preparation of copper p-toluenesulfonate solution

0.2 g of copper p-toluenesulfonate (obtained from Preparation 4) was added to 19.8 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain 1% p-toluene. Copper sulfonate solution in methanol.

Preparation Example 14: Preparation of zinc p-toluenesulfonate solution

0.2 g of zinc p-toluenesulfonate (obtained from Preparation 5) was added to 19.8 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain 1% p-toluene. Zinc sulfonate methanol solution.

Preparation 15: Preparation of a calcium p-toluenesulfonate solution

0.2 g of calcium p-toluenesulfonate (obtained from Preparation Example 6) was added to 19.8 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain 1% p-toluene. Calcium sulfonate methanol solution.

Preparation 16: Preparation of an aluminum p-toluenesulfonate solution

0.2 g of aluminum p-toluenesulfonate (obtained from Preparation Example 7) was added to 19.8 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain 1% p-toluene. Aluminum sulfonate solution in methanol.

Preparation 17: Preparation of a manganese p-toluenesulfonate solution

0.2 g of manganese p-toluenesulfonate (obtained from Preparation Example 8) was added to 19.8 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain 1% p-toluene. Manganese sulfonate methanol solution.

Preparation Example 18: Preparation of iron containing p-toluenesulfonate and cobalt p-toluenesulfonate I

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.06 g of a cobalt p-toluenesulfonic acid solution (obtained in Preparation Example 11), and 0.44 g of methanol were added, and the mixture was uniformly stirred to obtain iron p-toluenesulfonate. And iron-p-toluenesulfonic acid iron solution I, wherein the ratio of iron p-toluenesulfonate to cobalt p-toluenesulfonate is 1580.

Preparation Example 19: Preparation of iron containing p-toluenesulfonate and cobalt p-toluenesulfonate II

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.12 g of a cobalt p-toluenesulfonic acid solution (obtained in Preparation Example 11), and 0.38 g of methanol were stirred, and the mixture was uniformly stirred to obtain iron p-toluenesulfonate. And iron-p-toluenesulfonic acid iron cobalt solution II, wherein the ratio of iron p-toluenesulfonate to cobalt p-toluenesulfonate is 790.

Preparation Example 20: Preparation of iron containing p-toluenesulfonate and cobalt p-toluenesulfonate III

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.25 g of a cobalt p-toluenesulfonic acid solution (obtained from Preparation 11), and 0.25 g of methanol were added, and the mixture was uniformly stirred to obtain iron p-toluenesulfonate. And iron-p-toluenesulfonic acid solution III, wherein the ratio of iron p-toluenesulfonate to cobalt p-toluenesulfonate is 380.

Preparation Example 21: Preparation of iron containing p-toluenesulfonic acid and cobalt p-toluenesulfonate IV

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.5 g of a cobalt p-toluenesulfonic acid solution (obtained in Preparation Example 11), and 0.25 g of methanol were stirred, and the mixture was uniformly stirred to obtain iron p-toluenesulfonate. And iron-p-toluenesulfonic acid iron cobalt solution IV, wherein the ratio of iron p-toluenesulfonate to cobalt p-toluenesulfonate is 190.

Preparation 22-25: Preparation of iron-containing p-toluenesulfonic acid and nickel p-toluenesulfonate I-IV

The procedure described in Preparations 18-21 was carried out except that the cobalt p-toluenesulfonic acid solution (obtained in Preparation 11) was used instead of the nickel p-toluenesulfonate solution (obtained in Preparation Example 12), respectively Iron tosylate and nickel p-toluenesulfonate solution I-IV, wherein the ratio of iron p-toluenesulfonate to nickel-p-toluenesulfonate in iron-p-toluenesulfonic acid and nickel-p-toluenesulfonate I-IV is 1580, 790, 380, and 190.

Preparation 26-29: Preparation of iron-containing p-toluenesulfonate and copper p-toluenesulfonate I-IV

The procedure described in Preparations 18-21 was carried out except that the cobalt p-toluenesulfonate solution (obtained from Preparation 11) was changed to a copper p-toluenesulfonate solution (obtained in Preparation Example 13), respectively, to give a pair. Iron toluenesulfonic acid and copper p-toluenesulfonate solution I-IV, wherein in the iron-containing p-toluenesulfonic acid and copper p-toluenesulfonate solution I-IV, the ratio of iron p-toluenesulfonate to copper p-toluenesulfonate is 1580, 790, 380, and 190.

Preparation 30-33: Preparation of iron containing p-toluenesulfonate and zinc p-toluenesulfonate I-IV

The procedure described in Preparations 18-21 was carried out except that the cobalt p-toluenesulfonate solution (obtained from Preparation 11) was changed to a zinc p-toluenesulfonate solution (obtained from Preparation Example 14), respectively, to give a pair. Iron toluenesulfonic acid and zinc p-toluenesulfonic acid solution I-IV, wherein the ratio of iron p-toluenesulfonate to zinc p-toluenesulfonate in the solution of iron p-toluenesulfonate and zinc p-toluenesulfonate I-IV is 1580, 790, 380, and 190.

Preparation 34-37: Preparation of iron-containing p-toluenesulfonate and calcium p-toluenesulfonate solution I-IV

The procedure described in Preparations 18-21 was carried out except that the cobalt p-toluenesulfonate solution (obtained from Preparation 11) was changed to a calcium p-toluenesulfonate solution (obtained in Preparation Example 15) to obtain a pair. Iron toluenesulfonic acid and calcium p-toluenesulfonate solution I-IV, wherein the ratio of iron p-toluenesulfonate to calcium p-toluenesulfonate in the solution of iron p-toluenesulfonate and calcium p-toluenesulfonate I-IV is 1580, 790, 380, and 190.

Preparation 38-41: Preparation of iron-containing p-toluenesulfonate and aluminum p-toluenesulfonate solution I-IV

The procedure described in Preparations 18-21 was carried out except that the cobalt p-toluenesulfonate solution (obtained in Preparation 11) was changed to a p-toluenesulfonic acid aluminum solution (obtained in Preparation Example 16) to obtain a pair. Iron toluenesulfonic acid and aluminum p-toluenesulfonic acid solution I-IV, wherein in the iron-containing p-toluenesulfonic acid and aluminum p-toluenesulfonate solution I-IV, the ratio of iron p-toluenesulfonate to aluminum p-toluenesulfonate is 1580, 790, 380, and 190.

Preparation 42-45: Preparation of iron-containing p-toluenesulfonate and manganese p-toluenesulfonate solution I-IV

The procedure described in Preparations 18-21 was carried out except that the cobalt p-toluenesulfonate solution (obtained from Preparation 11) was changed to a manganese p-toluenesulfonate solution (obtained in Preparation Example 17) to obtain a pair. Iron toluenesulfonic acid and manganese p-toluenesulfonate solution I-IV, wherein in the solution of iron p-toluenesulfonate and manganese p-toluenesulfonate I-IV, the ratio of iron p-toluenesulfonate to manganese p-toluenesulfonate is 1580, 790, 380, and 190.

Preparation Example 46: Preparation of iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, and copper p-toluenesulfonate

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.06 g of a cobalt p-toluenesulfonic acid solution (obtained in Preparation Example 11), and a copper p-toluenesulfonate solution (obtained in Preparation Example 13) of 0.44 g were obtained. After stirring uniformly, a solution containing iron p-toluenesulfonate, cobalt p-toluenesulfonate and copper p-toluenesulfonate is obtained, wherein the ratio of iron p-toluenesulfonate: cobalt p-toluenesulfonate: p-toluenesulfonate is 2375:3. :11.

Preparation 47: Iron containing p-toluenesulfonate, copper p-toluenesulfonate, pair Preparation of calcium toluenesulfonate and manganese p-toluenesulfonate solution

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.01 g of a copper p-toluenesulfonate solution (obtained in Preparation Example 13), and a calcium p-toluenesulfonate solution (obtained in Preparation Example 15) of 0.01 g, And 0.3 g of a p-toluenesulfonic acid manganese solution (obtained in Preparation Example 17), and uniformly stirred to obtain a solution containing iron p-toluenesulfonate, copper p-toluenesulfonate, calcium p-toluenesulfonate, and manganese p-toluenesulfonate, wherein Iron toluenesulfonate: copper p-toluenesulfonate: calcium p-toluenesulfonate: manganese p-toluenesulfonate is 9500:1:2:30.

Preparation Example 48: Preparation of iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, and manganese p-toluenesulfonate

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.05 g of a p-toluenesulfonic acid cobalt solution (obtained in Preparation Example 11), and a nickel p-toluenesulfonic acid solution (obtained in Preparation Example 12) of 0.05 g, 0.1 g of a p-toluenesulfonate copper solution (obtained in Preparation Example 13) and 0.2 g of a p-toluenesulfonic acid manganese solution (obtained in Preparation Example 17) were stirred uniformly to contain iron p-toluenesulfonate and cobalt p-toluenesulfonate. Nickel tosylate, copper p-toluenesulfonate, and manganese p-toluenesulfonate, wherein iron p-toluenesulfonate: cobalt p-toluenesulfonate: nickel p-toluenesulfonate: copper p-toluenesulfonate: manganese p-toluenesulfonate The ratio is 1900:1:1:2:4.

Preparation Example 49: Preparation of iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, and calcium p-toluenesulfonate

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.05 g of a p-toluenesulfonic acid cobalt solution (obtained in Preparation Example 11), and a nickel p-toluenesulfonic acid solution (obtained in Preparation Example 12) of 0.1 g, Copper p-toluenesulfonate solution (Preparation Example 13 Obtained) 0.05 g, 0.1 g of a p-toluenesulfonic acid zinc solution (obtained from Preparation Example 14), and a calcium p-toluenesulfonate solution (obtained from Preparation Example 15) of 0.005 g, and uniformly stirred with iron p-toluenesulfonate and p-toluene Cobalt sulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, and calcium p-toluenesulfonate, wherein iron p-toluenesulfonate: cobalt p-toluenesulfonate: nickel p-toluenesulfonate: The ratio of copper tosylate: zinc p-toluenesulfonate: calcium p-toluenesulfonate solution was 19000:10:20:10:20:1.

Preparation Example 50: Preparation of iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate, and manganese p-toluenesulfonate

9.5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10), 0.005 g of a p-toluenesulfonic acid cobalt solution (obtained in Preparation Example 11), and a nickel p-toluenesulfonic acid solution (obtained in Preparation Example 12) of 0.05 g, 0.05 g of p-toluenesulfonic acid copper solution (obtained in Preparation Example 13), 0.01 g of p-toluenesulfonic acid zinc solution (obtained from Preparation Example 14), calcium p-toluenesulfonate solution (obtained from Preparation Example 15), 0.005 g, p-toluene The manganese sulfonate solution (obtained from Preparation Example 17) was 0.04 g, and 0.1 g of methanol, and after stirring uniformly, iron p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, p-toluenesulfonate Zinc acid, calcium p-toluenesulfonate, and manganese p-toluenesulfonate, wherein iron p-toluenesulfonate: cobalt p-toluenesulfonate: nickel p-toluenesulfonate: copper p-toluenesulfonate: p-toluenesulfonate: p-toluene The ratio of calcium sulfonate: manganese p-toluenesulfonate solution is 19000:1:10:10:2:1:8.

Comparative Example 1

5 g of an iron p-toluenesulfonic acid solution (obtained in Preparation Example 10) and 5 g of a 1% EDOT methanol solution (obtained in Preparation Example 9) were uniformly mixed and placed in a UV absorption tank at a wavelength of 350 nm. Measuring its UV absorbance versus time Change, the result is shown in Figure 2.

Comparative Example 2-8

Comparative Example 2-8 was carried out as in Comparative Example 1, except that an iron p-toluenesulfonic acid solution (obtained from Preparation Example 10) was respectively obtained from a cobalt p-toluenesulfonic acid solution (obtained from Preparation Example 11), p-toluenesulfonic acid. Nickel solution (obtained from Preparation Example 12), copper p-toluenesulfonate solution (obtained in Preparation Example 13), zinc p-toluenesulfonate solution (obtained in Preparation Example 14), calcium p-toluenesulfonate solution (obtained in Preparation Example 15) , a solution of aluminum p-toluenesulfonate (obtained in Preparation Example 16), and a manganese p-toluenesulfonate solution (obtained in Preparation Example 17). The resulting solution was uniformly mixed and placed in a UV absorption tank, and the change in UV absorbance with time was measured by UV light having a wavelength of 350 nm. The results are shown in Fig. 2.

As can be seen from Fig. 2, when EDOT is combined with cobalt pentatosylate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate, aluminum p-toluenesulfonate or p-toluene, respectively. After the reaction of manganese sulfonate, the UV absorption was almost zero, indicating that no PEDOT was produced. In other words, use only cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate, aluminum p-toluenesulfonate or manganese p-toluenesulfonate, The EDOT was subjected to polymerization (Comparative Examples 2-8). In contrast, in Comparative Example 1, EDOT reacts with iron p-toluenesulfonate, and as time increases, UV absorption also increases and gradually approaches a certain value.

Example 1

5 g of iron p-toluenesulfonate and cobalt p-toluenesulfonate solution I (obtained in Preparation Example 18) and 1% EDOT methanol solution (obtained in Preparation Example 9) were uniformly mixed and placed in a UV absorption tank. , measuring the UV light with a wavelength of 350 nm The change in UV absorbance with respect to time was compared with the result of Comparative Example 1, and reference is made to Fig. 3.

Example 2-4

Example 2-4 was carried out as in Example 1, except that iron p-toluenesulfonate and cobalt p-toluenesulfonate I (obtained as Preparation 18) were respectively contained from iron containing p-toluenesulfonate and cobalt p-toluenesulfonate. Solution II (obtained from Preparation Example 19), iron containing p-toluenesulfonate and cobalt p-toluenesulfonate III (obtained from Preparation Example 20), and iron containing p-toluenesulfonic acid and cobalt p-toluenesulfonate IV (prepared from Substituted in Example 21). The obtained solutions were uniformly mixed and placed in a UV absorption tank, and the change in UV absorbance with time was measured by UV light having a wavelength of 350 nm, and compared with the results of Comparative Example 1, please refer to Fig. 3.

Example 5

5 g of iron p-toluenesulfonate and nickel p-toluenesulfonate II (obtained from Preparation 23) and 5 g of 1% EDOT methanol solution (obtained in Preparation Example 9) were uniformly mixed and placed in a UV absorption tank. The change in UV absorbance with time was measured by the amount of UV light having a wavelength of 350 nm, and compared with the result of Comparative Example 1, please refer to Fig. 4.

Example 6-9

Example 6-9 was carried out as in Example 5 except that iron containing p-toluenesulfonate and nickel p-toluenesulfonate II (obtained from Preparation Example 23) were respectively contained from iron containing p-toluenesulfonate and copper p-toluenesulfonate. Solution II (obtained from Preparation Example 27), iron p-toluenesulfonate and zinc p-toluenesulfonate II (obtained from Preparation 31), iron p-toluenesulfonate and zinc p-toluenesulfonate II (by preparation) 35 obtained), and substituted with iron p-toluenesulfonate and manganese p-toluenesulfonate II (obtained from Preparation 43). Income After the solution was uniformly mixed, it was placed in a UV absorption tank, and the change in UV absorbance with time was measured by UV light having a wavelength of 350 nm, and compared with the result of Comparative Example 1, please refer to Fig. 4.

Comparative Example 9

5 g of iron p-toluenesulfonate and aluminum p-toluenesulfonate II (obtained from Preparation 39) and 5 g of a 1% EDOT methanol solution (obtained in Preparation Example 9) were uniformly mixed and placed in a UV absorption tank. The change in UV absorbance with time was measured by the amount of UV light having a wavelength of 350 nm, and compared with the result of Comparative Example 1, please refer to Fig. 4.

As can be seen from Figures 3 and 4, when further used, cobalt ortho toluenesulfonate (or nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate or manganese p-toluenesulfonate) When the EDOT polymerization was carried out in a methanol solution of p-toluenesulfonic acid iron, the UV absorbance obtained after the reaction for ten minutes was compared with the simple use of the iron p-toluenesulfonic acid solution for EDOT polymerization (Comparative Example 1). High absorbance (up to 20% to 80%), which means cobalt toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate, or p-toluene When the manganese sulfonate is combined with the iron p-toluenesulfonic acid solution, it can help the EDOT to carry out the polymerization reaction and increase the degree of polymerization of the obtained PEDOT. Further, when EDOT polymerization was carried out with aluminum p-toluenesulfonate in combination with iron p-toluenesulfonate, it was found that the UV absorbance of the obtained product was not further improved (combination with Comparative Example 1 using iron p-toluenesulfonic acid solution alone) In contrast, this means that a methanol solution containing iron p-toluenesulfonate and aluminum p-toluenesulfonate does not further increase the degree of polymerization of PEDOT.

Example 10

5 g of iron p-toluenesulfonate, cobalt p-toluenesulfonate, and copper p-toluenesulfonate solution (obtained in Preparation Example 46) and 1% EDOT methanol solution (obtained in Preparation Example 9) were uniformly mixed. The change in UV absorbance with time was measured by UV light having a wavelength of 350 nm in a UV absorption bath, and compared with the result of Comparative Example 1, please refer to Fig. 5.

Example 11-14

Examples 11-14 were carried out as in Example 11 except that iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, and copper p-toluenesulfonate (obtained from Preparation 46) were respectively separated from iron containing p-toluenesulfonate. , copper p-toluenesulfonate, calcium p-toluenesulfonate, and manganese p-toluenesulfonate (obtained from Preparation 47), iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, p-toluenesulfonate Copper acid, and manganese p-toluenesulfonate solution (obtained in Preparation Example 48), iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, and Calcium p-toluenesulfonate solution (obtained from Preparation Example 49), and containing iron p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, p-toluenesulfonic acid Calcium and a manganese p-toluenesulfonate solution (obtained in Preparation Example 50) were substituted. The obtained solution was uniformly mixed, and placed in a UV absorption tank, and the change in UV absorbance with time was measured by UV light having a wavelength of 350 nm, and compared with the result of Comparative Example 1, please refer to Fig. 5.

As can be seen from Fig. 5, when two or more kinds of p-toluenesulfonic acid metal salts were mixed with iron p-toluenesulfonate to carry out EDOT polymerization, the results showed that the two metal toluenesulfonic acid salts were combined with iron p-toluenesulfonate. Combination (Example 10), combination of three metal toluenesulfonic acid salts with iron p-toluenesulfonate (Example 11), and combination of four metal toluenesulfonic acid salts with iron p-toluenesulfonate (Examples) 12), using a combination of five tosylate metal salts with iron p-toluenesulfonate (Example 13), or a combination of six tosylate metal salts with iron p-toluenesulfonate (Example 14), and simple When the EDOT polymerization (Comparative Example 1) was carried out using the iron p-toluenesulfonic acid solution, the UV absorbance was improved, so that the degree of polymerization of PEDOT was improved.

Preparation of a composition for forming an electrolyte

Comparative Example 10

60 g of iron p-toluenesulfonate (obtained in Preparation Example 1) was added to 40 g of methanol, heated to 40-50 ° C for 30 minutes, dissolved, and then cooled to room temperature. The insoluble matter was removed by filtration to obtain iron p-toluenesulfonate. Methanol solution. Next, 10 g of the above iron toluenesulfonic acid methanol solution was taken, and 0.12 g of EDOT was added thereto, followed by stirring to obtain a composition I for forming an electrolyte.

Example 15

0.038 g of cobalt p-toluenesulfonate (obtained in Preparation Example 2), 60 g of iron p-toluenesulfonate (obtained in Preparation Example 1), and 39.962 g of methanol were added, and the mixture was uniformly stirred to obtain iron and p-toluenesulfonate. A cobalt toluenesulfonic acid solution in which the ratio of iron p-toluenesulfonate to cobalt p-toluenesulfonate was 1,580. Next, 10 g of the above-mentioned cobalt p-toluenesulfonic acid and cobalt p-toluenesulfonic acid solution were added, and 0.12 g of EDOT was added thereto, followed by stirring to obtain a composition II for forming an electrolyte.

Example 16

60 g of iron p-toluenesulfonate (obtained in Preparation Example 1), 0.076 g of cobalt p-toluenesulfonate (obtained in Preparation Example 2), 0.278 g of copper p-toluenesulfonate (obtained in Preparation Example 4), and ethanol 39.646 were added. Gram, after stirring evenly, a solution containing iron p-toluenesulfonate, cobalt p-toluenesulfonate and copper p-toluenesulfonate, wherein p-toluene is obtained The ratio of iron sulfonate: cobalt p-toluenesulfonate: copper p-toluenesulfonate was 2375:3:11. Next, 10 g of the above-mentioned iron p-toluenesulfonate, cobalt p-toluenesulfonate, and a copper p-toluenesulfonate solution were added, and 0.12 g of EDOT was added thereto, followed by stirring to obtain a composition III for forming an electrolyte.

Example 17

60 g of iron p-toluenesulfonate (obtained in Preparation Example 1), 0.006 g of copper p-toluenesulfonate (obtained in Preparation Example 4), and 0.012 g of p-toluenesulfonate (obtained in Preparation Example 6), p-toluenesulfonic acid were added. 0.18 g of manganese manganate (obtained in Preparation Example 8) and 39.802 g of butanol were stirred to obtain a solution containing iron p-toluenesulfonate, copper p-toluenesulfonate, calcium p-toluenesulfonate, and manganese p-toluenesulfonate. Iron p-toluenesulfonate: copper p-toluenesulfonate: calcium p-toluenesulfonate: manganese p-toluenesulfonate is 10000:1:2:30. Next, 10 g of the above-mentioned iron p-toluenesulfonate, copper p-toluenesulfonate, calcium p-toluenesulfonate, and manganese p-toluenesulfonate were added, and 0.12 g of EDOT was added thereto, followed by stirring to obtain a composition for forming an electrolyte. IV.

Example 18

60 g of iron p-toluenesulfonate (obtained in Preparation Example 1), 0.12 g of cobalt p-toluenesulfonate (obtained in Preparation Example 2), 0.12 g of nickel p-toluenesulfonate (obtained in Preparation Example 3), p-toluenesulfonate Aluminium silicate (obtained in Preparation Example 7), 0.012 g, manganese p-toluenesulfonate (obtained in Preparation Example 8), 0.06 g, and methanol (39.688 g) were uniformly stirred to obtain iron p-toluenesulfonate and cobalt p-toluenesulfonate. Nickel p-toluenesulfonate, aluminum p-toluenesulfonate, and manganese p-toluenesulfonate, wherein iron p-toluenesulfonate: cobalt p-toluenesulfonate: nickel p-toluenesulfonate: aluminum p-toluenesulfonate: manganese p-toluenesulfonate The ratio is 20000:10:10:1:5. Next, 10 g of the above-mentioned iron p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, aluminum p-toluenesulfonate, and p-toluene were taken. The manganese sulfonate solution was added with 0.12 g of EDOT and stirred to obtain a composition V for forming an electrolyte.

Example 19

60 g of iron p-toluenesulfonate (obtained in Preparation Example 1), 0.032 g of cobalt p-toluenesulfonate (obtained in Preparation 2), and 0.032 g of p-toluenesulfonic acid (obtained in Preparation Example 3), p-toluenesulfonic acid were added. 0.026 g of copper acid (obtained in Preparation Example 4), 0.063 g of aluminum p-toluenesulfonate (obtained in Preparation Example 7), 0.126 g of manganese p-toluenesulfonate (obtained in Preparation Example 8), and 39.684 g of methanol were stirred uniformly. Obtaining iron containing p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, aluminum p-toluenesulfonate, and manganese p-toluenesulfonate, wherein iron p-toluenesulfonate: p-toluenesulfonate Cobalt acid: nickel p-toluenesulfonate: copper p-toluenesulfonate: aluminum p-toluenesulfonate: manganese p-toluenesulfonate: 1900:1:2:1:2:4. Next, 10 g of the above-mentioned iron p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, aluminum p-toluenesulfonate, and manganese p-toluenesulfonate were added, and 0.12 g of EDOT was added. Stirring was carried out to obtain a composition VI for forming an electrolyte.

Example 20

60 g of iron p-toluenesulfonate (obtained in Preparation Example 1), 0.032 g of cobalt p-toluenesulfonate (obtained in Preparation Example 2), 0.063 g of nickel p-toluenesulfonate (obtained in Preparation Example 3), p-toluenesulfonate Acid copper (obtained from Preparation Example 4) 0.032 g, zinc p-toluenesulfonate (obtained in Preparation Example 5) 0.063 g, calcium p-toluenesulfonate (obtained from Preparation Example 6) 0.0006 g, manganese p-toluenesulfonate (prepared from In the case of Example 8, 0.0012 g and 39.7785 g of methanol were stirred to obtain iron p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate and p-toluenesulfonate. Calcium acid, and manganese p-toluenesulfonate solution, wherein iron p-toluenesulfonate: p-toluenesulfonic acid Cobalt: nickel p-toluenesulfonate: copper p-toluenesulfonate: zinc p-toluenesulfonate: calcium p-toluenesulfonate: manganese p-toluenesulfonate is 19000:10:20:10:20:1:2. Next, 10 g of the above-mentioned iron p-toluenesulfonate, cobalt p-toluenesulfonate, nickel p-toluenesulfonate, copper p-toluenesulfonate, zinc p-toluenesulfonate, calcium p-toluenesulfonate, and manganese p-toluenesulfonate And 0.12 g of EDOT was added and stirred to obtain a composition VII for forming an electrolyte.

Capacitor preparation

First, the anode aluminum foil and the cathode aluminum foil are respectively pinned to the guide pins, separated by a separator paper between the two electrodes, and the two electrodes are wound with the separator paper, and finally fixed by tape to obtain a capacitor element. Next, a capacitor element is oxidized by applying a voltage of 20 V to a 10% aqueous solution of diammonium adipate to form a dielectric layer (material is alumina (Al ₂ O ₃ )), which is washed with pure water, followed by 120. The mixture was dried at ° C for 30 minutes, and the release paper was carbonized at 250 ° C and cooled.

Next, the above-mentioned treated occluders were impregnated in the compositions described in Comparative Example 10 and Examples 15-20, respectively, and after completion of the impregnation, the reaction was carried out at 40 ° C for 30 minutes, at 60 ° C for 30 minutes, and at 80 ° C for 30 times. The reaction was carried out for 30 minutes at 100 ° C, 30 minutes at 120 ° C, and 30 minutes at 140 ° C. After cooling, capacitors I-VII were obtained (three for each capacitor). Next, the capacitance characteristics (including the capacitance value (Cs), the energy consumption coefficient (DF), and the equivalent series resistance (ESR)) of the capacitor I-VII were analyzed, and the results are shown in Table 1.

As can be seen from Table 1, with capacitor I (use only iron p-toluenesulfonate Compared to the oxidant to form an electrolyte, the capacitor (capacitor II-VII) produced by the composition of the present invention has a higher capacitance value due to the higher degree of polymerization of PEDOT as an electrolyte. And has a lower energy consumption coefficient and equivalent series resistance.

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

Claims (21)

An electrolyte comprising: a conductive polymer, a ferric ion, an auxiliary metal ion, and a pair of toluenesulfonic acid anion, wherein the auxiliary metal ion is cobalt ion, nickel ion, zinc ion, calcium ion, manganese ion, Or a combination thereof; and the conductive polymer is polymerized from a monomer having a structure represented by the formula (I) , wherein X ¹ and X ² are independently O or S; Y is ,or And each R is independently hydrogen or a C _1-6 alkyl group. The electrolyte of claim 1, wherein the electrolyte further comprises: an aluminum ion, or a copper ion. The electrolyte according to claim 1, wherein the single system is A composition for forming an electrolyte comprising: a pair of iron salts of toluenesulfonic acid; a metal salt of auxiliary p-toluenesulfonic acid, wherein the auxiliary p-toluenesulfonic acid metal salt is a cobalt salt of p-toluenesulfonic acid or nickel p-toluenesulfonate Salt, zinc p-toluenesulfonate, calcium p-toluenesulfonate, manganese p-toluenesulfonate, or a combination thereof; and a monomer having the structure shown in formula (I) Wherein, X ¹ and X ² are independently O or S; Y is ,or And each R is independently hydrogen or a C _1-6 alkyl group. The composition for forming an electrolyte according to claim 4, wherein the weight ratio of the p-toluenesulfonic acid iron salt and the auxiliary p-toluenesulfonic acid metal salt to the monomer is between 0.4 and 2. The composition for forming an electrolyte according to claim 4, wherein the weight ratio of the p-toluenesulfonic acid iron salt to the auxiliary p-toluenesulfonic acid metal salt is from 19,000 to 190. The composition for forming an electrolyte according to claim 4, further comprising a pair of aluminum tosylate or a pair of copper p-toluenesulfonate. The composition for forming an electrolyte according to claim 4, wherein the single system is . The composition for forming an electrolyte according to claim 4, wherein the p-toluenesulfonic acid iron salt, the auxiliary p-toluenesulfonic acid metal salt, and the single system having the structure represented by the formula (I) are dissolved. In a solvent, wherein the solvent is methanol, ethanol, butanol, or a combination thereof. A method for producing an electrolyte comprising: mixing a pair of toluenesulfonic acid iron salt, an auxiliary p-toluenesulfonic acid metal salt, and a monomer, and performing a polymerization reaction, wherein the auxiliary p-toluenesulfonic acid metal salt is toluene a sulfonic acid cobalt salt, a p-toluenesulfonic acid nickel salt, a p-toluenesulfonic acid zinc salt, a p-toluenesulfonic acid calcium salt, a p-toluenesulfonic acid manganese salt, or a combination thereof; and the monomer has a structure represented by the formula (I) Wherein, X ¹ and X ² are independently O or S; Y is ,or And each R is independently hydrogen or a C _1-6 alkyl group. The method for producing an electrolyte according to claim 10, wherein the weight ratio of the p-toluenesulfonic acid iron salt and the auxiliary p-toluenesulfonic acid metal salt to the monomer is between 0.4 and 2. The method for producing an electrolyte according to claim 10, wherein the weight ratio of the p-toluenesulfonic acid iron salt to the auxiliary p-toluenesulfonic acid metal salt is from 19,000 to 190. The method for producing an electrolyte according to claim 10, further comprising a pair of aluminum tosylate or a copper salt of a toluenesulfonate, and the iron salt of p-toluenesulfonate, the metal of the auxiliary p-toluenesulfonate The salt, and the monomer are mixed. The method for producing an electrolyte according to claim 10, wherein the single system is . The method for producing an electrolyte according to claim 10, wherein the p-toluenesulfonic acid iron salt, the auxiliary p-toluenesulfonic acid metal salt, and the single system are dissolved in a solvent, wherein the solvent is methanol. , ethanol, butanol, or a combination thereof. A capacitor comprising: a capacitor element; and an electrolyte formed on the capacitor element, wherein the electrolyte is formed by coating a composition for forming an electrolyte on the capacitor element, wherein the electrolyte is used to form an electrolyte The composition comprises the following components uniformly dispersed in a solvent: a pair of toluenesulfonic acid iron salt; a secondary p-toluenesulfonic acid metal salt, wherein the auxiliary p-toluenesulfonic acid metal salt is a p-toluenesulfonic acid cobalt salt, p-toluenesulfonic acid a nickel salt, a zinc salt of p-toluenesulfonate, a calcium salt of p-toluenesulfonate, a manganese salt of p-toluenesulfonate, or a combination thereof; and a monomer having a structure represented by the formula (I) Wherein, X ¹ and X ² are independently O or S; Y is ,or And each R is independently hydrogen or a C _1-6 alkyl group. The capacitor of claim 16, wherein the weight ratio of the p-toluenesulfonic acid iron salt and the auxiliary p-toluenesulfonic acid metal salt to the monomer is between 0.4 and 2. The capacitor of claim 16, wherein the weight ratio of the p-toluenesulfonic acid iron salt to the auxiliary p-toluenesulfonic acid metal salt is between 19,000 and 190. The capacitor of claim 16, wherein the electrolyte-forming composition further comprises a pair of aluminum tosylate salts or a pair of copper tosylate salts. The capacitor of claim 16, wherein the single system is . The capacitor of claim 16, wherein the solvent is methanol, ethanol, butanol, or a combination thereof.