Capacitor Based on Acid Polymerization Dispersion Liquid and Method for Producing the Same

Abstract

An improved dispersion particularly suitable for use in forming a hybrid capacitor, an improved method for forming a hybrid capacitor, and an improved capacitor are provided. The method consists of forming a dispersion comprising a conductive polymer, a dispersant, a monomer of the conductive polymer, and an anionic counterion in molar excess per mole of the conductive polymer and the monomer. The dispersion is homogenized to form a homogenized dispersion. A capacitor is formed having a conductive layer formed from the homogenized dispersion.

Description

Technical Field

[0001] Cross - reference to related applications This application claims the benefit of priority of U.S. Provisional Application No. 63 / 389,509, filed on July 15, 2022, which is hereby incorporated by reference in its entirety.

[0002] The present invention relates to improved capacitors, particularly hybrid capacitors. More specifically, the present invention relates to an improved method for forming a hybrid capacitor comprising a conductive polymer dispersion.

Background Art

[0003] Conductive polymers are widely used in electrolytic capacitors. The most promising systems are suitable for use in high - temperature environments and at high voltages. Solid conductive polymers can be combined with a liquid electrolyte called a hybrid capacitor to ensure low leakage current and high reliability during the operating life.

[0004] By using a conductive polymer dispersion in a hybrid capacitor, a significant advancement in the art has been achieved. An exemplary system is PEDOT / PSSA. In this exemplary system, 3,4-ethylenedioxythiophene (EDOT) polymerizes in a positively charged conductive polymer chain to form poly(3,4-ethylenedioxythiophene) (PEDOT). Poly(4-styrenesulfonic acid) (PSSA) is used as a dopant and anionic counterion. An excess amount of PSSA per mole is used to obtain a negative Z-potential at the particle surface to stabilize the polymer nanoparticles in a dispersion such as water. PSSA has a drawback in terms of the conductivity of the final polymer film because it may inhibit PEDOT from reaching the core in the film. However, PSSA can dissolve in a hybrid capacitor in which the conductive system is represented by both a solid and a liquid electrolyte. PSSA in solution is aggressive to some electrolytic capacitors such as aluminum capacitors. The acid can lead to an increase in leakage current, corrosion of the metal, and especially failure of the capacitor in a high humidity environment.

[0005] There has been a continuing need for improvement in hybrid capacitors, particularly with regard to stability. Provided herein are an improved hybrid capacitor and a method of forming an improved hybrid capacitor. SUMMARY OF THE INVENTION

[0006] It is an object of the present invention to provide an improved hybrid capacitor and a method of forming an improved hybrid capacitor.

[0007] Another object of the present invention is to provide a hybrid capacitor including a conductive polymer cathode, the conductive polymer cathode having a surface charge that is neutral or near positive.

[0008] Particularly characteristic of the present invention are improvements in capacitor characteristics, particularly stability of capacitance and reduction of ESR.

[0009] These and other advantages that may be realized are provided in a method of forming a hybrid capacitor that includes forming a dispersion that includes a conductive polymer, a dispersion, monomers of the conductive polymer, and a molar excess of anionic counterions per mole of conductive polymer and monomer; homogenizing the dispersion to form a homogenized dispersion; and forming a capacitor comprising a conductive layer formed from the homogenized dispersion.

[0010] In yet another embodiment, there is provided a method of forming a hybrid capacitor, the method comprising the steps of: forming a dispersion including a conductive polymer, a dispersion, a monomer of the conductive polymer, and a molar excess of anionic counterion per mole of conductive polymer and monomer; homogenizing the dispersion to form a homogenized dispersion; applying the homogenized dispersion onto an oxide layer of a metal to form a layer of homogenized dispersion; removing the dispersion from the layer; curing the monomer to form a coating film; forming a laminate structure including the coating film, a conductive layer, and a separator therebetween; rolling the laminate structure to form a working element; inserting the working element into a housing; adding a liquid electrolyte to the housing; and sealing the housing.

[0011] Yet another embodiment is a hybrid capacitor. The hybrid capacitor includes a sealed housing containing an anode, a dielectric on the anode, and a conductive polymer layer on the dielectric. The conductive polymer layer has a surface layer concentration of sulfur of at least 1% by weight. Between the cathode and anode is a separator and a liquid electrolyte.

[0012] Yet another embodiment is provided in a dispersion comprising a conductive polymer, a dispersion, a monomer of the conductive polymer, and a molar excess of an anionic counterion per mole of the conductive polymer and monomer. [Brief explanation of the drawings]

[0013]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0014] The present invention relates to an improved hybrid capacitor and an improved manufacturing method of a hybrid capacitor. More specifically, the present invention relates to the formation of a polymer dispersion comprising a prepolymer having an excess of anionic counterions and a monomer dispersed in a dispersion liquid. This polymer dispersion is used to form the solid cathode layer of a hybrid capacitor containing a liquid electrolyte. As a result, the characteristics of the capacitor are improved, particularly the equivalent series resistance (ESR) and the stability of the capacitance are improved.

[0015] An embodiment of the present invention will be described with reference to FIG. 1. FIG. 1 schematically shows an active element partially unwound before being inserted into a container and optionally, but preferably, impregnated with a liquid electrolyte. In FIG. 1, the active element, generally designated 10, includes an anode 12 and a cathode 14, and there is a separator 16 therebetween which may be a conductive separator. It will be understood by those skilled in the art that the anode has a dielectric. The conductive separator is one in which a conductive polymer is coated on the separator or the separator is impregnated with a conductive polymer, preferably saturated. The anode lead wire 20 and the cathode lead wire 22 extend from the wound capacitor and ultimately form an electrical connection to the circuit. It will be understood from the present specification that the anode lead is in electrical contact with the anode, the cathode lead is in electrical contact with the cathode, and is electrically insulated from the anode or the anode lead. Tabs 24 and 26 are generally employed to electrically connect the anode lead to the anode and the cathode lead to the cathode, as is known in the art. A closure 28, such as an adhesive tape, prevents the active element from being unwound during handling or assembly. Thereafter, the closure serves little purpose even though it is part of the completed capacitor.

[0016] The capacitor is shown in a cross-sectional schematic view in FIG. 2. In FIG. 2, the capacitor, generally designated 60, includes an active element 10 as described herein within a housing 64. The housing, which may also be called a can in the art, is preferably conductive and may function as a lead or be in electrical contact with the cathode lead 66. The cathode tab 68 is in electrical contact with the housing or the cathode lead. The anode tab 70 is in electrical contact with the anode lead 72. A lid 74, such as a gasket, and a seal 76 seal the housing to suppress air exchange between the interior of the housing and the outside air. In one embodiment, the seal is a hermetic seal.

[0017] The present invention is specific to the improvement of a conductive polymer layer, more specifically, a conductive polymer layer on at least one of an anode, a cathode, or a dielectric of a solid electrolyte forming a separator.

[0018] An embodiment of the present invention will be described with reference to FIGS. 3 and 4. FIGS. 3 and 4 schematically show a comparison between a conventional capacitor forming process and the process of the present invention. FIG. 3 shows a conventional process shown to clarify the present invention, and FIG. 4 shows the process of the present invention.

[0019] In FIG. 3, as schematically shown at A, a preformed polymer dispersion 100 is applied to a dielectric 102 such as an anode 12. The preformed polymer dispersion contains a conductive polymer 106 and an anionic counter ion 108 and is in the form of particles. Without being limited to theory, it is assumed that the conductive polymer and the anionic counter ion form core-shell particles in which the conductive polymer phase is at least partially surrounded by the anionic counter ion. The particles are suspended in a dispersion 110 such as water. The dispersion is removed by drying or the like, and as schematically shown at B, aggregated particles dispersed on the surface of the dielectric are obtained. Upon curing, the conductive polymer phase and the anionic counter ion phase combine, and it is assumed that a conductive polymer film having a negative surface is formed by at least partial encapsulation of the conductive polymer by the anionic counter ion phase, as schematically shown at C.

[0020] In FIG. 4, the dispersion 120 of the present invention comprises a preformed polymer dispersion comprising a conductive polymer 106 and an anionic counter ion 108, and has the shape of particles as discussed in connection with FIG. 3. The dispersion of the present invention further comprises a monomer 122 that is not particularly soluble in the dispersion 110, and thus preferably comprises a surfactant to stabilize the monomer, whereby the dispersed monomer forms a dispersed monomer that is assumed to be in the form of particles 122, as schematically shown at A. The conductive polymer, dispersed monomer, anionic counter ion, and any surfactant are homogenized to obtain a homogenized dispersion. When the dispersion is removed, for example, by drying, it is assumed that the dispersed monomer at least partially encapsulates the particles of the conductive polymer and the anionic counter ion, as schematically shown at B. The monomer polymerizes preferably by oxidation from oxygen by being exposed to air, as schematically shown at C, during removal of the dispersion. Instead of a core that is mainly positively charged and a shell that is mainly negatively charged, as schematically shown in FIG. 3, a conductive polymer layer is obtained in which the anionic counter ion is homogeneously dispersed throughout the conductive polymer layer, so that the surface is neutralized, i.e., positively charged, and as schematically shown in FIG. 4, the negative potential of the surface decreases and the resistivity of the surface layer decreases. Evidence of the structure was obtained by scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM EDS) and conductivity tests. As schematically shown in FIG. 3, the SEM EDS of the surface formed from the conventional dispersion has a surface layer concentration with a sulfur content of less than 0.75 wt%, whereas the sample of the present invention has a high surface layer concentration of sulfur of at least 1 wt%, more preferably at least 1.2 wt%, even more preferably at least 1.4 wt%. Zeta potential analysis of the solution supported the structure, the analysis of which. The zeta potential of the comparative solution was about -67.7 mV, whereas the zeta potential of the solution of the present invention was -56.6 mV, indicating that the sample of the present invention is more positively charged, supporting the conclusion that there is more polymer on the surface than the anionic counter ion.

[0021] As schematically shown in FIG. 4, the slurry of the present invention provides a compact polymer film surface where the conductive polymer is in contact with the liquid electrolyte. When using a conventional slurry, the surface of the conductive polymer layer is composed of anionic counterions, which are non-conductive substances. The non-conductive layer on the surface functions as an insulating layer, and there is a highly conductive layer inside it. A more compact conductive polymer film with a minimized amount of non-conductive components on the surface has a significantly higher conductivity and improves the electrical characteristics of the capacitor. The advantages of the process of the present invention include the capacitor of the present invention having a low ESR and excellent stability.

[0022] Without being limited to theory, it is assumed that during oxidative polymerization, an excessive amount of anionic counterions, called dopants, bind to the newly formed conductive polymer from the dispersed monomer, thereby inhibiting the dissolution of anionic counterions into the liquid electrolyte of the completed capacitor. Since the dissolved anionic counterions are aggressive substances that deteriorate some capacitor components, this is an important improvement in capacitor technology. The oxidative polymerization of the dispersed monomer results in a better bond between the polymer and the substrate, preventing the peeling of the polymer film, and thus improving the stability regarding the capacitance of the capacitor.

[0023] The present invention provides a method for forming a conductive polymer and a capacitor that mitigate the harmful effects of an excessive amount of PSSA on the performance of the capacitor. In the present invention, the polymer dispersion is prepared in a monomer emulsion. More specifically, pre-polymerized solid nanoparticles are co-dispersed in a dispersion, preferably water, and the monomer, and the monomer is in the form of micro- or nanometer-sized droplets. In this case, the main dispersion liquid is immiscible with the monomer liquid, and it is preferable to suppress oxidative polymerization by excluding the presence of an oxidizing agent in the slurry. The monomer droplets are preferably stabilized with a surfactant.

[0024] For the purpose of the present invention, the excess of the anionic counterion represented by PSSA exceeds the amount necessary to balance the charges of the conductive polymer represented by PEDOT and the monomer represented by EDOT. After oxidative polymerization, the monomer becomes a polymer, or typically a monomer and a polymer, and EDOT becomes PEDOT. The weight ratio of PEDOT to EDOT / PSSA in the dispersion is preferably at least 1:1.5 to 1:5, more preferably about 1:2 to 1:3. The ratio of PEDOT / PSSA in the capacitor is preferably at least 1:1.5 to 1:5, more preferably 1:2 to 1:3. The molar ratio of PEDOT / PSSA in the dispersion is preferably at least 1:1.16 to 1:3.9, more preferably at least 1:1.5 to 1:2.3. The molar ratio of PEDOT / PSSA in the capacitor is preferably at least 1:1.16 to 1:3.9, more preferably at least 1:1.5 to 1:2.3.

[0025] The anode is preferably a metal, more preferably a valve metal selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements, and conductive oxides such as NbO. Aluminum is a particularly preferred anode material.

[0026] The dielectric is not particularly limited. The oxide of the anode material is a particularly suitable dielectric because its use is established in the art and it has high manufacturing convenience, and there is no limitation thereto.

[0027] The preferred monomer is of formula A

[0028]

Chemical formula

[0029] <s defined by, n = 1, there is no bond between adjacent units, and the preferred polythiophene is represented by formula A (wherein R 1 and R 2is selected to prohibit polymerization at the β-site of the ring.). It is most preferable to allow only α-site polymerization. Therefore, R 1 and R 2 are preferably not hydrogen. More preferably, R 1 and R 2 are α-derivatives. Therefore, an ether bond is preferred over an alkyl bond. To avoid steric hindrance, it is most preferable that the groups are small. For these reasons, R 1 and R 2 are most preferably taken together as -O-(CH2)2-O-. In Formula 1, X is preferably selected from the group consisting of S, N, or O, and most preferably, X is S. The subscript n of the monomer is 1, and for the polymer, it is a number sufficient to achieve a molecular weight from 2 to 100,000 g / mol. A particularly preferred conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT).

[0030] R 1 and R 2 each independently represent a linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl; or a C3-C8 cycloalkyl, phenyl, or benzyl unsubstituted or substituted by C1-C6 alkyl, C1-C6 alkoxy, halogen, or OR 3 ; or R 1 and R 2 together are a linear C1-C6 alkylene unsubstituted or substituted by C1-C6 alkyl, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl, or halobenzyl, or a 5-membered, 6-membered, or 7-membered heterocyclic structure containing two oxygen elements. R 3preferably represents hydrogen, linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl; or is C3-C8 cycloalkyl, phenyl or benzyl, which are unsubstituted or substituted by C1-C6 alkyl.

[0031] The liquid electrolyte is preferably a solvent containing a supporting salt therein. Exemplary solvents include γ-butyrolactone, sulfolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, dimethylformamide, diethylformamide, water, silicone oil, polyethylene glycol, and mixtures thereof, and any conventional solvent can be used. Although not essential, it is desirable to have a supporting salt. Exemplary supporting salts include inorganic acid ammonium salts, inorganic acid amine salts, inorganic acid alkyl-substituted amide salts, organic ammonium salts, organic acid amide salts, organic acid alkyl-substituted amide salts and their derivatives. Any gas absorbent or cathodic electrochemical depolarizer can be used. Exemplary supported additives include nitro derivatives of aromatic derivatives such as organic alcohols, acids, esters, o-, m-, p-nitroanisole, o-, m-, p-nitrobenzoic acid, o-, m-, p-nitrobenzyl alcohol, etc. Particularly preferred hybrid capacitors contain up to 50% by weight of the liquid electrolyte.

[0032] Particularly preferred anionic counterions or dopants are polystyrene sulfonic acid and its derivatives, optionally Formula B AxByCz in the form of a random copolymer consisting of groups A, B and C represented by the ratio of: A is a salt of polystyrene sulfonic acid or polystyrene sulfonate; B and C are, separately, - carboxyl group, -C(O)OR 6 wherein, R 6An alkyl group having 1 to 20 carbon atoms, optionally substituted with a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, an epoxy group, a silane group, an amide group, an imide group, a thiol group, an alkene group, an alkyne group, an azide group, a phosphate ester group, an acrylate ester group, and an anhydride group, selected from the group consisting of -(CHR 7 CH2O)b-R 8 , wherein R 7 is selected from hydrogen or an alkyl having 1 to 7 carbon atoms, preferably hydrogen or methyl; b is an integer from 1 to a number sufficient for the molecular weight of the -CHR 7 CH2O- group to reach up to 200,000; and R 8 is selected from the group consisting of hydrogen, a silane, a phosphate, an acrylate, a hydroxyl, a carboxyl, an amine, an epoxy, a silane, an amide, an imide, a thiol, an alkene, an alkyne, a phosphate, an azide, an acrylate, and an anhydride, and is selected from the group consisting of an alkyl having 1 to 9 carbon atoms, optionally substituted with a functional group selected from the group; -C(O)-NHR 9 , wherein R 9 [[ID=2�]]is hydrogen or an alkyl having 1 to 20 carbon atoms, optionally substituted with a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, an epoxy group, a silane group, an amide group, an imide group, a thiol group, an alkene group, an alkyne group, a phosphate group, an azide group, an acrylate group, and an anhydride group; -C6H4-R 10 , wherein R 10 is selected from the following: hydrogen or an alkyl optionally substituted with a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, an epoxy group, a silane group, an amide group, an imide group, a thiol group, an alkene group, an alkyne group, a phosphate group, an azide group, an acrylate group, and an anhydride group; [[ID=�6]]a reactive group selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, an epoxy group, a silane group, an imide group, an amide group, a thiol group, an alkene group, an alkyne group, a phosphate group, an azide group, an acrylate group, and an anhydride group; -(O(CHR11 (CH2O)d-R 12 wherein R 11 is hydrogen or an alkyl group having 1 to 7 carbon atoms, preferably hydrogen or methyl; d is an integer from 1 until the molecular weight of the -CHR 11 CH2O- group reaches 200,000; R 12 is selected from the group consisting of alkyl groups having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride, -C6H4-O-R 13 wherein R 13 is selected from the following: hydrogen, or an alkyl group optionally substituted with a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; a reactive group selected from the group consisting of epoxy, silane, alkene, alkyne, acrylate, phosphate, and -(CHR 14 CH2O)e-R 15 wherein R 14 is hydrogen or an alkyl group having 1 to 7 carbon atoms, more preferably hydrogen or methyl; e is an integer from 1 until a number sufficient for the molecular weight of the -CHR 14 CH2O- group to reach 200,000; and R 15 is selected from the group consisting of hydrogen and alkyl groups having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride. In one embodiment, y and z are 0; and in another embodiment, x, y, and z together are sufficient to form a polyanion having a molecular weight of at least 100 to 500,000 or less, y / x is from 0.01 to 100; z is in a ratio z / x of from 0 to 100 or less; more preferably, among the total of x + y + z, x represents 50 to 99%, y represents 1 to 50%, and z represents 0 to 49%; even more preferably, among the total of x + y + z, x represents 70 to 90%; y represents 10 to 30%, and z represents 0 to 20%. A particularly preferred anionic counterion is polystyrene sulfonic acid (PSSA).

[0033] [Example 1] An aluminum anode with a dielectric layer formed in advance, an aluminum cathode, PEDOT / PSSA as a conductive polymer, gamma-butyrolactone (GBL), sulfolane, a quaternary alkylammonium phthalate, an electrolyte composed of polyethylene glycol, and a nitro compound as a stabilizer were used to fabricate an axial hybrid capacitor with a working voltage of 63V and a capacitance of 400 uF. This polymer is characterized in that the weight ratio of PEDOT / PSSA is 1:3 and the molar ratio of monomer EDOT / PSSA is about 1:2.5.

[0034] The capacitor group of the present invention was fabricated using the same conductive polymer dispersion containing 1% EDOT emulsion.

[0035] The capacitors were tested at 63V and 150°C.

[0036] After 250 hours of testing, the breakdown of both types of capacitors was carried out. In the capacitors of the comparative example, significant damage to the conductive polymer was observed, but not in the examples of the present invention. The damage was indicated by the presence of dark brown residues in the tab area where the tab was connected to the anode lead. Corrosion of the metal was confirmed from the residues. The residues were determined to be sulfone groups by Fourier transform infrared (FTIR) analysis.

[0037] The surfactant for dispersing the monomers in the dispersion of the present invention is preferably selected from the group consisting of nonionic surfactants, fluorosurfactants, anionic surfactants, cationic surfactants, and acetylene surfactants. Particularly preferred surfactants include Triton X, CapstoneR FS, Zonyl FS-300, sodium dodecyl sulfonate (SDS), tetraoctylammonium bromide (TOAB), SurfynolR 104, SurfynolR 420, Dynol*607, and Dynol*604.

[0038] Example 1 shows that the control polymer is aggressive towards hybrid capacitors and may lead to corrosion of the metal within the capacitor. The polymer of the present invention has improved material compatibility. Such a significant improvement is due to the oxidative polymerization of EDOT that occurs during modification. Curing is carried out at a temperature higher than 100°C, approximately 150°C, at which temperature EDOT polymerizes by air and binds an amount of PSSA exceeding PSSA from the solid polymer.

[0039] [Example 2] An aluminum anode with a dielectric layer pre-formed, an aluminum cathode, PEDOT / PSS as the conductive polymer, gamma-butyrolactone (GBL), sulfolane, quaternary alkyl ammonium phthalate, and polyethylene glycol as the electrolyte, and a nitro compound as the stabilizer were used to fabricate a 63V, 100uF V-chip hybrid capacitor. This polymer is characterized by a weight ratio of PEDOT / PSSA of 1:3.

[0040] A capacitor was fabricated by dispersing the same conductive polymer dispersion in a 1% EDOT emulsion.

[0041] The durability test of the capacitor was carried out at 135°C and 63V (DC).

[0042] The results showed a significant difference in the initial ESR value and the ESR stability over the test time. The results are shown graphically in Figure 5, where the ESR is shown as a function of time.

[0043] [Example 3] The conductivity of a representative slurry of the present invention containing PEDOT / PSSA / EDOT was evaluated by comparison with a representative comparative slurry containing PEDOT / PSSA. The results are summarized in Table 1 and Table 2.

[0044] To prepare the sample, EDOT was slowly added to PEDOT / PSS (1:3) with a Silverson L5MA homogenizer. After the addition, the rotation speed was increased to 900 rpm for 15 - 20 minutes.

[0045] According to the experimental results, the conductivity of the final polymer film formed from the slurry of the present invention in air was measured on a glass slide by drying 1 g of the slurry at 90 °C for 15 minutes and then at 150 °C for 15 minutes, and showed significantly higher conductivity than the comparative slurry as shown in Table 2. The examples of the present invention showed no significant change even after 10 days of storage and exhibited acceptable stability in terms of pH, conductivity, and viscosity.

[0046] Table 1 Viscosity and pH of PEDOT / PSS(1:3)+EDOT slurries (1%, 5%, 10%) before and after 10 - day storage (room temperature, sealed container, no special gas treatment)

[0047]

Table 1

[0048] Table 2 Variation of PEDOT / PSS(1:3)+EDOT and measurement parameters of normal slurries

[0049]

Table 2

[0050] The present invention has been described with reference to preferred embodiments, but is not limited thereto. Those skilled in the art will be able to implement additional embodiments and improvements that are not specifically described but are within the scope of the claims appended hereto.

Claims

1. A method of forming a hybrid capacitor, comprising: forming a dispersion comprising a conductive polymer, a dispersion liquid, a monomer of the conductive polymer, and an anionic counter ion in a molar excess per mole of the conductive polymer and the monomer; homogenizing the dispersion to form a homogenized dispersion; forming a capacitor comprising a conductive layer formed from the homogenized dispersion.

2. The method of forming a hybrid capacitor according to claim 1, wherein the conductive polymer and the monomer in the dispersion and the anionic counter ion are in a weight ratio of 1:1.5 to 1:

5.

3. The method of forming a hybrid capacitor according to claim 2, wherein the conductive polymer and the monomer in the dispersion and the anionic counter ion are in a weight ratio of 1:2 to 1:

3.

4. The method of forming a hybrid capacitor according to claim 1, wherein the conductive polymer and the anionic counter ion in the hybrid capacitor are in a weight ratio of 1:1.5 to 1:

5.

5. The method of forming a hybrid capacitor according to claim 4, wherein the conductive polymer and the anionic counter ion in the hybrid capacitor are in a weight ratio of 1:2 to 1:

3.

6. The method of forming a hybrid capacitor according to claim 1, further comprising applying the homogenized dispersion onto a metal or a metal oxide.

7. The method of forming a hybrid capacitor according to claim 6, wherein the metal or the metal oxide comprises a valve metal.

8. The method of forming a hybrid capacitor according to claim 6, wherein the valve metal is selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements, and conductive oxides thereof.

9. The method of forming a hybrid capacitor according to claim 8, wherein the valve metal is aluminum.

10. The monomer is of formula A 【Chemical 1】 defined by, n = 1, there is no bond between adjacent units, and the conductive polymer is defined by formula A, wherein X is selected from the group consisting of S, N or O; R １ and R ２ each independently represents a linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl; or C1-C6 alkyl, C1-C6 alkoxy, halogen or OR ３ which is unsubstituted or substituted with C3-C8 cycloalkyl, phenyl or benzyl which is unsubstituted or substituted with ３ ; Or, R １ and R ２ together are unsubstituted or are linear C1-C6 alkylene substituted by C1-C6 alkyl, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl or halobenzyl, or a 5-, 6- or 7-membered heterocyclic structure containing two oxygen elements. R ３ preferably represents hydrogen, a linear or branched C1-C16 alkyl or a C2-C18 alkoxyalkyl; or C3 - C8 cycloalkyl, phenyl or benzyl, which are unsubstituted or substituted by C1 - C6 alkyl. The method of forming a hybrid capacitor according to claim 1.

11. The method for forming a hybrid capacitor according to claim 10, wherein X is S.

12. The method for forming a hybrid capacitor according to claim 10, wherein the conductive polymer is 3,4-polyethylenedioxythiophene.

13. The method for forming a hybrid capacitor according to claim 10, wherein the monomer is 3,4-ethylenedioxythiophene.

14. The anionic counter ion is AxByCz The method for forming a hybrid capacitor according to claim 1: wherein A is a salt of polystyrene sulfonic acid or polystyrene sulfonate; B and C each independently represent a polymerized unit substituted with a group selected from: - a carboxyl group, -C(O)OR ６ , wherein R ６ is selected from the group consisting of: a hydroxyl group, carboxyl group, amine group, epoxy group, silane group, amide group, imide group, thiol group, alkene group, alkyne group, azide group, phosphate ester group, acrylate ester group, an alkyl group having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group consisting of anhydride groups), and -(CHR ７ CH ２ O)b-R ８ , wherein R ７ is selected from hydrogen or alkyl having 1 to 7 carbon atoms; b is an integer from 1 to a number sufficient for the molecular weight of the -CHR ７ CH ２ O-group to reach up to 200,000; and R ８ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, silane, phosphate, acrylate, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C(O)-NHR ９ , wherein R ９ is an alkyl having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, or hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C ６ H ４ -R １０ wherein R １０ is selected from the following: hydrogen or an alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; Hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride and -(O(CHR １１ CH ２ O)d-R １２ (wherein) is a reactive group selected from the group consisting of, wherein R １１ is hydrogen or an alkyl group having 1 to 7 carbon atoms, preferably hydrogen or methyl; d is an integer from 1 to a number sufficient for the molecular weight of the -CHR １１ CH ２ O- group to reach up to 200,000; R １２ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C ６ H ４ -O-R １３ wherein, R １３ is selected from the following: hydrogen, or an alkyl optionally substituted with a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; a reactive group selected from the group consisting of epoxy, silane, alkene, alkyne, acrylate, phosphate, and -(CHR １４ CH ２ O)e-R １５ , wherein R １４ is hydrogen or alkyl having 1 to 7 carbon atoms; e is an integer from 1 to a number sufficient for the molecular weight of the -CHR １４ CH ２ O- group to reach up to 200,000; and R １５ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, and hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; x, y and z are sufficient to form a polyanion having a molecular weight of at least 100 to 500,000 or less, and y / x is from 0.01 to 100; z is in the range from 0 to a ratio of z / x not exceeding 100.

15. The method for forming a hybrid capacitor according to claim 14, wherein among the total of x + y + z, x represents 50 to 99%, y represents 1 to 50%, and z represents 0 to 49%.

16. The method for forming a hybrid capacitor according to claim 15, wherein among the total of x + y + z, x represents 70 to 90%, y represents 10 to 30%, and z represents 0 to 20%.

17. The method for forming a hybrid capacitor according to claim 1, wherein the anionic counter ion is polystyrene sulfonic acid.

18. The method for forming a hybrid capacitor according to claim 1, wherein the homogenized dispersion further contains a surfactant.

19. The method for forming a hybrid capacitor according to claim 18, wherein the surfactant is selected from the group consisting of a nonionic surfactant, a fluorosurfactant, an anionic surfactant, a cationic surfactant, and an acetylene surfactant.

20. The method for forming a hybrid capacitor according to claim 1, wherein forming the capacitor further includes adding a liquid electrolyte.

21. The method for forming a hybrid capacitor according to claim 20, wherein the liquid electrolyte contains a solvent selected from the group consisting of γ-butyrolactone, sulfolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, dimethylformamide, diethylformamide, water, silicone oil, polyethylene glycol, and mixtures thereof.

22. The method for forming a hybrid capacitor according to claim 20, wherein the liquid electrolyte contains a salt selected from the group consisting of an inorganic acid ammonium salt, an inorganic acid amine salt, an inorganic acid alkyl-substituted amide salt, an organic ammonium salt, an organic acid amide salt, an organic acid alkyl, and a substituted amide salt.

23. A method for forming a hybrid capacitor, comprising: forming a dispersion containing a conductive polymer, a dispersion liquid, a monomer of the conductive polymer, and an anionic counter ion in a molar excess per mole of the conductive polymer and the monomer; homogenizing the dispersion to form a homogenized dispersion; applying the homogenized dispersion to form a layer of the homogenized dispersion on a metal oxide layer; removing the dispersion of the layer; curing the monomer to form a coating film; forming a laminated structure composed of the coating film, a conductive layer, and a separator; rolling the laminated structure to form an active element; inserting the active element into a housing; adding a liquid electrolyte to the housing; sealing the housing. The method for forming a hybrid capacitor comprising the above steps.

24. The method for forming a hybrid capacitor according to claim 23, wherein the conductive polymer and monomer in the dispersion liquid and the anionic counter ion have a weight ratio of 1:1.5 to 1:

5.

25. The method for forming a hybrid capacitor according to claim 24, wherein the conductive polymer and monomer in the dispersion liquid and the anionic counter ion have a weight ratio of 1:2 to 1:

3.

26. The method for forming a hybrid capacitor according to claim 23, wherein the conductive polymer and the anionic counter ion in the hybrid capacitor have a weight ratio of 1:1.5 to 1:

5.

27. The method for forming a hybrid capacitor according to claim 26, wherein the conductive polymer and the anionic counter ion in the hybrid capacitor have a weight ratio of 1:2 to 1:

3.

28. The method for forming a hybrid capacitor according to claim 23, wherein the coating film has a surface layer concentration of at least 1% by weight of sulfur.

29. The method for forming a hybrid capacitor according to claim 28, wherein the coating film has a surface layer concentration of at least 1.2% by weight of sulfur.

30. The method for forming a hybrid capacitor according to claim 29, wherein the coating film has a surface layer concentration of at least 1.4% by weight of sulfur.

31. The method for forming a hybrid capacitor according to claim 23, wherein the metal is a valve metal.

32. The method for forming a hybrid capacitor according to claim 31, wherein the valve metal is selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements, and conductive oxides thereof.

33. The method for forming a hybrid capacitor according to claim 32, wherein the valve metal is aluminum.

34. The method for forming a hybrid capacitor according to claim 23, wherein the monomer is defined by formula A, n = 1, there is no bond between adjacent units, and the conductive polymer is defined by formula A: Formula A 【Chemical 1】 In the formula, X is selected from the group consisting of S, N or O; R １ and R ２ each independently represents a linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl; unsubstituted or C1-C6 alkyl, C1-C6 alkoxy, halogen or OR ３ which is C3-C8 cycloalkyl, phenyl or benzyl optionally substituted by; or R １ and R ２ together are unsubstituted or are linear C1-C6 alkylene substituted by C1-C6 alkyl, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl or halobenzyl, or a 5-, 6- or 7-membered heterocyclic structure containing two oxygen elements, R ３ preferably represents hydrogen, a linear or branched C1-C16 alkyl or a C2-C18 alkoxyalkyl; Or C₃-C₈ cycloalkyl, phenyl or benzyl, which are unsubstituted or substituted by C₁-C₆ alkyl.

35. The method for forming a hybrid capacitor according to claim 34, wherein X is S.

36. The method for forming a hybrid capacitor according to claim 34, wherein the conductive polymer is 3,4-polyethylenedioxythiophene.

37. The method for forming a hybrid capacitor according to claim 34, wherein the monomer is 3,4-ethylenedioxythiophene.

38. The method for forming a hybrid capacitor according to claim 23, wherein the anionic counter ion is defined as follows: AxB yC z wherein, A is polystyrene sulfonic acid or a polystyrene sulfonate; B and C each independently represent a polymerized unit substituted with a group selected from the following: - carboxyl group, -C(O)OR ６ wherein R ６ is selected from the group consisting of: Alkyl having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, phosphate, acrylate, anhydride and -(CHR ７ CH ２ O)b-R ８ wherein the alkyl is optionally substituted with a functional group selected from the group consisting of -(CHR ７ CH ２ O)R ８ wherein R ７ is selected from hydrogen or alkyl having 1 to 7 carbon atoms; b is an integer from 1 to a number sufficient for the molecular weight of the -CHR ７ CH ２ O-group to reach up to 200,000; and R ８ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, silane, phosphate, acrylate, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C(O)-NHR ９ wherein R ９ is an alkyl having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, or hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C ６ H ４ -R １０ wherein R １０ is selected from the following: hydrogen or alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride; -(O(CHR １１ CH ２ O)d-R １２ wherein R １１ is hydrogen or alkyl having 1 to 7 carbon atoms, preferably hydrogen or methyl; d is an integer from 1 to a number sufficient for the molecular weight of the -CHR １１ CH ２ O-group to reach up to 200,000; R １２ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C ６ H ４ -O-R １３ wherein R １３ is selected from the following: hydrogen, or alkyl optionally substituted with a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; a reactive group selected from the group consisting of epoxy, silane, alkene, alkyne, acrylate, phosphate, and -(CHR １４ CH ２ O)e-R １５ , wherein R １４ is hydrogen or alkyl having 1 to 7 carbon atoms; e is an integer from 1 to a number sufficient for the molecular weight of the -CHR １４ CH ２ O-group to reach up to 200,000; and R １５ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, and hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; x, y and z are sufficient to form a polyanion having a molecular weight of at least 100 to 500,000 or less, and y / x is from 0.01 to 100; z ranges from 0 to a ratio of z / x not exceeding 100.

39. The method for forming a hybrid capacitor according to claim 38, wherein in the total of x + y + z, x represents 50 to 99%, y represents 1 to 50%, and z represents 0 to 49%.

40. The method for forming a hybrid capacitor according to claim 40, wherein in the total of x + y + z, x represents 70 to 90%, y represents 10 to 30%, and z represents 0 to 20%.

41. The method for forming a hybrid capacitor according to claim 38, wherein the anionic counter ion is polystyrene sulfonic acid.

42. The method for forming a hybrid capacitor according to claim 23, wherein the homogenized dispersion further contains a surfactant.

43. The method for forming a hybrid capacitor according to claim 42, wherein the surfactant is selected from the group consisting of a nonionic surfactant, a fluorosurfactant, an anionic surfactant, a cationic surfactant, and an acetylene surfactant.

44. The method for forming a hybrid capacitor according to claim 23, wherein the liquid electrolyte contains a solvent selected from the group consisting of γ-butyrolactone, sulfolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, dimethylformamide, diethylformamide, water, silicone oil, polyethylene glycol, and mixtures thereof.

45. The method for forming a hybrid capacitor according to claim 23, wherein the liquid electrolyte contains a salt selected from the group consisting of an inorganic acid ammonium salt, an inorganic acid amine salt, an inorganic acid alkyl-substituted amide salt, an organic ammonium salt, an organic acid amide salt, an organic acid alkyl, and a substituted amide salt.

46. A hybrid capacitor, comprising: A sealed housing, An anode having a dielectric thereon, A conductive polymer layer on the dielectric, the conductive polymer layer having a surface layer concentration of at least 1% by weight of sulfur, A separator, A liquid electrolyte, And a housing comprising the above components. Hybrid capacitor.

47. The hybrid capacitor according to claim 46, wherein the sulfur concentration of the surface layer is at least 1.2% by weight.

48. The hybrid capacitor according to claim 47, wherein the sulfur concentration of the surface layer is at least 1.4% by weight.

49. The hybrid capacitor according to claim 46, wherein the anode is made of a metal or a metal oxide.

50. The hybrid capacitor according to claim 49, wherein the metal or metal oxide is made of a valve metal.

51. The hybrid capacitor according to claim 50, wherein the valve metal is selected from the group consisting of tantalum, aluminum, niobium, titanium, zirconium, hafnium, alloys of these elements, and conductive oxides of these elements.

52. The hybrid capacitor according to claim 51, wherein the valve metal is aluminum.

53. The hybrid capacitor according to claim 46, wherein the conductive polymer layer contains a conductive polymer defined by Formula A: Formula A 【Chemical 1】 Wherein, X is selected from the group consisting of S, N or O; R １ and R ２ each independently represents a linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl; or C3-C8 cycloalkyl, phenyl or benzyl which is unsubstituted or substituted by C1-C6 alkyl, C1-C6 alkoxy, halogen or OR ３ ; or R １ and R ２ together are unsubstituted or are linear C1-C6 alkylene substituted by C1-C6 alkyl, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl or halobenzyl, or a 5-, 6- or 7-membered heterocyclic structure containing two oxygen elements, R ３ preferably represents hydrogen, a linear or branched C1-C16 alkyl or a C2-C18 alkoxyalkyl; or C3-C8 cycloalkyl, phenyl or benzyl, which are unsubstituted or substituted by C1-C6 alkyl. **Claim 54** The hybrid capacitor according to claim 53, wherein X is S. **Claim 55** The hybrid capacitor according to claim 53, wherein the conductive polymer is 3,4-polyethylenedioxythiophene. **Claim 56** The hybrid capacitor according to claim 36, wherein the conductive polymer layer contains an anionic counter ion defined below: AxByCz wherein A is polystyrene sulfonic acid or a polystyrene sulfonate; B and C each independently represent a polymerized unit substituted with a group selected from the following: - carboxyl group -C(O)OR ６ wherein, R ６ is selected from the group consisting of: alkyl having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, phosphate, acrylate, anhydride, and -(CHR ７ CH ２ O)b-R ８ wherein, R ７ is selected from hydrogen or alkyl having 1 to 7 carbon atoms; b is an integer from 1 to a number sufficient for the molecular weight of the -CHR ７ CH ２ O- group to reach up to 200,000; and R ８ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, silane, phosphate, acrylate, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C(O)-NHR ９ wherein R ９ is an alkyl having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, or hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C ６ H ４ -R １０ wherein, R １０ is selected from the following: hydrogen or alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride and, -(O(CHR １１ CH ２ O)d-R １２ (wherein), and in the formula, R １１ is hydrogen or an alkyl group having 1 to 7 carbon atoms, preferably hydrogen or methyl; d is an integer from 1 to a number sufficient for the molecular weight of the -CHR １１ CH ２ O- group to reach up to 200,000; R １２ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; -C ６ H ４ -O-R １３ wherein, R １３ is selected from the following: hydrogen, or alkyl optionally substituted with a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; a reactive group selected from the group consisting of epoxy, silane, alkene, alkyne, acrylate, phosphate, and -(CHR １４ CH ２ O)e-R １５ In the formula, R １４ is hydrogen or an alkyl group having 1 to 7 carbon atoms; e is an integer from 1 to a number sufficient for the molecular weight of the -CHR １４ CH ２ O- group to reach up to 200,000; and R １５ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, and hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; x, y and z are sufficient to form a polyanion having a molecular weight of at least 100 to 500,000 or less, and y / x is from 0.01 to 100; z is in the range from 0 to a ratio of z / x not exceeding 100. **Claim 57** The hybrid capacitor according to claim 56, wherein among the total of x + y + z, x represents 50 to 99%, y represents 1 to 50%, and z represents 0 to 49%. **Claim 58** The hybrid capacitor according to claim 56, wherein among the total of x + y + z, x represents 70 to 90%, y represents 10 to 30%, and z represents 0 to 20%.

59. The hybrid capacitor according to claim 46, wherein the anionic counter ion is polystyrene sulfonic acid.

60. The hybrid capacitor according to claim 46, wherein the liquid electrolyte contains a solvent selected from the group consisting of γ-butyrolactone, sulfolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, dimethylformamide, diethylformamide, water, silicone oil, polyethylene glycol, and mixtures thereof.

61. The hybrid capacitor according to claim 46, wherein the liquid electrolyte contains a salt selected from the group consisting of inorganic acid ammonium salts, inorganic acid amine salts, inorganic acid alkyl-substituted amide salts, organic ammonium salts, organic acid amide salts, organic acid alkyl and substituted amide salts.

62. A dispersion containing a conductive polymer, a dispersion liquid, a monomer of the conductive polymer, and an anionic counter ion in a molar excess per mole of the conductive polymer and the monomer, wherein the dispersion liquid is homogenized.

63. The dispersion according to claim 62, wherein the weight ratio of the conductive polymer and the monomer to the anionic counter ion in the dispersion is 1:1.5 to 1:

5.

64. The dispersion according to claim 63, wherein the weight ratio of the conductive polymer and the monomer to the anionic counter ion in the dispersion is 1:2 to 1:

3.

65. The dispersion according to claim 62, wherein the weight ratio of the conductive polymer to the anionic counter ion in the hybrid capacitor is 1:1.5 to 1:

5.

66. The dispersion according to claim 65, wherein the weight ratio of the conductive polymer to the anionic counter ion in the hybrid capacitor is 1:2 to 1:

3.

67. The monomer has n = 1 and is defined by formula A with no bond between adjacent units, and the conductive polymer is defined by formula A. The dispersion according to claim 62: Formula A 【Chemical Formula 1】 In the formula, X is selected from the group consisting of S, N, or O. R １ and R ２ each independently represents a linear or branched C1-C16 alkyl or C2-C18 alkoxyalkyl, or C3-C8 cycloalkyl, phenyl or benzyl, which is unsubstituted or substituted by C1-C6 alkyl, C1-C6 alkoxy, halogen or OR ３ substituted by or R １ and R ２ together form an unsubstituted or C1-C6 alkyl, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl or halobenzyl-substituted straight-chain C1-C6 alkylene, a 5-, 6- or 7-membered heterocyclic structure containing two oxygen elements R ３ preferably represents hydrogen, a linear or branched C1-C16 alkyl or a C2-C18 alkoxyalkyl, Or it is unsubstituted or C3 - C8 cycloalkyl, phenyl, or benzyl substituted with C1 - C6 alkyl.

68. The dispersion according to claim 67, wherein X is S.

69. The dispersion according to claim 67, wherein the conductive polymer is 3,4-polyethylenedioxythiophene.

70. The dispersion according to claim 67, wherein the monomer is 3,4-ethylenedioxythiophene.

71. The dispersion according to claim 62, wherein the anionic counterion is defined as follows: AxByCz wherein: A is polystyrene sulfonic acid or a polystyrene sulfonate; B and C each represent a polymerized unit substituted with a group selected from the following: - carboxyl group; -C(O)OR ６ (wherein R ６ is selected from the group consisting of): Hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, phosphate, acrylate, anhydride and -(CHR ７ CH ２ O)b-R ８ (wherein) alkyl having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group consisting of R ７ is selected from hydrogen or an alkyl group having 1 to 7 carbon atoms, b is an integer from 1 to a number sufficient for the molecular weight of the -CHR ７ CH ２ O-group to reach up to 200,000 R ８ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, silane, phosphate, acrylate, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, and anhydride; -C(O)-NHR ９ wherein R ９ is hydrogen or alkyl of 1 to 20 carbons, optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphoric acid, azide, acrylate and anhydride; -C ６ H ４ -R １０ wherein R １０ is selected from the following: hydrogen or alkyl optionally substituted with a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride; a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride; -(O(CHR １１ CH ２ O)d-R １２ wherein, R １１ is hydrogen or an alkyl group having 1 to 7 carbon atoms, preferably hydrogen or methyl. d ranges from 1 to an integer sufficient for the molecular weight of the -CHR １１ CH ２ O- group to be at most 200,000 R １２ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphoric acid, azide, acrylate and anhydride; -C ６ H ４ -O-R １３ wherein, R １３ is selected from the following: hydrogen or alkyl optionally substituted with a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride; a reactive group selected from the group consisting of epoxy, silane, alkene, alkyne, acrylate, phosphate; and -(CHR １４ CH ２ O)e-R １５ wherein R １４ is hydrogen or an alkyl group having 1 to 7 carbon atoms, e is an integer from 1 to a number sufficient for the molecular weight of the -CHR １４ CH ２ O-group to reach up to 200,000 R １５ is selected from the group consisting of alkyl having 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of hydrogen, and hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate and anhydride. x, y and z are sufficient to form a polyanion having a molecular weight of 100 or more and 500,000 or less, and y / x is 0.01 to 100; z is 0, and the ratio of z / x is 100 or less.

72. In the total of x + y + z, x represents 50 to 99%, y represents 1 to 50%, and z represents 0 to 49%, for the dispersion according to claim 71.

73. In the total of x + y + z, x represents 70 to 90%, y represents 10 to 30%, and z represents 0 to 20%, for the dispersion according to claim 72.

74. The dispersion according to claim 62, wherein the anionic counterion is polystyrene sulfonic acid.

75. ​ ​ The surfactant of the dispersion liquid according to claim 75 is selected from the group consisting of a nonionic surfactant, a fluorosurfactant, an anionic surfactant, a cationic surfactant, and an acetylene surfactant.

77. The step of forming the capacitor further includes adding a liquid electrolyte, for the dispersion liquid according to claim 62.

78. The liquid electrolyte of the dispersion liquid according to claim 77 includes a solvent selected from the group consisting of γ-butyrolactone, sulfolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, dimethylformamide, diethylformamide, water, silicone oil, polyethylene glycol, and mixtures thereof.

79. The liquid electrolyte of the dispersion liquid according to claim 77 includes a salt selected from the group consisting of an inorganic acid ammonium salt, an inorganic acid amine salt, an inorganic acid alkyl-substituted amide salt, an organic ammonium salt, an organic acid amide salt, an organic acid alkyl, and a substituted amide salt.

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