Capacitors with improved capacitance

Abstract

The present invention relates to an improved capacitor and an improved process for forming a capacitor. The process includes forming an anode having a dielectric thereon. A cathode layer is then formed on the dielectric, the cathode layer including a self-doped conductive polymer and a crosslinker, wherein the weight ratio of the crosslinker to the self-doped conductive polymer is 0.01 or more and 2 or less.

Description

[Technical Field]

[0001] This invention relates to an improved method for forming solid electrolytic capacitors and an improved capacitor formed thereby. More specifically, this invention relates to an improvement in the conductive polymer layer using a self-doped soluble conductive polymer and an improvement in the method for forming the cathode layer. [Background technology]

[0002] The structure and manufacturing methods of solid electrolytic capacitors are well known. In the structure of a solid electrolytic capacitor, valve metal preferably functions as the anode. The anode can be either a porous pellet obtained by pressing and sintering high-purity powder, or a foil obtained by etching to increase the anode surface area. Alternatively, it is preferable to electrolytically form an oxide of valve metal to cover the entire surface of the anode, and this oxide functions as the dielectric of the capacitor. The solid cathode electrolyte is usually selected from a very limited range of materials, such as manganese dioxide, or conductive organic materials such as polyaniline, polypyrrole, polythiophene, and their derivatives. Solid electrolytic capacitors with intrinsically conductive polymers as the cathode material are widely used in the electronics industry due to their advantageously low equivalent series resistance (ESR) and "unburned / non-ignited" failure mode. In the case of conductive polymer cathodes, the conductive polymer is usually applied by chemical oxidation polymerization, electrochemical oxidation polymerization, or spray technology, although other less preferred techniques have also been reported.

[0003] The anode is generally porous, as porosity increases the surface area and thus the capacitance per given volume. The conductive cathode layer is often composed of conductive materials such as conductive polymer, carbon, or silver layers for connection to the terminals. It is extremely important that the surface of the porous anode is sufficiently covered and tightly adhered to by the conductive cathode layer, and to obtain the target capacitance, it is particularly preferable that the conductive cathode layer completely impregnates the pores. In the manufacturing process of valve metal capacitors using conductive polymers, valve metal powder such as tantalum is mechanically pressed to form the anode, and then sintered to form a porous body. The anode is anodized in a liquid electrolyte at a predetermined voltage to form a dielectric layer, on which a conductive polymer cathode layer is formed. Subsequently, the conductive polymer is coated with graphite or a metal layer, and the finished product is obtained through assembly and molding.

[0004] Polythiophenes have long been the industry standard as conductive polymers used in the cathodes of solid electrolytic capacitors. While thiophenes are widely used, they have limitations, particularly in terms of counterions. Conductive polythiophenes are typically doped with counterions such as aromatic sulfonic acids (e.g., toluenesulfonic acid), polystyrenesulfonic acid, or their derivatives, and are referred to herein as excipient conductive polymers for clarity. Excipient conductive polymers are dispersions of particles with varying particle sizes. The non-uniformity of the particles, especially particle size, presents problems in forming coatings with sufficient coverage and adhesion. Furthermore, the difficulty in filling small pores with the dispersion makes excipient conductive polymers unsuitable for use as high-charge-density powders.

[0005] Self-doped conductive polymers are soluble and have been considered a promising option for avoiding the problems associated with externally added conductive polymers. One of the advantages of self-doped conductive polymers that is of interest to those skilled in the art is their solubility. Because self-doped conductive polymers are highly soluble, there is no need to apply a dispersion, and improved coatability can be expected. Furthermore, because soluble conductive polymers are expected to better fill small pores, they are also expected to be applicable to high-charge-density powders. An unexpected result was that, due to their high solubility, they dissolved the previously applied self-doped conductive polymer, degrading the coating and affecting capacitance. Although crosslinking has been described, if the crosslinking is too strong, the conductivity of the conductive layer decreases, so the expected advantages have not been obtained.

[0006] This invention provides a method for manufacturing a capacitor made of a self-doped conductive polymer with improved capacitance. [Overview of the project] [Means for solving the problem]

[0007] The present invention relates to improved compositions of self-doped conductive polymers and coatings using the same, more specifically to crosslinked self-doped conductive polymers and coatings using the same.

[0008] More specifically, the present invention relates to the use of an improved self-doped conductive polymer coating as the cathode of a solid electrolyte capacitor.

[0009] A key feature of the present invention is that it is possible to form a conductive coating on a dielectric anode having high capacitance and, consequently, very small pores.

[0010] In these and other embodiments, a process for forming an electrolytic capacitor is provided, as can be realized. This process includes forming an anode thereon which a dielectric is included. Next, a cathode layer is formed on the dielectric, the cathode layer comprising a self-doped conductive polymer and a crosslinking agent, wherein the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.01 or more and 2 or less.

[0011] In yet another embodiment, an electrolytic capacitor is provided which includes an anode having a dielectric thereon. The cathode layer is on the dielectric and comprises a crosslinked self-doped conductive polymer formed with a crosslinking agent. The cathode has a crosslinking agent weight ratio of 0.01 to 2 to the self-doped conductive polymer. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 is a schematic cross-sectional view of a capacitor. [Modes for carrying out the invention]

[0013] The present invention relates to a method for forming a solid electrolytic capacitor made of a self-doped conductive polymer, particularly a crosslinked self-doped conductive polymer, and an improved capacitor formed thereby. More specifically, the present invention relates to an improved conductive polymer composition based on a crosslinked self-doped conductive polymer and an improved capacitor formed therefrom.

[0014] The present invention will be described with reference to the diagrams which form essential, non-limiting components of this disclosure. In the diagrams, similar elements are numbered as appropriate.

[0015] One embodiment of the present invention is shown in Figure 1 in a schematic cross-sectional side view. In Figure 1, the capacitor, generally represented as 10, includes an anodized anode 12 and anode lead wires 14 extending from or attached thereto. The anode lead wires are preferably in electrical contact with an anode lead 16. A precursor conductive layer 15 is formed on the anode, and preferably the precursor conductive layer at least partially encompasses a portion of the dielectric of the anode. However, the precursor conductive layer is preferably formed by coating a self-doped or soluble conductive polymer solution and crosslinking a self-doped conductive polymer or an adjacent self-doped conductive polymer or a layer containing the same. Additional conductive polymer layers, collectively referred to as 18, are sequentially formed on the precursor conductive layer, at least partially enclosing at least a portion of the precursor conductive layer and forming a casing around at least a portion of the dielectric. The aggregate layer represented as 18 may also include intermediate layers between conductive polymer layers, as will be described in more detail herein. In preferred embodiments, all conductive cathode layers are formed from a soluble, self-doped conductive polymer, and more preferably, at least a portion of the layers contain crosslinking groups. As those skilled in the art will know, in a finished capacitor, the cathode and anode are not in direct electrical contact. The cathode leads 22 are in electrical contact with the cathode layer. It is well understood that soldering lead frames (external terminals) to a polymer cathode is difficult. Therefore, it is standard practice in the art to preferably provide a conductive interlayer consisting of a carbon-containing layer 20 and a metal-containing layer 23 that enables solder adhesion. In many embodiments, as those skilled in the art will readily understand, it is preferable to encapsulate the capacitor in a non-conductive resin 24 with at least a portion of the anode and cathode leads exposed for mounting to a circuit board.

[0016] Self-doped conductive polymers are soluble and dissolve completely in a solvent or solvent mixture without detecting particles. For the purposes of this invention, particle sizes of about 1 nm or less are considered to be below the typical particle size detection limit and are therefore defined as soluble. The solvent for soluble conductive polymers can be water or an organic solvent, or a mixture of water and a miscible solvent such as alcohol, or a non-hydroxy polar solvent such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), or dimethylacetamide (DMAc). Conductive polymer solutions can impregnate anode pores as effectively as conductive polymers formed by in-situ methods and more effectively than conductive polymer dispersions containing detectable particles. Examples of soluble conductive polymers include polyaniline, polypyrrole, and polythiophene, which may be substituted.

[0017] A preferred self-doped polymer contains repeating units represented by formula A;

[0018] [ka]

[0019] In formula A: R 1 and R 2 These are independently linear or branched C1-C 16 Alkyl or C2-C 18 Represents alkoxyalkyl; Or unsubstituted or C1-C6 alkyl, C1-C6 alkoxy, halogen or OR 3 A C3-C8 cycloalkyl, phenyl, or benzyl substituted by, or R 1 and R 2is a straight-chain C1-C6 alkylene which may be unsubstituted or substituted with 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 is preferably hydrogen, straight-chain or branched C1-C 16 alkyl or C2-C 18 alkoxyalkyl; or at least one of R 1 or R 2 is substituted with -SO3M, -CO2M or -PO3M, where M is H or preferably a cation selected from ammonium, sodium, lithium or potassium, and is unsubstituted or substituted C3-C8 cycloalkyl, phenyl or benzyl which is not substituted with C1-C6 alkyl; X is S, N or O, and most preferably X is S; R of formula A 1 and R 2 are most preferably selected to inhibit polymerization at the β-position of the ring so that only polymerization at the α-position proceeds. It is more preferable that R 1 and R 2 are not hydrogen, and more preferably R 1 and R 2 are α-directors in which an ether bond is preferred over an alkyl bond; and to avoid steric interference, it is most preferred that R 1 and R<00??0020>are small.

[0020] In a particularly preferred embodiment, R of formula A 1 and R 2 together represent O-(CHR 4 ) n -O-, where; n is an integer from 1 to 5, and most preferably 2; R 4These are independently linear or branched C1-C 18 Alkyl radical C5-C 12 Cycloalkyl radical, C6-C 14 Aryl radical C7-C 18 Selected from aralkyl radicals or C1-C4 hydroxyalkyl radicals; R 4 is substituted with -SO3M, -CO2M or -PO3M, and optionally substituted with at least one additional functional group selected from carboxylic acids, hydroxyls, amines, substituted amines, alkenes, acrylates, thiols, alkynes, azides, sulfates, sulfonates, sulfonic acids, imides, amides, epoxys, anhydrides, silanes, phosphates, or hydroxyl radicals; or R 4 is, -(CHR5) a -R 16 , -O(CHR5) a R 16 -CH2O(CHR 5 ) a R 16 ;CH2O(CH2CHR 5 O) a R 16 Selected from, or R 4 These are -SO3M, -CO2M, or -PO3M; R 5 A C1-C5 alkyl chain is optionally substituted with H or a functional group selected from carboxylic acids, hydroxyl groups, amines, alkenes, thiols, alkynes, azides, epoxys, acrylates, and anhydrides; R 16 -SO3M, -CO2M, or -PO3M or -SO3M, -CO2M, or -PO3M, optionally further substituted with at least one functional group selected from carboxylic acids, hydroxyls, amines, substituted amines, alkenes, thiols, alkynes, azides, amides, imides, sulfuric acids, amides, epoxys, anhydrides, silanes, acrylates, and phosphoric acids; a is an integer between 0 and 10; M is preferably H or a cation selected from ammonium, sodium, lithium, or potassium.

[0021] Exemplary self-doped conductive polymers are represented by S1 and S2.

[0022] [ka]

[0023] [ka]

[0024] S1 is a polymer commercially available as a 2% solution in water. S2 is a polymer commercially available as a 2% solution in water.

[0025] Self-doped conductive polymers can be formed in situ by polymerizing monomers during the deposition of the self-doped conductive polymer, as is well known in the art. It is preferable to use a pre-prepared self-doped conductive polymer, preferably formed in the presence of functional additives. Pre-forming the self-doped conductive polymer is preferable because it reduces leakage current and increases breakdown voltage.

[0026] The crosslinking agent is a compound having at least two reactive functional groups that can react ionically or covalently with adjacent functional groups. In one embodiment, a first functional group is on a self-doped conductive polymer, and then the first functional group reacts with a second functional group on the crosslinking agent. In another embodiment, the first functional group is on another crosslinkable material in a coating or adjacent layer having a self-doped conductive polymer, and the first functional group reacts with a second functional group on the crosslinking agent. When a crosslinkable material is used, the crosslinkable material is crosslinked by the crosslinking agent, thereby forming a matrix containing the self-doped conductive polymer. This is particularly advantageous because the matrix suppresses the dissolution of the self-doped conductive polymer without unnecessarily limiting conductivity within the layer.

[0027] The crosslinkable material is preferably a compound, oligomer, or polymer having at least one reactive group that can react with the crosslinking agent. The reactive functional group is carboxylic acid, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic acid anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, dicyclopentadiene unsaturated compound, or unsaturated C 12 -C 22 It is preferable to select from the group consisting of fatty esters or amides, carboxylates or ammonium salts. Polyols are particularly suitable as crosslinkable materials, and ethylene glycol and polyglycerin are particularly suitable for demonstrating the present invention. The crosslinkable material may have the same functional groups as the crosslinking agent, or may be the same compound, as long as the crosslinking reaction occurs. The crosslinkable material may also function as a crosslinking agent if it has two or more reactive functional groups that react with self-doped conductive polymers or other types of crosslinkable materials.

[0028] One embodiment includes a solid electrolytic capacitor comprising a crosslinkable material system which is an oligomer or polymer containing polyfunctional reactive groups. The oligomer or polymer is preferably composed of at least one polymerization monomer selected from the group consisting of polyester, polyurethane, polyamide, polyamine, polyimide, silicone polyester, hydroxyl group-containing silicone, hydroxyethylcellulose, polyvinyl alcohol, phenol, epoxy, butyral, copolymers thereof, or mixtures of polyfunctional polymers such as epoxy / amine, epoxy / anhydride, isocyanate / amine, isocyanate / alcohol, unsaturated polyester, vinyl ester, unsaturated polyester and vinyl ester blends, unsaturated polyester / urethane hybrid resin, polyurethane urea, reactive dicyclopentadiene resin, and reactive polyamide. The oligomer or polymer having polyfunctional groups or multiple reactive groups preferably contains at least one carboxylic acid group and at least one hydroxyl functional group. Particularly preferred as an oligomer or polymer having polyfunctional reactive groups is a polyester containing a carboxyl functional group and a hydroxyl functional group. In addition to oligomers and polymers, particles having surface functional groups can also participate in crosslinking. Particles having functional groups include carboxylic acids, hydroxyl groups, amines, epoxy, anhydrides, isocyanates, imides, amides, carboxyls, carboxylic anhydrides, silanes, oxazolines, (meth)acrylates, vinyls, maleates, maleimides, itaconates, allyl alcohol esters, dicyclopentadiene unsaturated, and unsaturated C. 12 -C 22 The particles are preferably selected from fatty esters or amides, carboxylates, or quaternary ammonium salts. The particles may be nanoparticles or microparticles. An example of functionalized nanoparticles is organically modified nanoclay. When a self-doped conductive polymer is crosslinked with the particles, the conductive polymer is useful not inside the pores, but as an external cathode coating outside the anode.

[0029] One embodiment includes a solid electrolytic capacitor comprising a crosslinkable material which is a cyclic organic compound containing at least one hydroxyl functional group, preferably at least one other hydroxyl or carboxyl functional group, and these are preferred because they also improve the thermal stability of the self-doped conductive polymer. The cyclic organic compound may be aromatic, heterocyclic, or alicyclic, with aromatic being the most preferred. Particularly preferred cyclic aromatic compounds are selected from phenol, cresol, nitrophenol, aminophenol, hydroxybenzoic acid (i.e., hydroxybenzene carboxylic acid), sulfosalicylic acid, dihydroxybenzene, dihydroxybenzoic acid (i.e., dihydroxybenzene carboxylic acid), methyl hydroxybenzoate (i.e., methyl hydroxybenzene carboxylic acid), ethyl hydroxybenzoate (i.e., ethyl hydroxybenzene carboxylic acid), ethylhexyl hydroxybenzoate (i.e., ethylhexyl hydroxybenzene carboxylic acid), methoxyphenol, ethoxyphenol, butoxyphenol, phenylphenol, cumylphenol, aminonitrophenol, hydroxynitrobenzoic acid (i.e., hydroxynitrobenzene carboxylic acid), methyl hydroxynitrobenzeneate (i.e., methyl hydroxynitrobenzene carboxylic acid), sulfonsalicylic acid, dihydroxybenzene, dihydroxybenzoic acid (i.e., dihydroxybenzene carboxylic acid), trihydroxybenzene, trihydroxybenzoic acid (i.e., trihydroxybenzene carboxylic acid), phenolsulfonic acid, cresolsulfonic acid, dihydroxybenzenesulfonic acid, nitrophenolsulfonic acid, and hydroxyindole.

[0030] Examples of naphthalene compounds may include naphthol, nitronaphthol, hydroxynaphthoic acid (i.e., hydroxynaphthalene carboxylic acid), dihydroxynaphthol, trihydroxynaphthol, naphtholsulfonic acid, dihydroxynaphtholsulfonic acid, and nitronaphtholsulfonic acid.

[0031] An example of an anthraquinone compound is hydroxyanthraquinone.

[0032] Examples of heterocyclic compounds as cyclic organic compounds having at least one hydroxyl group include 2,5-dicarboxy-3,4-dihydroxythiophene, (3-hydroxythiophene, 3,4-dihydroxythiophene, hydroxypyridine, and dihydroxypyridine.

[0033] Examples of alicyclic compounds include hydroxycyclohexane, hydroxycyclohexanecarboxylic acid, methyl hydroxycyclohexanecarboxylate, and dihydroxycyclohexane.

[0034] Phenolic acids are particularly preferred, and gallic acid and tannic acid are even more preferred.

[0035] Particularly preferred crosslinking agents consist of melamine, isocyanates, epoxy, hexamethoxymelamine, glyoxal, furfuralaldehyde, melamineformaldehyde condensate, divinyl sulfone, epoxy compounds, and carboxylic acid compounds.

[0036] Organic functional silanes and organic compounds having one or more crosslinking groups, particularly one or more epoxy groups, can be used particularly suitably as crosslinking agents of the present invention, especially when used in combination.

[0037] Organic functional silanes are given by formula XR 1 Si(R 3 ) 3-n (R 2 ) n Defined by, In the formula, X is an organic functional group such as amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, or alkyl; R 1 is aryl or alkyl (CH2) m (Here, m can be anywhere from 0 to 14); R 2 These are individually hydrolyzable functional groups such as alkoxy, acyloxy, halogen, amine or their hydrolysates; R 3Each of the alkyl groups has 1 to 6 carbon atoms; n is 1 to 3.

[0038] Organic functional silanes are given by formula Y(Si(R 3 ) 3-n (R 2 ) n ) It can also be bipolar as defined in formula 2, where Y is any organic moiety containing a reactive or nonreactive functional group such as alkyl, aryl, sulfide, or melamine, and R 3 , R 2 And n are defined above. The organically functional silane may also be a polyfunctional silane or polymer silane such as silane-modified polybutadiene or silane-modified polyamine.

[0039] Examples of organically functional silanes include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, and bis(triethoxysilyl)octane. These examples are for illustrative purposes only and are not definitive.

[0040] Particularly preferred organic functional silanes are given by formula:

[0041] [ka]

[0042] It is a glycidylsilane defined by the formula, where R 1 The R is an alkyl group having 1 to 14 carbon atoms, more preferably selected from methyl ethyl and propyl, and each R 2 These are independently alkyl groups or substituted alkyl groups having 1 to 6 carbon atoms.

[0043] A particularly preferred glycidylsilane is given by formula:

[0044] [ka]

[0045] This is 3-glycidoxypropyltrimethoxysilane as defined by , and for convenience, it is referred to herein as "silane A".

[0046] A crosslinking agent having at least two epoxy groups is referred to herein as an epoxy crosslinking compound, and is given the formula:

[0047] [ka]

[0048] Defined by the formula, where X is an alkyl or substituted alkyl, aryl or substituted aryl, ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether having 2 to 20 ethylene ether groups, or a combination thereof, having 0 to 14 carbon atoms, preferably 0 to 6 carbon atoms. Particularly preferred substituents are epoxy groups.

[0049] Examples of epoxy crosslinked compounds having two or more epoxy groups include ethylene glycol diglycidyl ether (EGDGE), propylene glycol diglycidyl ether (PGDGE), 1,4-butanediol diglycidyl ether (BDDGE), pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl ether (GDGE), glycerol polyglycidyl ether, diglycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. This includes ethers, sorbitol diglycidyl ether (sorbitol-DGE), sorbitol polyglycidyl ether, polyethylene glycol diglycidyl ether (PEGDGE), polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiene diepoxide, 1,5-hexadiene diepoxide, 1,2,7,8-dipoxyoctane, 1,2,5,6-dipoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, maleimide-epoxy compounds, and the like.

[0050] A preferred epoxy crosslinking compound is, formula:

[0051] [ka]

[0052] A glycidyl ether defined by, where R 3 is an alkyl or substituted alkyl having 1 to 14 carbon atoms, preferably 2 to 6 carbon atoms, and is an ethylene ether or polyethylene ether having 2 to 20 ethylene ether groups, and is an alkyl substituted with a group selected from hydroxyl, or

[0053] [ka]

[0054] or -(CH2OH) x CH2OH, where X is between 1 and 14.

[0055] Particularly preferred glycidyl ethers are:

[0056] [ka]

[0057] EGDGE: Ethylene glycol diglycidyl ether

[0058] [ka]

[0059] In the formula, n is an integer between 1 and 220; PEGDGE: Polyethylene glycol diglycidyl ether

[0060] [ka]

[0061] BDDGE: 1,4-butanediol diglycidyl ether

[0062] [ka]

[0063] GDGE: Glycerol diglycidyl ether

[0064] [ka]

[0065] It is represented as sorbitol-DGE, or sorbitol diglycidyl ether.

[0066] In this specification, a crosslinking agent having at least two carboxyl functional groups is referred to as a carboxyl crosslinkable compound.

[0067] Examples of carboxylic acid crosslinking compounds include, but are not limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, phthalic acid, maleic acid, muconic acid, citric acid, trimesic acid, and polyacrylic acid. Particularly preferred organic acids are aromatic acids such as phthalic acid, and orthophthalic acid in particular lowers the ESR. The reaction between the crosslinking functional group and the crosslinking agent occurs at high temperatures that occur in the normal processing steps of capacitor manufacturing.

[0068] Crosslinking immobilizes the self-doped conductive polymer, suppressing its dissolution in subsequent processes. However, crosslinking impairs the conductivity of the self-doped conductive polymer layer. The weight ratio of the crosslinking agent to the solid self-doped conductive polymer is preferably about 0.01 to 2. More preferably, the weight ratio of the crosslinking agent to the self-doped conductive polymer is about 0.02 to 1, and even more preferably 0.05 to 0.2. If the weight ratio is less than about 0.01, the degree of crosslinking is insufficient, and dissolution in subsequent processes cannot be sufficiently suppressed. If the weight ratio exceeds about 2, the conductivity of the self-doped conductive polymer layer decreases due to crosslinking.

[0069] Self-doped conductive polymers are preferably substantially free of foreign dopants due to harmful interactions between the dopant's anionic group and the self-doped conductive polymer, and it has been considered acceptable to use less than 5 wt%. However, it is now surprisingly recognized that using larger amounts of foreign dopants, particularly polystyrene sulfonic acid or its derivatives, actually provides advantages in terms of capacity, capacity stability, and dielectric breakdown voltage (BDV). While not theoretically limited, it is now understood that the thermal instability of the anionic moiety of self-doped conductive polymers is a particular problem. The addition of some foreign dopant, preferably a polymer foreign dopant, mitigates degradation that occurs during various thermal excursions that occur during polymer preparation and use. Polymer foreign dopants are preferably added in amounts of about 7 wt% to 100 wt% based on the weight of the self-doped conductive polymer. Foreign dopants exceeding about 100 wt% can significantly increase the ESR due to the excess polymer dopant. Furthermore, self-doped conductive polymers begin to solidify into particulate matter, which is undesirable as it contradicts the reasons for using self-doped conductive polymers. Below approximately 7 wt%, the mitigation of thermal instability is not achieved, making it insufficient to justify the addition. More preferably, the foreign dopant is added in an amount of 8 wt% to 20 wt%. Moreover, it is assumed that dopants present in sufficient quantities, particularly polymer dopants such as polystyrene sulfonic acid, interact with multiple sites of the self-doped conductive polymer, preventing the dissolution of the self-doped polymer when subsequent layers are applied. When crosslinking agents are used, excess polymer dopants may mitigate the effects of crosslinking, thereby potentially yielding a crosslinked self-doped conductive polymer with sufficient conductivity.

[0070] Particularly preferred polymer additives are polystyrene sulfonic acid and its derivatives, optionally in the form of a random copolymer consisting of groups A, B, and C represented in the ratio of formula B: AxByCz Formula B

[0071] During the ceremony: A is polystyrene sulfonic acid or a salt of polystyrene sulfonic acid; B and C separately represent polymerization units substituted with a group selected from the following: -carboxyl group; -C(O)OR 6 , where R 6 The following group is selected: A C1-C20 alkyl group 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, and anhydride, and -(CHR 7 CH2O) b -R 8 , in the formula: R 7 This is selected from hydrogen or an alkyl group having 1 to 7 carbon atoms, preferably hydrogen or methyl; b is 1, -CHR 7 For each CH2O- group, the integer is sufficient to provide a molecular weight up to 200,000; R 8 It consists of a C1-C9 alkyl group 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 , in the formula: R 9 (These are hydrogen atoms or C1-C20 alkyl groups optionally substituted with functional groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, and anhydride.) -C6H4-R 10 , in the formula: R 10 The following can be selected: 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 CH2O) 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 to provide a molecular weight up to 200,000 for the -CHR 11 CH2O- group; R 12 is selected from 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, -C6H4-O-R 13 , wherein: R 13 is 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;[[ID=三十一]] [[ID=三十二]]A reactive group selected from the group consisting of epoxy, silane, alkene, alkyne, acrylate, phosphate;[[ID=三十三]] [[ID=三十四]]-(CHR[[ID=三十五]] 14 [[ID=三十六]]CH2O)[[ID=三十七]] e [[ID=三十八]]-R[[ID=三十九]] 15 [[ID=四十]], wherein R[[ID=四十一]] 14 [[ID=四十二]]is hydrogen or alkyl having 1 to 7 carbon atoms, preferably hydrogen or methyl;[[ID=四十三]] [[ID=四十四]]e is from 1 to, -CHR[[ID=四十五]] 14For each CH2O- group, the integer is sufficient to provide a molecular weight up to 200,000; R 15 This is selected from the group consisting of hydrogen or C1-C9 alkyl groups 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; 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, with y / x being 0.01 to 100; z being a ratio z / x of 0 to 100; more preferably, x in the sum of x+y+z represents 50-99%, y represents 1-50%, and z represents 0-49%; even more preferably, x represents 70-90%, y represents 10-30%, and z represents 0-20%.

[0072] Monomer exogenous dopants have been shown to have a beneficial effect on the stability of power cycle capacity when applied to self-doped conductive polymers, either as additives to the self-doped polymer solution or as a separate layer adjacent to the conductive polymer. These monomer exogenous dopants improve the thermal stability of self-doped conductive polymers in addition to their capacitance effect. Aromatic sulfonic acids are more advantageous than aliphatic sulfonic acids, particularly in terms of thermal oxidation stability. Aromatic acids with added functional groups such as sulfonic acid groups, carboxylic acid groups, hydroxyl groups, and quinone groups are more effective and preferable. Aliphatic sulfonic acids with carboxyl functional groups exhibit superior thermal stability improvement compared to those without carboxyl groups. This is not surprising, as carboxylic acid functional groups also function as dopants for conductive polymers. Monomer exogenous dopants can reduce the swelling of dried self-doped conductive polymer films, which is attributed to the solubility of the self-doped conductive polymer. The monomer exogenous dopant is preferably added in an amount of about 7 wt% to 100 wt% based on the weight of the self-doped conductive polymer, and more preferably in an amount of about 8 wt% to 20 wt%.

[0073] Self-doped conductive polymers can be mixed with foreign dopants, as mentioned above. Alternatively, self-doped monomers can be polymerized in the presence of foreign dopants, or in the presence of both non-self-doped monomers and foreign dopants.

[0074] It is particularly preferable to incorporate functional additives into a coating containing a self-doped conductive polymer or an adjacent coating layer. Particularly preferred functional additives include ionic liquids; nonionic polyols, especially polyglycerols; and polyalkylene ethers. The weight ratio of the functional additive to the self-doped conductive polymer is preferably 0.05 to 5. Below a weight ratio of about 0.05, the function is insufficient. Above a weight ratio of about 5, the conductivity decreases. The weight ratio is preferably about 0.5 to about 1.

[0075] Ionic liquids are particularly suitable for use in this invention due to their ability to increase capacitance and improve thermal stability.

[0076] Ionic liquids (ILs) are generally defined as organic / inorganic salts with a melting point below 100°C, that are chemically and electrochemically stable, have low flammability, negligible vapor pressure, and high ionic conductivity. In their liquid state with negligible vapor pressure, ionic liquids are commonly considered green solvents for industrial production. Ionic liquids are organic salts with poor ionic coordination that dissolve below 100°C or even at room temperature. They have a wide electrochemical operating range and relatively high matrix mobility at room temperature. Because ionic liquids are composed entirely of ions, their charge density is significantly higher than that of ordinary salt solutions.

[0077] Particularly preferred ionic liquids are selected from the group consisting of the following:

[0078] [ka] TIFF0007872776000015.tif67119

[0079] Particularly preferred ionic liquids contain cations selected from the group consisting of 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, and 1,2,3-triethylimidazolinium. Exemplary ionic liquids are selected from the group consisting of 4-(3-butyl-1-imidazolium)-1-butanesulfonic acid triflate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-aryl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, lithium bis(trifluoromethane)sulfonimide and its derivatives.

[0080] Polyionic liquids (PILs), as described in Progress in Polymer Science Volume 38, Issue 7, July 2013, Pages 1009-1036, are a subclass of polymer electrolytes in which each monomer repeating unit contains an ionic liquid species, connected via a polymer backbone to form a polymer structure. By incorporating some of the unique properties of ionic liquids into the polymer chain, a new class of polymer material is created. Polymer ionic liquids expand the properties and applications of both ionic liquids and general polymer electrolytes. Due to the solvent-independent ionization state of the ionic liquid species, polymer ionic liquids are permanent and strong polymer electrolytes. The ability to absorb water is a common characteristic of both ionic liquids and polymer ionic liquids.

[0081] A group of similar polymer ionic liquids includes the following:

[0082] [ka]

[0083] Selected from the derivatives thereof.

[0084] For the purposes of the present invention, the nonionic polyol is an alkyl alcohol having multiple hydroxyl groups, or an alkyl ether having multiple hydroxyl groups on an alkyl group.

[0085] Particularly preferred nonionic polyols include CH2OH(CHOH)2CH2OH or erythritol, ribitol or xylitol as CH2OH(CHOH)3CH2OH, CH2OHC(CH2OH)2CH2OH or pentaerythritol, CH2OHC(CH3)2CH2OH or 2,2-dimethyl-1,3-propanediol, CH2OH(CHOH)4CH2OH or sorbitol, CH2OH(CHOH)4CH2OH or mannitol, CH3C(CH2OH)3 or trimethylolethane, O(CH2C(C2H5)CH2OH)2)2 or ditrimethylolpropane, CH2OH(CHOH)4COH or glucose, CH2OH(CHOH)3COCH2OH or fructose, C 12 H 22 O 11 Alternatively, it may be sucrose or lactose, glycerol, diglycerol, triglycerol, tetraglycerol, or polyglycerol.

[0086] Various hydroxyl-functional nonionic polymers can generally be used. In one embodiment, for example, the hydroxyl-functional polymer is a polyalkylene ether. Examples of polyalkylene ethers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polyepichlorohydrin; polyoxetane, polyphenylene ether, and polyether ketone. Polyalkylene ethers are usually linear nonionic polymers having terminal hydroxyl groups. Particularly preferred are polyethylene glycol, polypropylene glycol, and polytetramethylene glycol (polytetrahydrofuran). The diol component may be selected from saturated or unsaturated, branched or unbranched, aliphatic dihydroxy compounds or aromatic dihydroxy compounds containing 5 to 36 carbon atoms, such as pentane-1,5-diol, hexane-1,6-diol, neopentyl glycol, bis-(hydroxymethyl)-cyclohexane, bisphenol A, dimer diol, hydrogenated dimer diol, or even mixtures of the diols listed above.

[0087] In addition to the above, other hydroxy-functional nonionic polymers can also be adopted. Some examples of such polymers include, for example, ethoxylated alkylphenols, ethoxylated or propoxylated C6-C 24 fatty alcohols; general formula: CH3-(CH2) 10-16 -(O-C2H4) 1-25 -OH-containing polyoxyethylene glycol alkyl ethers, such as octaethylene glycol monododecyl ether and pentaethylene glycol monododecyl ether, etc.; general formula: CH3-(CH2) 10-16 -(O-C3H6) 1-25 -OH-containing polyoxypropylene glycol alkyl ethers; the following general formula: C8-H 17 -(C6H4)-(O-C2H4) 1-25 -OH-containing polyoxyethylene glycol octylphenol ethers, such as Triton (registered trademark) X-100; the following general formula: C9-H 19 -(C6H4)-(O-C2H4) 1-25 -OH-containing polyoxyethylene glycol alkylphenol ethers, such as nonoxynol-9, etc., C8-C 24Polyoxyethylene glycol esters of fatty acids, such as polyoxyethylene(20) sorbitan monolaurate, polyoxyethylene(20) sorbitan monopalmitate, polyoxyethylene(20) sorbitan alkyl esters, polyoxyethylene(20) sorbitan monostearate, polyoxyethylene(20) sorbitan monooleate, PEG-20 methyl glucose distearate, PEG-20 methyl glucose sesquistearate, PEG-80 castor oil, and polyoxyethylene glycerol alkyl esters such as PEG-20 castor oil, PEG-3 castor oil, PEG-600 diolate, PEG-400 diolate, polyoxyethylene-23 glycerol laurate and polyoxyethylene-20 glycerol stearate, polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearyl ether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether, polyoxyethylene-20 C8-C ethers such as isohexadecyl ether, polyoxyethylene-15 tridecyl ether, and polyoxyethylene-6 tridecyl ether. 24 Examples include polyoxyethylene glycol ethers of fatty acids and block copolymers of polyethylene glycol.

[0088] Functional additives can be in the same layer as the self-doped conductive polymer or applied as a protective layer on top of the conductive polymer. The functional additives stabilize ESR, capacitance, and power cycle capacity.

[0089] Functional additives can be used in combination with crosslinking agents, and in some cases, they may even exist within the same molecule.

[0090] The present invention is particularly suitable for use with high CV / g powders. Conductive polymers have small pore sizes, making it difficult to impregnate them with conductive polymer dispersions, thus making their use in combination with high CV / g powders difficult. While it is possible to impregnate small pores by forming conductive polymers in situ, controlling the formation of the conductive polymer is difficult, resulting in insufficient coating and leakage current problems. In other words, the present invention is particularly suitable for powders having a charge density of at least 45,000 CV / g, more preferably at least 100,000 CV / g, and even more preferably 200,000 CV / g, especially tantalum powder.

[0091] In one embodiment, the difference in dissolution rates of adjacent layers can be used to suppress the dissolution of previously coated layers. When performing multiple impregnation cycles of conductive polymers, the dissolution rate can be changed by mixing with different solvents. For example, by including alkylamines in the self-doped conductive polymer solution, it can be solubilized in polar solvents such as alcohol, DMG, DMAc, and DMSO. By changing the solvent between impregnation cycles of the self-doped conductive polymer, the possibility of redissolution of the previously impregnated and dried polymer film can be minimized. The advantage of using organic solvents for such self-doped conductive polymers is that the organic solvent improves wettability and impregnation, potentially resulting in excellent capacitance, especially for highly charged powders. Of course, capacitance can also be improved by adding cosolvents and surfactants to aqueous self-doped conductive polymer solutions. [Examples]

[0092] [Comparative Example 1] A series of 220 microfarad, 6V tantalum anodes were fabricated with a charge-to-weight ratio of 120,000 μFV / g. Tantalum was anodized to form a dielectric on the tantalum anode at a predetermined formation voltage (Vf). The formed anodes were immersed for 1 minute in a self-doped conductive polymer solution using polymer S2, and then dried in an oven to remove moisture. This step was repeated 9 times. A layer of diamine salt aqueous solution was applied and dried. Subsequently, an externally added polythiophene conductive polymer dispersion was applied to form a subsequent polymer layer. This step was repeated 4-5 more times to sequentially coat graphite and silver layers and fabricate a solid electrolytic capacitor. The components were assembled and packaged. Capacitance, ESR, and BDV were measured on the packaged components. Capacitance recovery rate was calculated by dividing the capacitance value by the wet capacitance tested after dielectric formation. The packaged components were mounted on a circuit board, and the capacitance change during power cycles was tested before and after 50,000 power surge cycles.

[0093] [Example 1] A series of tantalum capacitors were prepared as described in Comparative Example 1, except that the self-doped conductive polymer solution contained 0.1 wt% epoxysilane crosslinking agent.

[0094] [Example 2] A series of tantalum capacitors were prepared as described in Comparative Example 1, except that the self-doped conductive polymer solution contained 0.2 wt% polystyrene sulfonic acid.

[0095] [Comparative Example 2] A series of 47 microfarad, 16V tantalum anodes (specific charge 133,000 μFV / g) were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The resulting negative electrode was immersed for 1 minute in a self-doped conductive polymer solution using polymer S2, and then dried in an oven to remove moisture. This process was repeated 9 times. Subsequently, an externally added polythiophene conductive polymer dispersion was applied to form a subsequent polymer layer. After drying, a layer of diamine salt aqueous solution was applied and dried. Then, the externally added polythiophene conductive polymer dispersion was applied and dried 4-5 more times, and a graphite layer and a silver layer were sequentially applied to fabricate a solid electrolytic capacitor. The components were assembled and packaged. The capacitance and ESR of the packaged components were measured.

[0096] [Example 3] A series of tantalum capacitors were prepared as described in Comparative Example 2, except that the self-doped conductive polymer solution contained 0.2 wt% polystyrene sulfonic acid.

[0097] [Example 4] A series of tantalum capacitors were prepared as described in Comparative Example 2, except that the self-doped conductive polymer solution contained 0.5 wt% polystyrene sulfonic acid.

[0098] [Example 5] A series of tantalum capacitors were prepared as described in Comparative Example 2, except that the self-doped conductive polymer solution contained 1.0 wt% polystyrene sulfonic acid.

[0099] [Comparative Example 3] A series of 10 microfarad, 50V tantalum anodes (specific charge 12,000 μFV / g) were fabricated. The tantalum was anodized to form a dielectric on the anodes. The formed anodes were immersed for 1 minute in a self-doped conductive polymer solution using polymer S2, and dried in an oven to remove moisture. This process was repeated once more. Next, these anodes were immersed for 1 minute in a first commercially available conductive polymer dispersion, Clevios Knano LV, manufactured by Heraeus, and dried in an oven to remove moisture. This process was repeated until sufficient thickness was achieved. A second conductive polymer dispersion containing epoxy and silane compounds was applied to form an outer polymer layer. After drying, diamine salts and the second conductive polymer dispersion were applied alternately, and this process was repeated 4-5 times. After washing and drying the anodes with the conductive polymer layers, a graphite layer and a silver layer were sequentially coated to fabricate a solid electrolytic capacitor. The components were assembled and packaged. The packaged components were then mounted on the circuit board. For the power cycle mounted components, the capacitance percentage was measured before and after 50,000 power surge cycles.

[0100] [Example 6] A series of tantalum capacitors were prepared by the method described in Comparative Example 3, except that the self-doped conductive polymer solution contained 0.2 wt% 1,5-naphthalenesulfonic acid.

[0101] [Example 7] A series of tantalum capacitors were fabricated using the method described in Comparative Example 3, except that after two cycles of self-doping with a conductive polymer coating, the anode was immersed in a 0.5 wt% solution of 1,5-naphthalenesulfonic acid and dried before the subsequent processing steps.

[0102] [Comparative Example 4] A conductive polymer film was prepared by drying 0.5 g of a self-doped conductive polymer solution using polymer S2 on a glass slide at 150°C. The conductivity of the dried film was measured (day 0). This conductive polymer film was stored at 150°C for 9 days, and the conductivity was read on days 1, 6, and 9.

[0103] [Example 8] A conductive polymer film was prepared in the same manner as in Comparative Example 4, except that 1 wt% polystyrene sulfonic acid was added to the self-doped conductive polymer solution before drying using polymer S2, and its conductivity was tested.

[0104] [Example 9] A conductive polymer film was prepared using polymer S2 in the same manner as in Comparative Example 4, except that 1 wt% of p-toluenesulfonic acid was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0105] [Example 10] A conductive polymer film was prepared in the same manner as in Comparative Example 4, except that 1 wt% of 1,5-naphthalenesulfonic acid was added to a self-doped conductive polymer solution using polymer S2 before drying, and its conductivity was tested.

[0106] [Comparative Example 5] A conductive polymer film was prepared in the same manner as in Comparative Example 4, except that 1 wt% of 1,5-naphthalenesulfonic acid was added to a self-doped conductive polymer solution using polymer S2 before drying. The conductivity of the film was then tested. The conductivity of the dried film was measured (Day 0). The conductive polymer film was stored at 150°C for 7 days, and the conductivity was read on Day 1, Day 4, and Day 7.

[0107] [Example 11] A conductive polymer film was prepared in the same manner as in Comparative Example 5, except that 1 wt% sulfoacetic acid was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0108] [Example 12] A conductive polymer film was prepared in the same manner as in Comparative Example 5, except that 1 wt% of 2-sulfobenzonic acid was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0109] [Example 13] A conductive polymer film was prepared in the same manner as in Comparative Example 5, except that 1 wt% of sodium 5-sulfoisophthalate salt was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0110] [Example 14] A conductive polymer film was prepared in the same manner as in Comparative Example 5, except that 1 wt% of 5-sulfosalicylic acid was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0111] [Example 15] A conductive polymer film was prepared in the same manner as in Comparative Example 5, except that 1 wt% of sodium anthraquinone-2-sulfonate salt was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0112] [Example 16] A conductive polymer film was prepared in the same manner as in Comparative Example 5, except that 1 wt% gallic acid was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0113] [Example 17] A conductive polymer film was prepared in the same manner as in Comparative Example 5, except that 1 wt% tannic acid was added to the self-doped conductive polymer solution before drying, and its conductivity was tested.

[0114] [Comparative Example 6] A conductive polymer film was prepared by drying 0.5 g of a self-doped conductive polymer solution using polymer S2 on a glass slide at 150°C. The conductivity of the dried film was measured (day 0). This conductive polymer film was stored at 150°C for 7 days, and the conductivity was read on days 3 and 7.

[0115] [Example 18] A conductive polymer film was prepared in the same manner as in Comparative Example 6. 0.1 g of a 1 wt% aqueous solution of sodium 5-sulfoisophthalate was applied to the conductive polymer film and dried at 120°C. The conductivity of the dried film was measured (Day 0). The conductive polymer film was stored at 150°C for 7 days, and the conductivity was read on Day 3 and Day 7.

[0116] [Example 19] A conductive polymer film was prepared by the method described in Example 18, except that 0.1 g of a 1 wt% aqueous solution of anthraquinone-2-sulfonate sodium salt was cast onto the conductive polymer film and dried at 120°C.

[0117] [Example 20] A conductive polymer film was prepared by the method described in Example 18, except that 0.1 g of a 1 wt% aqueous solution of gallic acid was cast onto the conductive polymer film and dried at 120°C.

[0118] [Example 21] A conductive polymer film was prepared using the method described in Example 18, except that 0.1 g of a 1% aqueous solution of tannic acid was cast onto a conductive polymer film and dried at 120°C.

[0119] [Comparative Example 7] A series of 33 microfarad, 35V tantalum anodes with a specific charge of 22,000 μFV / g were prepared. The tantalum was anodized to form a dielectric on the anode. The formed anodes were immersed for 1 minute in a self-doped conductive polymer solution using polymer S1, and then dried in an oven to remove moisture. This process was repeated four more times. A commercially available conductive polymer dispersion KV2 from Heraeus was applied to form an outer polymer layer. After drying, diamine salt and a second conductive polymer dispersion were applied alternately, and this process was repeated four to five more times. After washing and drying the anodes with the conductive polymer layers, a graphite layer and a silver layer were sequentially coated to fabricate a solid electrolytic capacitor. The components were assembled and packaged. The packaged components were then mounted on a circuit board. The capacitance and ESR of the mounted components were measured.

[0120] [Example 22] A series of tantalum capacitors were prepared as described in Comparative Example 6, except that after five cycles of self-doping conductive polymer coating, the anode was immersed in a 40% isopropanol solution of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and dried before the subsequent process steps.

[0121] [Comparative Example 8] A series of 68 microfarad, 16V tantalum anodes with a charge specific of 48,000 μFV / g were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The formed anodes were immersed for 1 minute in a self-doped conductive polymer solution using polymer S1 containing 0.1% epoxysilane, and then dried in an oven to remove moisture. This process was repeated 6 to 11 times. A commercially available conductive polymer dispersion KV2 from Heraeus was applied to form an outer polymer layer. After drying, diamine salt and a second conductive polymer dispersion were applied alternately, and this process was repeated 4 to 5 times. After washing and drying the anodes with the conductive polymer layers, a graphite layer and a silver layer were sequentially coated to fabricate a solid electrolytic capacitor. After the washing process for swelling of the conductive polymer film, the anodes were inspected and the percentage of the swollen portion was calculated.

[0122] [Example 23] A series of tantalum capacitors were prepared by the method described in Comparative Example 8, except that the self-doped conductive polymer contained 0.1% epoxysilane and 0.5% sulfoacetic acid.

[0123] [Example 24] A series of tantalum capacitors were fabricated in the same manner as in Comparative Example 8, except that the self-doped conductive polymer contained 0.1% epoxysilane and 0.5% 1,5-naphthalenesulfonic acid.

[0124] [Table 1]

[0125] [Table 2]

[0126] [Table 3]

[0127] [Table 4]

[0128] [Table 5]

[0129] [Table 6]

[0130] [Table 7]

[0131] [Table 8]

[0132] The present invention has been described with reference to preferred embodiments, without limiting it thereto. Additional embodiments and improvements that are not specifically described herein but fall within the scope of the invention as more specifically described in the appended claims can be realized.

Claims

1. A process for forming an electrolytic capacitor, The process involves forming an anode containing a dielectric material on top of that, The step includes forming a cathode layer on the dielectric, The cathode layer comprises a self-doped conductive polymer and a crosslinking agent capable of crosslinking the self-doped conductive polymer, wherein the crosslinking agent is selected from the group consisting of melamine, isocyanate, epoxy containing a plurality of epoxy groups, hexamethoxymelamine, glyoxal, furfural aldehyde, melamine formaldehyde condensate, divinyl sulfone compounds, and carboxylic acid compounds, and the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.01 or more and 2 or less. The cathode layer further comprises a crosslinkable material and an organic functional silane, wherein the organic functional silane is of formula XR １ Si(R ３ ) ３－ｎ (R ２ ) ｎ During the ceremony: X is an organic functional group selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, and alkyl; R1 is an aryl or alkyl group having up to 14 carbon atoms, or Formula: Y (Si (R) ３ ) ３－ｎ (R) ２ ) ｎ ) ２ During the ceremony: Y is an organic moiety containing reactive or nonreactive functional groups; Each R ２ These are individually hydrolyzable functional groups; Each R ３ These are alkyl functional groups, each having 1 to 6 carbon atoms; n is between 1 and 3. Defined as, The process for forming electrolytic capacitors.

2. A process for forming an electrolytic capacitor according to claim 1, wherein the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.02 or more and 1 or less.

3. A process for forming an electrolytic capacitor according to claim 2, wherein the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.05 or more and 0.2 or less.

4. A process for forming an electrolytic capacitor according to claim 1, wherein the crosslinkable material comprises at least one oligomer or polymer selected from the group consisting of polyester, polyurethane, polyamide, polyamine, polyimide, silicone polyester, hydroxyl-functional silicone, hydroxyethylcellulose, polyvinyl alcohol, phenol, epoxy, butyral, epoxy / amine, epoxy / anhydride, isocyanate / amine, isocyanate / alcohol, unsaturated polyester, vinyl ester, unsaturated polyester and vinyl ester blend, unsaturated polyester / urethane hybrid resin, polyurethane urea, reactive dicyclopentadiene resin, or a mixture of copolymers or polyfunctional polymers containing reactive polyamide.

5. A process for forming an electrolytic capacitor according to claim 1, wherein the crosslinkable material is crosslinked with the crosslinking agent.

6. A process for forming an electrolytic capacitor according to claim 1, wherein the crosslinkable material is crosslinked with the self-doped conductive polymer by the crosslinking agent.

7. A process for forming an electrolytic capacitor according to claim 1, wherein the crosslinkable material comprises at least one reactive group that can react with the crosslinking agent.

8. The reactive group is carboxyl, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxyl anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, dicyclopentadiene unsaturated, unsaturated C １２－２２ A process for forming the electrolytic capacitor according to claim 7, selected from the group consisting of fatty esters or amides, carboxylates, and quaternary ammonium salts.

9. A process for forming an electrolytic capacitor according to claim 1, wherein the hydrolyzable functional group is selected from the group consisting of alkoxy, acyloxy, halogen, amine and their hydrolysates.

10. A process for forming an electrolytic capacitor according to claim 1, wherein the reactive or nonreactive functional group is selected from the group consisting of alkyl, aryl, sulfide, and melamine.

11. A process for forming an electrolytic capacitor according to claim 1, wherein the organic functional silane is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic acid) anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, and bis(triethoxysilyl)octane.

12. The crosslinking agent is 【Chemistry 1】 During the ceremony: A process for forming an electrolytic capacitor according to claim 1, wherein X is an alkyl or substituted alkyl having up to 14 carbon atoms, an aryl or substituted aryl, an ethylene ether or substituted ethylene ether, a polyethylene ether or substituted polyethylene ether having 2 to 20 ethylene ether groups, or a combination thereof.

13. The crosslinking agent is ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol polyglycidyl A process for forming an electrolytic capacitor according to claim 1, selected from the group consisting of diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiendipside, 1,5-hexadiendipside, 1,2,7,8-dipoxyoctane, 1,2,5,6-dipoxycyclooctane, 4-vinylcyclohexendipside, bisphenol A diglycidyl ether, and maleimide-epoxy compounds.

14. The aforementioned crosslinking agent is 【Chemistry 2】 Defined by, A process for forming the electrolytic capacitor described in claim 1: In the formula, R ３ This includes alkyls or substituted alkyls having 1 to 14 carbon atoms, ethylene ethers or polyethylene ethers having 2 to 20 ethylene ether groups, alkyls substituted with groups selected from hydroxyl, and 【Transformation 3】 or - (CH ２ OH) x CH ２ OH, in the formula, X is between 1 and 14.

15. The aforementioned crosslinking agent is 【Chemistry 4】 【Transformation 5】 Defined by: In the formula, n is an integer between 1 and 220; 【Transformation 6】 【Transformation 7】 【Transformation 8】 A process for forming an electrolytic capacitor according to claim 1, wherein the electrolytic capacitor is formed using sorbitol diglycidyl ether.

16. A process for forming an electrolytic capacitor according to claim 1, wherein the crosslinking agent is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, phthalic acid, maleic acid, muconic acid, citric acid, trimesic acid, and polyacrylate acid.

17. The process for forming an electrolytic capacitor according to claim 16, wherein the crosslinking agent is selected from the group consisting of phthalic acid and orthophthalic acid.

18. The self-doped conductive polymer, 【Chemistry 9】 A process for forming an electrolytic capacitor according to claim 1, as defined by During the ceremony: R １ and R ２ These are independently linear or branched C １ -C １６ Alkyl or C ２ -C １８ Represents an alkoxyalkyl group; or unsubstituted or C １ -C ６ Alkyl, C １ -C ６ Alkoxy, halogen or OR ３ Substitution C ３ -C ８ It is cycloalkyl, phenyl, or benzyl; or R １ and R ２ These are, together, non-substitutive or C １ -C ６ Alkyl, C １ -C ６ Alkoxy, halogen, C ３ -C ８ Cycloalkyl, phenyl, benzyl, C １ -C ４ Alkylphenyl, C １ -C ４ Alkoxyphenyls, halophenyls, C １ -C ４ Alkylbenzyl, C １ -C ４ Alkoxybenzyl or halobenzyl, a linear carbon substituted with a 5, 6, or 7-membered heterocyclic structure containing two oxygen elements. １ -C ６ It is alkylene; R ３ These are hydrogen, linear or branched C １ -C １６ Alkyl or C ２ -C １８ Represents alkoxyalkyl; or C ３ -C ８ Cycloalkyl, phenyl, or benzyl, unsubstituted or C １ -C ６ Substituted with alkyl, however, R １ or R ２ At least one of them is -SO ３ M, -CO ２ M or -PO ３ It is substituted with M, where M is a cation selected from H or ammonium, sodium, lithium, or potassium; X is S, N, or O, and n is an integer greater than or equal to 2.

19. R １ and R ２ Together they become O-(CHR) ４ ) ｎ A process for forming an electrolytic capacitor according to claim 18, wherein the formula represents -O-, n is an integer between 1 and 5; R ４ These are independently linear or branched C １ -C １８ Alkyl radical C ５ -C １２ Cycloalkyl radical, C ６ -C １４ Aryl radical C ７ -C １８ Aralkyl radical or C １ -C ４ Selected from hydroxyalkyl radicals, R ４ is, -SO ３ M, -CO ２ M or -PO ３ M is substituted, and optionally substituted with at least one additional functional group selected from carboxylic acids, hydroxyls, amines, substituted amines, alkenes, acrylates, thiols, alkynes, azides, sulfuric acids, sulfonic acids, imides, amides, epoxys, anhydrides, silanes, and phosphoric acids; hydroxyl radical; or R ４ is selected from -(CHR ５ ) ａ -R １６ , -O(CHR ５ ) ａ -R １６ , -CH ２ O(CHR ５ ) ａ R １６ , CH ２ O(CH ２ CHR ５ O) ａ R １６ or R ４ is -SO ３ M, -CO ２ M or -PO ３ M; R ５ is a C1-C5 alkyl chain optionally substituted with H or a functional group selected from carboxylic acids, hydroxyls, amines, alkenes, thiols, alkynes, azides, epoxys, acrylates, and anhydrides; R １６ is, -SO ３ M, -CO ２ M or -PO ３ M, or -SO ３ M, -CO ２ M or -PO ３ A C1-C5 alkyl chain substituted with M, optionally further substituted with at least one functional group selected from carboxylic acids, hydroxyls, amines, substituted amines, alkenes, thiols, alkynes, azides, amides, imides, sulfuric acids, amides, epoxys, anhydrides, silanes, acrylates, and phosphoric acids, R １６ is, -Si ２ M, -Si ３ M or -Si ３ An alkylene chain having 5 or more carbon atoms substituted with M, and substituted with a carboxyl group; a is an integer between 0 and 10; M is a cation selected from H or ammonium, sodium, lithium, or potassium.

20. A process for forming an electrolytic capacitor according to claim 18, wherein the self-doped conductive polymer is selected from the group consisting of S1 and S2. 【Chemistry 10】 【Chemistry 11】

21. A process for forming an electrolytic capacitor according to claim 1, wherein the cathode layer further comprises an exogenous dopant, the exogenous dopant present in an amount of 7 to 100 wt% based on the weight of the self-doped conductive polymer.

22. A process for forming an electrolytic capacitor according to claim 21, wherein the foreign dopant is present in an amount of 8 to 20 wt% based on the weight of the self-doped conductive polymer.

23. A process for forming an electrolytic capacitor according to claim 21, wherein the foreign dopant is defined by AxByCz. During the ceremony: A is polystyrene sulfonic acid or a salt of polystyrene sulfonic acid; B and C separately represent polymerization units substituted with groups selected from the following: -Carboxyl group; -C(O)OR ６ , where R ６ The following group is selected: A C1-C20 alkyl group 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, and anhydride, and - (CHR) ７ CH ２ O) ｂ -R ８ In the formula: R ７ This is selected from hydrogen or alkyl groups having 1 to 7 carbon atoms; b is 1, -CHR ７ CH ２ An integer up to a number sufficient to provide a molecular weight of up to 200,000 for the O-group; and R ８ This is a C1-C9 alkyl group 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 , where R ９ is a C1-C20 alkyl group optionally substituted with hydrogen or a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, and anhydride; -C ６ H ４ -R １０ In the formula, R １０ The following can be selected: Hydrogen or alkyl groups optionally substituted with functional groups 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, and anhydride, and - (O (CHR) １１ CH ２ O) ｄ -R １２ In the formula: R １１ is hydrogen or an alkyl group having 1 to 7 carbon atoms, and is hydrogen or methyl; d is 1, -CHR １１ CH ２ An integer up to a number sufficient to provide a molecular weight of up to 200,000 for the O-group; R １２ (Selected from alkyl groups having 1 to 9 carbon atoms, which are optionally substituted with functional groups 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 -OR １３ In the formula, R １３ The following can be selected: Hydrogen or alkyl groups optionally substituted with reactive groups 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, and phosphate; - (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 1, -CHR １４ CH ２ An integer up to a number sufficient to provide a molecular weight of up to 200,000 for the O-group; and R １５ It consists of a C1-C9 alkyl group optionally substituted with hydrogen and a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphoric acid, and anhydride; and y and z are 0, or x, y and z together are sufficient to form a polyanion having a molecular weight of at least 100 to 500,000, with y / x being 0.01 to 100, or z having a ratio z / x of 0 to 100.

24. R ７ A process for forming an electrolytic capacitor of claim 23, wherein is hydrogen or methyl.

25. R １４ A process for forming an electrolytic capacitor of claim 23, wherein is hydrogen or methyl.

26. A process for forming an electrolytic capacitor according to claim 23, wherein the sum of x + y + z represents 50 to 99%, y 1 to 50%, and z 0 to 49%.

27. A process for forming an electrolytic capacitor according to claim 26, wherein the sum of x + y + z represents 70-90%, y 10-30%, and z 0-20%.

28. A process for forming an electrolytic capacitor according to claim 1, wherein the cathode layer further comprises an aromatic compound having at least one hydroxyl functional group and at least one other hydroxyl functional group or carboxyl functional group.

29. A process for forming an electrolytic capacitor according to claim 28, wherein the aromatic compound is a phenolic acid.

30. A process for forming an electrolytic capacitor according to claim 29, wherein the phenolic acid is selected from the group consisting of gallic acid and tannic acid.

31. A process for forming an electrolytic capacitor according to claim 1, wherein the cathode layer further comprises a functional additive.

32. A process for forming an electrolytic capacitor according to claim 31, wherein the weight ratio of the functional additive to the self-doped conductive polymer is 0.05 to 5.

33. A process for forming an electrolytic capacitor according to claim 32, wherein the weight ratio of the functional additive to the self-doped conductive polymer is 0.5 to 1.

34. A process for forming an electrolytic capacitor according to claim 31, wherein the functional additive is selected from the group consisting of ionic liquids and polyalkylene ethers.

35. The process for forming an electrolytic capacitor according to claim 34, wherein the ionic liquid is selected from the group consisting of 4-(3-butyl-1-imidazolio)-1-butanesulfonic acid triflate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazolium trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-aryl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, lithium bis(trifluoromethane)sulfonimido and its derivatives.

36. A process for forming an electrolytic capacitor according to claim 34, wherein the polyalkylene ether is selected from the group consisting of polyalkylene glycol, polyepichlorohydrin, polyoxetane, polyphenylene ether, and polyether ketone.

37. A process for forming an electrolytic capacitor according to claim 36, wherein the polyalkylene ether is selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

38. The functional additive is ethoxylated alkylphenol; ethoxylated or propoxylated C ６ -C ２４ fatty alcohols; General formula: CH ３ - (CH ２ ) １０－１６ - (O-C) ２ H ４ ) １－２５ Polyoxyethylene glycol alkyl ether having an -OH group; General formula: CH ３ - (CH ２ ) １０－１６ - (O-C) ３ H ６ ) １－２５ -OH-containing polyoxypropylene glycol alkyl ether; the following general formula: C ８ -H １７ - (C ６ H ４ )-(O-C ２ H ４ ) １－２５ Polyoxyethylene glycol octylphenol ether having an -OH group; the following general formula: C ９ -H １９ - (C ６ H ４ )-(O-C ２ H ４ ) １－２５ -OH-containing polyoxyethylene glycol alkylphenol ether; C ８ -C ２４ Fatty acid polyoxyethylene glycol esters, polyoxyethylene glycol alkyl esters, and C ８ -C ２４ A process for forming an electrolytic capacitor according to claim 31, selected from the group consisting of fatty acid polyoxyethylene glycol ethers.

39. The aforementioned functional additives are octaethylene glycol monodecyl ether, pentaethylene glycol monodecyl ether, nonoxynol-9, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, PEG-20 methyl glucose distearate, PEG-20 methyl glucose sesquistearate, PEG-80 castor oil, PEG-20 castor oil, PEG-3 castor oil, PEG-600 diolate, PEG-400 diolate, polyoxyethylene-23 glycerol laurate, polyoxyethylene-20 glycerol stearate, polyoxyethylene-10 cetyl ether, and polyoxyethylene-10 stearyl ether. A process for forming an electrolytic capacitor according to claim 38, selected from the group consisting of polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether, polyoxyethylene-20 oleyl ether, polyoxyethylene-20 isohexadecyl ether, polyoxyethylene-15 tridecyl ether, and polyoxyethylene-6 tridecyl ether.

40. A process for forming an electrolytic capacitor according to claim 1, wherein the self-doped conductive polymer is polymerized in the presence of at least one of an exogenous dopant or a functional additive.

41. An electrolytic capacitor comprising an anode containing a dielectric thereon, and a cathode layer on the dielectric, wherein the cathode layer is crosslinked with a crosslinking agent and comprises a self-doped conductive polymer, the self-doped conductive polymer being defined by the following formula, 【Chemistry 12】 In the formula, R １ and R ２ Together, O(CHR) ４ ) ｎ O represents all R except one ４ H and -CH ３ Selected from the group consisting of one R ４ is, -SO ３ It is an alkyl group substituted with Na, where X is S, and n is 2 or more; in the formula, the crosslinking agent is Selected from the group consisting of melamine, isocyanate, epoxy containing two or more epoxy groups, hexamethoxymelamine, glyoxal, furfural aldehyde, melamine formaldehyde condensate, divinyl sulfone, and carboxylic acid compounds, The cathode layer further comprises a crosslinkable material and an organic functional silane, wherein the organic functional silane is of formula XR １ Si(R ３ ) ３－ｎ (R ２ ) ｎ Defined by, in the formula: X is an organic functional group selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, and alkyl; R １ is an aryl or alkyl group having up to 14 carbon atoms, or Formula: Y (Si (R) ３ ) ３－ｎ (R) ２ ) ｎ ) ２ During the ceremony: Y is an organic moiety containing reactive or nonreactive functional groups; Each R ２ These are functional groups that can be individually hydrolyzed; Each R ３ These are alkyl functional groups, each having 1 to 6 carbon atoms; n is between 1 and 3. An electrolytic capacitor, as defined.

42. The electrolytic capacitor according to claim 41, wherein the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.02 or more and 1 or less.

43. The electrolytic capacitor according to claim 42, wherein the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.05 or more and 0.2 or less.

44. The electrolytic capacitor according to claim 41, wherein the cathode layer further comprises a crosslinkable material.

45. The electrolytic capacitor according to claim 44, wherein the crosslinkable material comprises at least one oligomer or polymer selected from the group consisting of a copolymer or polyfunctional polymer mixture comprising polyester, polyurethane, polyamide, polyamine, polyimide, silicone polyester, hydroxyl-functional silicone, hydroxyethylcellulose, polyvinyl alcohol, phenol, epoxy, butyral, epoxy / amine, epoxy / anhydride, isocyanate / amine, isocyanate / alcohol, unsaturated polyester, vinyl ester, unsaturated polyester and vinyl ester blend, unsaturated polyester / urethane hybrid resin, polyurethane urea, reactive dicyclopentadiene resin, or reactive polyamide.

46. The electrolytic capacitor according to claim 45, wherein the crosslinkable material is crosslinked with the crosslinking agent.

47. The electrolytic capacitor according to claim 44, wherein the crosslinkable material is crosslinked with the self-doped conductive polymer by the crosslinking agent.

48. The electrolytic capacitor according to claim 44, wherein the crosslinkable material comprises at least one reactive group that can react with the crosslinking agent.

49. The reactive group is carboxyl, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic acid anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, dicyclopentadiene unsaturated, unsaturated C １２－２２ The electrolytic capacitor according to claim 48, selected from the group consisting of fatty esters or amides, carboxylates, and quaternary ammonium salts.

50. The electrolytic capacitor according to claim 41, wherein the hydrolyzable functional group is selected from the group consisting of alkoxy, acyloxy, halogen, amine and their hydrolysates.

51. The electrolytic capacitor according to claim 41, wherein the reactive or nonreactive functional group is selected from the group consisting of alkyl, aryl, sulfide, and melamine.

52. The crosslinking agent is 【Chemistry 13】 During the ceremony: The electrolytic capacitor according to claim 41, wherein X is an alkyl or substituted alkyl having up to 14 carbon atoms, an aryl or substituted aryl, an ethylene ether or substituted ethylene ether, a polyethylene ether or substituted polyethylene ether having 2 to 20 ethylene ether groups, or a combination thereof.

53. The crosslinking agent is ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol The electrolytic capacitor according to claim 41, selected from the group consisting of rupolyglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiendipside, 1,5-hexadiendipside, 1,2,7,8-dipoxyoctane, 1,2,5,6-dipoxycyclooctane, 4-vinylcyclohexendipside, bisphenol A diglycidyl ether, and maleimide-epoxy compounds. 【Request Item 54】 【Chemistry 14】 The electrolytic capacitor according to claim 41, which is the crosslinking agent as defined by: In the formula, R ３ This includes alkyls or substituted alkyls having 1 to 14 carbon atoms, ethylene ethers or polyethylene ethers having 2 to 20 ethylene ether groups, alkyls substituted with groups selected from hydroxyl, and 【Chemistry 15】 or - (CH ２ OH) ｘ CH ２ OH, in the formula, X is between 1 and 14.

55. The aforementioned crosslinking agent is 【Chemistry 16】 The electrolytic capacitor according to claim 41, as defined by: In the formula, n is an integer between 1 and 220; 【Chemistry 17】 Or sorbitol diglycidyl ether.

56. The electrolytic capacitor according to claim 41, wherein the crosslinking agent is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, phthalic acid, maleic acid, muconic acid, citric acid, trimesic acid, and polyacrylic acid.

57. The electrolytic capacitor according to claim 56, wherein the crosslinking agent is selected from the group consisting of phthalic acid and orthophthalic acid.

58. The electrolytic capacitor according to claim 41, wherein the cathode layer further contains an exogenous dopant, the exogenous dopant present in an amount of 7 to 100 wt% based on the weight of the self-doped conductive polymer.

59. The electrolytic capacitor according to claim 58, wherein the foreign dopant is present in an amount of 8 to 20 wt% based on the weight of the self-doped conductive polymer.

60. The electrolytic capacitor according to claim 58, wherein the foreign dopant is defined by AxByCz. During the ceremony: A is polystyrene sulfonic acid or a salt of polystyrene sulfonic acid; B and C separately represent polymerization units substituted with groups selected from the following: -Carboxyl group; -C(O)OR ６ , where R ６ The following group is selected: A C1-C20 alkyl group 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, and anhydride, and - (CHR) ７ CH ２ O) ｂ -R ８ In the formula: R ７ This is selected from hydrogen or alkyl groups having 1 to 7 carbon atoms; b is 1, -CHR ７ CH ２ An integer up to a number sufficient to provide a molecular weight of up to 200,000 for the O-group; and R ８ This is a C1-C9 alkyl group 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 In the formula: R ９ is a C1-C20 alkyl group optionally substituted with hydrogen or a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, and anhydride; -C ６ H ４ -R １０ In the formula: R １０ The following can be selected: Hydrogen or alkyl groups optionally substituted with functional groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, and anhydride; Reactive groups selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, imide, amide, thiol, alkene, alkyne, phosphate, azide, acrylate, and anhydride; and - (O (CHR) １１ CH ２ O) ｄ -R １２ In the formula: R １１ is hydrogen or an alkyl group having 1 to 7 carbon atoms, and is hydrogen or methyl; d is 1, -CHR １１ CH ２ An integer up to a number sufficient to provide a molecular weight of up to 200,000 for the O-group; R １２ This is selected from 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; -C ６ H ４ -OR １３ In the formula: R １３ The following can be selected: Alkyls optionally substituted with hydrogen or reactive groups 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, and phosphate; - (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 1, -CHR １４ CH ２ An integer up to a number sufficient to provide a molecular weight of up to 200,000 for the O-group; and R １５ This is a group consisting of hydrogen and an alkyl group 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, phosphoric acid, and anhydride; and y and z are either 0, or x, y, and z together are sufficient to form a polyanion having a molecular weight of at least 100 to 500,000, with y / x being 0.01 to 100, or z having a ratio z / x of 0 to 100.

61. R ７ The electrolytic capacitor according to claim 60, wherein is hydrogen or methyl.

62. R １４ The electrolytic capacitor according to claim 60, wherein is hydrogen or methyl.

63. The electrolytic capacitor according to claim 60, wherein x represents 50 to 99% of the sum of x + y + z, y represents 1 to 50% of the sum of x + y + z, and z represents 0 to 49% of the sum of x + y + z.

64. The electrolytic capacitor according to claim 63, wherein x represents 70-90% of the sum of x + y + z, y represents 10-30% of the sum of x + y + z, and z represents 0-20% of the sum of x + y + z.

65. The electrolytic capacitor according to claim 41, wherein the cathode layer further comprises an aromatic compound having at least one hydroxyl functional group and at least another hydroxyl or carboxyl functional group.

66. The electrolytic capacitor according to claim 65, wherein the aromatic compound is a phenolic acid.

67. The electrolytic capacitor according to claim 66, wherein the phenolic acid is selected from the group consisting of gallic acid and tannic acid.

68. The electrolytic capacitor according to claim 41, wherein the cathode layer further comprises a functional additive.

69. The electrolytic capacitor according to claim 68, wherein the weight ratio of the functional additive to the self-doped conductive polymer is 0.05 to 5.

70. The electrolytic capacitor according to claim 69, wherein the weight ratio of the functional additive to the self-doped conductive polymer is 0.5 to 1.

71. The electrolytic capacitor according to claim 68, wherein the functional additive is selected from the group consisting of ionic liquids and polyalkylene ethers.

72. The aforementioned ionic liquid is [Chemistry 18] The electrolytic capacitor according to claim 71, selected from the group consisting of 4-(3-butyl-1-imidazolium)-1-butanesulfonic acid triflate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-aryl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, lithium bis(trifluoromethane)sulfonimide and its derivatives.

73. The electrolytic capacitor according to claim 71, wherein the polyalkylene ether is selected from the group consisting of polyalkylene glycol, polyepichlorohydrin, polyoxetane, polyphenylene ether, and polyether ketone.

74. The electrolytic capacitor according to claim 73, wherein the polyalkylene ether is selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

75. The functional additive is ethoxylated alkylphenol; ethoxylated or propoxylated C ６ -C ２４ fatty alcohols; General formula: CH ３ - (CH ２ ) １０－１６ - (O-C) ２ H ４ ) １－２５ - Polyoxyethylene glycol alkyl ether having -; General formula: OH, CH ３ - (CH ２ ) １０－１６ - (O-C) ３ H ６ ) １－２５ -OH-containing polyoxypropylene glycol alkyl ether; the following general formula: C ８ -H １７ - (C ６ H ４ )-(O-C ２ H ４ ) １－２５ Polyoxyethylene glycol octylphenol ether having an -OH group; the following general formula: C ９ -H １９ - (C ６ H ４ )-(O-C ２ H ４ ) １－２５ -OH-containing polyoxyethylene glycol alkylphenol ether; C ８ -C ２４ Polyoxyethylene glycol esters of fatty acids, and C ８ -C ２４ The electrolytic capacitor according to claim 68, selected from the group consisting of fatty acid polyoxyethylene glycol ethers.

76. The functional additives include octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, nonoxynol-9, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, PEG-20 methyl glucose distearate, PEG-20 methyl glucose sesquistearate, PEG-80 castor oil, PEG-20 castor oil, PEG-3 castor oil, PEG-600 diolate, PEG-400 diolate, polyoxyethylene-23 glycerol laurate, polyoxyethylene-20 glycerol stearate, polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearyl ether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether, and polyoxyethylene-20 The electrolytic capacitor according to claim 68, selected from the group consisting of oleyl ether, polyoxyethylene-20 isohexadecyl ether, polyoxyethylene-15 tridecyl ether, and polyoxyethylene-6 tridecyl ether.

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