JP2023541228A - Capacitors with improved capacitance - Google Patents

Abstract

The present invention relates to improved capacitors and improved processes for forming capacitors. The process includes forming an anode with a dielectric thereon. A cathode layer is then formed on the dielectric material, and the cathode layer includes a self-doped conductive polymer and a crosslinking agent, and the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.01 or more and 2 or less.

Description

The present invention relates to an improved method of forming solid electrolytic capacitors and improved capacitors formed thereby. More specifically, the present invention relates to improvements in conductive polymer layers utilizing self-doped soluble conductive polymers and methods for forming cathode layers.

The structure and manufacturing methods of solid electrolytic capacitors are well known. In the construction of solid electrolytic capacitors, preferably the valve metal functions as an anode. The anode body can be either a pressed and sintered porous pellet of high purity powder or a foil that has been etched to increase the anode surface area. Further, it is preferable that an oxide of the valve metal is electrolytically formed so as to cover the entire surface of the anode, and that the oxide functions as a dielectric of the capacitor. The solid cathode electrolyte is usually selected from a very limited variety 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 cathode materials are widely used in the electronics industry due to their advantageously low equivalent series resistance (ESR) and "unfired/ignited" failure mode. For conductive polymer cathodes, the conductive polymer is typically applied by either chemical oxidative polymerization, electrochemical oxidative polymerization, or spray techniques, although other less preferred techniques have also been reported.

This is because the anode body generally has a porous structure, and the porous structure increases the surface area and increases the capacitance for a given volume. The conductive cathode layer is often comprised of a conductive material such as a conductive polymer, carbon, or silver layer for connection with the terminal. It is extremely important that the surface of the porous anode is well covered and adhered to by the conductive cathode layer; in order to obtain the targeted capacitance, the pores must be completely impregnated with the conductive cathode layer. It is said that it is particularly preferable that the The manufacturing process for valve metal capacitors using conductive polymers involves mechanically pressing a valve metal powder such as tantalum to form an anode, and then sintering it 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. The conductive polymer is then coated with graphite or metal layers, assembled and molded into the finished product.

Polythiophene has long been the industry standard as a conductive polymer used in solid electrolytic capacitor cathodes. Although thiophenes are widely used, they have limitations, particularly in terms of counterions. Conductive polythiophenes are typically doped with a counterion that is an aromatic sulfonic acid such as toluene sulfonic acid, polystyrene sulfonic acid, or a derivative thereof; It is called. The externally added conductive polymer is a dispersion of particles having various particle sizes. The non-uniformity of the particles, particularly the particle size, creates problems when trying to form coatings with sufficient coverage and adhesion. Furthermore, since it is difficult to fill small pores with a dispersion liquid, it becomes difficult to use an externally added conductive polymer as a high charge density powder.

Self-doped conductive polymers are soluble and have been considered a promising option to avoid the problems of externally added conductive polymers. One advantage of interest to those skilled in the art is solubility. Since self-doped conductive polymers have high solubility, there is no need to apply a dispersion liquid, and an improvement in coating properties is expected. In addition, soluble conductive polymers are expected to better fill small pores, so they are also expected to be applied to high-charge density powders. An unexpected result was that due to its high solubility, it dissolved the previously applied self-doped conductive polymer, deteriorating 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 advantage is not obtained.

The present invention provides a method for manufacturing capacitors comprised of self-doped conductive polymers with improved capacitance.

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

More specifically, the present invention relates to the use of improved self-doped conductive polymer films as cathodes of solid electrolyte capacitors.

A feature of the invention is that a conductive coating can be formed on an anode dielectric having high capacitance with necessarily very small pores.

In these and other embodiments, as implemented, a process for forming an electrolytic capacitor is provided. This step includes forming an anode including a dielectric thereon. Next, a cathode layer is formed on the dielectric, and the cathode layer includes a self-doped conductive polymer and a crosslinking agent, and the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.01 or more and 2 or less. .

In yet another embodiment, an electrolytic capacitor is provided that includes an anode having a dielectric thereon. A cathode layer is on the dielectric, and the cathode layer includes a crosslinked self-doped conductive polymer formed by a crosslinker. In the cathode, the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.01 or more and 2 or less.

FIG. 1 is a schematic cross-sectional view of a capacitor.

The present invention relates to a method for forming solid electrolytic capacitors made of self-doped conductive polymers, particularly crosslinked self-doped conductive polymers, and improved capacitors formed thereby. More specifically, the present invention relates to improved conductive polymer compositions based on crosslinked self-doped conductive polymers and improved capacitors formed thereby.

The invention will be described with reference to the figures which form essential, non-limiting elements of the disclosure. In the figures, similar elements are numbered appropriately.

An embodiment of the present invention is shown in FIG. 1 in a schematic cross-sectional side view. In FIG. 1, a capacitor, generally designated 10, includes an anodized anode 12 and an anode lead 14 extending from or attached thereto. Preferably, the anode lead wire is in electrical contact with the 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 formed by applying a self-doped or soluble conductive polymer solution and crosslinking the self-doped conductive polymer or an adjacent self-doped conductive polymer or layer containing it. It is preferable to do so. Additional conductive polymer layers, collectively referred to as 18, are sequentially formed over the precursor conductive layer to at least partially envelop at least a portion of the precursor conductive layer and provide an enclosure around at least a portion of the dielectric. Form. The assembly layer represented by 18 may also include interlayers between conductive polymer layers, as described in more detail herein. In preferred embodiments, all conductive cathode layers are formed from self-doped conductive polymers that are soluble, and more preferably at least some of the layers contain crosslinking groups. As one skilled in the art will appreciate, in the finished capacitor, the cathode and anode are not in direct electrical contact. Cathode lead 22 is in electrical contact with the cathode layer. It is well understood that it is difficult to solder lead frames (external terminals) to polymer cathodes. It is therefore standard in the art to provide a conductive interlayer preferably consisting of a carbon-containing layer 20 and a metal-containing layer 23 to enable solder bonding. In many embodiments, the capacitor is encapsulated in a non-conductive resin 24 with at least a portion of the anode and cathode leads exposed for attachment to a circuit board, as will be readily understood by those skilled in the art. It is preferable.

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

Preferred self-doping polymers include repeating units of formula A;

In formula A:
R ¹ and R ² independently represent linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl;
or C ₃ -C ₈ cycloalkyl, unsubstituted or substituted by C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen or OR ³ , phenyl or benzyl, or R ¹ and R ² together unsubstituted 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 alkoxyphenyl , halophenyl, C ₁ -C ₄ alkylbenzyl, C ₁ -C ₄ alkoxybenzyl or halobenzyl, a straight chain C ₁ -C ₆ alkylene substituted with a 5, 6 or 7 membered heterocyclic structure containing two oxygen elements; be. R ³ preferably represents hydrogen, linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl; or at least one of R ¹ or R ² is -SO ₃ M, - substituted with CO ₂ M or -PO ₃ M, where M is H or a cation preferably selected from ammonium, sodium, lithium or potassium, unsubstituted or substituted with C ₁ -C ₆ alkyl C ₃ -C ₈ cycloalkyl, phenyl or benzyl;
X is S, N or O, most preferably X is S;
R ¹ and R ² of formula A are preferably selected to inhibit polymerization at the β site of the ring, as it is most preferred that only α site polymerization proceed, and R ¹ and R ² are hydrogen. More preferably, R ¹ and R ² are α-directors in which an ether bond is preferred over an alkyl bond; in order to avoid steric interference, R ¹ and R ² is most preferably small.

In a particularly preferred embodiment, R ¹ and R ² of formula A together represent O-(CHR ⁴ ) _n -O-, in which;
n is an integer from 1-5, most preferably 2;
R ⁴ is independently a 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 - selected from C ₄ hydroxyalkyl radicals; R ⁴ is substituted with -SO ₃ M, -CO ₂ M or -PO ₃ M, optionally carboxylic acids, hydroxyls, amines, substituted amines, alkenes, acrylates, thiols, alkynes, substituted with at least one additional functional group selected from azide, sulfate, sulfonate, sulfonic acid, imide, amide, epoxy, anhydride, silane, phosphate, hydroxyl radical; or R ⁴ is , -(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 an alkyl chain having 1 to 5 carbon atoms optionally substituted with H or a functional group selected from carboxylic acid, hydroxyl group, amine, alkene, thiol, alkyne, azide, epoxy, acrylate and anhydride;
R ¹⁶ is an alkyl chain having 1 to 5 carbon atoms substituted with -SO ₃ M, -CO ₂ M, -PO ₃ M, -SO ₃ M, -CO ₂ M or -PO ₃ M, and optionally further carbon substituted with at least one functional group selected from acids, hydroxyls, amines, substituted amines, alkenes, thiols, alkynes, azides, amides, imides, sulfates, amides, epoxies, anhydrides, silanes, acrylates and phosphoric acids;
a is an integer from 0 to 10;
M is preferably H or a cation selected from ammonium, sodium, lithium or potassium.

Exemplary self-doped conductive polymers are designated S1 and S2.

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

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

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

The crosslinkable material is preferably a compound, oligomer, or polymer having at least one reactive group capable of reacting with a crosslinking agent. Reactive functional groups include carboxylic acid, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconic acid Preferably, it is selected from the group consisting of salts, allyl alcohol esters, dicyclopentadiene unsaturations, unsaturated C ₁₂ -C ₂₂ fatty esters or amides, carboxylates or ammonium salts. Polyols are particularly suitable as crosslinkable materials, and ethylene glycol and polyglycerol are particularly suitable for demonstrating the invention. The crosslinkable material may have the same functional group as the crosslinking agent or may be the same compound as long as the crosslinking reaction occurs. Crosslinkable materials may also function as crosslinking agents if they have two or more reactive functional groups that react with self-doped conductive polymers or other types of crosslinkable materials.

One embodiment includes a solid electrolytic capacitor that includes a crosslinkable material system that is an oligomer or polymer that includes multifunctional reactive groups. The oligomer or polymer is preferably polyester, polyurethane, polyamide, polyamine, polyimide, silicone polyester, hydroxyl-containing silicone, hydroxyethyl cellulose, polyvinyl alcohol, phenol, epoxy, butyral, copolymers thereof, or epoxy/amine, epoxy/ Mixtures of multifunctional polymers such as anhydrides, isocyanates/amines, isocyanates/alcohols, unsaturated polyesters, vinyl esters, unsaturated polyesters and vinyl ester blends, unsaturated polyester/urethane hybrid resins, polyurethaneureas, reactive dicyclopentadiene resins , and at least one polymerizable monomer selected from the group consisting of reactive polyamides. Preferably, the oligomer or polymer with multiple functional groups or multiple reactive groups contains at least one carboxylic acid group and at least one hydroxyl functional group. Particularly preferred oligomers or polymers with polyfunctional reactive groups are polyesters containing carboxyl and hydroxyl functions. In addition to oligomers and polymers, particles with surface functional groups can also participate in crosslinking. Particles having a functional group include carboxylic acid, hydroxyl group, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide. , itaconates, allyl alcohol esters, dicyclopentadiene unsaturated, unsaturated C ₁₂ -C ₂₂ fatty esters or amides, carboxylates or quaternary ammonium salts. The particles may be nanoparticles or microparticles. An example of a functionalized nanoparticle is an organically modified nanoclay. When the particles are used to crosslink a self-doped conductive polymer, the conductive polymer is useful as an outer cathode coating on the outside of the anode rather than in the pores.

One embodiment includes a solid electrolytic capacitor comprising a crosslinkable material that is a cyclic organic compound containing at least one hydroxy functional group, preferably at least another hydroxy or carboxyl functional group, which is a thermal stabilizer of a self-doped conductive polymer. It is preferable because it also improves properties. The cyclic organic compound may be aromatic, heterocyclic, or alicyclic, with aromatic being most preferred. Particularly preferred cyclic aromatic compounds are phenol, cresol, nitrophenol, aminophenol, hydroxybenzoic acid (i.e., hydroxybenzenecarboxylic acid), sulfosalicylic acid, dihydroxybenzene, dihydroxybenzoic acid (i.e., dihydroxybenzenecarboxylic acid), hydroxybenzoic acid Methyl acid (i.e., methyl hydroxybenzenecarboxylate), ethyl hydroxybenzoate (i.e., ethyl hydroxybenzenecarboxylate), ethylhexyl hydroxybenzoate (i.e., ethylhexyl hydroxybenzenecarboxylate), methoxyphenol, ethoxyphenol, butoxyphenol, Phenylphenol, cumylphenol, aminonitrophenol, hydroxynitrobenzoic acid (i.e., hydroxynitrobenzenecarboxylic acid), methyl hydroxynitrobenzenate (i.e., methyl hydroxynitrobenzenecarboxylate), sulfonesalicylic acid, dihydroxybenzene, dihydroxybenzoic acid (i.e. dihydroxybenzenecarboxylic acid), trihydroxybenzene, trihydroxybenzoic acid (i.e. trihydroxybenzenecarboxylic acid), phenolsulfonic acid, cresolsulfonic acid, dihydroxybenzenesulfonic acid, nitrophenolsulfonic acid, hydroxyindole.

Examples of naphthalene compounds include naphthol, nitronaphthol, hydroxynaphthoic acid (i.e., hydroxynaphthalenecarboxylic acid), dihydroxynaphthol, trihydroxynaphthol, naphtholsulfonic acid, dihydroxynaphtholsulfonic acid, and nitronaphtholsulfonic acid. Is possible.

Examples of anthraquinone compounds include hydroxyanthraquinone.

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, dihydroxy Examples include pyridine.

Examples of alicyclic compounds include hydroxycyclohexane, hydroxycyclohexanecarboxylic acid, methyl hydroxycyclohexanecarboxylate, dihydroxycyclohexane, and the like.

Particularly preferred are phenolic acids, more preferred are gallic acid and tannic acid.

Particularly preferred crosslinking agents consist of melamine, isocyanates, epoxies, hexamethoxymelamine, glyoxal, furfuraldehyde, melamine formaldehyde condensates, divinyl sulfones, epoxy compounds and carboxylic acid compounds.

Organofunctional silanes and organic compounds having one or more crosslinking groups, in particular one or more epoxy groups, can be particularly suitably used as crosslinking agents according to the invention, especially when used in combination.

The organofunctional silane is defined by the formula XR ¹ Si(R ³ ) _3-n (R ² ) _n ,
In the formula, X is _an organic functional group such as amino, epoxy ^, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, _alkyl ; (Here, m may be 0 to 14); R ² is individually a hydrolyzable functional group such as alkoxy, acyloxy, halogen, amine or a hydrolyzate thereof; R ³ is individually a carbon number of 1 to 6 an alkyl group; n is 1 to 3;

The organofunctional silane can also be dipolar, defined by the formula Y(Si(R ³ ) _3-n (R ² ) _n ) ₂ , where Y is alkyl, aryl, sulfide or Any organic moiety containing reactive or non-reactive functional groups such as melamine, where R ³ , R ² and n are defined above. Further, the organic functional silane may be a polyfunctional silane or a polymer silane such as silane-modified polybutadiene or silane-modified polyamine.

Examples of organofunctional silanes include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilane triol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxy Examples include silane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, and bis(triethoxysilyl)octane. These examples are illustrative of the invention and are not conclusive.

Particularly preferred organofunctional silanes have the formula:

wherein R ¹ is alkyl having 1 to 14 carbon atoms, more preferably selected from methylethyl and propyl, and each R ² is independently alkyl having 1 to 14 carbon atoms; 6 alkyl or substituted alkyl.

Particularly preferred glycidylsilanes have the formula:

3-glycidoxypropyltrimethoxysilane, which is defined herein as "silane A" for convenience.

Crosslinking agents having at least two epoxy groups are referred to herein as epoxy crosslinking compounds and have the formula:

where X is an alkyl or substituted alkyl having 0 to 14 carbon atoms, preferably 0 to 6 carbon atoms, aryl or substituted aryl, ethylene ether or substituted ethylene ether, 2 to 20 ethylene ether groups; or a substituted polyethylene ether or a combination thereof. A particularly preferred substituent is an epoxy group.

Examples of epoxy crosslinking compounds having two or more epoxy groups include ethylene glycol diglycidyl ether (EGDGE), propylene glycol diglycidyl ether (PGDGE), 1,4-butanediol diglycidyl ether (BDDGE), and pentylene. Glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl ether (GDGE), glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, 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-dipoxyyoctane, 1,2,5,6-dipoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, Contains maleimide-epoxy compounds, etc.

Preferred epoxy crosslinking compounds have the formula:

wherein R ³ is alkyl or substituted alkyl having 1 to 14 carbon atoms, preferably 2 to 6 carbon atoms, and ethylene ether having 2 to 20 ethylene ether groups or polyethylene ether, alkyl substituted with a group selected from hydroxy, or

or -(CH ₂ OH) _x CH ₂ OH, where X is 1-14.

Particularly preferred glycidyl ethers are:

EGDGE: Ethylene glycol diglycidyl ether

In the formula, n is an integer from 1 to 220;
PEGDGE: Polyethylene glycol diglycidyl ether

BDDGE: 1,4-butanediol diglycidyl ether

GDGE: Glycerol diglycidyl ether

Sorbitol-DGE, represented by sorbitol diglycidyl ether.

A crosslinking agent having at least two carboxyl functional groups is referred to herein as a carboxyl crosslinking compound.

Examples of carboxylic acid crosslinking compounds include 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, Examples include citric acid, trimesic acid, polyacrylic acid, etc., but are not particularly limited. Particularly preferred organic acids are aromatic acids such as phthalic acid, especially orthophthalic acid, which lowers the ESR. The reaction between the crosslinking functional group and the crosslinking agent occurs at the high temperatures that occur during normal processing steps in capacitor manufacturing.

By crosslinking, the self-doped conductive polymer can be immobilized and elution in subsequent steps can be suppressed. Also, crosslinking impairs the conductivity of the self-doped conductive polymer layer. The weight ratio of crosslinker to solid self-doped conductive polymer is preferably about 0.01 to 2. More preferably, the weight ratio of crosslinker to self-doped conductive polymer is about 0.02 to 1, and even more preferably 0.05 to 0.2. When the weight ratio is less than about 0.01, the degree of crosslinking is insufficient and dissolution in subsequent steps cannot be sufficiently suppressed. Above a weight ratio of about 2, crosslinking reduces the conductivity of the self-doped conductive polymer layer.

The self-doped conductive polymer is preferably substantially free of extraneous dopants, and 5 wt% or less is considered acceptable due to deleterious interactions between the anionic groups of the dopant and the self-doped conductive polymer. I've been exposed to it. It is now surprisingly recognized that the use of higher amounts of exogenous dopants, particularly polystyrene sulfonic acid or its derivatives, does indeed have benefits such as capacity, capacitance stability, and breakdown voltage (BDV). Although not limited by theory, it is currently understood that a particular problem with self-doped conductive polymers is the thermal instability of the anionic portion of the self-doped conductive polymer. The addition of any exogenous dopant, preferably a polymer exogenous dopant, will alleviate the degradation that occurs during the various thermal excursions that occur during the preparation of the polymer and during its use. Preferably, the polymeric extrinsic dopant is added in an amount of about 7 wt% to 100 wt% based on the weight of the self-doped conductive polymer. Exogenous dopants above about 100 wt% can significantly increase ESR due to excess polymer dopant. Furthermore, since the self-doped conductive polymer begins to coagulate into particles, it is undesirable, contrary to the reason for using the self-doped conductive polymer. If the amount was less than about 7 wt%, the thermal instability could not be alleviated, so it was insufficient to justify its addition. More preferably, the foreign dopant is added in an amount of 8wt% to 20wt%. Furthermore, dopants present in sufficient amounts, especially polymeric dopants such as polystyrene sulfonic acid, interact with multiple sites of the self-doped conductive polymer and prevent dissolution of the self-doped polymer upon application of subsequent layers. I'm assuming you can. When using a crosslinking agent, an excess of polymer dopant may mitigate the effects of crosslinking, thereby obtaining a crosslinked self-doped conductive polymer with sufficient conductivity.

Particularly preferred polymeric external additives are polystyrene sulfonic acid and its derivatives, optionally in the form of a random copolymer consisting of groups A, B and C, expressed in the ratio of formula B:
AxByCz
Formula B

During the ceremony:
A is polystyrene sulfonic acid or a salt of polystyrene sulfonic acid;
B and C independently represent polymerized units substituted with groups selected from:
-carboxyl group;
-C(O)OR ⁶ , where R ⁶ is selected from the group consisting of:
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, and anhydride. alkyl), and -(CHR ⁷ CH ₂ O) _b -R ⁸ , where:
R ⁷ is selected from hydrogen or alkyl having 1 to 7 carbon atoms, preferably hydrogen or methyl;
b is an integer from 1 to a number sufficient to provide a molecular weight of up to 200,000 for the -CHR ⁷ CH ₂ O- group;
^R8 is 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. consisting of an alkyl group having 1 to 9 carbon atoms optionally substituted with a functional group;
-C(O)-NHR ⁹ , in the formula:
R ⁹ is hydrogen or alkyl having 1 to 20 carbon atoms),
-C ₆ H ₄ -R ¹⁰ , in the formula:
^R10 is selected from:
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 , where:
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 of up to 200,000 for the -CHR ¹¹ CH ₂ O- group;
^R12 is 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. selected from alkyl having 1 to 9 carbon atoms,
-C ₆ H ₄ -O-R ¹³ , in the formula:
^R13 is 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. hydrogen or alkyl;
reactive groups selected from the group consisting of epoxies, silanes, alkenes, alkynes, acrylates, phosphates;
-(CHR ¹⁴ CH ₂ O) _e -R ¹⁵ , where R ¹⁴ is hydrogen or alkyl having 1 to 7 carbon atoms, preferably hydrogen or methyl;
e is an integer from 1 to a number sufficient to provide a molecular weight of up to 200,000 for the -CHR ¹⁴ CH ₂ O- group;
^R15 is hydrogen 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. or selected from the group consisting of alkyl having 1 to 9 carbon atoms;
In one embodiment y and z are 0;
In another embodiment, x, y and z are sufficient together to form a polyanion having a molecular weight of at least 100 and no more than 500,000, and y/x is from 0.01 to 100; z is a ratio z/x from 0 to 100; more preferably x of the sum of x+y+z represents 50 to 99% of the sum of x+y+z, y is 1 to 50% of the sum of x+y+z, and z is the sum of x+y+z Even more preferably, 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.

Monomeric exogenous dopants can have a beneficial effect on power cycling capacity stability when applied to self-doped conductive polymers, either as an additive to the self-doped polymer solution or as a separate layer next to the conductive polymer. It was shown that it shows. In addition to the capacitive effect, these monomeric extrinsic dopants improve the thermal stability of self-doped conductive polymers. Aromatic sulfonic acids have advantages over aliphatic sulfonic acids, particularly in terms of thermal oxidative stability. Aromatic acids to which functional groups such as sulfonic acid groups, carboxylic acid groups, hydroxyl groups, and quinone groups are added are more effective and are more preferred. Aliphatic sulfonic acids having a carboxyl functional group have a superior thermal stability improving function compared to those having no carboxyl group. This is not surprising since carboxylic acid functional groups also function as dopants in conductive polymers. The monomeric exogenous dopant can reduce the swelling of the dried self-doped conductive polymer film, where the swelling is due to the solubility of the self-doped conductive polymer. The monomeric exogenous dopant is preferably added in an amount of about 7 wt% to 100 wt%, more preferably about 8 wt% to 20 wt%, based on the weight of the self-doped conductive polymer.

Self-doped conductive polymers can be mixed with exogenous dopants as described above. There is also a method in which a self-doping group-containing monomer is polymerized in the presence of an exogenous dopant, or in the presence of both a non-self-doping monomer and an exogenous dopant.

It is particularly preferred to incorporate functional additives into the coating or adjacent coating layers comprising the self-doped conductive polymer. 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. When the weight ratio is less than about 0.05, the function is insufficient. When the weight ratio exceeds about 5, the conductivity decreases. Preferably, the weight ratio is from about 0.5 to about 1.

Ionic liquids are particularly suitable for use in the present invention due to their increased capacitance and improved thermal stability.

Ionic liquids (ILs) are generally defined as organic/inorganic salts with melting points below 100°C, which are chemically and electrochemically stable, have low flammability, negligible vapor pressure, and high ionic conductivity. be done. As liquids with negligible vapor pressure, ionic liquids are commonly considered as green solvents for industrial production. Ionic liquids are organic salts that have poor ion coordination and are soluble at temperatures below 100°C or even at room temperature. Ionic liquids 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 much higher than that of ordinary salt solutions.

Particularly preferred ionic liquids are selected from the group consisting of:

Particularly preferred ionic liquids include 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-tetraethyl-imidazolinium, 1,2,3- a cation selected from the group consisting of trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium and 1,2,3-triethylimidazolinium; Contains. Exemplary ionic liquids include 4-(3-butyl-1-imidazolium)-1-butanesulfonic acid triflate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium trifluoride. lomethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-aryl-3-methylimidazolium bis(trifluoromethanesulfonate) fluoromethylsulfonyl)imide, 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, lithium bis(trifluoromethane)sulfonimide and derivatives thereof.

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 that have an ionic liquid species in each monomer repeat unit; They are connected via a polymer backbone to form a polymer structure. Incorporating some of the unique properties of ionic liquids into polymer chains creates a new class of polymeric materials. Polymer ionic liquids extend the properties and applications of ionic liquids and polymer electrolytes in general. Polymer ionic liquids are permanent and strong polymer electrolytes due to the solvent-independent ionization state of the ionic liquid species. The ability to absorb water is a common feature of ionic liquids and polymer ionic liquids.

Exemplary polymeric ionic liquids are from the group consisting of;

and derivatives thereof.

For the purposes of the present invention, nonionic polyols are alkyl alcohols with multiple hydroxyl groups or alkyl ethers with multiple hydroxyl groups on the alkyl group.

Particularly preferred nonionic polyols are _CH2OH (CHOH) _{2CH2OH or erythritol} , ribitol _or xylitol as _CH2OH (CHOH) _3CH2OH , _CH2OHC ( _CH2OH ) _2CH2OH or Pentaerythritol, CH ₂ OHC(CH ₃ ) ₂ CH ₂ OH or 2,2-dimethyl-1,3-propanediol, CH ₂ OH(CHOH) ₄ CH ₂ OH or Sorbitol, CH ₂ OH(CHOH) ₄ CH ₂ OH 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, _C12H22O11 or sucrose or _lactose , _glycerol , diglycerol, triglycerol, tetraglycerol, polyglycerol.

Generally, various hydroxy-functional nonionic polymers can be employed. In one embodiment, for example, the hydroxy-functional polymer is a polyalkylene ether. Examples of the polyalkylene ether 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 with terminal hydroxyl groups. Particularly suitable are polyethylene glycol, polypropylene glycol, polytetramethylene glycol (polytetrahydrofuran). The diol component is in particular a saturated or unsaturated, branched or unbranched, aliphatic or aromatic dihydroxy compound containing 5 to 36 carbon atoms, for example pentane-1,5-diol, hexane-1 , 6-diol, neopentyl glycol, bis-(hydroxymethyl)-cyclohexane, bisphenol A, dimer diols, hydrogenated dimer diols or even mixtures of the mentioned diols.

In addition to the above, other hydroxy-functional nonionic polymers may also be employed. Some examples of such polymers include, for example, ethoxylated alkylphenols, ethoxylated or propoxylated C ₆ -C ₂₄ fatty alcohols; general formula: CH ₃ -(CH ₂ ) _10-16 -(O- Polyoxyethylene glycol alkyl ethers with C ₂ H ₄ ) _1-25 -OH, such as octaethylene glycol monododecyl ether and pentaethylene glycol monododecyl ether; general formula: CH ₃ -(CH ₂ ) _10-16 - Polyoxypropylene glycol alkyl ether with (O-C ₃ H ₆ ) _1-25 -OH; following general formula: C ₈ -H ₁₇ -(C ₆ H ₄ )-(O-C ₂ H ₄ ) _{1- Polyoxyethylene glycol octylphenol} ethers _{with 25 -OH} , _{such as} Triton® Polyoxyethylene glycol alkylphenol ethers with ₂₅ -OH, such as nonoxynol-9, polyoxyethylene glycol esters of C ₈ -C ₂₄ fatty acids, such as polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan Polyoxyethylene glycol sorbitan alkyl esters such as monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, PEG-20 methylglucose distearate, PEG-20 methylglucose sesqui stearate, PEG-80 castor oil, and polyoxyethylene glycerol alkyl esters such as PEG-20 castor oil, PEG-3 castor oil, PEG600 diolate, PEG400 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 oleyl ether, polyoxyethylene-20 isohexadecyl ether , polyoxyethylene glycol ethers of C ₈ -C ₂₄ fatty acids such as polyoxyethylene-15 tridecyl ether and polyoxyethylene-6 tridecyl ether, and block copolymers of polyethylene glycol.

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

The functional additive can be used in combination with the crosslinking agent, and in some cases may exist within the same molecule.

The present invention is particularly suitable for use with powders having a high CV/g. Conductive polymers have small pore diameters and are difficult to impregnate with conductive polymer dispersions, so it has been difficult to use them together with high CV/g powders. Forming conductive polymers in situ can impregnate small pores, but the formation of conductive polymers is difficult to control, coatings are poor, and there are problems with leakage current. Thus, the present invention is particularly suitable for powders, especially tantalum powders, having a charge density of at least 45,000 CV/g, more preferably at least 100,000 CV/g, even more preferably 200,000 CV/g.

In one embodiment, differences in dissolution rates of adjacent layers can be used to inhibit dissolution of previously applied layers. When performing multiple impregnation cycles of the conductive polymer, the rate of dissolution can be varied by mixing with different solvents. For example, when a self-doped conductive polymer solution contains an alkylamine, it can be solubilized in a polar solvent such as alcohol, DMG, DMAc, or DMSO. By changing the solvent between impregnation cycles of self-doped conductive polymers, the possibility of re-dissolution 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 organic solvents improve wetting and impregnating properties, resulting in superior capacitance, especially for highly charged powders. It is a possibility. Of course, the capacitance can also be improved by adding a co-solvent and a surfactant to the aqueous self-doping conductive polymer solution.

[Comparative example 1]
A series of 220 microfarad, 6V tantalum anodes were fabricated with a specific charge of 120,000 μFV/g. Tantalum was anodized to form a dielectric on the tantalum anode at a predetermined formation voltage (Vf). The anode thus formed was immersed in a self-doped conductive polymer solution with polymer S2 for 1 minute and dried in an oven to remove moisture. This step was repeated 9 times. A layer of diamine salt aqueous solution was applied and allowed to dry. Thereafter, an externally added polythiophene conductive polymer dispersion was applied to form a subsequent polymer layer. This step was repeated four to five more times, and a graphite layer and a silver layer were sequentially coated to produce a solid electrolytic capacitor. The parts were assembled and packaged. Capacitance, ESR, and BDV were measured on the packaged parts. Capacity 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 changes during power cycles were tested before and after 50,000 power surge cycles.

[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 crosslinker.

[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.

[Comparative example 2]
A series of 47 microfarad, 16V tantalum anodes (specific charge of 133,000 μFV/g) were fabricated. The tantalum was anodized to form a dielectric on the tantalum anode. The negative electrode thus formed was immersed in a self-doped conductive polymer solution using polymer S2 for 1 minute and dried in an oven to remove moisture. This process was repeated nine times. Thereafter, 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. Thereafter, an externally added polythiophene conductive polymer dispersion was applied and dried 4 to 5 times, and a graphite layer and a silver layer were sequentially applied to produce a solid electrolytic capacitor. The parts were assembled and packaged. The capacitance and ESR of the package parts were measured.

[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.

[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.

[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.

[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 tantalum anode. The anode thus formed was immersed in a self-doped conductive polymer solution with polymer S2 for 1 minute and dried in an oven to remove moisture. This process was repeated one more time. The anode was then immersed in the first commercially available conductive polymer dispersion Clevios Knano LV from Heraeus for 1 minute and dried in an oven to remove moisture. This process was repeated until sufficient thickness was obtained. A second conductive polymer dispersion containing an epoxy compound and a silane compound was applied to form an outer polymer layer. After drying, the diamine salt and the second conductive polymer dispersion were alternately coated and repeated 4 to 5 times. After washing the anode with the conductive polymer layer formed thereon and drying it, a graphite layer and a silver layer were sequentially coated to produce a solid electrolytic capacitor. The parts were assembled and packaged. The packaged components were then mounted on a circuit board. The capacitance % of the power cycle mounted components was measured before and after 50,000 power surge cycles.

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

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

[Comparative example 4]
0.5 g of a self-doped conductive polymer solution using polymer S2 was dried on a slide glass at 150° C. to produce a conductive polymer film. 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 the 1st, 6th, and 9th days.

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

[Example 9]
Using Polymer S2, a conductive polymer film was prepared 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. did.

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

[Comparative example 5]
Using Polymer S2, 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 the self-doped conductive polymer solution before drying, and its conductivity was was 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 the 1st, 4th, and 7th day.

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

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

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

[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.

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

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

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

[Comparative Example 6]
0.5 g of a self-doped conductive polymer solution using polymer S2 was dried on a slide glass at 150° C. to produce a conductive polymer film. 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 the 3rd and 7th day.

[Example 18]
A conductive polymer film was produced in the same manner as in Comparative Example 6. 0.1 g of a 1 wt % aqueous solution of 5-sulfoisophthalic acid sodium salt was applied onto 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 the 3rd and 7th day.

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

[Example 20]
A conductive polymer film was produced 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.

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

[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 tantalum anode. The anode thus formed was immersed in a self-doped conductive polymer solution with polymer S1 for 1 minute and 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 the outer polymer layer. After drying, the diamine salt and the second conductive polymer dispersion were alternately coated and repeated 4 to 5 times. After washing the anode with the conductive polymer layer formed thereon and drying it, a graphite layer and a silver layer were sequentially coated to produce a solid electrolytic capacitor. The parts were assembled and packaged. The packaged components were then mounted on a circuit board. The capacitance and ESR of the mounted components were measured.

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

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

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

[Example 24]
A series of tantalum capacitors were prepared 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.

The invention has been described with reference to preferred embodiments without being limited thereto. Additional embodiments and modifications may be realized that are not specifically described herein, but are within the scope of the invention as more specifically described in the appended claims.

Claims (100)

A process for forming an electrolytic capacitor, the process comprising:
forming an anode including a dielectric thereon;
forming a cathode layer on the dielectric,
A process for forming an electrolytic capacitor, wherein the cathode layer includes a self-doped conductive polymer and a crosslinking agent, and the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.01 or more and 2 or less. The 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. The 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. A process for forming an electrolytic capacitor according to claim 1, wherein the cathode layer further comprises a crosslinkable material. The crosslinkable material is polyester, polyurethane, polyamide, polyamine, polyimide, silicone polyester, hydroxyl functional silicone, hydroxyethyl cellulose, 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, copolymers thereof, or multifunctional polymers thereof. 5. The process for forming the electrolytic capacitor of claim 4, comprising at least one oligomer or polymer selected from the group consisting of mixtures of. 5. A process for forming an electrolytic capacitor according to claim 4, wherein the crosslinkable material is crosslinked by the crosslinking agent. 5. The process for forming an electrolytic capacitor of claim 4, wherein the crosslinkable material is crosslinked to the self-doped conductive polymer by the crosslinker. 5. A process for forming an electrolytic capacitor according to claim 4, wherein the crosslinkable material includes at least one reactive group capable of reacting with the crosslinking agent. The reactive group is carboxyl, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxyl anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, forming the electrolytic capacitor of claim 8 selected from the group consisting of allyl alcohol esters, dicyclopentadiene unsaturations, unsaturated C _12-22 fatty esters or amides, carboxylic acid salts and quaternary ammonium salts. process for. 5. A process for forming an electrolytic capacitor according to claim 4, wherein the crosslinkable material comprises a polyol. 11. A process for forming an electrolytic capacitor according to claim 10, wherein the polyol is selected from ethylene glycol and polyglycerin. A process for forming an electrolytic capacitor according to claim 1, wherein the self-doped conductive polymer is crosslinked by the crosslinking agent. 2. The crosslinking agent is selected from the group consisting of melamine, isocyanate, epoxy, hexamethoxymelamine, glyoxal, furfuraldehyde, melamine formaldehyde condensate, divinyl sulfone, epoxy compounds, organofunctional silanes, and carboxylic acid compounds. A process for forming electrolytic capacitors as described in . 14. The process for forming an electrolytic capacitor of claim 13, wherein the crosslinking agent includes a plurality of epoxy groups. 14. A process for forming an electrolytic capacitor according to claim 13, wherein the organofunctional silane is defined by the 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 aryl or alkyl having up to 14 carbon atoms;
each R ² is an individually hydrolyzable functional group;
each R ³ is individually an alkyl functional group having 1 to 6 carbon atoms;
n is 1-3. 16. A process for forming an electrolytic capacitor according to claim 15, wherein the hydrolyzable functional group is selected from the group consisting of alkoxy, acyloxy, halogen, amine and hydrolysates thereof. 14. A process for forming an electrolytic capacitor according to claim 13, wherein the organofunctional silane is defined by the formula: Y(Si( ^R3 ) _3-n ( ^R2 ) _n ) ₂ .
During the ceremony:
Y is an organic moiety containing a reactive or non-reactive functional group;
each R ² is individually a hydrolyzable functional group;
each R ³ is individually an alkyl functional group having 1 to 6 carbon atoms;
n is 1-3. 18. A process for forming an electrolytic capacitor according to claim 17, wherein the reactive or non-reactive functional groups are selected from the group consisting of alkyl, aryl, sulfide, and melamine. The organofunctional silane is 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilane triol, (triethoxysilyl)propylsuccinic acid) anhydride, 3-mercaptopropyltrimethoxysilane. , vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane and bis(triethoxysilyl)octane, claim 13. process for forming electrolytic capacitors. The organofunctional silane is
selected from the group of:
where R ¹ is alkyl of 1 to 14 carbons;
each R ² is independently alkyl or substituted alkyl having 1 to 6 carbon atoms;
as well as
During the ceremony:
5. X is an alkyl or substituted alkyl of 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. 14. A process for forming an electrolytic capacitor according to 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 ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene Glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiene dipside, 1,5-hexadiene dipside, 1,2,7,8-dipoxyyoctane, 1,2,5,6- 14. A process for forming an electrolytic capacitor according to claim 13, wherein the process is selected from the group consisting of dipoxycyclooctane, 4-vinylcyclohexenedipside, bisphenol A diglycidyl ether, maleimide-epoxy compounds, and the like. The crosslinking agent is
defined by,
A process for forming an electrolytic capacitor according to claim 13:
In the formula, R ³ is alkyl or substituted alkyl having 1 to 14 carbon atoms, ethylene ether or polyethylene ether having 2 to 20 ethylene ether groups, alkyl substituted with a group selected from hydroxy, and
or -(CH ₂ OH) x CH ₂ OH, where X is 1-14. The crosslinking agent is
defined by:
In the formula, n is an integer from 1 to 220;
or sorbitol diglycidyl ether. The crosslinking agent is 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. 14. A process for forming an electrolytic capacitor according to claim 13 selected from the group consisting of: and polyacrylate acid. 25. The process for forming an electrolytic capacitor of claim 24, wherein the crosslinking agent is selected from the group consisting of phthalic acid, and orthophthalic acid. The self-doped conductive polymer is
A process for forming an electrolytic capacitor according to claim 1, defined by:
During the ceremony:
R ¹ and R ² independently represent linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl; or unsubstituted or C ₁ -C ₆ alkyl, C ₁ - C ₃ -C ₈ cycloalkyl, phenyl or benzyl substituted by C ₆ alkoxy, halogen or OR ³ ; or R ¹ and R ² together are unsubstituted 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 alkoxyphenyl, halophenyl, C ₁ -C ₄ alkylbenzyl, C ₁ - C ₄ alkoxybenzyl or halobenzyl, a straight chain C ₁ -C ₆ alkylene substituted with a 5, 6 or 7 membered heterocyclic structure containing two oxygen elements;
R ³ preferably represents hydrogen, linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl; or C ₃ -C ₈ cycloalkyl, phenyl or benzyl, unsubstituted or C ₁ -C ₆ alkyl, provided that at least one of R ¹ or R ² is substituted with -SO ₃ M, -CO ₂ M or -PO ₃ M, and M is H or preferably is a cation selected from ammonium, sodium, lithium or potassium;
X is S, N or O. 27. A process for forming an electrolytic capacitor according to claim 26, wherein R ¹ and R ² together represent O-(CHR ⁴ ) _n -O-,
n is an integer from 1 to 5, most preferably 2;
R ⁴ is independently a 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 - selected from C ₄ hydroxyalkyl radicals, R ⁴ substituted with -SO ₃ M, -CO ₂ M or -PO ₃ M, optionally carboxylic acids, hydroxyls, amines, substituted amines, alkenes, acrylates, thiols, alkynes , azide, sulfuric acid, sulfonic acid, imide, amide, epoxy, anhydride, silane and phosphoric acid; a hydroxyl radical;
Or R ⁴ is -(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 H or an alkyl chain having 1 to 5 carbon atoms optionally substituted with a functional group selected from carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, epoxy, acrylate and anhydride;
R ¹⁶ is -SO ₃ M, -CO ₂ M or -PO ₃ M, or an alkyl chain having 1 to 5 carbon atoms substituted with -SO ₃ M, -CO ₂ M or -PO ₃ M, optionally and 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, epoxies, anhydrides, silanes, acrylates, and phosphoric acids. , R ¹⁶ is an alkylene chain having 5 or more carbon atoms substituted with -Si ₂ M, -Si ₃ M or -Si ₃ M, and substituted with a carboxyl group;
a is an integer from 0 to 10;
M is H or a cation preferably selected from ammonium, sodium, lithium or potassium. 27. The process for forming an electrolytic capacitor of claim 26, wherein the self-doped conductive polymer is selected from the group consisting of S1 and S2.
The process for forming an electrolytic capacitor of claim 1, wherein the cathode layer further comprises an exogenous dopant, the exogenous dopant being present in an amount of 7 to 100 wt% based on the weight of the self-doped conductive polymer. . 30. The process for forming an electrolytic capacitor of claim 29, wherein the exogenous dopant is present in an amount of 8 to 20 wt% based on the weight of the self-doped conductive polymer. 30. A process for forming an electrolytic capacitor according to claim 29, wherein the exogenous dopant is defined by AxByCz.
During the ceremony:
A is polystyrene sulfonic acid or a salt of polystyrene sulfonic acid;
B and C independently represent polymerized units substituted with groups selected from:
-carboxyl group;
-C(O)OR ⁶ , where R ⁶ is selected from the group consisting of:
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, and anhydride. alkyl, and -(CHR ⁷ CH ₂ O) _b -R ⁸ , in the formula:
R ⁷ is selected from hydrogen or alkyl having 1 to 7 carbon atoms;
b is an integer from 1 to a number sufficient to provide a molecular weight of up to 200,000 for the -CHR ⁷ CH ₂ O- group; and R ⁸ is hydrogen, silane, phosphate, acrylate, 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, phosphate, azide, acrylate, and anhydride. is an alkyl;
-C(O)-NHR ⁹ , where R ⁹ is hydrogen or consists of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate and anhydride is an alkyl having 1 to 20 carbon atoms optionally substituted with a functional group selected from the group;
-C ₆ H ₄ -R ¹⁰ , in the formula,
^R10 is selected from:
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 , where:
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 of up to 200,000 for the -CHR ¹¹ CH ₂ O- group;
^R12 is 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. (selected from alkyl having 1 to 9 carbon atoms),
-C ₆ H ₄ -O-R ¹³ , in the formula,
^R13 is selected from:
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;
reactive groups selected from the group consisting of epoxies, silanes, alkenes, alkynes, acrylates, phosphates;
-(CHR ¹⁴ CH ₂ O) _e -R ¹⁵ , in the formula:
R ¹⁴ is hydrogen or alkyl having 1 to 7 carbon atoms;
e is an integer from 1 to a number sufficient to provide a molecular weight of up to 200,000 for the -CHR ¹⁴ CH ₂ O- group; and R ¹⁵ is hydrogen, and hydroxyl, carboxyl, amine, epoxy , silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphoric acid, and anhydride; and y and z is 0, or 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 0.01 to 100; or z has a ratio z/x of 0 to 100 or less. 32. The process for forming an electrolytic capacitor of claim 31, wherein ^R7 is hydrogen or methyl. 32. The process for forming an electrolytic capacitor of claim 31, wherein ^R14 is hydrogen or methyl. 32. A process for forming an electrolytic capacitor according to claim 31, wherein x represents 50-99%, y represents 1-50%, and z represents 0-49% of the sum of x+y+z. 35. A process for forming an electrolytic capacitor according to claim 34, wherein x represents 70-90%, y represents 10-30%, and z represents 0-20% of the sum of x+y+z. 2. The process for forming an electrolytic capacitor of claim 1, wherein the cathode layer further comprises an aromatic compound containing at least one hydroxy functional group and at least another hydroxy or carboxyl functional group. 37. A process for forming an electrolytic capacitor according to claim 36, wherein the aromatic compound is a phenolic acid. 38. A process for forming an electrolytic capacitor according to claim 37, wherein the phenolic acid is selected from the group consisting of gallic acid and tannic acid. The process for forming an electrolytic capacitor of claim 1, wherein the cathode layer further includes a functional additive. 40. The process for forming an electrolytic capacitor of claim 39, wherein the weight ratio of the functional additive to the self-doped conductive polymer is from 0.05 to 5. 41. A process for forming an electrolytic capacitor according to claim 40, wherein the weight ratio of the functional additive to the self-doped conductive polymer is from 0.5 to 1. 40. A process for forming an electrolytic capacitor according to claim 39, wherein the functional additive is selected from the group consisting of ionic liquids, nonionic polyols, and polyalkylene ethers. 43. A process for forming an electrolytic capacitor according to claim 42, wherein the nonionic polyol is polyglycerin. The ionic liquid includes 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)sulfonimide and its derivatives. 43. A process for forming an electrolytic capacitor according to claim 42 selected from the group consisting of: 42. The nonionic polyol has a linear, branched or cyclic alkyl or alkyl ether having 3 to 20 carbon atoms, and at least two carbons are each substituted with at least one hydroxyl group. A process for forming electrolytic capacitors as described in . The nonionic polyol is erythritol, ribitol, xylitol, pentaerythritol, 2,2-dimethyl-1,3-propanediol, sorbitol, mannitol, trimethylolethane, ditrimethylolpropane, glucose, fructose, sucrose and lactose, glycerol , diglycerol, triglycerol, tetraglycerol, polyglycerol, sorbitol, mannitol, trimethylolethane, ditrimethylolpropane, glucose, fructose, sucrose, lactose, glycerol, diglycerol, triglycerol, tetraglycerol, polyglycerol 43. A process for forming an electrolytic capacitor according to claim 42, wherein the process is selected. 43. A process for forming an electrolytic capacitor according to claim 42, wherein the polyalkylene ether is selected from the group consisting of polyalkylene glycols, polyepichlorohydrins, polyoxetanes, polyphenylene ethers, and polyether ketones. 48. A process for forming an electrolytic capacitor according to claim 47, wherein the polyalkylene ether is selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. The functional additive is ethoxylated alkylphenol; ethoxylated or propoxylated C ₆ -C ₂₄ fatty alcohol; general formula: CH ₃ -(CH ₂ ) _10-16 -(O-C ₂ H ₄ ) _1-25 Polyoxyethylene glycol alkyl ether with -OH; general formula: CH ₃ -(CH ₂ ) _10-16 -(OC ₃ H ₆ ) _1-25 polyoxypropylene glycol alkyl ether with -OH; the following general formula: Polyoxyethylene glycol octylphenol ether with the formula: C ₈ -H ₁₇ -(C ₆ H ₄ )-(OC ₂ H ₄ ) _1-25 -OH; the following general formula: C ₉ -H ₁₉ -(C Polyoxyethylene glycol alkylphenol ethers with ₆ H ₄ )-(OC ₂ H ₄ ) _1-25 -OH; polyoxyethylene glycol esters of C ₈ -C ₂₄ fatty acids and polyoxy of C ₈ -C ₂₄ fatty acids 40. A process for forming an electrolytic capacitor according to claim 39 selected from the group consisting of ethylene glycol ether (and block copolymers of polyethylene glycol). The functional additives include 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 methylglucose distearate, PEG-20 methylglucose sesquistearate, PEG-80 castor oil, PEG-20 castor oil, PEG-3 castor oil , PEG600 diolate, PEG400 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, polyoxyethylene-20 oleyl ether, polyoxyethylene-20 isohexadecyl ether, polyoxyethylene-15 tridecyl ether, polyoxyethylene-6 tridecyl 50. A process for forming an electrolytic capacitor according to claim 49, wherein the electrolytic capacitor is selected from the group consisting of ethers. 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. The electrolytic capacitor has an anode including a dielectric thereon, a cathode layer on the dielectric, the cathode layer is made of a crosslinked self-doping conductive polymer formed by a crosslinking agent, and the cathode has an anode including a dielectric. An electrolytic capacitor, wherein a weight ratio of the crosslinking agent to the self-doping conductive polymer is 0.01 or more and 2 or less. 53. The electrolytic capacitor according to claim 52, wherein a weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.02 or more and 1 or less. 54. The electrolytic capacitor according to claim 53, wherein the weight ratio of the crosslinking agent to the self-doped conductive polymer is 0.05 or more and 0.2 or less. 53. The electrolytic capacitor of claim 52, wherein the cathode layer further comprises a crosslinkable material. The crosslinkable material may be polyester, polyurethane, polyamide, polyamine, polyimide, silicone polyester, hydroxyl functional silicone, hydroxyethyl cellulose, polyvinyl alcohol, phenol, epoxy, butyral, epoxy/amine, epoxy/anhydride, isocyanate/amine, isocyanate. /alcohols, unsaturated polyesters, vinyl esters, unsaturated polyester and vinyl ester blends, unsaturated polyester/urethane hybrid resins, polyurethane ureas, reactive dicyclopentadiene resins or reactive polyamides, copolymers of these or multifunctional polymers. 56. The electrolytic capacitor of claim 55, comprising at least one oligomer or polymer selected from the group consisting of mixtures. 56. The electrolytic capacitor of claim 55, wherein the crosslinkable material is crosslinked by the crosslinking agent. 56. The electrolytic capacitor of claim 55, wherein the crosslinkable material is crosslinked to the self-doped conductive polymer by the crosslinker. 56. The electrolytic capacitor of claim 55, wherein the crosslinkable material includes at least one reactive group capable of reacting with the crosslinker. The reactive group is carboxyl, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate. 60. The electrolytic capacitor of claim 59, wherein the electrolytic capacitor is selected from the group consisting of , allyl alcohol esters, dicyclopentadiene unsaturations, unsaturated C _12-22 fatty esters or amides, carboxylic acid salts, and quaternary ammonium salts. 56. The electrolytic capacitor of claim 55, wherein the crosslinkable material comprises a polyol. 62. The electrolytic capacitor of claim 61, wherein the polyol is selected from ethylene glycol and polyglycerin. 53. The electrolytic capacitor of claim 52, wherein the self-doped conductive polymer is crosslinked by the crosslinker. 52. The crosslinking agent is selected from the group consisting of melamine, isocyanate, epoxy, hexamethoxymelamine, glyoxal, furfuraldehyde, melamine formaldehyde condensate, divinyl sulfone, epoxy compounds, organofunctional silanes, and carboxylic acid compounds. Electrolytic capacitors listed. 65. The electrolytic capacitor of claim 64, wherein the crosslinker includes two or more epoxy groups. 65. The electrolytic capacitor of claim 64, wherein the organofunctional silane is defined by the formula: XR ¹ Si(R ³ ) _3-n (R ² ) _n .
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 aryl or alkyl having up to 14 carbon atoms;
each R ² is an individually hydrolyzable functional group;
each R ³ is individually an alkyl functional group having 1 to 6 carbon atoms;
n is 1-3. 67. The electrolytic capacitor of claim 66, wherein the hydrolyzable functional group is selected from the group consisting of alkoxy, acyloxy, halogen, amine, and hydrolysates thereof. 65. The electrolytic capacitor of claim 64, wherein the organofunctional silane is defined by the formula: Y(Si(R ³ ) _3-n (R ² ) _n ) ₂ .
Y is an organic moiety containing a reactive or non-reactive functional group;
each R ² is an individually hydrolyzable functional group;
each R ³ is individually an alkyl functional group having 1 to 6 carbon atoms;
n is 1-3. 69. The electrolytic capacitor of claim 68, wherein the reactive or non-reactive functional group is selected from the group consisting of alkyl, aryl, sulfide, and melamine. The organofunctional silane is 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilane triol, (triethoxysilyl)propyl anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxy 65. selected from the group consisting of silane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propane) sulfonic acid, octyltriethoxysilane and bis(triethoxysilyl)octane. Electrolytic capacitor. The organofunctional silane is
65. The electrolytic capacitor of claim 64, selected from the group consisting of:
where R ¹ is alkyl of 1 to 14 carbons;
each R ² is independently alkyl or substituted alkyl having 1 to 6 carbon atoms;
as well as
During the ceremony:
X is alkyl or substituted alkyl of up to 14 carbon atoms, aryl or substituted aryl, ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether having 2 to 20 ethylene ether groups, or combinations thereof. 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 ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene Glycol diglycidyl ether, di(2,3-epoxypropyl) ether, 1,3-butadiene dipside, 1,5-hexadiene dipside, 1,2,7,8-dipoxyyoctane, 1,2,5,6- 65. The electrolytic capacitor of claim 64, wherein the electrolytic capacitor is selected from the group consisting of dipoxycyclooctane, 4-vinylcyclohexene dipside, bisphenol A diglycidyl ether, and maleimide-epoxy compounds. 65. The electrolytic capacitor of claim 64, wherein the crosslinking agent is defined by:
In the formula, R ³ is alkyl or substituted alkyl having 1 to 14 carbon atoms, ethylene ether or polyethylene ether having 2 to 20 ethylene ether groups, alkyl substituted with a group selected from hydroxy, and
or -(CH ₂ OH) _x CH ₂ OH, where X is 1-14. The crosslinking agent is
65. The electrolytic capacitor of claim 64, defined by:
In the formula, n is an integer from 1 to 220;


or sorbitol diglycidyl ether. The crosslinking agent is 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 polyacrylic acid. 76. The electrolytic capacitor of claim 75, wherein the crosslinking agent is selected from the group consisting of phthalic acid and orthophthalic acid. The self-doped conductive polymer is
53. The electrolytic capacitor of claim 52, defined by
During the ceremony:
R ¹ and R ² independently represent linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl; or unsubstituted or C ₁ -C ₆ alkyl, C ₁ -C ₃ -C ₈ cycloalkyl, phenyl or benzyl substituted by C ₆ alkoxy, halogen or OR ³ ;
or R ¹ and R ² are, together, unsubstituted or C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen, C ₃ -C ₈ cycloalkyl, phenyl, benzyl, C ₁ -C ₄ alkyl phenyl, C ₁ -C ₄ alkoxyphenyl, halophenyl, C ₁ -C ₄ alkylbenzyl, C ₁ -C ₄ alkoxybenzyl or halobenzyl, substituted with a 5-, 6- or 7-membered heterocyclic structure containing two oxygen elements is a linear C ₁ -C ₆ alkylene;
R ³ preferably represents hydrogen, linear or branched C ₁ -C ₁₆ alkyl or C ₂ -C ₁₈ alkoxyalkyl; or C ₃ -C ₈ cycloalkyl, phenyl or benzyl; Unsubstituted or substituted by C ₁ -C ₆ alkyl, provided that at least one of R ¹ or R ² is substituted with -SO ₃ M, -CO ₂ M or -PO ₃ M, and M is H or preferably a cation selected from ammonium, sodium, lithium or potassium;
and X is S, N or O. 78. The electrolytic capacitor of claim 77, wherein R ¹ and R ² together represent O-(CHR ⁴ ) _n -O-, wherein:
n is an integer from 1 to 5, most preferably 2;
R ⁴ is a 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 hydroxyalkyl independently selected from radicals, where R ⁴ is substituted with -SO ₃ M, -CO ₂ M or -PO ₃ M, optionally carboxylic acids, hydroxides, amines, substituted amines, alkenes, acrylates, thiols, substituted with at least one additional functional group selected from alkynes, azides, sulfates, sulfonates, sulfonic acids, imides, amides, epoxies, anhydrides, silanes, and phosphates, hydroxyl radicals;
Or R ⁴ is -(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 H or an alkyl chain having 1 to 5 carbon atoms optionally substituted with a functional group selected from carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, epoxy, acrylate and anhydride;
R ¹⁶ is -SO ₃ M, -CO ₂ M or -PO ₃ M, or an alkyl chain having 1 to 5 carbon atoms substituted with -SO ₃ M, -CO ₂ M or -PO ₃ M, optionally and 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, epoxies, anhydrides, silanes, acrylates, and phosphoric acids. ;
R ¹⁶ is an alkylene chain having 5 or more carbon atoms substituted with -Si ₂ M, -Si ₃ M or -Si ₃ M, and substituted with a carboxyl group;
a is an integer from 0 to 10;
M is H or a cation preferably selected from ammonium, sodium, lithium or potassium. 78. The electrolytic capacitor of claim 77, wherein the self-doped conductive polymer is selected from the group consisting of S1 and S2.
53. The electrolytic capacitor of claim 52, wherein the cathode layer further comprises an exogenous dopant, the exogenous dopant being present in an amount of 7 to 100 wt% based on the weight of the self-doped conductive polymer. 81. The electrolytic capacitor of claim 80, wherein the exogenous dopant is present in an amount of 8 to 20 wt% based on the weight of the self-doped conductive polymer. 81. The electrolytic capacitor of claim 80, wherein the exogenous dopant is defined by AxByCz.
During the ceremony:
A is polystyrene sulfonic acid or a salt of polystyrene sulfonic acid;
B and C independently represent polymerized units substituted with groups selected from;
-carboxyl group;
-C(O)OR ⁶ , where R ⁶ is selected from the group consisting of:
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, and anhydride. alkyl, and -(CHR ⁷ CH ₂ O) _b -R ⁸ , in the formula:
R ⁷ is selected from hydrogen or alkyl having 1 to 7 carbon atoms;
b is an integer from 1 to a number sufficient to provide a molecular weight of up to 200,000 for the -CHR ⁷ CH ₂ O- group; and R ⁸ is hydrogen, silane, phosphate, acrylate, 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, phosphate, azide, acrylate, and anhydride. is an alkyl;
-C(O)-NHR ⁹ , in the formula:
R ⁹ is 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. is an alkyl having 1 to 20 carbon atoms;
-C ₆ H ₄ -R ¹⁰ , in the formula:
^R10 is selected from:
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 , where:
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 of up to 200,000 for the -CHR ¹¹ CH ₂ O- group;
^R12 is 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. selected from alkyl having 1 to 9 carbon atoms;
-C ₆ H ₄ -O-R ¹³ , in the formula:
^R13 is selected from:
alkyl optionally substituted with hydrogen or a reactive group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, azide, acrylate, phosphate, and anhydride; ;
reactive groups selected from the group consisting of epoxies, silanes, alkenes, alkynes, acrylates, phosphates;
-(CHR ¹⁴ CH ₂ O) _e -R ¹⁵ , in the formula:
R ¹⁴ is hydrogen or alkyl having 1 to 7 carbon atoms;
e is an integer from 1 to a number sufficient to provide a molecular weight of up to 200,000 for the -CHR ¹⁴ CH ₂ O- group; and R ¹⁵ is hydroxyl, carboxyl, amine, epoxy, silane, a group consisting of hydrogen and alkyl having from 1 to 9 carbon atoms optionally substituted with a functional group selected from the group consisting of amides, imides, thiols, alkenes, alkynes, azides, acrylates, phosphoric acids, and anhydrides; and y and z are 0, or x, y and z are taken together and are sufficient to form a polyanion having a molecular weight of at least 100 and no more than 500,000, and y/x is 0.01 to 100, or z has a ratio z/x of 0 to 100 or less. 83. The electrolytic capacitor of claim 82, wherein ^R7 is hydrogen or methyl. 83. The electrolytic capacitor of claim 82, wherein ^R14 is hydrogen or methyl. 83. The electrolytic capacitor of claim 82, wherein x represents 50-99% of the sum of x+y+z, y represents 1-50% of the sum of x+y+z, and z represents 0-49% of the sum of x+y+z. 86. The electrolytic capacitor of claim 85, 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. 53. The electrolytic capacitor of claim 52, wherein the cathode layer further comprises an aromatic compound containing at least one hydroxy functional group and at least another hydroxy or carboxyl functional group. 88. The electrolytic capacitor of claim 87, wherein the aromatic compound is a phenolic acid. 89. The electrolytic capacitor of claim 88, wherein the phenolic acid is selected from the group consisting of gallic acid and tannic acid. 53. The electrolytic capacitor of claim 52, wherein the cathode layer further includes a functional additive. 91. The electrolytic capacitor of claim 90, wherein the weight ratio of the functional additive to the self-doped conductive polymer is from 0.05 to 5. 92. The electrolytic capacitor of claim 91, wherein the weight ratio of the functional additive to the self-doped conductive polymer is from 0.5 to 1. 91. The electrolytic capacitor of claim 90, wherein the functional additive is selected from the group consisting of ionic liquids, nonionic polyols, and polyalkylene ethers. The ionic liquid is
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- selected from the group consisting of hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, lithium bis(trifluoromethane)sulfonimide and derivatives thereof; 94. The electrolytic capacitor of claim 93. 94. The nonionic polyol has a linear, branched or cyclic alkyl or alkyl ether having 3 to 20 carbon atoms, and at least two carbons are each substituted with at least one hydroxyl group. Electrolytic capacitors listed. The nonionic polyol is erythritol, ribitol, xylitol, pentaerythritol, 2,2-dimethyl-1,3-propanediol, sorbitol, mannitol, trimethylolethane, ditrimethylolpropane, glucose, fructose, sucrose and lactose, glycerol 94. The electrolytic capacitor of claim 93, wherein the electrolytic capacitor is selected from the group consisting of , diglycerol, triglycerol, tetraglycerol, and polyglycerol. 94. The electrolytic capacitor of claim 93, wherein the polyalkylene ether is selected from the group consisting of polyalkylene glycols, polyepichlorohydrins, polyoxetanes, polyphenylene ethers, and polyether ketones. 98. The electrolytic capacitor of claim 97, wherein the polyalkylene ether is selected from the group consisting of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. The functional additive is ethoxylated alkylphenol; ethoxylated or propoxylated C ₆ -C ₂₄ fatty alcohol; general formula: CH ₃ -(CH ₂ ) _10-16 -(O-C ₂ H ₄ ) _1-25 - polyoxyethylene glycol alkyl ether; general formula: OH, CH ₃ -(CH ₂ ) _10-16 -(OC ₃ H ₆ ) _1-25 -OH; polyoxypropylene glycol alkyl ether having the following Polyoxyethylene glycol octylphenol ether with the general formula: C ₈ -H ₁₇ -(C ₆ H ₄ )-(OC ₂ H ₄ ) _1-25 -OH; the following general formula: C ₉ -H ₁₉ -( Polyoxyethylene glycol alkyl phenol ethers with C ₆ H ₄ )-(O-C ₂ H ₄ ) _1-25 -OH; polyoxyethylene glycol esters of C ₈ -C ₂₄ fatty acids and polyoxyethylene glycol esters of C ₈ -C ₂₄ fatty acids; 91. The electrolytic capacitor of claim 90 selected from the group consisting of oxyethylene glycol ether (and block copolymers of polyethylene glycol). 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 methylglucose distearate, PEG-20 methylglucose sesquistearate, PEG-80 castor oil, PEG-20 castor oil, PEG-3 castor oil , PEG600 diolate, PEG400 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, polyoxyethylene-20 oleyl ether, polyoxyethylene-20 isohexadecyl ether, polyoxyethylene-15 tridecyl ether, polyoxyethylene-6 tridecyl 91. The electrolytic capacitor of claim 90, wherein the electrolytic capacitor is selected from the group consisting of ethers.

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