Capacitor with improved power cycling

Abstract

To provide a mordant layer which is a new mordanting layer between adjacent conductive polymer layers and reduces peeling or breakage of a conductive polymer cathode.SOLUTION: In the electrolytic capacitor 10, a mordant layer 20 is provided on a primary conductive polymer layer 18 provided on a dielectric 16, the mordant layer is composed of a crosslinking agent and a predetermined mordant compound, a secondary conductive polymer layer 22 is provided on the mordant layer, and the mordant layer is crosslinked to the primary conductive polymer layer 18 and the secondary conductive polymer layer 22.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to improvements in electrolytic capacitors, particularly with respect to capacitance stability during cycling.The present invention particularly relates to an improved electrolytic capacitor including a mordant layer that improves capacitance stability. [Background technology]

[0002] There is an ever-increasing demand for electronic devices with enhanced functionality that can be used for longer periods of time without failure. The effort to provide such benefits has affected all elements of electronic devices. The present invention is concerned with eliminating failure modes that occur at the electronic component level, most specifically within electrolytic capacitors.

[0003] Solid electrolyte capacitors have emerged as a major tool in the development of electronic components. Solid electrolytic capacitors, especially those utilizing valve metal anodes, originally comprised a pressed powder anode with a dielectric on the anode and manganese dioxide as a conductive layer on the dielectric, with the manganese dioxide acting as the cathode. Manganese dioxide has been replaced, in part, by capacitors containing conductive polymers as the cathode layer due to its non-burnout failure mode. Of these, solid electrolytic capacitors containing polythiophene-based conductive polymers have proven to be the most desirable.

[0004] As demand continues to increase, those skilled in the art have continued to refine the techniques for valve metal capacitor manufacturing, resulting in powders with higher charge densities, such as 50,000 CV / g or greater. As the charge density of a powder increases, the internal surface area of ​​anodes formed with that powder increases, and the pore size of the pressed powder decreases. This complicates the use of conductive polymer cathodes, as it is difficult to deposit conductive polymer on the interstitial surfaces of the anode to the extent necessary to provide sufficient dielectric coverage.

[0005] The problem of poor coverage of interstitial surface areas has been significantly alleviated by applying multiple layers of conductive polymer, with the inner and outer layers having different formulations. One approach that has met with considerable success is to form a primary conductive polymer layer and apply it directly to the dielectric by in situ polymerization, in which the polymer's monomers are polymerized in situ. While this is advantageous for forming the initial layer, the outer conductive polymer layer is preferably formed from a preformed conductive polymer slurry. The conductive polymer slurry is prepared from a dispersion of PEDOT, polyanion particles, and other additives in water. The polyanion can be polystyrene sulfonic acid or a copolymer thereof. Such polyanion copolymers are described in U.S. Pat. No. 10,340,091. An alternative method is to form the primary conductive polymer layer from a preformed conductive polymer slurry, which has very small conductive polymer particles below the detection limit; the conductive polymer is referred to herein as soluble. Both of these methods are advantageous for coating the interstitial areas of a porous anode, since they form a coating on the dielectric on the anode. A secondary conductive layer is then preferably formed on the primary conductive polymer layer by deposition of a slurry containing a preformed conductive polymer.

[0006] The use of different formulations or techniques for depositing conductive polymers has led to reduced capacitor stability, particularly during power cycling. Without being limited by theory, it is hypothesized that either the polymer layers are incompatible, the pores do not fill sufficiently, or a charge barrier occurs. Incompatibility between adjacent layers can lead to delamination during power cycling, either within the polymer layer itself or in the dielectric. The creation of a charge barrier, also referred to as anomalous charging current, can lead to failure of the conductive polymer layer, although the mechanism is not understood. Summary of the Invention [Problem to be solved by the invention]

[0007] Provided herein is a novel mordanting layer between adjacent conductive polymer layers that mitigates delamination or breakage of the conductive polymer cathode. [Means for solving the problem]

[0008] The present invention particularly relates to an improved capacitor that includes a mordant layer that is stable during power cycling.

[0009] A particular feature of the present invention is a mordant layer which improves the stability of the conductive polymer layer, particularly reducing damage to the polymer layer during power cycling.

[0010] Another feature of the present invention is the ability to manufacture improved capacitors containing mordanting layers using existing manufacturing methods.

[0011] These and other advantages are provided, as will be appreciated, in an electrolytic capacitor comprising an anode including a dielectric layer thereon, a primary conductive polymer layer disposed on the dielectric, and a mordant layer disposed on the primary conductive layer, the mordant layer having a structure of formula A

[0012] [ka]

[0013] wherein R 1 ~R 6 are each independently H and -PO(OR 7 )2, and each R 7 are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, or alkylaryl having 7 to 21 carbon atoms, with R 1 ~R 6 is —PO(OH)2. A secondary conductive polymer layer is provided on the mordant layer.

[0014] Yet another embodiment is provided in a method of forming an electrolytic capacitor, the method including forming an anode, forming a dielectric on the anode, forming a primary conductive polymer layer on the dielectric, and forming a mordant layer on the primary conductive layer, the mordant layer being a compound represented by Formula A

[0015] [ka]

[0016] wherein R 1 ~R 6 are each independently H and -PO(OR 7 )2, and each R 7 are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, or alkylaryl having 7 to 21 carbon atoms, with R 1 ~R 6 is —PO(OH) 2 ; and forming a secondary conductive polymer layer on the mordant layer. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic cross-sectional view of an embodiment of the present invention. [Figure 2] FIG. 2 is a flow chart representation according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention relates to improved electrolytic capacitors that exhibit significantly improved stability over multiple cycles of power cycling tests. In particular, the present invention relates to electrolytic capacitors that include a mordant between adjacently applied conductive polymer layers, where the mordant mitigates failures associated with failures of the conductive polymer layers.

[0019] The present invention will now be described with reference to the drawings, which form an integral and non-limiting part of the specification and are provided to clarify the invention.

[0020] An embodiment of the present invention will be described with reference to FIG. 1. In FIG. 1, a capacitor 10 of the present invention is shown schematically in cross section. The capacitor includes an anode 12, preferably a porous monolith formed by pressing powder. An anode wire 14 extends from the anode. The anode wire can be embedded in the powder prior to pressing, which is preferred; alternatively, the anode wire can be attached to the surface of the pressed anode by welding or other methods. A dielectric 16 is formed on the surface of the anode. While shown as a layer of constant thickness, the actual dielectric layer is disposed on the interstitial surface of the porous monolith. A primary conductive polymer layer 18 is disposed on the dielectric, preferably extending into the interstitial surface of the monolith to increase the surface area of ​​the conductive polymer coating on the dielectric. While shown as a single layer for purposes of illustration, multiple primary conductive polymer layers are typically applied. A mordant layer 20 is formed on the primary conductive layer, comprising a mordant compound of Formula A, described below, and optionally, preferably, a crosslinker. A secondary conductive polymer layer 22 is formed on the mordant layer. An adhesive layer 24 is optionally, but preferably, formed on the secondary conductive polymer layer. The adhesive layer allows a cathode lead 26 to be electrically attached to the secondary conductive polymer layer, such as by soldering or a conductive adhesive. Attaching leads to conductive polymer layers is known in the art to be difficult, and adhesive layers are typically used to achieve good physical and electrical contact between the secondary conductive polymer layer and the cathode lead. An anode lead 28 is in electrical contact with the anode wire. An optional, preferably electrically insulating resin 30 surrounds the cathode and anode leads, except for their bottom portions.

[0021] The process for forming an electrolytic capacitor is described with reference to FIG. 2. In FIG. 2, the process for forming an electrolytic capacitor is depicted in a flow chart. An anode is prepared at 40. The anode can be a foil, and can be prepared by pressing a powder. A pressed powder anode preferably includes an anode wire extending therefrom. The anode is preferably sintered, particularly when niobium or tantalum powder is used as the anode powder. A dielectric is formed on the anode at 42. The method for forming the dielectric is not limited to typical methods known to those skilled in the art that are suitable for demonstrating the present invention. A primary conductive polymer layer is formed on the dielectric at 44. The primary conductive polymer layer is formed by in-situ polymerization or by applying a preformed conductive polymer from a polymer solution or slurry. In-situ polymerization is known to those skilled in the art to involve polymerization of a monomer in the presence of a surface that forms the polymer. In this case, the surface is the dielectric. Preformed conductive polymers suitable for use in forming the primary layer have particle sizes less than 20 nm, preferably less than 1 nm, which are considered undetectable; in this regard, the preformed conductive polymers are referred to as soluble polymers. The primary conductive polymer layer is typically formed by multiple applications of an in-situ layer or a conductive polymer solution or slurry. A mordant layer is formed on the primary conductive polymer layer at 46. The mordant layer is formed by applying a solution containing a compound defined by Formula A and, optionally, a crosslinker, followed by drying. The solvent for applying the mordant layer is not particularly limited, and in one embodiment of the present invention, water is used. The mordant layer may be formed by a single application of the solution or by continuous application. A secondary conductive polymer layer is formed on the mordant layer at 48. The secondary conductive polymer layer is preferably formed by applying a slurry containing the conductive polymer, where the conductive polymer has an average particle size of at least 50 nm and not more than 200 nm. The secondary conductive polymer may also have a bimodal particle size distribution. Such properties of conductive polymers are described in US Pat. Nos. 10,650,980 and 10,658,121.The secondary conductive polymer layer is preferably formed by multiple applications of the slurry. An adhesion layer is preferably formed on the secondary conductive polymer layer at 50, the adhesion layer preferably comprising at least one carbon-containing layer and at least one metal-containing layer, as known in the art. The capacitor is completed at 52, which typically includes attachment of a cathode external termination, an anode external termination, and a resin enclosure. Testing and any electrical or physical processing may also be included as part of the completion step.

[0022] The secondary conductive polymer may preferably have a primer layer containing a crosslinker or a weak ionic acid between adjacent conductive polymer sublayers to improve adhesion between the layers. In one embodiment, a conductive polymer sublayer is deposited directly onto a previously applied conductive polymer sublayer without a primer between them. Primers are well known in the art, such as those exemplified in U.S. Patent Nos. 8,882,856, 9,761,347, 9,761,378, 10,109,428, and 10,643,796, which are incorporated herein by reference. Particularly suitable primers are amine salts selected from amines and weak acids.

[0023] Particularly preferred anode materials are metals, and particularly preferred metals are valve metals or conductive oxides of valve metals. Particularly preferred anodes include materials selected from the group consisting of niobium, aluminum, tantalum, and NbO. Tantalum is the most preferred anode material. The benefits of the present invention are most easily achieved with powders having a high charge density, such as, but not limited to, 50,000 CV / g. Below about 50,000 CV / g, power cycling issues are less prevalent, and the benefits offered by the present invention are not as readily apparent. However, power cycling issues are observed with powders having even lower charges than when the primer conductive layer is prepared with only a conductive polymer slurry. The benefits of this type of primary conductive polymer layer and its effect on capacity recovery and power cycling are described in U.S. Pat. No. 10,879,010. As the powder charge density increases, the benefits of the present invention become more readily apparent. Particularly suitable powders have a charge density of greater than 100,000 CV / g, more preferably greater than 200,000 CV / g, and even more preferably from about 250,000 CV / g to about 350,000 CV / g.

[0024] The anode wire may be embedded or attached to the anode, with embedding the anode wire being preferred. The conductive material for the anode wire is not particularly limited, but for ease of manufacturing, it is preferred that the anode wire be made of the same material as the anode.

[0025] The dielectric and the method for forming the dielectric are not particularly limited herein. A particularly suitable dielectric is the oxide of the anode because of its ease of manufacture.

[0026] The primary conductive layer comprises a conductive polymer. The primary conductive layer is formed by in-situ polymerization of a monomer, or the primary conductive layer is formed as a coating of a semi-polymerized conductive polymer, more preferably a soluble conductive polymer, having a small average particle size of less than about 20 nm. The primary conductive polymer layer can also be a combination of an in-situ polymerized layer, a soluble conductive polymer layer, and a semi-polymerized conductive polymer slurry.

[0027] It is hypothesized that the in situ formed conductive polymer penetrates more effectively into the interstitial portion of the porous anodized anode, thereby forming an improved capacitor.

[0028] A soluble conductive polymer is one that dissolves completely in a solvent or solvent mixture without detectable particles, with a typical particle size detection limit of less than about 1 nm.

[0029] The solvent for the soluble conductive polymer can be water, an organic solvent, a mixture of water and a miscible solvent such as alcohols and non-hydroxy polar solvents such as dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), dimethyl acetamide (DMAc), etc.

[0030] Soluble conductive polymers are believed to be as effective as conductive polymers formed by in situ methods and to impregnate the pores of the anode better than conductive polymers containing detectable particles. Neither in situ nor soluble conductive polymers contain polyanion dopants such as polystyrene sulfonate. In many cases, soluble conductive polymers contain self-doping functionality.

[0031] The mordant layer comprises a mordant compound defined by Formula A and, optionally, preferably a crosslinker. The mordant compound of Formula A is

[0032] [ka]

[0033] where R 1 ~R 6 are each independently H and -PO(OR 7 )2, and each R 7 are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, or alkylaryl having 7 to 21 carbon atoms, with R 1 ~R 6 is —PO(OH)2. Preferably, R 1 ~R 5 At least two of R are -PO(OH). 1 ~R 5 At least three of R are -PO(OH). 1 ~R 5 At least four of R are -PO(OH). 1 ~R 5 At least five of R are —PO(OH). Most preferably, R 1 ~R 5 are each -PO(OH)2. 7 can be unsubstituted alkyl, aryl, or alkylaryl; R 7 can be substituted with at least one functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride, or an alkali metal, preferably selected from lithium, sodium, and potassium.

[0034] The mordant layer optionally includes a crosslinker. The crosslinker in the mordant layer is capable of crosslinking with the compound of Formula A and the conductive polymer. Crosslinking involves using a material with at least two crosslinkable functionalities, one crosslinkable functionality forming a first bond and a second crosslinkable functionality forming a second bond to form a crosslinked molecular bridge between two molecules, oligomers, polymers, or portions of a polymer. For purposes of this disclosure, the term "crosslinked crosslinker" refers to a crosslinker that does not exist as a separate compound after crosslinking. It is defined as the reaction product of a crosslinker. The crosslinkable functionality may form covalent or ionic bonds.

[0035] Crosslinks may be between functional groups on conductive polymers or molecules, oligomers, or polymers. Crosslinkable functionality can be added to conductive polymers to improve layer integrity and surface coverage, or crosslinkable materials may be added to conductive polymer layers. Once exposed to curing conditions, typically a thermal cure, the crosslinkable molecules react with the crosslinking agent to form a tightly interpenetrating network of covalent and ionic bonds. The crosslinkable material preferably comprises two components, one of which is preferably a carboxy, hydroxy, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylates, vinyls, maleate, maleimides, itaconate, allyl alcohol esters, dicyclopentadiene-based unsaturated, unsaturated C 12 ~C 22The polyfunctional or multi-reactive group compounds, oligomers, or polymers are well known in the art and are selected from the group consisting of fatty acid esters or amides, carboxylates, quaternary ammonium salts, polyesters, polyurethanes, polyamides, polyamines, polyimides, silicone polyesters, hydroxyl-functional silicones, hydroxyethyl cellulose, polyvinyl alcohol, phenols, epoxies, butyrals, and copolymers thereof, or mixtures of these multifunctional polymers, such as epoxy / amine, epoxy / anhydride, isocyanate / amine, isocyanate / alcohol, unsaturated polyesters, vinyl esters, unsaturated polyester and vinyl ester blends, unsaturated polyester / urethane hybrid resins, polyurethane-ureas, reactive dicyclopentadiene resins, or reactive polyamides. The polyfunctional or multi-reactive group oligomer or polymer contains at least one carboxylic acid group and at least one hydroxyl functional group. A particularly suitable polyfunctional oligomer or polymer is a polyester containing both carboxyl and hydroxyl functionality. In addition to oligomers or polymers, particles with surface functional groups can also participate in cross-linking.

[0036] The crosslinking agent includes a silane compound and an epoxy compound. Particularly suitable crosslinking agents include melamines, isocyanates, epoxies, hexamethoxymelamines, glyoxals, furfuralaldehydes, melamine formaldehyde condensates, divinyl sulfones, and epoxy compounds.

[0037] Organofunctional silanes and organic compounds having more than one crosslinking group, especially more than one epoxy group, are particularly suitable for use as crosslinkers in the present invention, especially when used in combination.

[0038] An exemplary organofunctional silane is represented by the formula XR1Si(R3) 3-n (R2) n where X is an organic functional group such as amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, alkyl, etc., and R1 is an aryl or alkyl (CH2) m wherein m can be 0 to 14; R2 is individually a hydrolyzable functional group such as alkoxy, acyloxy, halogen, amine, or hydrolyzates thereof; R3 is individually an alkyl functional group having 1 to 6 carbon atoms; and n is 1 to 3.

[0039] The organofunctional silanes are dipodal and have the formula Y(Si(R3) 3-n )R2) n )2 where Y is any organic moiety containing a reactive or non-reactive functional group, such as alkyl, aryl, sulfide, or melamine, and R, R, and n are defined above. The organofunctional silane can also be a multifunctional or polymeric silane, such as a silane-modified polybutadiene or a silane-modified polyamine.

[0040] Examples of organofunctional silanes include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, bis(triethoxysilyl)octane, etc. Examples are used to illustrate the invention, but should not be construed as definitive. Examples of organofunctional silanes include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, bis(triethoxysilyl)octane, etc. Examples are used to illustrate the invention, but should not be considered definitive.

[0041] Particularly suitable organofunctional silanes are those of the formula

[0042] [ka]

[0043] wherein R 8 is alkyl having 1 to 14 carbon atoms, more preferably selected from methyl, ethyl, and propyl; R 9 is each independently alkyl or substituted alkyl having 1 to 6 carbon atoms.

[0044] Particularly suitable glycidyl silanes are those of the formula

[0045] [ka]

[0046] and for convenience will be referred to herein as "Silane A."

[0047] Crosslinkers with at least two epoxy groups are referred to herein as epoxy crosslinking compounds and have the formula

[0048] [ka]

[0049] where X is 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, polyethylene ether or substituted polyethylene ether having 2 to 20 ethylene ether groups, or a combination thereof. An especially preferred substituent is an epoxy group.

[0050] Examples of epoxy crosslinking compounds having more than one epoxy group include ethylene glycol diglycidyl ether (EGDGE), propylene glycol diglycidyl ether (PGDGE), 1,4-butanediol diglycidyl ether (BDDGE), pentylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol glycidyl ether, glycerol diglycidyl ether (GDGE), glycerol polyglycidyl ethers, diglycerol polyglycidyl ethers, and trimethylolpropane polyglycidyl ether. , sorbitol diglycidyl ether (sorbitol-DGE), sorbitol polyglycidyl ethers, polyethylene glycol diglycidyl ether (PEG-DGE), 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-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, maleimide-epoxy compounds, and the like.

[0051] Suitable epoxy crosslinking compounds have the formula

[0052] [ka]

[0053] wherein R 10 is alkyl or substituted alkyl having 1 to 14 carbon atoms, preferably 2 to 6 carbon atoms, ethylene ether or polyethylene ether having 2 to 20 ethylene ether groups, or hydroxy,

[0054] [ka]

[0055] , or -(CHOH) x CH2OH, where X is alkyl substituted with a group selected from 1 to 14.

[0056] Particularly suitable glycidyl ethers are

[0057] [ka]

[0058] EGDGE: ethylene glycol diglycidyl ether;

[0059] [ka]

[0060] In the formula, n is an integer of 1 to 220. PEGDGE: polyethylene glycol diglycidyl ether;

[0061] [ka]

[0062] BDDGE: 1,4-butanediol diglycidyl ether;

[0063] [ka]

[0064] where one R 11 is H and other R 11 are respectively,

[0065] [ka]

[0066] That is, GDGE: glycerol diglycidyl ether;

[0067] [ka]

[0068] Sorbitol DGE: Sorbitol diglycidyl ether.

[0069] Mixtures of crosslinkers may also be used.

[0070] The secondary conductive polymer layer is formed from a slurry containing a prepolymerized polythiophene and, optionally, a dopant such as styrene sulfonic acid or a polymer containing styrene sulfonic acid groups. A preferred polymerization method uses stata screen, which provides uniform droplet size, resulting in an average polymer particle size of at least about 50 nm to about 200 nm or less, more preferably 150 nm, and even more preferably less than about 100 nm.

[0071] Polythiophene monomers suitable for polymerization are shown as polymerizable in Formula B:

[0072] [ka]

[0073] In the formula, R 1 and R 2 are independently C1-C6 alkyl, C1-C6 alkoxy, halogen, or OR 3 C1-C, straight or branched, substituted or unsubstituted 16 Alkyl, C2-C 18 alkoxyalkyl, C3-C8 cycloalkyl, phenyl, or benzyl, or R 1 and R2 are both C1-C6 alkyl, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl or halobenzyl, or a straight-chain C1-C6 alkene unsubstituted or substituted with a 5-, 6-, or 7-membered heterocyclic structure containing two oxygen atoms. 3 is hydrogen, straight or branched C1-C 16 or C2-C alkyl, or unsubstituted C1-C6 alkyl 18 represents an alkoxyalkyl, a C3-C8 cycloalkyl, phenyl, or benzyl. X is S. n represents that the compound of Formula B is a polymer having a range of molecular weights, typically N is an integer from 2 to a number sufficient to reach an average molecular weight of about 500,000.

[0074] R in Formula B 1 and R 2 is preferably chosen to inhibit polymerization at the β-site of the ring, with polymerization most preferably only allowed to proceed at the α-site. 1 and R 2 is preferably not hydrogen, and more preferably R 1 and R 2 is an alpha director, and either bond is preferably an alkyl bond or longer. R 1 and R 2 is most preferably small to avoid steric hindrance.

[0075] In a particularly preferred embodiment, R of formula B 1 and R 2 are both -O-(CHR4) m R represents —O—, where m is an integer of 1 to 5, and is most preferably 2. 4are each independently hydrogen or a straight or branched C1-C optionally substituted with a functional group selected from carboxylic acid, hydroxyl, amine, substituted amines, alkene, acrylate, thiol, alkyne, azide, sulfate, sulfonate, sulfonic acid, imide, amide, epoxy, anhydride, silane, and phosphate. 18 Alkyl radicals, C5-C 12 Cycloalkyl radicals, C6-C 14 Aryl radicals, C7-C 18 or a C1-C4 hydroxyalkyl radical, a hydroxyl radical, or R 4 is -(CHR 5 ) a -R 16 , -O(CHR 5 ) a R 16 , -CHO(CHR) a R 16 , -CH2O(CH2CHR 5 O) a R 16 or R 4 is H or a functional group selected from the group consisting of hydroxy, carboxyl, amine, epoxy, amide, imide, anhydride, hydroxymethyl, alkene, thiol, alkyne, azide, sulfonic acid, benzenesulfonic acid, sulfate, SO3M, anhydride, silane, acrylate, and phosphate; and R 5 R 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. 16 is H, -SO3M, or an alkyl chain having 1 to 5 carbon atoms optionally substituted with a functional group selected from carboxylic acid, hydroxyl, amine, substituted amines, alkene, thiol, alkyne, azide, amide, imide, sulfate, SO3M, amide, epoxy, anhydride, silane, acrylate, and phosphate. a is an integer from 0 to 10. M is H or a cation selected from ammonia, sodium, or potassium.

[0076] A particularly suitable polymer is 3,4-polyethylenedioxythiophene (PEDOT), which is prepared from the monomer 3,4-ethylenedioxythiophene (EDOT).

[0077] Particularly preferred conductive polymers include poly(3,4-ethylenedioxythiophene), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salt), poly(4 -(2,3-Dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy alcohol, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole) ), poly(3-hydroxypyrrole), poly(3-methoxypyrrole), polythiophene, poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3-methoxythiophene) , poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-aniline sulfonate), poly(3-aniline sulfonate).

[0078] Particularly suitable polymers or copolymers are selected from the group consisting of poly(4-(2,3-dihydrothieno-[3,4-b][1,4-]dioxin-2-yl)methoxy)-1-butane-sulfonic acid, salts), poly(4-(2,3-dihydrothieno-[3.4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salts), poly(N-methylpyrrole), poly(3-methylthiophene), poly(3-methoxythiophene), and poly(3,4-ethylenedioxythiophene).

[0079] The insulating resin is not particularly limited herein, but any conductive compatible resin is suitable for demonstrating the present invention. If the electrolytic capacitor is embedded or housed, the resin is optional. [Example]

[0080] The ESR (equivalent series resistance) of the capacitors was measured at 100kHz using an Aglient E4980A Precision LCR Meter. The power cycling test (surge voltage) was performed at rated voltage for 5 seconds at an ambient temperature of 85°C, and then the voltage was turned off for 5 seconds. The voltage on / off cycle was repeated 60,000 times. The capacitance of the parts was tested before and after the power cycling cycle, and the percentage of capacitance change was calculated.

[0081] Comparative Example 1 A series of tantalum anodes (100 microfarads, 35 V) were prepared. The tantalum was anodized to form a dielectric on the tantalum anode. A silane-based organic compound was applied to the dielectric. The anodes thus formed were immersed in the oxidant iron tosylate, followed by immersion in EDOT monomer, followed by drying and rinsing. This process was repeated several times to build a PEDOT film within the anode cavity. A conductive polymer containing an epoxy and silane compound was applied to form the next polymer layer. After drying, alternating layers of amine salt and secondary conductive polymer dispersion were applied, and this process was repeated four to five more times. The anodes with the conductive polymer layer were then rinsed and dried, followed by successive coatings of graphite and silver layers to form solid electrolytic capacitors. The components were assembled and packaged. The capacitance and ESR of the packaged components were measured.

[0082] Comparative Example 2 A series of tantalum anodes (100 microfarads, 35 V) were prepared. The tantalum was anodized to form a dielectric on the tantalum anode. A silane-based organic compound was applied to the dielectric. The anode thus formed was immersed in the oxidant iron tosylate, followed by immersion in EDOT monomer, followed by drying and rinsing. This process was repeated several times to build a PEDOT film within the anode cavity. A crosslinker selected from bifunctional epoxy compounds was applied to the surface of the PEDOT film thus formed. A conductive polymer containing an epoxy and silane compound was applied to form the next polymer layer. After drying, alternating layers of amine salt and secondary conductive polymer dispersion were applied, and this process was repeated four to five more times. The anode with the conductive polymer layer was washed and dried, and then successively coated with graphite and silver layers to form a solid electrolytic capacitor. The components were assembled and packaged. The capacitance and ESR of the packaged components were measured.

[0083] Comparative Example 3 A series of tantalum anodes (100 microfarads, 35 V) were prepared. The tantalum was anodized to form a dielectric on the tantalum anode. A silane-based organic compound was applied to the dielectric. The thus-formed anode was immersed in the oxidizing agent iron tosylate, followed by immersion in EDOT monomer, followed by drying and rinsing. This process was repeated several times to build a PEDOT film within the anode cavity. A crosslinker prepared from a bifunctional epoxy compound and polyethylene oxide was applied to the surface of the thus-formed PEDOT film. A conductive polymer containing an epoxy and silane compound was applied to form the next polymer layer. After drying, alternating layers of amine salt and secondary conductive polymer dispersion were applied, and this process was repeated four to five more times. The anodes with the conductive polymer layer were washed and dried, and then successively coated with graphite and silver layers to form solid electrolytic capacitors. The components were assembled and packaged. The capacitance and ESR of the packaged components were measured.

[0084] Example 1 of the present invention A series of tantalum anodes (100 microfarads, 35 V) were prepared. The tantalum was anodized to form a dielectric on the tantalum anode. A silane-based organic compound was applied to the dielectric. The anodes thus formed were immersed in the oxidant iron tosylate, followed by immersion in EDOT monomer, followed by drying and rinsing. This process was repeated several times to build a PEDOT film within the anode cavity. A coating containing inositol hexaphosphate, also known as phytic acid, was applied onto the PEDOT film. A conductive polymer containing epoxy and silane compounds was applied to form the next polymer layer. After drying, alternating layers of amine salt and secondary conductive polymer dispersion were applied, and this process was repeated four to five more times. The anodes with the conductive polymer layer were washed and dried, and then successively coated with graphite and silver layers to form solid electrolytic capacitors. The components were assembled and packaged. The capacitance and ESR of the packaged components were measured.

[0085] Example 2 of the present invention A series of tantalum anodes (100 microfarads, 35 V) were prepared. The tantalum was anodized to form a dielectric on the tantalum anode. A silane-based organic compound was applied to the dielectric. The anodes thus formed were immersed in the oxidant iron tosylate, followed by immersion in EDOT monomer, followed by drying and rinsing. This process was repeated several times to build a PEDOT film within the anode cavity. A coating containing inositol hexaphosphate and a bifunctional crosslinker was applied to the PEDOT film. A conductive polymer containing epoxy and silane compounds was applied to form the next polymer layer. After drying, alternating layers of amine salt and secondary conductive polymer dispersion were applied, and this process was repeated four to five more times. The anodes with the conductive polymer layer were washed and dried, and then successively coated with graphite and silver layers to form solid electrolytic capacitors. The components were assembled and packaged. The capacitance and ESR of the packaged components were measured.

[0086] [Table 1]

[0087] Examples of the present invention demonstrate the effects of lower initial ESR and significant improvements in capacity loss and ESR after 50,000 power cycles. As demonstrated, the capacitors of the present invention have a capacity loss of less than 10%, and more preferably less than 5%, of the capacity before power cycling after 50,000 power cycles. In addition to improving power cycling characteristics, the method of the present invention also demonstrates improved ESR stability and improved anomalous charge current characteristics. Anomalous charge current in solid electrolytic capacitors has been described elsewhere (Y. Freeman et al., 2013, ECS J. Solid State Sci. Technol. 2N197; Chacko et al., 9,793,058).

[0088] The present invention has been described with reference to non-limiting preferred embodiments. Those skilled in the art will recognize additional embodiments illustrated and described in the accompanying specification.

Claims

1. An electrolytic capacitor, an anode comprising a dielectric layer on the anode; a primary conductive polymer layer on the dielectric; a mordant layer on the primary conductive polymer layer, the mordant layer comprising a compound having at least two crosslinkable functional groups crosslinked by a crosslinker and a compound of formula A; 【Chemistry 1】 In the formula, R １ ~R ６ are each independently H and -PO(OR ７ ) ２ and each R ７ are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, or alkylaryl having 7 to 21 carbon atoms, with R １ ~R ６ At least one of the groups is —PO(OH) ２ the mordant layer, a secondary conductive polymer layer on the mordant layer, The electrolytic capacitor wherein the mordant layer is crosslinked to the primary conductive polymer layer and the secondary conductive polymer layer.

2. R １ ~R ６ At least two of the groups are -PO(OH) ２ 2. The electrolytic capacitor according to claim 1, wherein

3. R １ ~R ６ At least three of the groups are -PO(OH) ２ 3. The electrolytic capacitor according to claim 2, wherein

4. R １ ~R ６ At least four of the groups are -PO(OH) ２ 4. The electrolytic capacitor according to claim 3, wherein

5. R １ ~R ６ At least five of the groups are -PO(OH) ２ 5. The electrolytic capacitor according to claim 4, wherein

6. R １ ~R ６ are each -PO(OH) ２ 6. The electrolytic capacitor according to claim 5,

7. R ７ is substituted with at least one functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride, and alkali metal.

8. 10. The electrolytic capacitor of claim 1, wherein the anode comprises a valve metal.

9. 9. The electrolytic capacitor of claim 8, wherein the valve metal is selected from the group consisting of aluminum, tantalum, and niobium.

10. 10. The electrolytic capacitor of claim 1, wherein the anode comprises a powder having a charge density of at least 50,000 CV / g.

11. 11. The electrolytic capacitor of claim 10, wherein the anode comprises a powder having a charge density of at least 100,000 CV / g.

12. 12. The electrolytic capacitor of claim 11, wherein the anode comprises a powder having a charge density of at least 200,000 CV / g.

13. 10. The electrolytic capacitor of claim 1, having a capacity loss of less than 10% after 50,000 power cycles compared to the capacity before power cycling.

14. 14. The electrolytic capacitor of claim 13, having a capacity loss of less than 5% after 50,000 power cycles compared to the capacity before power cycling.

15. 10. The electrolytic capacitor of claim 1, wherein the primary conductive polymer layer comprises a polymer selected from the group consisting of primary conductive polymer layers formed by in-situ polymerization, and wherein the polymer layer formed from a semi-polymerized polymer has a particle size of less than 20 nm.

16. 16. The electrolytic capacitor of claim 15, wherein the semi-polymerized polymer has a particle size of less than 1 nm.

17. 17. The electrolytic capacitor of claim 16, wherein the semi-polymerized polymer is a soluble polymer.

18. The crosslinking agent may be a carboxyl, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic acid anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, dicyclopentadiene-based unsaturated, unsaturated C １２ ~C ２２ Fatty acid esters of unsaturated C １２ ~C ２２ 10. The electrolytic capacitor of claim 1, having a crosslinked functionality selected from the group consisting of fatty acid amides, carboxylates, quaternary ammonium salts, polyesters, polyurethanes, polyamides, polyamines, polyimides, silicone polyesters, hydroxyl functional silicones, hydroxyethyl cellulose, polyvinyl alcohol, phenols, epoxies, butyrals, and mixtures thereof.

19. The electrolytic capacitor according to claim 1 , wherein the cross-linking agent contains at least an amine group.

20. 10. The electrolytic capacitor of claim 1, wherein the crosslinking agent comprises at least one group selected from melamine, isocyanate, epoxy, hexamethoxymelamine, glyoxal, furfuralaldehyde, melamine formaldehyde condensate, divinyl sulfone, and epoxy compounds.

21. The crosslinking agent has the formula XR １ Si(R ３ ) ３－ｎ (R ２ ) ｎ An organofunctional silane defined by: wherein X is an organic functional group selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, alkyl, and the like; R １ is aryl or alkyl (CH ２ ) ｍ and m is 0 to 14; R ２ are each a hydrolyzable functional group selected from the group consisting of alkoxy, acyloxy, halogen, amine, or hydrolyzed forms thereof; R ３ are individually alkyl functional groups having 1 to 6 carbon atoms; 2. The electrolytic capacitor according to claim 1, wherein n is 1 to 3.

22. The crosslinking agent has the formula Y (Si (R) ３ ) ３－ｎ (R) ２ ) ｎ ) ２ is defined by wherein Y is an organic moiety containing a reactive or non-reactive functional group; R ２ are individually hydrolyzable functional groups selected from the group consisting of alkoxy, acyloxy, halogen, amine, and hydrolyzed forms thereof; R ３ are individually alkyl functional groups having 1 to 6 carbon atoms; 2. The electrolytic capacitor according to claim 1, wherein n is 1 to 3.

23. 2. The electrolytic capacitor according to claim 1, wherein the crosslinking agent is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, and bis(triethoxysilyl)octane.

24. The crosslinking agent has the formula 【Chemistry 2】 wherein R ８ is alkyl having 1 to 14 carbon atoms, more preferably selected from methyl, ethyl and propyl; R ９ 10. The electrolytic capacitor of claim 1, wherein each is independently alkyl or substituted alkyl having 1 to 6 carbon atoms.

25. The crosslinking agent has the formula 【Transformation 3】 wherein X is alkyl or substituted alkylaryl or substituted aryl having 0 to 14 carbon atoms, ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether containing 2 to 20 ethylene ether groups, or a combination thereof.

26. The crosslinking agent may be 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 ethers, diglycerol polyglycidyl ethers, trimethylolpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol 2. The electrolytic capacitor according to claim 1, wherein the epoxy group is selected from the group consisting of alkyl polyglycidyl ethers, polyethylene glycol diglycidyl ether, 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-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, maleimide-epoxy compounds, and the like.

27. The crosslinking agent has the formula 【Chemistry 4】 wherein R １０ is alkyl or substituted alkyl having 1 to 4 carbon atoms, ethylene ether or polyethylene ether having 2 to 20 ethylene ether groups, or hydroxy, 【Transformation 5】 , -(CH ２ OH) ｘ CH ２ 2. The electrolytic capacitor of claim 1, wherein X is alkyl substituted with a group selected from the group consisting of 1 to 14.

28. The crosslinking agent is 【Transformation 6】 【Transformation 7】 wherein n is an integer from 1 to 220; 【Transformation 8】 、 【Chemistry 9】 And wherein one R １１ is H, and other R １１ are respectively, 【Chemistry 10】 and 【Chemistry 11】 2. The electrolytic capacitor of claim 1, wherein the electrolytic capacitor is selected from the group consisting of:

29. 10. The electrolytic capacitor of claim 1, wherein the secondary conductive polymer layer comprises a primer.

30. At least one of the primary conductive polymer layer or the secondary conductive polymer layer is a polymer having Formula B 【Chemistry 12】 and a polymer defined by the formula: R in the formula B １ and R ２ are independently linear or branched C １ ~C １６ alkyl or C ２ ~C １８ or C １ ~C ６ Alkyl, C １ ~C ６ Alkoxy, halogen, or OR ３ C is unsubstituted or substituted with ３ ~C ８ cycloalkyl, phenyl or benzyl; or R in the formula B １ and R ２ Both are 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 Alkyl benzyl of C １ ~C ４ a straight-chain C unsubstituted or substituted with an alkoxybenzyl, halobenzyl, or 5-, 6-, or 7-membered heterocyclic structure containing two oxygen atoms; １ ~C ６ is an alkylene of the formula R ３ is hydrogen or C １ ~C ６ A straight or branched C alkyl group which is not substituted or substituted with １ ~C １６ Alkyl, C ２ ~C １８ Alkoxyalkyl of C ３ ~C ８ or phenyl or benzyl, X is S; 2. The electrolytic capacitor of claim 1, wherein n is an integer from 2 to a number sufficient to reach a molecular weight of about 500,000.

31. R １ and R ２ are both -O-(CHR ４ ) ｍ -O-, m is an integer from 1 to 5, R ４ are independently hydrogen or a carboxylic acid, a hydroxyl, an amine, an alkene, an acrylate, a thiol, an alkyne, an azide, a sulfate, a sulfonate, a sulfonic acid, an imide, an amide, an epoxy, an anhydride, a silane, a phosphate, a hydroxyl, -(CHR ５ ) ａ -R １６ , -O(CHR ５ ) ａ R １６ , -CH ２ O (CHR ５ ) ａ R １６ , or -CH ２ O (CH ２ CHR ５ O) ａ R １６ A linear or branched C unsubstituted or substituted with a functional group selected from １ ~C １８ alkyl radicals of C ５ ~C １２ a cycloalkyl radical of C ６ ~C １４ an aryl radical of C ７ ~C １８ an aralkyl radical of C １ ~C ４ or is selected from the hydroxyalkyl radicals R ４ are hydroxyl, carboxyl, amine, epoxy, amide, imide, anhydride, hydroxymethyl, alkene, thiol, alkyne, azide, sulfonic acid, benzenesulfonic acid sulfate, SO ３ M is a functional group selected from the group consisting of anhydride, silane, acrylate, and phosphate; R ５ is an alkyl chain having 1 to 5 carbon atoms unsubstituted or substituted with H or a functional group selected from the group consisting of carboxylic acid, hydroxyl, amine, alkene, thiol, alkene, azide, epoxy, acrylate, and anhydride; R １６ is H, -SO ３ M, or carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, amide, imide, sulfate, -SO ３ M is an alkyl chain having 1 to 5 carbon atoms that is unsubstituted or substituted with a functional group selected from the group consisting of amide, epoxy, anhydride, silane, acrylate, and phosphate; a is an integer from 0 to 10, 31. The electrolytic capacitor of claim 30, wherein M is H or a cation selected from the group consisting of ammonia, sodium, and potassium.

32. 31. The electrolytic capacitor of claim 30, wherein the polymer is 3,4-polyethylenedioxythiophene.

33. The polymers include poly(3,4-ethylenedioxythiophene), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl ... Hydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy alcohol, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly poly(3-hydroxypyrrole), poly(3-methoxypyrrole), polythiophene, poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3-methoxythiophene), poly poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonate), and poly(3-anilinesulfonate).

34. 31. The electrolytic capacitor of claim 30, wherein the polymer is selected from the group consisting of poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salt), poly(N-methylpyrrole), poly(3-methylthiophene), poly(3-methoxythiophene), and poly(3,4-ethylenedioxythiophene).

35. 1. A method for forming an electrolytic capacitor, comprising: forming an anode; forming a dielectric on the anode; forming a primary conductive polymer layer on the dielectric; forming a mordant layer on the primary conductive polymer layer, the mordant layer comprising a crosslinker and a compound of Formula A 【Chemistry 13】 wherein R １ ~R ６ are each independently H and -PO(OR ７ ) ２ and each R ７ are independently selected from H, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, or alkylaryl having 7 to 21 carbon atoms, with R １ ~R ６ At least one of the groups is —PO(OH) ２ and forming a secondary conductive polymer layer on the mordant layer; crosslinking said mordant layer to said primary conductive polymer layer and said secondary conductive polymer layer.

36. R １ ~R ６ At least two of the groups are -PO(OH) ２ 36. The method of forming an electrolytic capacitor according to claim 35, wherein

37. R １ ~R ６ At least three of the groups are -PO(OH) ２ 37. The method of forming an electrolytic capacitor according to claim 36, wherein:

38. R １ ~R ６ At least four of the groups are -PO(OH) ２ 38. The method of forming an electrolytic capacitor according to claim 37, wherein

39. R １ ~R ６ At least five of the groups are -PO(OH) ２ 39. The method of forming an electrolytic capacitor according to claim 38, wherein

40. R １ ~R ６ are each -PO(OH) ２ 40. The method of forming an electrolytic capacitor according to claim 39, wherein

41. R ７ is substituted with at least one functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, silane, amide, imide, thiol, alkene, alkyne, phosphate, azide, acrylate, anhydride, and alkali metal.

42. 36. The method of forming an electrolytic capacitor of claim 35, wherein the anode comprises a valve metal.

43. 43. The method of forming an electrolytic capacitor of claim 42, wherein the valve metal is selected from the group consisting of aluminum, tantalum, and niobium.

44. 36. The method of forming an electrolytic capacitor of claim 35, wherein the anode comprises a powder having a charge density of at least 50,000 CV / g.

45. 45. The method of forming an electrolytic capacitor of claim 44, wherein the anode comprises a powder having a charge density of at least 100,000 CV / g.

46. 46. ​​The method of forming an electrolytic capacitor of claim 45, wherein the anode comprises a powder having a charge density of at least 200,000 CV / g.

47. 36. The method of forming an electrolytic capacitor of claim 35, wherein the capacitor has a capacity loss of less than 10% after 50,000 power cycles compared to the capacity before power cycling.

48. 48. The method of forming an electrolytic capacitor of claim 47, wherein the capacitor has a capacitance loss of less than 5% after 50,000 power cycles compared to the capacitance before power cycling.

49. 36. The method of forming an electrolytic capacitor of claim 35, wherein forming the primary conductive polymer layer comprises in-situ polymerization.

50. 36. The method of forming an electrolytic capacitor of claim 35, wherein forming the primary conductive polymer layer comprises applying a semi-polymerized polymer having a particle size of less than 20 nm.

51. 51. The method of forming an electrolytic capacitor of claim 50, wherein the semi-polymerized polymer has a particle size of less than 1 nm.

52. 52. The method of forming an electrolytic capacitor of claim 51, wherein the semi-polymerized polymer is a soluble polymer.

53. 36. The method of forming an electrolytic capacitor of claim 35, wherein forming the mordant layer further comprises adding a cross-linking agent.

54. The crosslinking agent may be a carboxyl, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic acid anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, dicyclopentadiene-based unsaturated, unsaturated C １２ ~C ２２ Fatty acid esters of unsaturated C １２ ~C ２２ 54. The method of forming an electrolytic capacitor of claim 53, wherein the crosslinkable functionality is selected from the group consisting of fatty acid amides, carboxylates, quaternary ammonium salts, polyesters, polyurethanes, polyamides, polyamines, polyimides, silicone polyesters, hydroxyl functional silicones, hydroxyethyl cellulose, polyvinyl alcohol, phenols, epoxies, butyrals, and mixtures thereof.

55. 54. The method of forming an electrolytic capacitor of claim 53, wherein the cross-linking agent comprises at least an amine group.

56. 54. The method of forming an electrolytic capacitor of claim 53, wherein the crosslinker comprises at least one group selected from melamine, isocyanate, epoxy, hexamethoxymelamine, glyoxal, furfuralaldehyde, melamine formaldehyde condensate, divinyl sulfone, and epoxy compounds.

57. The crosslinking agent has the formula XR １ Si(R ３ ) ３－ｎ (R ２ ) ｎ An organofunctional silane defined by: wherein X is an organic functional group selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, alkyl, and the like; R １ is aryl or alkyl (CH ２ ) ｍ and m is 0 to 14; R ２ are each a hydrolyzable functional group selected from the group consisting of alkoxy, acyloxy, halogen, amine, or hydrolyzed forms thereof; R ３ are individually alkyl functional groups having 1 to 6 carbon atoms; 54. The method for forming an electrolytic capacitor according to claim 53, wherein n is 1 to 3.

58. The crosslinking agent has the formula Y (Si (R) ３ ) ３－ｎ (R) ２ ) ｎ ) ２ is defined by wherein Y is an organic moiety containing a reactive or non-reactive functional group; R ２ are individually hydrolyzable functional groups selected from the group consisting of alkoxy, acyloxy, halogen, amine, and hydrolyzed forms thereof; R ３ are individually alkyl functional groups having 1 to 6 carbon atoms; 54. The method for forming an electrolytic capacitor according to claim 53, wherein n is 1 to 3.

59. 54. The method of forming an electrolytic capacitor of claim 53, wherein the crosslinker is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminopropylsilanetriol, (triethoxysilyl)propylsuccinic anhydride, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trihydroxysilyl-1-propanesulfonic acid, octyltriethoxysilane, and bis(triethoxysilyl)octane.

60. The crosslinking agent has the formula 【Chemistry 14】 wherein R ８ is alkyl having 1 to 14 carbon atoms, more preferably selected from methyl, ethyl and propyl; R ９ is each independently an alkyl or a substituted alkyl having 1 to 6 carbon atoms.

61. The crosslinking agent has the formula 【Chemistry 15】 wherein X is alkyl or substituted alkyl having 0 to 14 carbon atoms, aryl or substituted aryl, ethylene ether or substituted ethylene ether, polyethylene ether or substituted polyethylene ether containing 2 to 20 ethylene ether groups, or a combination thereof.

62. The crosslinking agent may be 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 ethers, diglycerol polyglycidyl ethers, trimethylolpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol polyglycidyl ether, sorbitol diglycidyl ether, sorbitol diglycidyl ether, sorbitol diglycidyl ether, glycerol ...

54. The method of forming an electrolytic capacitor of claim 53, wherein the epoxy group is selected from the group consisting of glycidyl ethers, polyethylene glycol diglycidyl ether, 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-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, maleimide-epoxy compounds, and the like.

63. The crosslinking agent has the formula 【Chemistry 16】 wherein R １０ is alkyl or substituted alkyl having 1 to 4 carbon atoms, ethylene ether or polyethylene ether having 2 to 20 ethylene ether groups, or hydroxy, 【Chemistry 17】 , -(CH ２ OH) ｘ CH ２ 54. The method of forming an electrolytic capacitor of claim 53, wherein X is alkyl substituted with a group selected from the group consisting of 1-14.

64. The crosslinking agent is [Chemistry 18] 、 【Chemistry 19】 wherein n is an integer from 1 to 220; 【Chemistry 20】 、 【Chemistry 21】 And wherein one R １１ is H, and other R １１ are respectively, 【Chemistry 22】 and 【Chemistry 23】 54. The method of forming an electrolytic capacitor of claim 53, wherein the electrolytic capacitor is selected from the group consisting of:

65. 36. The method of forming an electrolytic capacitor of claim 35, wherein the secondary conductive polymer layer further comprises the addition of a primer.

66. 66. The method of forming an electrolytic capacitor of claim 65, wherein the primer is between adjacent conductive polymer sublayers.

67. At least one of the primary conductive polymer layer or the secondary conductive polymer layer is a polymer having Formula B 【Chemistry 24】 and a polymer defined by the formula: R in the formula B １ and R ２ are independently linear or branched C １ ~C １６ alkyl or C ２ ~C １８ or C １ ~C ６ Alkyl, C １ ~C ６ Alkoxy, halogen, or OR ３ C is unsubstituted or substituted with ３ ~C ８ cycloalkyl, phenyl or benzyl; or R in the formula B １ and R ２ Both are 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 Alkyl benzyl of C １ ~C ４ a straight-chain C unsubstituted or substituted with an alkoxybenzyl, halobenzyl, or 5-, 6-, or 7-membered heterocyclic structure containing two oxygen atoms; １ ~C ６ is an alkylene of the formula R ３ is hydrogen or C １ ~C ６ A straight or branched C alkyl group which is not substituted or substituted with １ ~C １６ Alkyl, C ２ ~C １８ Alkoxyalkyl of C ３ ~C ８ or phenyl or benzyl, X is S; 36. The method of forming an electrolytic capacitor of claim 35, wherein n is an integer from 2 to a number sufficient to reach a molecular weight of about 500,000.

68. R １ and R ２ are both -O-(CHR ４ ) ｍ -O-, m is an integer from 1 to 5, R ４ are independently hydrogen or a carboxylic acid, a hydroxyl, an amine, an alkene, an acrylate, a thiol, an alkyne, an azide, a sulfate, a sulfonate, a sulfonic acid, an imide, an amide, an epoxy, an anhydride, a silane, a phosphate, a hydroxyl, -(CHR ５ ) ａ -R １６ , -O(CHR ５ ) ａ R １６ , -CH ２ O (CHR ５ ) ａ R １６ , or -CH ２ O (CH ２ CHR ５ O) ａ R １６ A linear or branched C unsubstituted or substituted with a functional group selected from １ ~C １８ alkyl radicals of C ５ ~C １２ a cycloalkyl radical of C ６ ~C １４ an aryl radical of C ７ ~C １８ an aralkyl radical of C １ ~C ４ or is selected from the hydroxyalkyl radicals R ４ are hydroxyl, carboxyl, amine, epoxy, amide, imide, anhydride, hydroxymethyl, alkene, thiol, alkyne, azide, sulfonic acid, benzenesulfonic acid sulfate, SO ３ M is a functional group selected from the group consisting of anhydride, silane, acrylate, and phosphate; R ５ is an alkyl chain having 1 to 5 carbon atoms unsubstituted or substituted with H or a functional group selected from the group consisting of carboxylic acid, hydroxyl, amine, alkene, thiol, alkene, azide, epoxy, acrylate, and anhydride; R １６ is H, -SO ３ M, or carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, amide, imide, sulfate, -SO ３ M is an alkyl chain having 1 to 5 carbon atoms that is unsubstituted or substituted with a functional group selected from the group consisting of amide, epoxy, anhydride, silane, acrylate, and phosphate; a is an integer from 0 to 10, 68. The method of forming an electrolytic capacitor of claim 67, wherein M is H or a cation selected from the group consisting of ammonia, sodium, and potassium.

69. 68. The method of forming an electrolytic capacitor of claim 67, wherein the polymer is 3,4-polyethylenedioxythiophene.

70. The polymers include poly(3,4-ethylenedioxythiophene), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-sulfonic acid, salt), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl ... Hydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy alcohol, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly poly(3-hydroxypyrrole), poly(3-methoxypyrrole), polythiophene, poly(3-methylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3-methoxythiophene), poly poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,68. The method of forming an electrolytic capacitor according to claim 67, wherein the thiophene is selected from the group consisting of poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonate), and poly(3-anilinesulfonate).

71. 68. The method of claim 67, wherein the polymer is selected from the group consisting of poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-butane-sulfonic acid, salts), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-methyl-1-propane-sulfonic acid, salts), poly(N-methylpyrrole), poly(3-methylthiophene), poly(3-methoxythiophene), and poly(3,4-ethylenedioxythiophene).

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