Solid electrolytic capacitors with improved reliability

Abstract

To provide techniques for reducing an anomalous charge current (ACC) in an electrolytic capacitor.SOLUTION: When a conductive polymer 18 is applied to an electrolytic capacitor, processing of forming mordant layers (20, 21) of a phytic acid or the like is performed. Examples of sites where the mordant layers are formed are preferably between primary and secondary conductive polymers (18 / 22), between a dielectric 16 and the primary conductive polymer, on each layer of the primary conductive polymer, and the like.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This invention is a continuation-in-part of pending U.S. patent application Ser. No. 17 / 178,631, filed February 18, 2021, and is incorporated herein by reference. [Background technology]

[0002] The present invention relates to an improved method of operating a solid electrolytic capacitor and the improved capacitors formed thereby. More specifically, the present invention relates to improving reliability and reducing abnormal charging current (ACC) of a capacitor by incorporating a mordant layer between the dielectric and the conductive polymer layer and between adjacent conductive polymer layers.

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 Manganese dioxide has been superseded by capacitors with conductive polymers as the cathode layer, in part due to its non-flammable failure mode.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

[0004] However, when a solid electrolytic capacitor containing a polythiophene-based conductive polymer is completely dried, it exhibits an anomalous charging current (ACC) that exceeds the theoretical charging current (I(t)), which is calculated as follows: I(t)=C*dv / dt where C is the capacitance and dV / dt is the voltage ramp. Abnormal charging current (ACC) has the potential to interfere with intended circuit function. Further details about abnormal charging current in solid electrolytic capacitors are described elsewhere (Non-Patent Documents 1-3). [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Freeman et al., J.Solid State Sci.Technol.2013, 2, N197~N204 [Non-patent document 2] Freeman et al., Appl.Sci.2021, 11, 5514 [Non-patent document 3] Chacko et al., 9,793,058 Summary of the Invention

[0006] Provided herein is a novel mordant layer disposed between a dielectric and a conductive polymer layer, and between adjacent conductive polymer layers, that significantly reduces abnormal charging current (ACC) in solid electrolytic capacitors.

[0007] The present invention is directed to an improved capacitor with a mordant layer.

[0008] A special feature of the present invention is a mordant layer that reduces the abnormal charging current (ACC) of the capacitor.

[0009] Another feature of the present invention is the improved reliability of capacitors with mordant layers in high temperature and humidity conditions.

[0010] The electrolytic capacitor includes an anode with a dielectric layer thereon, a mordant layer between the dielectric and the conductive polymer layer, and optionally between adjacent conductive polymer layers or within adjacent conductive polymer layers, the mordant layer comprising a mixture or reaction product represented by a mordant compound of Formula A and a crosslinker.

[0011] An exemplary mordant compound is defined by Formula A below:

[0012] [ka]

[0013] In the formula, R1 and R2 are independently selected from H, a cation, a linear alkyl, a cyclic alkyl, or a substituted alkyl having 1 to 10 carbon atoms. R3 is selected from -CR4R5R6, R4 represents hydrogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms, and R4 and R5 together represent cyclic alkyl, or substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) n R5 represents an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms, and R4 and R5 together represent a cyclic alkyl, a substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) n wherein R6 represents hydrogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; and n is an integer of 1 to 20.

[0014] As will be appreciated, these and other advantages are provided by an electrolytic capacitor comprising an anode with a dielectric layer thereon, a first mordant layer disposed on the dielectric and comprising a mordant compound of Formula A:

[0015] [ka]

[0016] wherein R1 and R2 are independently selected from H, a cation, a linear alkyl, a cyclic alkyl, or a substituted alkyl having 1 to 10 carbon atoms; R3 is selected from -CR4R5R6; R4 represents hydrogen, an alkyl having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms; and R4 and R5 together represent a cyclic alkyl, or a substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) n R5 represents an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms, and R4 and R5 together represent a cyclic alkyl, a substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) nwherein R6 represents hydrogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms, and n is an integer of 1 to 20. The compound includes a mordant compound and a crosslinker. The primary conductive polymer layer is disposed on the first mordant layer.

[0017] Yet another embodiment is a method of forming an electrolytic capacitor comprising forming an anode, forming a dielectric on the anode, and forming a first mordant layer on the dielectric, the first mordant layer comprising a mordant compound of Formula A: wherein R1 and R2 are independently selected from H, a cation, a linear alkyl, a cyclic alkyl, or a substituted alkyl having 1 to 10 carbon atoms; R3 is selected from -CR4R5R6; R4 represents hydrogen, an alkyl having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms; and R4 and R5 together represent a cyclic alkyl, or a substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) n R5 represents an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms, and R4 and R5 together represent a cyclic alkyl, a substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) n wherein R6 represents hydrogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms, and n is an integer of 1 to 20. The method includes forming a first mordant layer comprising a mordant compound and a crosslinker; and forming a primary conductive polymer layer on the first mordant layer.

[0018] [ka] [Brief explanation of the drawings]

[0019] [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 diagram of an embodiment of the present invention. [Figure 3] FIG. 3 is a schematic partial cross-sectional view of an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0020] The present invention relates to an improved electrolytic capacitor that exhibits significantly lower abnormal charging current (ACC). More specifically, the present invention relates to an electrolytic capacitor that includes a mordant between a dielectric and a conductive polymer layer, and optionally between or within adjacent conductive polymer layers, where the mordant layer significantly reduces the abnormal charging current (ACC) of the capacitor.

[0021] The present invention will now be described with reference to the drawings, which are an integral part of the specification and are provided to clarify the invention and not to limit it.

[0022] 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, but the anode wire can also be attached to the surface of the anode after pressing, such as by welding. A dielectric 16 is formed on the surface of the anode. While shown as a layer of constant thickness, the actual dielectric layer is applied to the interstitial surfaces of the porous monolith. A first mordant layer 21 overlies the dielectric and is disposed between the dielectric and a primary conductive polymer layer 18, which is disposed on the mordant layer and preferably extends into the interstitial surfaces 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, the primary conductive polymer layer is typically applied multiple times. A second mordant layer 20 is optionally formed on or within the primary conductive layer. The mordant layer comprises a mordant compound of Formula A, described herein below, and a crosslinker. A secondary conductive polymer layer 22 is formed on the mordant layer or the primary conductive polymer 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. It is known in the art that attaching leads to conductive polymer layers can be difficult, and an adhesive layer is typically used to ensure 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 electrically insulating resin 30 is optionally, but preferably, surrounding all but the bottom and anode leads of the cathode and anode leads.

[0023] An embodiment of the present invention is shown schematically in Figure 3. In Figure 3, an anode 12 has a dielectric 16 thereon, the dielectric being formed on the gap surface of the anode. A first mordant layer 21 is provided on the dielectric, preferably extending into the gap surface of the anode to form a coating on the dielectric. A primary conductive polymer layer 18 forms a coating on the first mordant layer 21. In one embodiment, coated on the primary conductive polymer layer is a mordant 20. 1 ~20 n , a secondary conductive polymer layer 21 1 ~22 n and the number n of alternating layers of mordant and secondary conductive polymer layers is at least 1, and preferably at least 2 to 20 or less.

[0024] Referring to FIG. 2, the process for forming an electrolytic capacitor is described. In FIG. 2, the process for forming an electrolytic capacitor is illustrated in a flow chart. An anode is provided at 40. The anode can be a foil, or can be prepared by pressing a powder. A solid 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 general methods known to those skilled in the art that are suitable for demonstrating the present invention. A mordant layer is formed on the dielectric at 43. A primary conductive polymer layer is formed on the mordant layer 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 involves polymerization of a monomer in the presence of a surface on which the polymer is to be formed, and is well known to those skilled in the art. In this case, the surface is a 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. A first mordant layer and a second mordant layer are independently formed by applying a solution containing a mordant compound defined by Formula A and a crosslinker, followed by drying. The first mordant layer and the optional second mordant layer may contain the same compound defined by Formula A, or they may be different. The solvent for applying the first mordant layer is not particularly limited, although water is an illustrative example of the present invention. The second mordant layer may be formed by a single application of the solution or successive applications. 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 a conductive polymer having an average particle size of at least 50 nm to 200 nm.The secondary conductive polymer layer is preferably formed in multiple applications of slurry. The sequential formation of secondary mordant layers and secondary conductive polymer layers is repeated n times until the desired number of alternating layers is reached. An adhesive layer is preferably formed on the terminal secondary conductive polymer layer at 50, the adhesive 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 the attachment of a cathode external terminal, an anode external terminal, and a resin enclosure. Testing and any electrical or physical processing may also be included as part of this completion step.

[0025] Each secondary conductive polymer layer may include multiple sublayers with a primer layer between them. It is known in the art that primer layers may include a crosslinker or a weak ionic acid between adjacent conductive polymer sublayers to improve interlayer adhesion. Suitable primer layers for demonstrating the present invention are taught in U.S. Patent Nos. 8,882,856, 9,761,347, 9,761,378, 10,109,428, and 10,643,796, each of which is incorporated herein by reference. A particularly suitable primer is an amine salt selected from an amine and a weak acid.

[0026] 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. While not limited thereto, the benefits of the present invention are most readily observed in powders with high charge densities, such as those greater than 50,000 CV / g. Below about 50,000 CV / g, problems related to power cycling do not occur frequently, and the benefits offered by the present invention are not readily apparent. The higher the powder charge density, the more readily the benefits of the present invention become apparent. Particularly preferred powders have charge densities greater than about 100,000 CV / g, preferably greater than 200,000 CV / g, and more preferably between about 250,000 CV / g and about 350,000 CV / g.

[0027] The anode wire may be embedded in or attached to the anode, with embedded anode wire being preferred. The material of construction of the anode wire is not particularly limited, but the anode wire is preferably the same material as the anode for ease of manufacture.

[0028] The dielectric and the method for forming the dielectric are not particularly limited herein. A particularly suitable dielectric is an oxide of the anode in view of manufacturing.

[0029] 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 pre-polymerized conductive polymer having a small average particle size of less than about 20 nm, or more preferably a soluble conductive polymer.

[0030] It is hypothesized that the in situ formed conductive polymer will more effectively penetrate the interstices of the porous anodized anode, thereby forming an improved capacitor.

[0031] A soluble conductive polymer is a conductive polymer that is completely dissolved in a solvent or solvent mixture without detectable particles, with below about 1 nm being considered below the detection limit for typical particle sizes.

[0032] The solvent for the soluble conductive polymer can be water, an organic solvent, or a mixture of water and a miscible solvent such as an alcohol, or a non-hydroxy polar solvent such as dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), or dimethyl acetamide (DMAc).

[0033] Soluble conductive polymers are believed to fill the pores of the anode as effectively as conductive polymers formed by in situ methods and better than conductive polymer dispersions 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.

[0034] The mordant layer comprises a mordant compound of Formula A and a crosslinker, where Formula A is defined by the following: wherein R1 and R2 are independently selected from H, a cation, a linear alkyl, a cyclic alkyl, or a substituted alkyl having 1 to 10 carbon atoms; R3 is selected from -CR4R5R6; R4 represents hydrogen, an alkyl having 1 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms; and R4 and R5 taken together represent a cyclic alkyl, or a substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) n R5 represents an alkyl having 1 to 20 carbon atoms or an aryl having 6 to 20 carbon atoms, and R4 and R5 together represent a cyclic alkyl, a substituted cyclic alkyl, or (-CR6OP(O)OR1OR2) n wherein R6 represents hydrogen, alkyl having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms; and n is an integer of 1 to 20.

[0035] [ka]

[0036] A preferred embodiment of the mordant compound is represented by the following formula: 13 ~R 18 are each independently H, -PO(OH)2, or -POOR 19 Selected from R 7 ~R 12 are each independently H or R 7 ~R 12 may each be captured by one adjacent group representing an alkene, and R 19are each independently H, alkyl, or substituted alkyl having 1 to 10 carbon atoms, provided that R 13 ~R 18 At least one of the groups is —PO(OH)2.

[0037] [ka]

[0038] Examples of mordant compounds of Formula A include orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, tri- or tetrapolyphosphoric acid, vinylphosphonic acid, polyvinylphosphoric acid, allylphosphonic acid monoammonium salt, 11-phosphonoundecyl acrylate, 2-hydroxyethyl methacrylate phosphate, phytic acid, phytic acid sodium salt, inositol phosphate, ethyl dihydrogen phosphate, diethyl hydrogen phosphate, triethyl phosphate, trimetaphosphate, adenosine monophosphate, diphosphate, or triphosphate, organic phosphates, and the like.

[0039] Crosslinkers include carboxylic acid, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic anhydride, silane, oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, dicyclopentadiene-based unsaturated, unsaturated C 12 ~C 22 Fatty acid ester, unsaturated C 12 ~C 22The oligomer or polymer containing one or more functional groups 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, phenolic acids, epoxies, butyrals, 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 oligomer or polymer containing multifunctional or multiple reactive groups preferably contains at least one carboxylic acid group and at least one hydroxyl group. Particularly suitable oligomers or polymers containing multifunctional reactive groups are polyesters containing carboxyl or hydroxyl functionality. In addition to the oligomer or polymer, inorganic particles with surface functional groups are also available.

[0040] Crosslinking agents include organometallic compounds, epoxy compounds, inorganic oxides, etc. Particularly suitable crosslinking agents include melamines, isocyanates, epoxies, hexamethoxymelamines, glyoxals, furfural anhydride, melamine formaldehyde condensates, divinyl sulfones, and epoxy compounds.

[0041] Particularly preferred organometallics are selected from organofunctional silanes, titanates, and the like.

[0042] 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.

[0043] An exemplary organofunctional silane has the formula XR1Si(R3) 3-n (R2) nwherein X is an organofunctional group selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, methacryloxy, ester, alkyl, and the like; and R is an aryl or alkyl (CH). m wherein m is 0 to 14; R2 is individually a hydrolyzable functional group selected from the group consisting of alkoxy, acyloxy, halogen, amine, or hydrolysis products thereof; R3 is individually an alkyl functional group having 1 to 6 carbon atoms; and n is 1 to 3.

[0044] The organofunctional silanes can also be bipodal and have the formula Y(Si(R) 3-n (R2) n )2, where Y is any organic moiety containing reactive or non-reactive functional groups, such as alkyl, aryl, sulfide, or melamine, and R3, R2, and n are as defined above. The organofunctional silane can also be multifunctional or polymeric silanes, such as silane-modified polybutadiene or silane-modified polyamine.

[0045] 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, and the like. These examples are used to illustrate the invention and should not be considered conclusive. 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. These examples are used to illustrate the invention and should not be considered conclusive.

[0046] Particularly suitable organofunctional silanes are glycidyl silanes defined by the formula below, where R1 is alkyl having 1 to 14 carbon atoms, more preferably selected from methyl, ethyl, and propyl, and R2 is independently alkyl or substituted alkyl having 1 to 6 carbon atoms.

[0047] [ka]

[0048] A particularly suitable glycidyl silane is 3-glycidoxypropyltrimethoxysilane, defined by the formula below, and for convenience referred to herein as "Silane A."

[0049] [ka]

[0050] Particularly preferred organometallics are neoalkoxy titanates such as titanium IV 2,2(bis-2-propenolate methyl)butanolate, trisneodecanoate-O, titanium IV 2,2(bis-2-propenolate methyl)butanolate, iris(dodecyl)benzenesulfonate-O, titanium IV 2,2(bis-2-propenolate methyl)butanolate, tris(dioctyl)phosphate-O, titanium IV 2,2(bis-2-propenolate methyl)tris(dioctyl)pyrophosphatebutanolate-O, titanium IV 2,2(bis-2-propenolate methyl)butanolate, tris(2-ethylenediamino)ethylate, and titanium IV 2,2(bis-2-propenolate methyl)butanolate, and tris(3-amino)phenylate are representative neoalkoxy titanates and their derivatives.

[0051] Crosslinkers having at least two epoxy groups are referred to herein as epoxy crosslinking compounds and are defined by the following formula, where X is alkyl or a substituted alkyl having 0 to 14 carbon atoms, preferably 0 to 6 carbon atoms, aryl or a substituted aryl, ethylene ether or a substituted ethylene ether, polyethylene ether or a substituted polyethylene ether having 2 to 20 ethylene ether groups, or a combination thereof. An especially preferred substituent is an epoxy group.

[0052] [ka]

[0053] 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, trimethylolpropane polyglycidyl ether, and the like. ethers, sorbitol diglycidyl ether (sorbitol DGE), sorbitol polyglycidyl ethers, 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-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, 4-vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, maleimide-epoxy compounds, and the like.

[0054] Suitable epoxy crosslinking compounds are glycidyl ethers defined by the following formula:

[0055] [ka]

[0056] In the formula, R3 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, hydroxy, or a group represented by the following formula, or -(CHOH) X CH2OH, where X is alkyl substituted with a group selected from 1 to 14.

[0057] [ka]

[0058] Particularly suitable glycidyl ethers are represented by the formula:

[0059] [ka] EGDGE: Ethylene glycol diglycidyl ether

[0060] [ka] wherein n is an integer of 1 to 220. PEGDGE: Polyethylene glycol diglycidyl ether

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

[0062] [ka] GDGE: glycerol diglycidyl ether

[0063] [ka] Sorbitol DGE: Sorbitol diglycidyl ether

[0064] Mixtures of cross-linking agents may also be used.

[0065] The secondary conductive polymer layer is formed from a slurry containing a prepolymerized polymer of polythiophene and, optionally, a dopant such as styrene sulfonic acid or a polymer containing styrene sulfonic acid groups. A preferred polymerization method uses a stata screen that provides uniform droplet sizes resulting in average polymer particle sizes of at least about 50 nm to about 200 nm, more preferably less than 150 nm, and even more preferably less than 100 nm.

[0066] A polythiophene monomer suitable for polymerization is shown as polymerized below in Formula B, where R 14 and R 15 are independently linear or branched C1 to C 16 Alkyl or C2-C 18 Alkoxyalkyl, C3-C8 cycloalkyl, phenyl or benzyl substituted or unsubstituted with C1-C6 alkyl, C1-C6 alkoxy, halogen, or OR 17 or R 14 and R 15 are collectively a straight-chain C1-C6 alkylene, C1-C6 alkoxy, halogen, C3-C8 cycloalkyl, phenyl, benzyl, C1-C4 alkylphenyl, C1-C4 alkoxyphenyl, halophenyl, C1-C4 alkylbenzyl, C1-C4 alkoxybenzyl, halobenzyl, or a 5-, 6-, or 7-membered heterocyclic structure containing two oxygen atoms, which may or may not be substituted with C1-C6 alkyl. 17 is hydrogen, straight chain or branched C1-C 16 Alkyl, C2-C 18 represents phenyl or benzyl, which may or may not be substituted with alkoxyalkyl, C3-C8 cycloalkyl, or C1-C6 alkyl; X is S; and n represents that the compound of formula B is a polymer having a range of molecular weights, generally n is an integer from 2 to a number sufficient to reach a molecular weight of about 500,000.

[0067] [ka]

[0068] R in Formula B 14 and R 15 is preferably selected so as to inhibit polymerization at the β-site of the ring, since it is most preferable that polymerization proceed only at the α-site. 14 and R 15 is more preferably not hydrogen, and R 14 and R 15 It is more preferred that R is an α-director where ether bonds are preferred over alkyl bonds. 14 and R 15 is most preferably small to avoid steric interference.

[0069] In a particularly preferred embodiment, R of formula B 14 and R 15 are collectively referred to as -O-(CHR 18 ) m -O-, where m is an integer from 1 to 5, most preferably 2, and each R 4 are independently hydrogen, straight-chain or branched C1-C 18 Alkyl radicals, C5-C 12 Cycloalkyl radicals, C6-C 14 Aryl radicals, C7-C 18 an aralkyl radical, or a C1-C4 hydroxyalkyl radical, 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; a hydroxyl radical; 4 is -(CHR 19 ) a -R 19 , -O(CHR 19 ) a R 20 , -CHO(CHR 19 ) a R 20 , -CH2O(CH2CHR 19 O) a R 20 Selected from R18 R is a functional group selected from the group consisting of hydroxyl, carboxyl, amine, epoxy, amide, imide, anhydride, hydroxymethyl, alkene, thiol, alkyne, azide, sulfonic acid, benzenesulfonic acid sulfate, SO3M, silane, acrylate, and phosphate. 19 R is H or an alkyl chain containing 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. 20 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, epoxy, anhydride, silane, acrylate, and phosphate. a is an integer from 0 to 10. M is H or a cation preferably selected from ammonia, sodium, or potassium.

[0070] A particularly suitable polymer is 3,4-polyethylenedioxythiophene (PEDOT), prepared from the monomer 3,4-ethylenedioxythiophene (EDOT).

[0071] 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, salts), poly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-yl)methoxy)-1-propane-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(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-sulfonic acid aniline), poly(3-sulfonic acid aniline), etc.

[0072] 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).

[0073] The insulating resin is not particularly limited in this specification, and a non-conductive compatible resin is suitable for demonstrating the present invention. If the electrolytic capacitor is embedded or housed, the resin is optional.

[0074] Comparative Example 1: A series of tantalum anodes (330 microfarads, 16V rated voltage) were prepared. The tantalum was anodized to form a dielectric on the tantalum anode. The primary conductive polymer was formed by immersing the anode in the oxidizing agent iron tosylate, followed by immersion in EDOT monomer, drying, and rinsing. This process was repeated several times to build up PEDOT within the anode gap. A secondary conductive polymer layer was formed by applying a conductive polymer dispersion containing epoxy and silane compounds. After drying, alternating layers of amine salt and secondary conductive polymer dispersion were applied, and this process was repeated four to five additional times. After rinsing and drying the anode with the conductive polymer layer, successive graphite and silver layers were coated to form solid electrolytic capacitors. The components were assembled and packaged. The capacitance and ESR of the packaged components were measured.

[0075] Example 1: A series of solid electrolytic capacitors were prepared in the same manner as Comparative Example 1, except that a solution containing phytic acid silane was applied between the primary and secondary conductive polymers.

[0076] Example 2: A series of solid electrolytic capacitors were prepared in a manner similar to Comparative Example 1, except that a solution containing phytic acid and silane was applied between the dielectric and the primary conductive polymer, and optionally washed with methanol or water.

[0077] Example 3: A series of solid electrolytic capacitors were prepared in a manner similar to Comparative Example 1, except that a solution containing phytic acid and silane was applied between the dielectric and the primary conductive polymer and on each layer of the primary conductive polymer, and optionally washed with methanol or water.

[0078] [Table 1]

[0079] Comparative Example 2: A series of solid electrolytic capacitors were prepared in the same manner as Comparative Example 1, except that a 470 microfarad, 16V tantalum anode was used.

[0080] Example 4: A series of solid electrolytic capacitors were prepared in a manner similar to Comparative Example 2, except that a solution containing phytic acid and silane was applied onto each layer of the primary conductive polymer, and optionally washed with methanol or water.

[0081] Example 5: A series of solid electrolytic capacitors were prepared in the same manner as Comparative Example 2, except that a solution containing phytic acid and silane was applied between the dielectric and the primary conductive polymer and on each layer of the primary conductive polymer, and optionally washed with methanol or water.

[0082] [Table 2]

[0083] As shown in Tables 1 and 2, the examples including the mordant layer exhibit a reduction in anomalous charging current.

[0084] [Table 3]

[0085] [Table 4]

[0086] As shown in Tables 3 and 4, the examples including the mordant layer showed improved ESR and leakage reliability at high temperature and humidity at rated voltage, which was 55% of the forming voltage.

[0087] The present invention has been described with reference to preferred embodiments, without limitation thereto. Those skilled in the art will recognize further embodiments from the description and appended claims.

Claims

1. An electrolytic capacitor, an anode with a dielectric layer thereon; a first mordant layer is provided on the dielectric layer, the first mordant layer comprising a mordant compound, the mordant compound being phytic acid; An electrolytic capacitor comprising: a primary conductive polymer layer provided on the first mordant layer; and a cross-linking agent cross-linked to the first mordant layer.

2. 10. The electrolytic capacitor of claim 1, wherein the mordant compound further comprises orthophosphoric acid.

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

4. 4. The electrolytic capacitor of claim 3, wherein the valve metal is selected from the group consisting of aluminum, tantalum, and niobium.

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

6. 6. The electrolytic capacitor of claim 5, wherein the anode comprises a powder having a charge density of at least 100,000 CV / g.

7. 7. The electrolytic capacitor of claim 6, wherein the anode comprises a powder having a charge density of at least 200,000 CV / g.

8. 2. The electrolytic capacitor of claim 1, having an abnormal charging current less than 10 times the theoretical value.

9. 9. The electrolytic capacitor of claim 8, having an abnormal charging current less than 5 times the theoretical value.

10. 10. The electrolytic capacitor of claim 9, having an abnormal charging current less than 2x the theoretical value.

11. 10. The electrolytic capacitor of claim 1, having a leakage current of less than 50 microamperes measured at rated voltage for 300 seconds.

12. 10. The electrolytic capacitor of claim 1, having a leakage current of less than 10 microamperes measured at rated voltage for 300 seconds.

13. 10. The electrolytic capacitor of claim 1, having a leakage current of less than 200 microamperes after being subjected to a life test at 105°C for 500 hours at rated voltage and measured for 300 seconds at rated voltage.

14. 10. The electrolytic capacitor of claim 1, having a leakage current of less than 50 microamps after being tested at rated voltage for 500 hours at 105°C and measured at rated voltage for 300 seconds.

15. 10. The electrolytic capacitor of claim 1, having an ESR shift of less than 15% after being subjected to a 60[deg.] C. / 90% RH humidity load for 1000 hours.

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

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

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

19. The crosslinking agent may be a carboxylic acid, a hydroxyl, an amine, an epoxy, an anhydride, an isocyanate, an imide, an amide, a carboxyl, a carboxylic acid anhydride, a silane, an oxazoline, a (meth)acrylate, a vinyl, a maleate, a maleimide, an itaconate, an allyl alcohol ester, a dicyclopentadiene-based unsaturated, an unsaturated C １２ ~C ２２ Fatty acid ester, unsaturated C １２ ~C ２２ 10. The electrolytic capacitor of claim 1, having a 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, phenolic acids, epoxies, butyrals, and mixtures thereof.

20. 20. The electrolytic capacitor of claim 19, wherein the cross-linking agent comprises at least one amine group.

21. 20. The electrolytic capacitor of claim 19, wherein the cross-linking agent comprises at least one selected from the group consisting of melamine, isocyanate, epoxy, hexamethoxymelamine, glyoxal, furfural anhydride, melamine formaldehyde condensate, divinyl sulfone, and epoxy compounds.

22. 2. The electrolytic capacitor according to claim 1, wherein the cross-linking agent is an organometallic compound.

23. The organometallic compound has the formula XR １ Si(R ３ ) ３－ｎ (R ２ ) ｎ and wherein the organofunctional silane is as defined in wherein X is an organic functional group selected from the group consisting of amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, and methacryloxy; R １ is aryl or alkyl (CH ２ ) ｍ and m is 0 to 14; R ２ are individually hydrolyzable functional groups selected from the group consisting of alkoxy, acyloxy, halogen, amine, or hydrolysis products thereof; R ３ are each an alkyl functional group having 1 to 6 carbon atoms; 23. The electrolytic capacitor according to claim 22, wherein n is 1 to 3.

24. The organometallic compound has the formula Y(Si(R ３ ) ３－ｎ (R ２ ) ｎ ) ２ is defined by wherein Y is an organic moiety with 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 their hydrolysis products; R ３ are each an alkyl functional group having 1 to 6 carbon atoms; 23. The electrolytic capacitor according to claim 22, wherein n is 1 to 3.

25. 23. The electrolytic capacitor of claim 22, wherein the organometallic compound 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.

26. The organometallic compound has the formula 【Chemical 1】 is defined by In the formula, R １ is alkyl having 1 to 14 carbon atoms, and each R ２ and each are an alkyl or a substituted alkyl having 1 to 6 carbon atoms.

27. The crosslinking agent has the formula 【Chemistry 2】 is defined by 20. The electrolytic capacitor according to claim 19, wherein X is alkyl or a substituted alkyl having 0 to 14 carbon atoms, aryl or a substituted aryl, ethylene ether or a substituted ethylene ether, polyethylene ether or a substituted polyethylene ether having 2 to 20 ethylene ether groups, or a combination thereof.

28. 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, trimethylpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol The electrolytic capacitor according to claim 19, wherein the epoxy group is selected from the group consisting of 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, and maleimide-epoxy compounds.

29. The crosslinking agent has the formula 【Chemistry 3】 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, hydroxy, 【Chemistry 4】 - (CH ２ OH) Ｘ CH ２ 20. The electrolytic capacitor of claim 19, wherein X is alkyl substituted with a group selected from the group consisting of OH and 1 to 14.

30. The crosslinking agent is 【Chemistry 5】 【Chemistry 6】 wherein n is an integer from 1 to 220; 【Chemistry 7】 【Chemistry 8】 and 【Chemistry 9】 20. The electrolytic capacitor of claim 19, wherein the electrolytic capacitor is selected from the group consisting of:

31. 10. The electrolytic capacitor of claim 1, further comprising a second mordant layer, the second mordant layer being disposed between adjacent conductive polymer layers or incorporated into a secondary conductive polymer layer.

32. 32. The electrolytic capacitor of claim 31, wherein the second mordant layer independently comprises phytic acid.

33. 32. The electrolytic capacitor of claim 31, wherein the second mordant layer further comprises a second of the cross-linking agents.

34. At least one of the primary conductive polymer layers comprises a polymer defined by Formula B: 【Chemistry 10】 During the ceremony, R １４ and R １５ are independently linear or branched C １ ~C １６ Alkyl or C ２ ~C １８ Alkoxyalkyl, C ３ ~C ８ Cycloalkyl, C １ ~C ６ Phenyl or benzyl, substituted or unsubstituted with alkyl, C １ ~C ６ Alkoxy, halogen, or OR １７ represents, or R １４ and R １５ Collectively, C １ Straight chain C substituted or unsubstituted with C to C alkyl １ ~C ６ Alkylene, 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 an alkoxybenzyl, halobenzyl, or 5-, 6-, or 7-membered heterocyclic structure containing two oxygen atoms; R １７ is hydrogen, linear or branched C １ ~C １６ Alkyl, C ２ ~C １８ Alkoxyalkyl, C ３ ~C ８ Cycloalkyl, C １ ~C ６ represents phenyl or benzyl, which may or may not be substituted by alkyl; 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.

35. R １４ and R １５ are collectively referred to as -O-(CHR １８ ) ｍ represents —O—, m is an integer from 1 to 5, R １８ are independently hydrogen, straight-chain 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, C １ ~C ４ Hydroxyalkyl radical or carboxylic acid, hydroxyl, amine, alkene, acrylate, thiol, alkyne, azide, sulfate, sulfonate, sulfonic acid, imide, amide, epoxy, anhydride, silane, phosphate, hydroxyl, -(CHR ５ ) ａ -R １６ , -O(CHR １９ ) ａ R ２０ , -CH ２ O (CHR １９ ) ａ R ２０ , or CH ２ O (CH ２ CHR １９ O) ａ R ２０ and wherein the functional group is selected from the group consisting of: R １８ 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 silane, acrylate, and phosphate; R １９ is H or an alkyl chain of 1 to 5 carbon atoms unsubstituted or substituted with a functional group selected from the group consisting of carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, epoxy, acrylate, and anhydride; R ２０ 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, which may or may not be substituted with a functional group selected from the group consisting of epoxy, anhydride, silane, acrylate, and phosphate; a is an integer from 0 to 10, 35. The electrolytic capacitor of claim 34, wherein M is H or a cation selected from the group consisting of ammonia, sodium, and potassium.

36. 35. The electrolytic capacitor of claim 34, wherein the polymer is 3,4-polyethylenedioxythiophene.

37. 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,The electrolytic capacitor according to claim 34, wherein the thiophene is selected from the group consisting of poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene), polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-sulfonic acid aniline), and poly(3-sulfonic acid aniline).

38. 35. The electrolytic capacitor of claim 34, 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).

39. 1. A method for forming an electrolytic capacitor, comprising: forming an anode; forming a dielectric on the anode; a first mordant layer is provided on the dielectric layer, the first mordant layer comprising a mordant compound, the mordant compound being phytic acid; forming the first mordant layer comprising a crosslinker; a primary conductive polymer layer on said first mordant layer.

40. 40. The method of forming an electrolytic capacitor of claim 39, wherein the mordant compound further comprises orthophosphoric acid.

41. 40. The method of forming an electrolytic capacitor of claim 39, wherein the anode comprises a valve metal.

42. 42. The method of forming an electrolytic capacitor of claim 41, wherein the valve metal is selected from the group consisting of aluminum, tantalum, and niobium.

43. 40. The method of forming an electrolytic capacitor of claim 39, wherein the anode comprises a powder having a charge density of at least 50,000 CV / g.

44. 44. The method of forming an electrolytic capacitor of claim 43 comprising a powder having a charge density of at least 100,000 CV / g.

45. 45. The method of forming an electrolytic capacitor of claim 44, comprising powder having a charge density of at least 200,000 CV / g.

46. 40. The method of forming an electrolytic capacitor of claim 39, having an anomalous charging current less than 10*theoretical value.

47. 47. The method of forming an electrolytic capacitor of claim 46, having an anomalous charging current less than 5*theoretical value.

48. 48. The method of forming an electrolytic capacitor of claim 47, having an anomalous charging current less than 2*theoretical value.

49. 40. The method of forming an electrolytic capacitor of claim 39 having a leakage current of less than 50 microamps measured at rated voltage for 300 seconds.

50. 50. The method of forming an electrolytic capacitor as recited in claim 49, having a leakage current of less than 10 microamps measured at rated voltage for 300 seconds.

51. 40. The method of forming the electrolytic capacitor of claim 39, wherein the electrolytic capacitor has a leakage current of less than 200 microamps after being subjected to a life test at 105°C for 500 hours at rated voltage and measured for 300 seconds at rated voltage.

52. 52. The method of forming the electrolytic capacitor of claim 51, wherein the electrolytic capacitor has a leakage current of less than 50 microamps after being tested at rated voltage for 500 hours at 105°C and measured at rated voltage for 300 seconds.

53. 40. The method of forming an electrolytic capacitor of claim 39, having an ESR shift of less than 15% after being subjected to 1000 hours of 60°C / 90% RH humidity loading.

54. 40. The method of forming an electrolytic capacitor of claim 39, wherein forming the primary conductive polymer layer comprises in-situ polymerization.

55. 40. The method of forming an electrolytic capacitor of claim 39, wherein forming the primary conductive polymer layer comprises applying a pre-polymerized polymer having a particle size of less than 20 nm.

56. 56. The method of forming an electrolytic capacitor of claim 55, wherein the pre-polymerized polymer has a particle size of less than 1 nm.

57. 56. The method of forming an electrolytic capacitor of claim 55, wherein the pre-polymerized polymer is a soluble polymer.

58. The crosslinking agent may be a carboxylic acid, hydroxyl, amine, epoxy, anhydride, isocyanate, imide, amide, carboxyl, carboxylic acid anhydride, silane oxazoline, (meth)acrylate, vinyl, maleate, maleimide, itaconate, allyl alcohol ester, dicyclopentadiene-based unsaturated, C １２ ~C ２２ Fatty acid ester, unsaturated C １２ ~C ２２ 40. The method of forming an electrolytic capacitor of claim 39, 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-modified silicones, hydroxyethyl cellulose, polyvinyl alcohol, phenolic acids, epoxies, butyrals, and mixtures thereof.

59. 59. The method of forming an electrolytic capacitor of claim 58, wherein the cross-linking agent comprises at least an amine group.

60. 59. The method of forming an electrolytic capacitor of claim 58, wherein the cross-linking agent comprises at least one selected from the group consisting of melamine, isocyanate, epoxy, hexamethoxymelamine, glyoxal, furfural anhydride, melamine formaldehyde condensates, divinyl sulfone, and epoxy compounds.

61. 40. The method of forming an electrolytic capacitor of claim 39, wherein the cross-linking agent is an organometallic compound.

62. The organometallic compound has the formula XR １ Si(R ３ ) ３－ｎ (R ２ ) ｎ and wherein the organofunctional silane is as defined in wherein X is an organic functional group selected from amino, epoxy, anhydride, hydroxy, mercapto, sulfonate, carboxylate, phosphonate, halogen, vinyl, and methacryloxy; R １ is aryl or alkyl (CH ２ ) ｍ and m is 0 to 14; R ２ are individually hydrolyzable functional groups selected from the group consisting of alkoxy, acyloxy, halogen, amine, or hydrolysis products thereof; R ３ are each an alkyl functional group having 1 to 6 carbon atoms; 62. The method for forming an electrolytic capacitor according to claim 61, wherein n is 1 to 3.

63. The organometallic compound has the formula Y(Si(R ３ ) ３－ｎ (R ２ ) ｎ ) ２ is defined by wherein Y is an organic moiety with 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 their hydrolysis products; R ３ are each an alkyl functional group having 1 to 6 carbon atoms; 62. The method for forming an electrolytic capacitor according to claim 61, wherein n is 1 to 3.

64. 62. The method of forming an electrolytic capacitor of claim 61, wherein the organometallic compound 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.

65. The organometallic compound has the formula 【Chemistry 11】 is defined by In the formula, R １ is alkyl having 1 to 14 carbon atoms, and each R ２ is independently an alkyl or a substituted alkyl having 1 to 6 carbon atoms.

66. The crosslinking agent has the formula 【Chemistry 12】 is defined by 40. The method of claim 39, 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 having 2 to 20 ethylene ether groups, or a combination thereof.

67. 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, trimethylpropane polyglycidyl ether, sorbitol diglycidyl ether, sorbitol polyglycidyl ether, 40. The method of forming an electrolytic capacitor of claim 39, 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, and maleimide-epoxy compounds.

68. The crosslinking agent has the formula 【Chemistry 13】 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, hydroxy, 【Chemistry 14】 - (CH ２ OH) Ｘ CH ２ 40. The method of forming an electrolytic capacitor of claim 39, wherein X is alkyl substituted with a group selected from 1-14.

69. The crosslinking agent is 【Chemistry 15】 【Chemistry 16】 wherein n is an integer from 1 to 220; 【Chemistry 17】 【Chemistry 18】 and 【Chemistry 19】 40. The method of forming an electrolytic capacitor of claim 39, wherein the compound is selected from the group consisting of:

70. 40. The method of forming an electrolytic capacitor of claim 39, wherein the mordant layer comprises a mordant compound, phytic acid, and a cross-linking agent in a ratio of at least 1:0.1 to no more than 0.1:

1.

71. 40. The method of claim 39, wherein the mordant layer is formed by adding the mordant compound and the crosslinking agent to a solution containing the mordant compound and the crosslinking agent, followed by drying.

72. 72. The method of claim 71, wherein the mordant layer solution concentration is at least 1% to 50%.

73. 40. The method of forming an electrolytic capacitor of claim 39, further comprising forming a second mordant layer, the second mordant layer being disposed between adjacent conductive polymer layers or incorporated within a conductive polymer layer.

74. 74. The method of forming an electrolytic capacitor of claim 73, wherein the second mordant layer independently comprises phytic acid.

75. 74. The method of forming an electrolytic capacitor of claim 73, wherein the second mordant layer further comprises a second of the cross-linking agents.

76. At least one of the primary conductive polymer layer or the secondary conductive polymer layer comprises a polymer defined by Formula B: 【Chemistry 20】 During the ceremony, R １４ and R １５ are independently linear or branched C １ ~C １６ Alkyl or C ２ ~C １８ Alkoxyalkyl, C ３ ~C ８ Cycloalkyl, C １ ~C ６ Phenyl or benzyl, substituted or unsubstituted with alkyl, C １ ~C ６ Alkoxy, halogen, or OR １７ represents, or R １４ and R １５ Collectively, C １ ~C ６ A linear C substituted or unsubstituted with alkyl １ ~C ６ Alkylene, 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 an alkoxybenzyl, halobenzyl, or 5-, 6-, or 7-membered heterocyclic structure containing two oxygen atoms; R １７ is hydrogen, linear or branched C １ ~C １６ Alkyl, C ２ ~C １８ Alkoxyalkyl, C ３ ~C ８ Cycloalkyl, C １ ~C ６ represents phenyl or benzyl, which may or may not be substituted by alkyl; X is S; 40. The method of forming an electrolytic capacitor of claim 39, wherein n is an integer from 2 to a number sufficient to reach a molecular weight of about 500,000.

77. R １４ and R １５ are collectively referred to as -O-(CHR １８ ) ｍ represents —O—, m is an integer from 1 to 5, R １８ are independently hydrogen, straight-chain 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, C １ ~C ４ Hydroxyalkyl radical or carboxylic acid, hydroxyl, amine, alkene, acrylate, thiol, alkyne, azide, sulfate, sulfonate, sulfonic acid, imide, amide, epoxy, anhydride, silane, phosphate, hydroxyl, -(CHR ５ ) ａ -R １６ , -O(CHR １９ ) ａ R ２０ , -CH ２ O (CHR １９ ) ａ R ２０ , or CH ２ O (CH ２ CHR １９ O) ａ R ２０ and wherein the functional group is selected from the group consisting of: R １８ 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 silane, acrylate, and phosphate; R １９ is H or an alkyl chain of 1 to 5 carbon atoms unsubstituted or substituted with a functional group selected from the group consisting of carboxylic acid, hydroxyl, amine, alkene, thiol, alkyne, azide, epoxy, acrylate, and anhydride; R ２０ 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, which may or may not be substituted with a functional group selected from the group consisting of epoxy, anhydride, silane, acrylate, and phosphate; a is an integer from 0 to 10, 77. The method of forming an electrolytic capacitor of claim 76, wherein M is H or a cation selected from the group consisting of ammonia, sodium, and potassium.

78. 77. The method of forming an electrolytic capacitor of claim 76, wherein the polymer is 3,4-polyethylenedioxythiophene.

79. 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(3,77. The method of forming an electrolytic capacitor according to claim 76, 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-sulfonic acid aniline), and poly(3-sulfonic acid aniline).

80. 77. The method of claim 76, 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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