STABLE SOLID ELECTROLYTE CAPACITOR CONTAINING NANOCOMPOSITE

专利摘要:
A solid electrolyte capacitor includes an anode body, a dielectric covering the anode body, and a solid electrolyte that covers the dielectric. The solid electrolyte includes a nanocomposite that contains a plurality of nanofibrils dispersed within a conductive polymer matrix. The nanofibrils have a relatively small size and a high aspect ratio, which, as discovered by the present inventors, can greatly improve the thermomechanical stability and robustness of the resulting capacitor.
公开号:FR3015106A1
申请号:FR1460706
申请日:2014-11-06
公开日:2015-06-19
发明作者:Ladislav Vilc；Irena Pfitznerova
申请人:AVX Corp；
IPC主号:

专利说明:

[0001] STABLE SOLID ELECTROLYTE CAPACITOR CONTAINING NANOCOMPOSITE Solid electrolyte capacitors (eg, tantalum capacitors) have largely contributed to the miniaturization of electronic circuits and have allowed the use of these circuits in extreme environments. Conventional solid electrolyte capacitors are often formed by compressing a metal powder (eg, tantalum) around a wire, sintering the compressed element, anodizing the sintered anode, and then applying a solid electrolyte . The solid electrolyte layer may be formed from a conductive polymer (e.g., poly (3,4-ethylenedioxythiophene)) as disclosed in US Pat. Nos. 5,457,862 to Sakata et al., 5,473. 503 of Sakata et al., 5,729,428 to Sakata et al. and 5,812,367 to Kudoh et al. The conductive polymer electrolyte of these capacitors has traditionally been formed by sequential soaking in separate solutions containing the ingredients of the polymer layer. For example, the monomer used to form the conductive polymer is often applied in a single solution, while the catalyst and the dopant are applied in a separate solution (s). A problem with this technique, however, is that it is often difficult and expensive to obtain a relatively thick solid electrolyte, which is useful for obtaining good mechanical strength and good electrical performance. Various attempts have been made to address this problem. U.S. Patent No. 6,987,663 to Merker et al., For example, discloses the use of a polymeric outer layer that covers a surface of the solid electrolyte.
[0002] Unfortunately, this technique remains problematic because it is difficult to obtain good adhesion and good mechanical strength of the polymer outer layer to the graphite / silver layer used to finalize the solid electrolyte capacitor.
[0003] As such, it remains currently necessary to provide a liquid electrolytic capacitor which has good mechanical strength and good electrical performance. One embodiment of the present invention discloses a solid electrolyte capacitor that includes an anode body, a dielectric that covers the anode body, and a solid electrolyte that covers the dielectric. The solid electrolyte includes a nanocomposite that contains a plurality of nanofibrils dispersed within a conductive polymer matrix. The nanofibrils have a number average sectional size of about 500 nanometers or less and an aspect ratio of about 25 to about 500.
[0004] Other features and aspects of the present invention are defined in more detail hereinafter. A complete and enabling description of the present invention, including the best embodiment thereof and intended for those skilled in the art, is made more particularly in the remainder of the Memoir, which refers to the appended figure: Figure 1 is a schematic representation of an embodiment of a capacitor that may be formed in accordance with the present invention. The repeated use of reference characters in this memo and in the drawing is intended to represent identical or similar features or elements of the invention. It should be understood by those skilled in the art that the present disclosure is only a description of exemplary embodiments, and is not intended to limit the broader aspects of the present invention, which broader aspects are encompassed. in the build example. As a general rule, the present invention relates to a solid electrolyte capacitor which includes an anode body, a dielectric covering the anode body, and a solid electrolyte which covers the dielectric. The solid electrolyte includes a nanocomposite that contains a plurality of nanofibrils and a conductive polymer matrix. The nanofibrils may be dispersed within the matrix, or present in the nanocomposite as a separate layer. Independently, the nanofibrils have a relatively small size and a high aspect ratio, which, as discovered by the present inventors, can greatly improve the thermomechanical stability and robustness of the resulting capacitor. The nanofibrils may, for example, have a number average sectional size (e.g., a diameter) of about 500 nanometers or less, in some embodiments, from about 1 to about 100 nanometers and in some embodiments from about 2 to about 40 nanometers. The nanofibrils may also have an aspect ratio (average length divided by average diameter) of about 25 to about 500, in some embodiments, from about 50 to about 300, and in some embodiments, about The nanofibrils may, for example, have a number average length of from 0.1 to about 10 micrometers, in some embodiments from about 0.2 to about 5 micrometers and in some embodiments, from about 0.5 to about 3 microns. The average diameter and number average length can be determined by any technique known to those skilled in the art, such as transmission electron microscopy ("TEM") coupled to a software image analysis technique.
[0005] We will now describe various embodiments of the present invention in more detail. I. Nanocomposite As noted above, in some embodiments of the present invention, the nanofibrils can be dispersed within the conductive polymer matrix. In other embodiments, the nanofibrils and the conductive polymer matrix may be present as separate layers of the nanocomposite. In these embodiments, the nanofibril layer may cover the dielectric, and the conductive polymer matrix may cover the nanofibril layer or be positioned between the dielectric and the nanofibril layer.
[0006] Independently, the relative amount of the nanofibrils in the nanocomposite can be selectively controlled to help achieve the desired mechanical properties without having a negative impact on the properties. For example, the nanofibrils may comprise from about 0.5 wt% to about 40 wt%, in some embodiments, from about 1 wt% to about 30 wt%, and in some embodiments, from about 5% by weight to about 20% by weight of the nanocomposite. The conductive polymer matrix may also comprise from about 60% by weight to about 99.5% by weight, in some embodiments, from about 70% by weight to about 99% by weight, and in some embodiments from about 80% by weight to about 95% by weight of the nanocomposite.
[0007] A. Nanofibrils Any of a variety of nanofibrils having the characteristics indicated above can generally be employed in the present invention.
[0008] Examples of these nanofibrils include non-conductive nanofibrils, such as glass nanofibers, mineral nanoparticles (for example, talc, mica, clay, alumina, silica, etc.), and others; conductive nanofibrils, such as carbon black, carbon nanotubes, carbon nanofibers, metal nanopellets, and others; as well as the combinations thereof. Conductive nanofibrils are particularly suitable for minimizing the RSE of the capacitor obtained. In a particular embodiment, for example, carbon nanotubes are employed in the nanocomposite. The term "carbon nanotube" generally refers to a nanostructure containing at least one layer of graphene in the form of a hollow cylinder. The cylinder can be wound at specific and discrete chiral angles and can be capped at one or both ends of fullerene. The carbon nanotubes may contain only a monolayer of graphene, in which case they are known as single wall nanotubes ("SWNT"). The carbon nanotubes can also be a coaxial set of several single wall nanotubes of different diameters, in which case they are generally known as multiwall nanotubes ("MWNTs"). The multi-walled nanotubes particularly suitable for use in the present invention are those which include, for example, from 2 to 100, and in some embodiments, from 5 to 50 coaxial single wall nanotubes. These multi-walled nanotubes are commercially available under the brand name Nanocyl®. Nanocyl® NC210 and NC7000, for example, are multi-walled nanotubes with average diameters of 3.5 nanometers and 9.5 nanometers, respectively (with lengths between 1 and 10 micrometers).
[0009] Any of a variety of known techniques can be used to form carbon nanotubes, such as catalytic carbon vapor deposition. Independently, the carbon nanotubes obtained usually have a high level of carbon purity to provide a more controlled and narrow particle size distribution. For example, the purity of the carbon may be about 80% or more, in some embodiments, about 85% or more, and in some embodiments, about 90% to 100%. If desired, the carbon nanotubes may optionally be chemically modified with functional groups to improve, for example, their hydrophilicity. Suitable functional groups may include, for example, hydroxyl groups, amine groups, thiol groups, hydroxy groups, and the like. B. Conductive Polymer Matrix The conductive polymer matrix generally contains one or more conductive polymers. The conductive polymer (s) employed in the matrix are usually n-conjugated and have an electrical conductivity after oxidation or reduction, such as at least about one electrical conductivity. 1 μS / cm. Examples of these n-conjugated conductive polymers include polyheterocycles (eg, polypyrroles, polythiophenes, polyanilines, etc.), polyacetylenes, poly-p-phenylenes, polyphenolates, and the like. In one embodiment, for example, the polymer is a substituted polythiophene, such as those having the following general structure: wherein, T is 0 or S; D is an optionally substituted C1-C5 alkylene radical (for example, methylene, ethylene, n-propylene, n-butylene, n-pentylene, etc.); R7 is a linear or branched, optionally substituted C1-C18 alkyl radical (for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, 1-methylbutyl , 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.); an optionally substituted C5-C12 cycloalkyl radical (e.g., cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc.); an optionally substituted C6-C14 aryl radical (e.g., phenyl, naphthyl, etc.); an optionally substituted C7-C18 aralkyl radical (e.g., benzyl, o-, m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2-6, 3-4-, 3,5-xylyl, mesityl, etc.); an optionally substituted C1-C4 hydroxyalkyl radical, or a hydroxyl radical; and q is an integer of 0 to 8, in some embodiments, 0 to 2, and in one embodiment, 0; and n is 2 to 5000, in some embodiments 4 to 2000, and in some embodiments 5 to 1000. Examples of substituents for radicals "D" or "R7" include alkyl, cycloalkyl, aryl, aralkyl, alkoxy, halogen, ether, thioether, disulfide, sulfoxide, sulfone, sulfonate, amino, aldehyde, keto, carboxylic acid ester, carboxylic acid, carbonate, carboxylate, cyano, alkylsilane and alkoxysilane, the carboxylamide groups, and the like. Particularly suitable thiophene polymers are those in which "D" is an optionally substituted C2 to C3 alkylene radical. For example, the polymer may be an optionally substituted poly (3,4-ethylenedioxythiophene), which has the following general structure: The methods of forming conductive polymers, as described above, are well known in the art . For example, U.S. Patent No. 6,987,663 to Merker et al. Discloses various techniques for forming substituted polythiophenes from a monomeric precursor. The monomeric precursor may, for example, have the following structure: ## STR3 ## wherein T, D, R 7 and q are defined above, The thiophene monomers particularly suitable are those in which "D" is a radical. optionally substituted C.sub.2 to C.sub.3 alkylene For example, optionally substituted 3,4-alkylenedioxythiophenes may be employed which have the general structure: wherein R 7 and q are as defined above In a particular embodiment, Is 0. A commercially suitable example of 3,4-ethylenedioxthiophene is available from Heraeus Precious Metals GmbH & Co. KG under the designation Clevios ™ M. Other suitable monomers are also disclosed in US Patent Nos. 5,111,327 to Blohm. et al., and 6,635,729 to Groenendaal et al., It is also possible to employ derivatives of these monomers which are, for example, dimers or trimers of the above monomers. Higher molecular weight derivatives, namely, tetramers, pentamers, etc. monomers are suitable for use in the present invention. The derivatives can consist of identical or different monomer units and used in pure form and mixed with each other and / or with the monomers. Oxidized or reduced forms of these precursors may also be employed. Any of a variety of techniques can generally be employed to form the conductive polymer matrix. In a particular embodiment, for example, the conductive polymer (s) can be polymerized in situ on the capacitor by chemical or electrochemical polymerization techniques, optionally in the presence of a dopant. to help increase the conductivity. For example, the nomomer may be polymerized in the presence of a dopant which also has an oxidative capacity in that it includes a cation (eg, transition metal) and an anion (eg, sulfonic acid). For example, the dopant may be a transition metal salt that includes iron (III) cations, such as iron (III) halides (for example, FeCl 3) or iron (III) salts of others. inorganic acids such as Fe (C104) 3 or Fe2 (SO4) 3 and iron (III) salts of organic acids and inorganic acids comprising organic radicals. Examples of iron (III) salts of inorganic acids having organic radicals are the iron (III) salts of sulfuric acid monoesters of C1 to C20 alkanols (eg, iron salt (III)). ) of lauryl sulfate). Similarly, among the examples of iron (III) salts of organic acids are the iron (III) salts of C 1 -C 20 alkane sulfonic acids (for example, methane sulfonic acid, ethane, propane). butane or dodecane); iron (III) salts of aliphatic perfluorosulfonic acids (e.g., trifluoromethane sulfonic acid, perfluorobutane sulfonic acid or perfluorooctane sulfonic acid); iron (III) salts of aliphatic C1-C20 carboxylic acids (e.g., 2-ethylhexylcarboxylic acid); iron (III) salts of aliphatic perfluorocarboxylic acids (e.g., trifluoroacetic acid or perfluorooctane); iron (III) salts of aromatic sulfonic acids optionally substituted by C1-C20 alkyl groups (eg, benzene sulfonic acid, o-toluene sulfonic acid, p-toluene sulfonic acid or dodecylbenzene sulfonic acid) ; iron (III) salts of cycloalkane sulfonic acids (e.g., camphor sulfonic acid); and others. Mixtures of these aforementioned iron (III) salts can also be used. Iron (III) p-toluene sulfonate, iron (III) o-toluenesulfonate and mixtures thereof are particularly suitable. A commercially suitable example of iron (III) p-toluenesulfonate is available from Heraeus Precious Metals GmbH & Co. KG as Clevios ™ C. The monomer and dopant can be applied sequentially or together to initiate the polymerization reaction. in situ. Suitable application techniques for applying these components include screen printing, dipping, electrophoretic coating and spraying. For example, the monomer may be initially mixed with a dopant to form a precursor solution. Once the mixture is formed, it can be applied to the anode member and then allowed to polymerize so as to obtain a conductive coating on the surface. Alternatively, the dopant and the monomer may be applied in sequence. In one embodiment, for example, the dopant is dissolved in an organic solvent (eg, butanol) and then applied as a dipping solution. The anode element can then be dried to remove the solvent. Then, the element can be immersed in a solution containing the monomer. Independently, the polymerization is usually carried out at temperatures of about 10 ° C to about 250 ° C, and in some embodiments, from about 0 ° C to about 200 ° C, depending on the oxidizing agent and the desired reaction time. Suitable polymerization techniques, as described above, may be described in more detail in U.S. Patent No. 7,515,396 to Biler. Other methods of applying such / such a conductive coating (s) can be described in US Pat. Nos. 5,457,862 to Sakata et al., 5,473,503 to Sakata et al. 729,428 to Sakata et al. and 5,812,367 to Kudoh et al. In addition to in situ polymerization, the conductive polymer matrix may also be formed from a pre-polymerized particle dispersion. One advantage of using a dispersion is that it can minimize the presence of ionic species (eg Fe2 + or Fe3 +) produced in conventional in situ polymerization processes. Thus, by applying the conductive polymer in the form of a dispersion, the resulting capacitor can have a relatively high breakdown voltage. The shape of the particles in the dispersion may vary. In a particular embodiment, for example, the particles are spherical in shape. However, it should be understood that other forms are also contemplated by the present invention such as plates, rods, discs, bars, tubes, irregular shapes, etc. The concentration of the particles in the dispersion may vary depending on the desired viscosity of the dispersion and the particular manner in which the dispersion is to be applied to the capacitor. Typically, however, the particles comprise from about 0.1 to about 10% by weight, in some embodiments, from about 0.4 to about 5% by weight, and in some embodiments, about 0.5 to about 4% by weight of the dispersion. Solvent (s) may also be from about 90% by weight to about 99.9% by weight, in some embodiments from about 95% by weight to about 99.6% by weight. and in some embodiments from about 96% by weight to about 99.5% by weight of the dispersion. The nature of the solvent may vary depending on the intended application method. In one embodiment, for example, water may be the main solvent so that the dispersion is considered an "aqueous" dispersion. In these embodiments, the water may be at least about 50% by weight, in some embodiments at least about 75% by weight and in some embodiments from about 90% by weight to about 100%. by weight of the solvent (s) used in the dispersion. In other embodiments, however, organic solvents (e.g., methanol, ethanol, acetone, 2-butanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.) may be employed in the dispersion. For example, organic solvents are the major solvents employed and constitute at least about 50% by weight, in some embodiments at least about 75% by weight and in some embodiments from about 90% by weight to about 100% by weight of the solvent (s) used in the dispersion. The polymer dispersion may also contain a counterion which improves the stability of the particles. That is, the conductive polymer (e.g., polythiophene or derivative thereof) usually has a charge on the main polymer chain that is neutral or positive (cationic). Polythiophene derivatives, for example, usually carry a positive charge in the main polymer chain. In some cases, the polymer may have positive and negative charges in the structural unit, the positive charge being placed on the main chain and the negative charge optionally on the substituents of the "R" radical, such as sulfonate or carboxylate groups. The positive charges of the main chain can be partially or fully saturated with the anionic groups possibly present on the radicals "R". Overall, polythiophenes can in these cases be cationic, neutral or even anionic. Nevertheless, they are all considered cationic polythiophenes since the main chain of polythiophene has a positive charge.
[0010] The counterion may be a monomeric or polymeric anion which counteracts the charge of the conductive polymer. Polymeric anions may, for example, be anions of polymeric carboxylic acids (e.g., polyacrylic acids, polymethacrylic acids, polymaleic acids, etc.); polymeric sulfonic acids (e.g., polystyrene sulfonic acids ("PSS"), polyvinyl sulfonic acids, etc.); and others. The acids may also be copolymers, such as copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene. Likewise, suitable monomeric anions include, for example, sulfonic acids as described above.
[0011] When employed, the weight ratio of these counterions to conductive polymers in the dispersion and in the resulting layer is typically from about 0.5: 1 to about 50: 1, in some embodiments. from about 1: 1 to about 30: 1, and in some embodiments from about 2: 1 to about 20: 1. The weight of the electrically conductive polymers corresponding to the aforementioned weight ratios refers to the weighted portion of the monomers used, considering that complete conversion occurs during the polymerization.
[0012] In addition to the conductive polymer (s) and the possible counter-ion (s), the dispersion may also contain one or more binders to further improve the adhesive nature of the polymer layer and also increase the stability of the particles inside the dispersion. The binders may be organic in nature, such as polyvinyl alcohols, polyvinylpyrrolidones, polyvinyl chlorides, vinyl polyacetates, vinyl polybutyrates, polyacrylic acid esters, polyacrylic acid amides, polymethacrylic acid, polymethacrylic acid amides, polyacrylonitriles, styrene / acrylic acid ester, vinyl acetate / acrylic acid ester and ethylene / vinyl acetate copolymers, polybutadienes, polyisoprenes, polystyrenes, polyethers, polyesters, polycarbonates, polyurethanes, polyamides, polyimides, polysulfones, melamine formaldehyde resins, epoxy resins, silicone resins or celluloses. Crosslinking agents can also be used to improve the adhesiveness of the binders. These crosslinking agents may include, for example, melamine compounds, masked isocyanates or functional silanes, such as 3-glycidoxypropyltrialkoxysilane, tetraethoxysilane and tetraethoxysilane hydrolyzate or crosslinkable polymers, such as polyurethanes, polyacrylates or polyolefins, and others. The polymeric dispersion can be applied to the element using a variety of known techniques, such as spin coating, impregnation, casting, drip, injection, spraying, doctoring, painting, printing, for example, inkjet printing, screen printing or stamping) or soaking. Although it may vary depending on the application technique employed, the viscosity of the dispersion is typically from about 0.1 to about 100,000 mPa-s (measured at a shear rate of 100 seconds). 1), in some embodiments, from about 1 to about 10,000 mPa-s, in some embodiments, from about 10 to about 1500 mPa-s, and in some embodiments, from about 100 at about 1000 mPa-s. Once applied, the layer can be dried and washed. Regardless of how the conductive polymer matrix is formed, any of a variety of techniques can be employed to incorporate the nanofibrils into the capacitor. For example, the nanofibrils can simply be added as an aqueous dispersion, and the conductive polymer matrix can then be applied. Alternatively, the nanofibrils may be mixed with the solution or dispersion used to form the polymer matrix. In a particular embodiment, the nanofibrils are mixed with a dispersion containing pre-polymerized conductive polymer particles as described above. To facilitate the application process, the nanofibrils can also be provided in the form of a dispersion. In these embodiments, the nanofibrils are typically from about 0.1 to about 10% by weight, in some embodiments, from about 0.4 to about 5% by weight, and in some embodiments from about 0.5 to about 4% by weight of the dispersion. The solvent (s) may also be from about 90% by weight to about 99.9% by weight, in some embodiments from about 95% by weight to about 99.6% by weight. in some embodiments, from about 96% by weight to about 99.5% by weight of the dispersion. The nature of the solvent may vary as described above. In one embodiment, for example, water may be the main solvent so that the dispersion is considered an "aqueous" dispersion.
[0013] C. Other Components In addition to the nanofibrils and conductive polymer matrix, it should also be understood that the nanocomposite may optionally contain other components. In one embodiment, for example, a crosslinking agent may also be employed in the nanocomposite to improve the degree of adhesion. Suitable crosslinking agents are described, for example, in U.S. Patent Publication No. 2007/0064376 to Merker et al. and include, for example, amines (especially, diamines, triamines, oligomeric amines, polyamines, etc.); polyvalent metal cations, such as salts or compounds of Mg, Al, Ca, Fe, Cr, Mn, Ba, Ti, Co, Ni, Cu, Ru, Ce or Zn, phosphonium compounds, sulfonium compounds , 10 etc. Particularly suitable examples include 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, ethylenediamine, 1,6-hexanediamine, 1,7-heptane diamine, 1,8-octanediamine, and the like. , 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, N, N-dimethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, W, N-tetramethyl-1,4-butanediamine, etc., as well as mixtures thereof. The crosslinking agent is usually applied from a solution or dispersion having a pH of from 1 to 10, in some embodiments from 2 to 7, in some embodiments from 3 to 6, as determined at 25 ° C. Acidic compounds can be employed to help achieve the desired pH level. Examples of solvents or dispersants for the crosslinking agent include water or organic solvents, such as alcohols, ketones, carboxylic esters, and the like. The crosslinking agent can be applied by any known method, such as spin coating, impregnation, molding, drip application, spray application, vapor deposition, sputtering, sublimation, knife coating. , painting or printing, for example, inkjet printing, screen printing or stamping.
[0014] If desired, the nanocomposite may also contain a hydroxy functional nonionic polymer. The term "hydroxy functional" generally means that the compound contains at least one hydroxyl functional group or is capable of having such a functional group in the presence of a solvent. Without wishing to be bound by the theory, it is believed that the hydroxy-functional nonionic polymers can improve the degree of contact between the polymer and the surface of the inner dielectric, which is usually relatively smooth in nature as a result of voltages. higher training. This unexpectedly increases the breakdown voltage and the wet / dry capacitance of the resulting capacitor. In addition, it is believed that the use of a hydroxy-functional polymer having a certain molecular weight can also minimize the probability of chemical decomposition at high voltages. For example, the molecular weight of the hydroxyfunctional polymer may be from about 100 to 10,000 grams per mole, in some embodiments from about 200 to 2,000, in some embodiments, from about 300 to about 1200, and in some embodiments from about 400 to about 800. Any variety of hydroxy functional nonionic polymers can generally be employed for this purpose. In one embodiment, for example, the hydroxy-functional polymer is a polyalkylene ether. Among the polyalkylene ethers are, for example, polyalkylene glycols (for example, polyethylene glycols, polypropylene glycols, polytetramethylene glycols, polyepichlorohydrins, etc.), polyoxetanes, polyphenylene ethers, polyetherketones, and others. Polyalkylene ethers are usually essentially linear nonionic polymers having terminal hydroxy groups. Polyethylene glycols, polypropylene glycols and polytetramethylene glycols (polytetrahydrofurans), which are produced by polyaddition of ethylene oxide, propylene oxide or tetrahydrofuran to water are particularly suitable. The polyalkylene ethers can be prepared by polycondensation reactions from diols or polyols. The diol component may be chosen, in particular, from saturated or unsaturated, branched or unbranched dihydroxy aliphatic compounds containing from 5 to 36 carbon atoms or aromatic dihydroxy compounds, such as, for example, pentane-1,5- diol, hexane-1,6-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes, bisphenol A, diol dimers, hydrogenated diol dimers or even mixtures of the diols mentioned. In addition, polyhydric alcohols may also be used in the polymerization reaction, and in particular glycerol, di- and polyglycerol, trimethylolpropane, pentaerythritol or sorbitol.
[0015] In addition to those noted above, other hydroxy functional nonionic polymers may also be employed in the present invention. Examples of these polymers include, in particular, ethoxylated alkylphenols; ethoxylated or propoxylated C 6 -C 24 fatty alcohols; polyoxyethylene glycol alkyl ethers having the general formula: CH3- (CH2) 10-16- (O-C2F14) 1-25-OH (e.g., octaethylene glycol monododecyl ether and pentaethylene glycol monododecyl ether); polyoxypropylene glycol alkyl ethers having the general formula: CH3- (CH2) 10-16- (O-C3116) 1-25-0H; polyoxyethylene glycol octylphenol ethers having the following general formula: C8H1-7- (C6H4) - (O-C2H4) 1-25-0H (e.g., TritonTM X-100); polyoxyethylene glycol alkylphenol ethers having the following general formula: C9H19- (C6H4) - (O-C2H4) 1-25-OH (e.g., nonoxynol-9); polyoxyethylene glycol esters of C8-C24 fatty acids, such as polyoxyethylene glycol sorbitan alkyl esters (e.g., polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, monooleate of polyoxyethylene (20) sorbitan, PEG-20 methylglucose distearate, PEG-20 methylglucose sesquistearate, PEG-80 castor oil and PEG-20 castor oil, PEG-3 castor oil, PEG 600 dioleate and PEG 400 dioleate) and alkyl esters of polyoxyethyleneglycerol (e.g., polyoxyethylene-glycerol laurate and polyoxyethylene-20 glycerol stearate); polyoxyethylene glycol ethers of C8-C24 fatty acids (e.g., polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearyl ether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether, polyoxyethylene-20 oleyl ether, ether polyoxyethylene-20 isohexadecyl, polyoxyethylene-15 tridecyl ether and polyoxyethylene-6 tridecyl ether); block copolymers of polyethylene glycol and polypropylene glycol (eg, Poloxamers); and others, as well as mixtures thereof.
[0016] II. Capacitor Construction As noted above, the nanocomposite of the present invention is generally incorporated into a solid electrolyte of a capacitor, which covers an anode which contains an anode body and a dielectric. The manner in which the nanocomposite is incorporated into the solid electrolyte may vary depending on the desired application. Nevertheless, various examples of embodiments of the capacitor are described in more detail hereinafter. A. Solid Electrolyte The solid electrolyte of the capacitor may contain one or more conductive polymer layers, at least one of which contains the nanocomposite of the present invention. In a particular embodiment, for example, the solid electrolyte may contain an inner conductive polymer layer and an outer conductive polymer layer. The inner layer is designed to impregnate into the pores of the anode body, while the outer layer is designed to cover the edge region of the capacitor body, thereby increasing the adhesion to the dielectric and resulting in a more robust element. mechanically. It should be understood that the term "external" as used herein simply means that the layer covers the inner layer. Other polymer layers may also be disposed on an outer layer or below the inner layer, as well as between an inner layer and an outer layer. Independently, the conductive polymer employed in at least one of the inner and outer layers is usually in the form of prepolymerized particles, as described above. In one embodiment, for example, the inner layer is formed by the in situ polymerization of a monomer, but the outer layer is formed from prepolymerized particles. In yet other embodiments, the two layers are formed from prepolymerized particles. To allow good impregnation of the anode body, the conductive polymer employed in the inner layer may be of relatively small size, such as an average size (for example, a diameter) of about 1 to about 150 nanometers, in some embodiments, from about 2 to about 50 nanometers, and in some embodiments, from about 5 to about 40 nanometers. Since it is generally supposed to improve the degree of edge coverage, the particles used in the outer layer may be larger in size than those used in the inner layer. For example, the ratio of the average particle size employed in the outer layer to the average particle size employed in the inner layer is typically from about 1.5 to about 30, in some embodiments, about 2 to about 20, and in some embodiments, about 5 to about 15. The particles employed in the dispersion of the outer layer may have an average size of about 50 to about 500 nanometers, in some embodiments, from about 80 to about 250 nanometers, and in some embodiments, from about 100 to about 200 nanometers. It should be understood that multiple internal and external layers may be formed from the dispersions to achieve the total target thickness. For example, the total thickness of the formed inner layers is from about 0.1 to about 5 μm, in some embodiments from about 0.1 to about 3 μm, and in some embodiments from about 0.2 to about 1 μm. Likewise, the total thickness of the outer layers can range from about 1 to about 50 μm, in some embodiments from about 2 to about 40 μm, and in some embodiments from about 5 to about 20 μm. pm. If desired, intermediate layer (s) may also be employed between the inner and outer layers. In one embodiment, for example, an intermediate layer is employed which is formed from a dispersion of pre-polymerized particles in combination with a hydroxy-functional polymer, as described above. In these embodiments, the inner layer and / or outer layer may generally be free of such hydroxy-functional nonionic polymers.
[0017] Regardless of its particular configuration, the nanocomposite of the present invention can generally be employed in any part of the solid electrolyte. In some embodiments, for example, the nanocomposite may be employed to form one or more of the outer layers of the solid electrolyte so as to achieve the desired mechanical strength. Of course, it should be understood that the nanocomposite may also be employed in one or more of the inner layers, one or more of the intermediate layers, as well as combinations of these layers. B. Anode The anode body of the anode can be formed from a valve metal composition. The specific charge of the composition may vary, such as from about 2000 pF * V / g to about 250,000 × 1, F * V / g, in some embodiments, from about 3000 pF * V / g to about 200,000. pF * V / g or higher, and in some embodiments, from about 5000 to about 150,000, F * V / g. As known in the art, the specific charge can be determined by multiplying the capacitance by the anodizing voltage employed, and then dividing this product by the weight of the anodized electrode body. The valve metal composition generally contains a valve metal (i.e., a metal that is capable of oxidizing) or a valve metal compound, such as tantalum, niobium, aluminum, hafnium , titanium, their alloys, their oxides, their nitrides, and others. For example, the valve metal composition may contain an electroconductive niobium oxide, such as a niobium oxide having an atomic ratio of niobium to oxygen of 1: 1.0 ± 1.0, in some embodiments. 1: 1.0 ± 0.3, in some embodiments, 1: 1.0 ± 0.1 and in some embodiments, 1: 1.0 ± 0.05. For example, the niobium oxide can be Nb00.7, Nb01, o, Nb01.1 and Nb02. Examples of such valve metal oxides are disclosed in U.S. Patent Nos. 6,322,912 to Fife; 6,391,275 to Fife et al. ; 6,416,730 to Fife et al. ; 6,527,937 to Fife; 6,576,099 to Kimmel et al. ; 6,592,740 to Fife et al. ; 6,639,787 to Kimmel et al. and 7,220,397 to Kimmel et al., and Schnitter U.S. Patent Application Publication Nos. 2005/0019581; 2005/0103638 to Schnitter et al. and 2005/0013765 of Thomas et al. To form the anode body, a powder of the valve metal composition is generally employed. The powder may contain particles of any of a variety of shapes, such as nodular, angular, flake, etc., as well as mixtures thereof. Some other components may also be included in the powder. For example, the powder may optionally be mixed with a binder and / or lubricant to ensure that the particles adhere properly to each other when pressed to form the anode body. Suitable binders include, for example, polyvinyl butyral; polyvinyl acetate; polyvinyl alcohol; polyvinylpyrollidone; cellulosic polymers, such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroethyl cellulose and methyl hydroxyethyl cellulose; atactic polypropylene, polyethylene; polyethylene glycol (e.g., Carbowax from Dow Chemical Co.); polystyrene, poly (butadiene / styrene); polyamides, polyimides and polyacrylamides, polyethers of high molecular weight; copolymers of ethylene oxide and propylene oxide; fluoropolymers, such as polytetrafluoroethylene, polyvinylidene fluoride and fluoroolefin copolymers; acrylic polymers, such as sodium polyacrylate, lower alkyl polyacrylates, lower alkyl polymethacrylates and copolymers of lower alkyl acrylates and methacrylates; and fatty acids and waxes, such as stearic fatty acids and other soapy fatty acids, vegetable wax, microwaxes (purified paraffins), and the like. The binder can be dissolved and dispersed in a solvent. Examples of the solvent may include water, alcohols, and the like. When used, the percentage of binders and / or lubricants can vary from about 0.1% to about 8% by weight of the total mass. It should be understood, however, that binders and / or lubricants are not necessarily required in the present invention.
[0018] The resulting powder can then be compacted to form a pellet using any conventional powder compression device. For example, a press mold consisting of a single compost press containing a die and one or more punches may be employed. Alternatively, it is possible to use anvil type compaction press molds which use only one die and one lower punch. Single-compost press molds are available in several basic types, such as cam presses, toggle / toggle and eccentric / crank with varying capacities, such as single action, double action, floating die, moving platen, opposite pusher, screw, impact, hot compression, stamping or calibration. The powder can be compacted around an anode wire (eg, tantalum wire). It should further be understood that the anode wire may alternatively be attached (eg, welded) to the anode body following compression and / or sintering of the anode body. After compacting, the obtained anode body can then be cut into any desired shape, such as square, rectangular, circular, oval, triangular, hexagonal, octagonal, heptagonal, pentagonal, etc. The anode body may also have a "fluted" shape in that it contains one or more furrows, grooves, depressions, or indentations to increase the surface-to-volume ratio to minimize the CSR and extend the frequency response of the capacitance. The anode body may then be subjected to a heating step in which most, if not all, of any binder / lubricant is removed. For example, the anode body is usually heated by means of an oven that operates at a temperature of about 150 ° C to about 500 ° C. Alternatively, the binder / lubricant may also be removed by contacting the pellet with an aqueous solution as described in U.S. Patent No. 6,197,252 to Bishop et al. Then, the porous body is sintered to form a solid mass. The temperature, atmosphere, and time of the sintering may depend on a variety of factors, such as the type of anode, the size of the anode, and so on. Typically, the sintering occurs at a temperature of about 800 ° C to about 1900 ° C, in some embodiments, from about 1000 ° C to about 1500 ° C, and in some embodiments, about 1100 ° C to about 1400 ° C, for a period of about 5 minutes to about 100 minutes, and in some embodiments, about 30 minutes to about 60 minutes. If desired, sintering can occur in an atmosphere that limits the transfer of oxygen atoms to the anode. For example, sintering can occur in a reducing atmosphere, such as in a vacuum, an inert gas, hydrogen, etc. The reducing atmosphere can be at a pressure of about 10 Torr to about 2000 Torr, in some embodiments from about 100 Torr to about 1000 Torr, and in some embodiments from about 100 Torr to about 930 Torr. Torr. Mixtures of hydrogen and other gases (eg, argon or nitrogen) may also be employed. The anode obtained may have a relatively low carbon and oxygen content. For example, the anode may have no more than about 50 ppm carbon, and in some embodiments, no more than about 10 ppm carbon. Similarly, the anode can have no more than about 3500 ppm oxygen, in some embodiments, no more than about 3000 ppm oxygen, and in some embodiments, about 500 to about 2500 ppm of oxygen. The oxygen content can be measured by means of a LECO oxygen analyzer and includes oxygen in the natural oxide on the tantalum surface and oxygen in bulk in the tantalum particles. The bulk oxygen content is monitored by period of tantalum crystal lattice, increasing linearly with increasing oxygen content in tantalum until the solubility limit is reached. This method has been described in "Critical Oxygen Content In Porous Anodes Of Solid Tantalum Capacitors", Pozdeev-Freeman et al., Journal of Materials Science: Materials In Electronics 9, (1998) 309-311 where X-ray diffraction analysis (XRD) was used to measure the period of the tantalum crystal lattice. The oxygen in the sintered tantalum anodes may be limited to a thin natural surface oxide, while the tantalum mass is substantially free of oxygen. As noted above, an anode wire may also be connected to the anode body extending in a longitudinal direction therefrom.
[0019] The anode wire may be in the form of a cable, a sheet, etc., and may be formed from a valve metal compound, such as tantalum, niobium, oxide niobium, etc. The wire connection can be accomplished by known techniques, such as by welding the wire to the body or incorporating it into the anode body during formation (for example, prior to compacting and / or sintering ).
[0020] A dielectric also covers or covers the anode body. The dielectric may be formed by anodic oxidation ("anodizing") of the sintered anode so that a dielectric layer is formed above and / or inside the anode body. For example, a tantalum anode body (Ta) may be anodized to tantalum pentoxide (Ta2O5). Typically, anodizing is performed by initially applying a solution to the anode, such as by plunging the anode body into the electrolyte. A solvent is generally employed, such as water (e.g., deionized water). To improve the ionic conductivity, it is possible to employ a compound that is capable of dissociating in the solvent to form ions. Examples of these compounds include in particular the acids, as described below with respect to the electrolyte. For example, an acid (especially, a phosphoric acid) may comprise from about 0.01% by weight to about 5% by weight, in some embodiments from about 0.05% by weight to about 0.8% by weight. % by weight, and in some embodiments, from about 0.1% by weight to about 0.5% by weight of the anodizing solution.
[0021] If desired, acid mixtures may also be employed. Current is passed through the anodizing solution to form the dielectric layer. The value of the formation voltage controls the thickness of the dielectric layer. For example, the power supply can initially be set to a galvanostatic mode until the required voltage is reached. Then, the power supply can be switched to a potentiostatic mode to ensure that the desired dielectric thickness is formed over the entire surface of the anode body. Of course, other known methods may also be employed, such as pulse or step potentiostatic methods. The voltage at which the anodic oxidation occurs is typically from about 4 to about 250 volts, and in some embodiments from about 9 to about 200 volts, and in some embodiments from about 20 to about 200 volts. at about 150 V. During oxidation, the anodizing solution can be maintained at a high temperature, such as about 30 ° C or higher, in some embodiments, from about 40 ° C to about 200 ° C. C, and in some embodiments, from about 50 ° C to about 100 ° C.
[0022] The anodic oxidation can also be carried out at room temperature or at a lower temperature. The resulting dielectric layer may be formed on a surface of the anode body and within its pores.
[0023] C. Other Layers If desired, the capacitor may also contain other layers as known in the art. For example, an adhesion layer may optionally be formed between the dielectric and the solid electrolyte, such as a layer made of a relatively insulating resin material (natural or synthetic). These materials may have a specific resistivity greater than about 10 S2-cm, in some embodiments greater than about 100, in some embodiments greater than about 1000 S2-cm, in some embodiments greater than about 1 x 105 S2. in some embodiments, greater than about 1 x 1010 S2-cm. Some resinous materials that can be used in the present invention include, but are not limited to, polyurethane, polystyrene, unsaturated or saturated fatty acid esters (eg, glycerides), and others. For example, suitable fatty acid esters include, but are not limited to, lauric acid esters, myristic acid esters, palmitic acid esters, stearic acid esters, oleostearic acid esters, oleic acid esters, linoleic acid, aleuritic acid, shellolic acid, and others. These fatty acid esters are particularly useful when used in relatively complex combinations to form a "drying oil", which allows the resulting film to rapidly polymerize into a stable layer. These drying oils may include mono-, di- and / or tri-glycerides, which have a glycerol backbone respectively comprising one, two and three fatty acyl residues which are esterified. For example, certain suitable drying oils that can be used include, but are not limited to, olive oil, linseed oil, castor oil, china oil, soybean oil and the like. shellac. These and other protective coating materials are described in more detail in U.S. Patent No. 6,674,635 to Fife et al. If desired, it is also possible to apply to the element a layer of carbon (for example, graphite) and a layer of silver, respectively. The silver coating may, for example, act as a solderable conductor, a contact layer and / or a charge collector for the capacitor and the carbon coating may limit the contact of the silver layer with the solid electrolyte . These coatings may cover some or all of the solid electrolyte.
[0024] D. Assembly The capacitor may also have terminations, particularly when used in surface mount applications. For example, the capacitor may contain an anode termination to which the anode wire of the capacitor element is electrically connected and a cathode termination to which the cathode of the capacitor element is electrically connected. Any conductive material may be used to form terminations, such as a conductive metal (eg, copper, nickel, silver, nickel, zinc, tin, palladium, lead, copper, aluminum, molybdenum, titanium, iron, zirconium, magnesium and alloys thereof). Particularly suitable metals include, for example, copper, copper alloys (for example, copper-zirconium, copper-magnesium, copper-zinc or copper-iron), nickel and nickel alloys (e.g. , nickel-iron). The thickness of the terminations is generally chosen to minimize the thickness of the capacitor. For example, the thickness of the termini can range from about 0.05 to about 1 millimeter, in some embodiments, from about 0.05 to about 0.5 millimeter, and from about 0.07 to about 0 , 2 millimeters. An example of a conductive material is a copper-iron alloy metal plate available from Wieland (Germany). If desired, the surface of the terminations may be electrogalvanized with nickel, silver, gold, tin, etc., as known in the art to ensure that the final element is mountable on the printed circuit board. In a particular embodiment, both surfaces of the terminations are plated with thin films of nickel and silver, respectively, while the mounting surface is also plated with a solder layer of tin.
[0025] Fig. 1 shows an embodiment of an electrolytic capacitor 30 which includes an anode termination 62 and a cathode termination 72 in electrical connection with a capacitor element 33. The capacitor element 33 has an upper surface 37, a surface 39, a front surface 36 and a rear surface 38. Although it may be in electrical contact with any of the surfaces of the capacitor element 33, the cathode termination 72 in the illustrated embodiment is in contact with the lower surface 39 and the rear surface 38. More specifically, the cathode termination 72 contains a first component 73 positioned substantially perpendicular to a second component 74. The first component 73 is in electrical contact and generally parallel to the lower surface 39 of the capacitor element 33. The second component 74 is in electrical contact and generally p arallel to the rear surface 38 of the capacitor element 33. Although shown as being integral, it should be understood that these parts may alternatively be separate parts which are connected together, either directly or via an additional conductive element ( for example, metal). On the other hand, in some embodiments, it should be understood that the second component 74 can be removed from the cathode termination 72. The anode termination 62 likewise contains a first component 63 positioned substantially perpendicular to a second component 64. The first component 63 is in electrical contact and generally parallel to the lower surface 39 of the capacitor element 33. The second component 64 contains a region 51 which comprises an anode wire 16. In the illustrated embodiment, the region 51 has a "U-shape" to further improve the surface contact and mechanical stability of the wire 16.
[0026] The terminations may be connected to the capacitor element using any technique known in the art. In one embodiment, for example, a lead frame that defines the cathode termination 72 and the anode termination 62 may be provided. To attach the electrolytic capacitor element 33 to the lead frame, a conductive adhesive may initially be applied to a surface of the cathode termination 72. The conductive adhesive may include, for example, conductive metal particles containing a resin. The metal particles can be silver, copper, gold, platinum, nickel, zinc, bismuth, etc. The resin composition may include a thermoset resin (e.g., an epoxy resin), a curing agent (e.g., an acid anhydride), and a coupling agent (e.g., a silane coupling agent). Suitable conductive adhesives can be described in U.S. Patent Publication No. 2006/0038304 to Osako et al. Any of a variety of techniques can be used to apply the conductive adhesive to the cathode termination 72. For example, printing techniques can be employed because of the practical and cost saving advantages they provide. exhibit. Several methods can generally be employed to attach terminations to the capacitor. In one embodiment, for example, the second component 64 of the anode termination 62 and the second component 74 of the cathode termination 72 are initially flexed upward to the position shown in FIG. The capacitor element 33 is positioned on the cathode termination 72 so that its lower surface 39 contacts the adhesive and the anode wire 16 is received by the upper U-region 51. If desired, an insulating material ( not shown), such as a plastic pad or ribbon, can be positioned between the lower surface 39 of the capacitor element 33 and the first component 63 of the anode termination 62 to electrically isolate the anode and cathode. The anode wire 16 is then electrically connected to the region 51 using any technique known in the art, such as mechanical welding, laser welding, conductive adhesives, etc. For example, the anode wire 16 may be soldered to the anode termination 62 by means of a laser. Lasers generally contain resonators that contain a laser medium capable of releasing stimulated emission photons and a source of energy that excites the elements of the laser medium. A suitable type of laser is a laser in which the laser medium is made of yttrium and aluminum garnet (YAG), doped with neodymium (Nd). The excited particles are Nd3 + neodymium ions. The energy source can provide continuous energy to the laser medium to emit a continuous laser beam or energy discharges to emit a pulsed laser beam. Upon electrical connection of the anode lead 16 to the anode termination 62, the conductive adhesive can then be cured. For example, a heat press can be used to apply heat and pressure to ensure that the electrolytic capacitor element 33 adhere adequately to the cathode termination 72 by means of the adhesive. Once the capacitor element is attached, the lead frame is enclosed within a resin housing, which can then be filled with silica and any other known encapsulating material. The length and width of the case may vary depending on the intended application. Suitable enclosures may include, for example, "A", "B", "C", "D", "E", "F", "G", "H", "J", "K", " L "," M "," N "," P "," R "," S "," T "," V "," W "," Y "," X "or" Z "(AVX Corporation) . Regardless of the size of the housing employed, the capacitor element is encapsulated so that at least a portion of the anode and cathode terminations are exposed for mounting on a printed circuit board. As shown in Figure 1, for example, the capacitor element 33 is encapsulated in a housing 28 so that a portion of the anode termination 62 and a portion of the cathode termination 72 are exposed.
[0027] Regardless of the particular way in which it is formed, the resulting capacitor can exhibit excellent electrical properties. The equivalent series resistance ("ESR") may, for example, be about 300 milliohms or less, in some embodiments, about 200 milliohms or less, and in some embodiments, about 1 to about 100 milliohms, as measured with a 2.2 volt DC bias and a 0.5 volt peak-to-peak sinusoidal signal, without harmonic, at a frequency of 100 kHz. On the other hand, the leakage current, which generally refers to the current passing from a conductor to an adjacent conductor through an insulator, can be maintained at relatively low levels. For example, the leakage current may be about 40 pA or less, in some embodiments, about 25 pA or less, and in some embodiments, about 15 pA or less. The numerical value of the capacitor normalized leakage current can likewise be about 0.2 pA / pF * V or less, in some embodiments, about 0.1 pA / pF * V or less, and some embodiments, of about 0.05 pA / pF * V or less, where pA stands for microamperes and pF * V is the product of capacity and rated voltage. RSE values and standard leakage currents can even be maintained at relatively high temperatures. For example, the values may be maintained after reflux (e.g., for 10 seconds) at a temperature of about 100 ° C to about 350 ° C, and in some embodiments from about 200 ° C to about 300 ° C. C (for example, 240 ° C) The capacitor may also have a relatively high "breakdown voltage" (voltage to which the capacitor fails), such as about 35 volts or more, in some embodiments of the invention. about 50 volts or more, and in some embodiments, about 60 volts or more. The capacitor may also have a relatively high percentage of its capacity in the wet state, which allows it to exhibit only a small loss of capacity and / or fluctuation in the presence of atmospheric moisture. This performance characteristic is quantified by the "Wet / Dry Capacity Percentage", which is determined by the equation: Wet / Dry Capacity = (capacity to wet) dry state / wet capacity) x 100 The capacitor of the present invention can have, for example, a wet / dry capacity percentage of about 50% or more, in some cases. embodiments, of about 60% or more, in some embodiments, about 70% or more, and in some embodiments, about 80% to 100%.
[0028] The present invention may be better understood by reference to the following examples. Test Procedures Equivalent Series Resistance (ESR) Equivalent Series Resistance can be measured using a Keithley 3330 Precision LCZ Kelvin Wire with a 2.2 volt DC bias and a peak to peak sine wave of 0.5 volt. The operating frequency can be 100 kHz and the temperature can be 23 ° C + 2 ° C.
[0029] Capacity (CAP) Capability can be measured using a Keithley 3330 Precision LCZ Kelvin wire with a 2.2 volt DC bias and 0.5 volt peak-to-peak sinusoidal signal. The operating frequency can be 120 Hz and the temperature can be 23 ° C + 2 ° C.
[0030] Leakage current (DCL) The leakage current can be measured using a leak-testing device at a temperature of 23 ° C + 2 ° C and at the rated voltage after a minimum of 60 seconds.
[0031] Stability tests were run at the reflux temperature. The CSR, CAP and DCL of an individual capacitor were recorded after every 1st, 2nd and 3rd reflux.
[0032] Example 1 40,000 pFV / g of tantalum powder was used to form anode samples. Each anode sample was embedded with tantalum wire, sintered at 1500 ° C and compressed to a density of 5.3 g / cm 3. The pellets obtained had a size of 1.20 x 1.85 x 2.50 mm. The pellets were anodized at 75 V in a phosphoric acid / water electrolyte having a conductivity of 8.6 mS at a temperature of 85 ° C to form the dielectric layer. A conductive polymer coating was then formed by dipping the anodes in a butanolic solution of iron (III) toluenesulfonate (Clevios ™ C, HC Starck) for 5 minutes and then in 3,4-ethylenedioxythiophene (Clevios ™ M, HC Starck). for 1 minute. After 45 minutes of polymerization, a thin layer of poly (3,4-ethylenedioxythiophene) was formed on the surface of the dielectric. The elements were washed in methanol to remove reaction by-products, anodized in a liquid electrolyte and washed again in methanol. The polymerization cycle was repeated 6 times. Then the elements were immersed in a poly (3,4-ethylenedioxythiophene) dispersed having a solids content of 2% and a viscosity of 20 mPa.s (CleviosTM K, H.C. Starck). During coating, the elements were dried at 125 ° C for 20 minutes. This process was not repeated. Then, the elements were immersed in a poly (3,4-ethylenedioxythiophene) dispersed having a solid content of 2% and a viscosity of 160 mPa.s (CleviosTM K, H.C. Starck). During coating, the elements were dried at 125 ° C for 20 minutes. This process was repeated 8 times. The elements were dipped into a graphite dispersion and dried. Finally, the elements were immersed in a silver dispersion and dried. Multiple elements (250) of capacitors 10 μF / 25V were made in this way. Example 2 Capacitors were formed as described in Example 1 except that a different conductive polymer coating was used. More particularly, after coating with the dispersed poly (3,4-ethylenedioxythiophene), the elements were immersed in multi-walled nanotubes dispersed in an aqueous mixture having a solids content of 2% and a viscosity of 1250 mPa.s (AquacylTM, Nanocyl). During coating, the elements were dried at 125 ° C for 20 minutes. This process was repeated 2 times. The elements were then dipped into a graphite dispersion and dried. Finally, the elements were immersed in a silver dispersion and dried. Multiple elements (250) of capacitors 10 μF / 25V were made in this way.
[0033] Example 3 Capacitors were formed as described in Example 1 except that a different conductive polymer coating was used. More particularly, after coating with the dispersed poly (3,4-ethylenedioxythiophene), the elements were immersed in a dispersion which contained poly (3,4-ethylenedioxythiophene) having a solids content of 2% and a viscosity of 160 mPa.s (CleviosTM). K, HC
[0034] Starck) and multi-walled nanotubes having a solids content of 2% (Nanocyl). During coating, the elements were dried at 125 ° C for 20 minutes. This process was repeated 8 times. The elements were then dipped into a graphite dispersion and dried. Finally, the elements were immersed in a silver dispersion and dried. Multiple elements (250) of capacitors 10 μF / 25V were made in this way. The finished capacitors of Examples 1 to 3 were then tested for their stability characteristics at reflux. The average results of RSE, CAP and DCL are shown below in Tables 1, 2 and 3. Table 1: Temperature stability characteristics (CSR [mS]] 1st 1st 2nd Example 94.5 122, 1 133.7 139.2 Example 2 90.0 104.2 105.0 106.6 Example 3 92.3 119.4 130.5 131.0 Table 2: Stability characteristics at temperature (CAP [AF]) 1st 2nd Example 1 10.14 9.59 9.46 9.35 Example 2 9.80 9.61 9.50 9.41 Example 3 10.16 9.74 9.59 9.47 Table 3: Characteristics Temperature Stability (DCL [A]) 1st 2nd Sem. Example 1 0.147 0.196 0.245 0.270 Example 2 0.196 0.294 0.588 1.568 Example 3 0.147 0.220 0.294 0.514 As indicated, the elements formed from multi-walled nanotubes exhibited a stability of CSR with improved reflux.
[0035] These modifications and variations and other modifications and variations of the present invention may be practiced by those skilled in the art without departing from the spirit and scope of the present invention. On the other hand, it should be understood that aspects of the various embodiments may be interchanged both wholly and in part. In addition, those skilled in the art will understand that the foregoing description is provided by way of example only and is not intended to limit the invention as defined in the appended claims. In particular, the solid electrolyte capacitor can be seen as comprising an anode termination which is in electrical connection with the anode body and a cathode termination which is in electrical connection with the solid electrolyte.

权利要求:
Claims (20)
[0001]
REVENDICATIONS1. A solid electrolyte capacitor comprising an anode body, a dielectric which covers the anode body, and a solid electrolyte which covers the dielectric, wherein the solid electrolyte includes a nanocomposite which contains a plurality of nanofibrils and a polymer matrix nanofibrils having a number average sectional dimension of about 500 nanometers or less and an aspect ratio of about 25 to about 500.
[0002]
The solid electrolyte capacitor of claim 1, wherein the nanofibrils have a number average sectional dimension of about 1 to about 100 nanometers, and preferably about 2 to about 40 nanometers.
[0003]
The solid electrolyte capacitor of claim 1, wherein the nanofibrils have an aspect ratio of from about 50 to about 300.
[0004]
The solid electrolyte capacitor according to claim 1, wherein the nanofibrils have a number average length of 0.1 to about 10 microns.
[0005]
The solid electrolyte capacitor according to claim 1, wherein the nanofibrils are non-conductive. 25
[0006]
The solid electrolyte capacitor according to claim 1, wherein the nanofibrils are conductive.
[0007]
The solid electrolyte capacitor of claim 6 wherein the conductive nanofibrils include carbon nanotubes.
[0008]
8. The solid electrolyte capacitor according to claim 7, wherein the carbon nanotubes are multi-walled carbon nanotubes.
[0009]
The solid electrolyte capacitor of claim 1, wherein the nanofibrils and the conductive polymer matrix form separate layers of the nanocomposite.
[0010]
The solid electrolyte capacitor of claim 1, wherein the nanofibrils are dispersed within the conductive polymer matrix. 15
[0011]
The solid electrolyte capacitor of claim 1, wherein the conductive polymer is poly (3,4-ethylenedioxythiophene).
[0012]
The solid electrolyte capacitor of claim 1, wherein the conductive polymer matrix is formed from prepolymerized conductive polymer particles.
[0013]
The solid electrolyte capacitor according to claim 1, wherein the solid electrolyte contains an inner layer and an outer layer, and wherein the outer layer contains the nanocomposite.
[0014]
The solid electrolyte capacitor according to claim 13, wherein the outer layer contains prepolymerized conductive polymer particles having an average size of about 50 to about 500 nanometers, preferably about 80 to about 250 nanometers, and more preferably, from about 100 to about 200 nanometers.
[0015]
The solid electrolyte capacitor of claim 1, wherein the nanocomposite further comprises a crosslinking agent.
[0016]
The solid electrolyte capacitor of claim 1, wherein the anode body is formed from a powder that contains tantalum, niobium, or an electroconductive oxide thereof. 10
[0017]
The solid electrolyte capacitor according to claim 1, further comprising an anode termination which is in electrical connection with the anode body and a cathode termination which is in electrical connection with the solid electrolyte. 15
[0018]
The solid electrolyte capacitor of claim 17, wherein an anode wire extends from the anode body and is connected to the anode termination.
[0019]
19. The method of forming the solid electrolyte capacitor according to claim 1, the method comprising applying the nanofibrils to the dielectric and then applying a pre-polymerized conductive polymer particle dispersion.
[0020]
20. The method of claim 19, wherein the nanofibrils are in the form of an aqueous dispersion.

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同族专利:

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公开号 | 公开日

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CN111524711A|2020-08-11|

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US20150170844A1|2015-06-18|

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KR102278453B1|2021-07-20|

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CN111524711B|2021-08-31|

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JP6681138B2|2020-04-15|

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DE102014225816A1|2015-06-18|

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US9589733B2|2017-03-07|

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CN104715930A|2015-06-17|

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JP2015119183A|2015-06-25|

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HK1207202A1|2016-01-22|

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KR20150070965A|2015-06-25|

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法律状态:
2015-10-27| PLFP| Fee payment|Year of fee payment: 2 |

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2016-09-16| PLSC| Search report ready|Effective date: 20160916 |

优先权:

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