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    • 专利摘要:
    The present invention relates to a wet electrolytic capacitor (10) which contains a cathode, a working fluid electrolyte and a planar anode (200) formed from an anodically oxidized sintered porous pellet. The pellet may be formed from a compressed valve metal powder, which in turn is formed by reacting an oxide of a valve metal compound (eg, tantalum pentoxide) with a reducing agent which contains a metal having an oxidation state of 2 or more (for example, magnesium). By the use of such a powder, the present inventors have found that higher capacity levels can be achieved than previously possible for high voltage capacitors used in implantable medical devices.
    公开号:FR3029006A1
    申请号:FR1560795
    申请日:2015-11-12
    公开日:2016-05-27
    发明作者:Lotfi Djebara；Jan Petrzilek
    申请人:AVX Corp；
    IPC主号:
    专利说明:

    [0001] 1 WET ELECTROLYTIC CAPACITOR FOR IMPLANTABLE MEDICAL DEVICE High voltage electrolytic capacitors are often used in implantable medical devices. These capacitors must have a high energy density since it is desirable to minimize the overall size of the implanted device. This is particularly true of an implantable cardioverter defibrillator ("ICD"), which is also referred to as an implantable defibrillator, since the high voltage capacitors used to deliver the defibrillation pulse can occupy up to one third of the implantable defibrillator. volume of the DCI. ICDs typically use two to four electrolytic capacitors in series to achieve the desired high voltage for shock delivery. Typically, metal foils (eg aluminum foil) are used in the electrolytic capacitor because of their small size. Since the electrostatic capacitance of the capacitor is proportional to its electrode area, the surface of the metal foil may be, prior to the formation of the dielectric film, roughened or chemically converted to increase its effective area. This step of roughening the surface of the metal sheet is called etching. The etching is normally carried out either by the method (chemical etching) of carrying out an immersion in a solution of hydrochloric acid or by the method 3029006 2 (electrochemical etching) of carrying out an electrolysis in an aqueous solution of hydrochloric acid . The capacitance of the electrolytic capacitor is determined by the degree of roughness (the surface area) of the anode sheet and the thickness and dielectric constant of the oxide film. Due to the limited surface area that can be provided by etching metal foils, it has also been attempted to use sintered porous pellets in wet electrolytic capacitors, in other words, wet tantalum capacitors. ". A tantalum pellet, for example, can be formed by compacting a high pressure powder and sintering at an elevated temperature to form a sponge-like structure which is very strong and dense but also very porous. As a result of the high voltages encountered in medical devices, however, low specific charge powders must generally be used. Specifically, if the specific charge is too high, relatively fine sintering bridges tend to form between adjacent particles, which can cause the dielectric layer to fail near these bridges at high voltages. Thus, there is currently a need for an improved wet electrolytic capacitor for use in implantable medical devices such as defibrillators.
    [0002] According to one embodiment of the present invention, a wet electrolytic capacitor is disclosed which comprises a planar anode, a cathode and a working fluid electrolyte in communication with the anode and the cathode. The anode comprises an anodically oxidized pellet formed from a compressed and sintered valve metal powder. The valve metal powder is formed by reacting an oxide of a valve metal compound with a reducing agent that contains a valve metal having an oxidation state of 2 or more. The cathode comprises a metal substrate 10 coated with a conductive coating. In another embodiment of the present invention, a wet electrolytic capacitor is disclosed which includes a planar anode, a cathode, and a working fluid electrolyte in communication with the anode and the cathode. The anode comprises an anodically oxidized pellet formed from a compressed and sintered tantalum powder. The powder is nodular or angular and has a specific charge of about 15,000 pF * V / g or more. The cathode comprises a metal substrate coated with a conductive coating. According to yet another embodiment of the present invention, a method of forming a wet electrolytic capacitor is disclosed which comprises pressing a tantalum powder into a pellet form, the powder being formed by tantalum pentoxide reaction with a reducing agent which contains magnesium, calcium, strontium, barium, cesium, aluminum, or a combination thereof; sintering the pellet; Anodic oxidation of the sintered pellet to form a dielectric layer which covers the anode; and positioning the anode and a working fluid electrolyte within a housing. Other features and aspects of the present invention are discussed in more detail below. A complete description of the present invention which allows its reproduction, including its best mode, intended for those skilled in the art, is proposed more particularly in the remainder of the specification, which refers to the appended figures in which: FIG. 1 is a perspective view of an embodiment of the wet electrolytic capacitor of the present invention; Figure 2 is a top view of an embodiment of an anode that may be used in the capacitor of the present invention; Figure 3 is a front view of the anode of Figure 2; and FIG. 4 is a perspective view illustrating the entire anode of FIG. 2 with housing components to form the capacitor shown in FIG. 1. The repeated use of reference characters in the present description and the The drawings are intended to represent like or similar features or elements of the invention. It will be understood by those skilled in the art that the present discussion is a description of exemplary embodiments only, which is not intended to limit the broader aspects of the present invention, said broader aspects being implemented. in the build example. In general, the present invention relates to a wet electrolytic capacitor which contains a cathode, a working fluid electrolyte, and a planar anode formed from an anodically oxidized, sintered porous pellet. The pellet may be formed from a compressed valve metal powder, which is itself formed by reacting an oxide of a valve metal compound (eg, tantalum pentoxide) with a propellant. reduction which contains a metal having an oxidation state of 2 or more. Examples of such metals may include, for example, alkaline earth metals (eg, magnesium, calcium, strontium, barium, cesium, etc.), aluminum, and so on. Through the use of such a powder, the present inventors have found that higher levels of capacity can be achieved than previously possible for high voltage capacitors used in implantable medical devices. Various embodiments of the present invention will now be described in more detail.
    [0003] I. Anode The anode is formed from a valve metal powder that contains a valve metal (in other words a metal that is capable of oxidation) or a valve metal-based compound, such as tantalum, niobium, aluminum, hafnium, titanium, alloys thereof, oxides thereof, nitrides thereof, and so on. For example, the valve metal powder may contain an electroconductive niobium oxide, such as niobium oxide having an atomic ratio of niobium to oxygen of 1 / 1.0 ± 1.0, in some embodiments of the invention. 1 / 1.0 ± 0.3, in some embodiments 1 / 1.0 ± 0.1, and in some embodiments, 1 / 1.0 ± 0.05. The niobium oxide can be Nb00.7, Nb01.0, Nb01.1, and Nb02.
    [0004] As pointed out above, the valve metal powder may be formed by reacting an oxide of a valve metal compound with a reducing agent which contains a metal having a relatively high oxidation state (eg for example, magnesium). The valve metal oxide is typically a tantalum oxide and / or niobium oxide which can be reduced, for example Ta2O. (x 5) (for example, Ta205) or Nb20. (x 5) (for example, Nb205). The reducing agent may be provided in a gaseous, liquid or solid state, and may also be in the form of a metal, as well as alloys or salts thereof. In one embodiment, for example, a halide salt (e.g., chloride, fluoride, etc.) may be used. If desired, other components may also be added before, during or after the reaction, such as dopants, alkali metals, etc. The reduction of the oxide is typically carried out at a temperature of about 400 ° C to about 1200 ° C, and in some embodiments from about 600 ° C to about 1000 ° C, for about 20 to about 300 minutes. The heating may be carried out in a reactor under an inert atmosphere (eg, argon or nitrogen atmosphere) such that a melt is formed. Suitable reactors may include, for example, vertical tube furnaces, rotary kilns, fluidized bed furnaces, multiple hearth furnaces, high temperature self-propagating synthesis reactors, and the like. The reactor can be maintained under an inert gas until the mass in the reaction vessel is cooled to room temperature. Further details of such a reduction reaction can be described in US Patent Publication Nos. 2003/0110890 to He, et al. and 2004/0163491 to Shekhter, et al. After the reduction, the product can be cooled, crushed and washed to remove excess impurities or reagents. The wash solution may include, for example, a mineral acid and water. If desired, the powder may be further processed to remove any tantalate / niobate (eg, magnesium tantalate) that may have formed during the reaction. In one embodiment, for example, a technique for removing tantalates / niobates involves heating the powder under vacuum at a temperature of about 1100 ° C to about 1400 ° C for about 15 minutes to about 6 hours. Similarly, another technique for eliminating tantalates / niobates involves heating the powder at a temperature of about 800 ° C to about 1300 ° C in the presence of a getter material, such as magnesium Calcium and / or aluminum, for about 15 minutes to 6 hours. These techniques can be described in more detail in US Pat. No. 7,431,751 issued to Shekhter et al. The powder may be subjected to subsequent refining steps known in the art, such as doping, deoxidation, etc. ; However, this is not necessary. Regardless of the particular steps used, the powder obtained has a variety of beneficial properties. The powder may, for example, be a fine, free-flowing powder which contains primary particles having a three-dimensional shape, for example a nodular or angular shape. These particles are generally not flat, and thus have a relatively low "aspect ratio", the aspect ratio being the average diameter or the particle width divided by the average thickness ("D / T"). "). For example, the aspect ratio of the particles may be about 4 or less, in some embodiments about 3 or less, and in some embodiments about 1 to about 2. The powder may also be have a relatively high specific surface area, for example about 1 square meter per gram ("m2 / g"), in some embodiments of about 2 m2 / g or more, and in some embodiments, from about 4 to about 30 m 2 / g. The term "specific surface area" generally refers to the surface area as determined by Brunauer's physical gas adsorption (B.E.T.) method, Emmet, and Teller, Journal of the American Chemical Society, Vol. 60, 1938, p. 309, with nitrogen as an adsorption gas. The test can be performed with a MONOSORB® specific surface area analyzer available from QUANTACHROME Corporation, Syosset, NY, which measures the amount of adsorbed nitrogen gas adsorbed to a solid surface by detection of the modification. thermal conductivity of a mixture flowing from adsorbate and inert carrier gas (eg, helium). The primary particles of the powder may also have a median size (D50) of about 5 to about 1000 nanometers, and in some embodiments from about 10 to about 500 nanometers, for example using a laser distribution analyzer BECKMAN COULTER Corporation particle sizes (e.g., LS-230), optionally after subjecting the particles to vibration by an ultrasonic wave of 70 seconds. Because of its high surface area and small particle size, the powder can have a high specific charge, for example more than about 15,000 microfarads * volts per gram ("pF * V / g"), in some embodiments from about 18,000 to about 80,000 pF * V / g, and in some embodiments, from about 20,000 to about 45,000 pF * V / g. As known in the art, the specific charge can be determined by multiplying the capacitance by the anodization voltage used, and then by dividing this product by the weight of the anodized electrode body. Despite the use of these high specific charge powders with three dimensional particles, the present inventors have nevertheless discovered that the ability to achieve high voltages can be achieved by the way in which the powder is formed. More particularly, it is believed that the particular reduction process used can achieve "sintering bridges" between adjacent, relatively large sized agglomerated particles. The sintering bridges are the small cross sectional area of the electrical path inside the metal structure. Typically, the sintering bridges have a size of about 200 nanometers or more, in some embodiments of about 250 nanometers or more, and in some embodiments, from about 300 to about 800 nanometers. Since the bridges are of a relatively large size, the dielectric layer near the bridge will no longer be likely to fail at high forming voltages. The powder (as well as the anode) can also have a relatively low content of alkali metal, carbon and oxygen. For example, the powder may have no more than about 50 ppm carbon or alkali metals and in some embodiments no more than about 10 ppm carbon or alkali metals. Likewise, the powder may not have more than about 0.15 ppm / μC / g oxygen and in some embodiments no more than about 0.10 ppm / μC / g oxygen. . The oxygen content can be measured by a LECO oxygen analyzer and includes oxygen in the natural oxide on the surface of the tantalum and oxygen in bulk in the tantalum particles. The bulk oxygen content is regulated by the period of the tantalum crystal lattice, which increases linearly with the increase in tantalum oxygen content 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 diffraction ray analysis X (XRDA) was used to measure the period of the tantalum crystal lattice. Oxygen in the sintered tantalum anodes may be limited to the fine natural surface oxide, while most of the tantalum is substantially free of oxygen. To facilitate the construction of the anode, some additional components may also be included in the powder. For example, the powder may optionally be mixed with a binder and / or a lubricant to ensure that the particles adhere appropriately to each other when compressed or squeezed to form the pellet. Suitable binders include, for example, polyvinyl butyral; poly (vinyl acetate); polyvinyl alcohol; poly (vinyl pyrrolidone); cellulosic polymers, such as carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, and methylhydroxyethylcellulose; atactic polypropylene, polyethylene; polyethylene glycol (for example, Carbowax from Dow Chemical Co.); polystyrene, poly (butadiene / styrene); polyamides, polyimides, and polyacrylamides, polyl ethers of high molecular weight; copolymers of ethylene oxide and propylene oxide; fluorinated polymers, such as polytetrafluoroethylene, polyvinylidene fluoride, and fluoroolefin copolymers; acrylic polymers, such as sodium polyacrylate, poly (lower alkyl acrylates), poly (lower alkyl methacrylates) and copolymers of lower alkyl acrylates and methacrylates; and fatty acids and waxes, such as stearic and other saponified fatty acids, vegetable wax, microwaxes (purified paraffins), and the like. The binder can be dissolved and dispersed in a solvent. Examples of solvents may include water, alcohols, and so on. 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.
    [0005] The resulting powder can be compressed to form a pellet using any conventional powder press device. For example, a press die may be used which is a single station compaction press containing a die and one or more punches. Alternatively, anvil-type compaction press dies may be used which use only a die and a single lower punch. The single station compaction press dies are available in several basic types, for example, cam, toggle and eccentric / crank presses having variable, eg single action, double action, die-type capabilities. Floating, moving plate, opposed piston, screw, impact, hot pressing, stamping or sizing. The powder may be compressed around an anode lead wire. The wire may be formed from any electroconductive material, such as tantalum, niobium, aluminum, hafnium, titanium, etc., as well as electroconductive oxides and / or their nitrides.
    [0006] Any binder / lubricant can be removed after compression by heating the vacuum pellet to a certain temperature (e.g., from about 150 ° C to about 500 ° C) for several minutes. Alternatively, the binder / lubricant may also be removed by contacting the pellet with an aqueous solution, as described in US Patent No. 6,197,252 issued to Bishop, et al. After this, the pellet is sintered to form a porous integral mass. The pellet is typically sintered at a temperature of about 800 ° C to about 2000 ° C, in some embodiments from about 1200 ° C to about 1800 ° C, and in some embodiments, about 1500 ° C to about 1700 ° C, for a period of about 5 minutes to about 100 minutes, and in some embodiments, about 8 minutes to about 15 minutes. This can happen in one or more steps. 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, for example in a vacuum, an inert gas, hydrogen, etc.
    [0007] 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 about 100 Torr. at around 930 Torr. Mixtures of hydrogen and other gases (eg, argon or nitrogen) may also be used. Under the effect of sintering, the pellet shrinks due to the growth of metallurgical bonds between the particles. Since shrinkage generally increases the density of the wafer, lower ("green") press densities can be used to still achieve the desired target density. For example, the target density of the pellet after sintering is typically from about 5 to about 8 grams per cubic centimeter. As a result of the retraction phenomenon, however, it is not necessary to press the pellet to such high densities, but it can instead be pressed at densities of less than about 6.0 grams per cubic centimeter, and in some embodiments, from about 4.5 to about 5.5 grams per cubic centimeter. Among other things, the ability to utilize lower green densities can provide significant savings and can increase processing efficiency. Because of the thin nature of the planar anode, it is sometimes desirable to regulate the manner in which the anode is inserted to limit the extent to which the stresses applied during manufacture will result in the extraction of the anode wire. For example, in one embodiment, at least a portion of the wire within the anode is bent at an angle relative to the longitudinal axis of the wire. This "bending" reduces the ease of extraction of the yarn in the longitudinal direction after compaction and sintering of the anode. Referring to FIGS. 2 and 3, for example, an embodiment of a planar anode 200 is provided which contains anode wire 220. The anode wire contains a first portion 221 which extends in a longitudinal direction ("y" direction) from the anode 200. Inside the body of the anode, the wire 200 also contains a second portion 222 which is bent at an angle "a" relative to the first part 221. The angle "a" is typically from about 40 ° to about 120 °, in some embodiments from about 60 ° to about 110 ° and in some embodiments, about 80 ° at about 100 ° (e.g. about 90 °). Such flexural configuration can be achieved in a variety of different ways. For example, in one embodiment, a press die may be partially filled with the powder, and then a "pre-curved" anode wire may be inserted into the press die. After this, the mold can be filled with powder and the whole in its entirety compressed into a pellet. In addition to its geometric configuration, the degree to which the anode wire is inserted into the anode can also be regulated to help minimize the risk of shrinkage during manufacture. In other words, the deeper the wire is inserted into the anode, the less likely it is to be extracted from it. Of course, excessive wire insertion may alter the uniformity of the pressing density, which may impact the resulting electrical performance of the anode. In this regard, the present inventors have found that the ratio of the length of the anode over which the wire is inserted over the entire length of the anode is typically from about 0.1 to about 0.6 and in some cases embodiments of about 0.2 to about 0.5. In FIG. 2, for example, the length "L1" represents the length of the anode 200 on which the anode wire 220 is inserted, while the length "L" represents the total length of the anode 200. In some cases, the length "L" of the anode 200 may be in the range of about 1 to about 80 millimeters, in some embodiments from about 10 to about 60 millimeters, and in some embodiments from about 20 to about 50 millimeters. Similarly, the length "L1" may be from about 1 to about 40 millimeters, in some embodiments, from about 2 to about 20 millimeters, and in some embodiments from about 5 to about 15 millimeters. The width "W" of the anode may also be from about 0.05 to about 40 millimeters, in some embodiments from about 0.5 to about 35 millimeters, and in some embodiments, from about 2 to about 25 millimeters. The planar anode is generally small in thickness to improve electrical performance and volumetric efficiency of the resulting capacitor. For example, in FIG. 3, the thickness of a planar anode 200 is represented by the dimension "H". Typically, the thickness of the anode is about 5 millimeters or less, for example about 0.05 to about 4 millimeters, and in some embodiments, about 0.1 to about 3.5 millimeters. millimeters. The ratio of the length of the anode to the thickness of the anode is from about 5 to about 50, in some embodiments from about 6 to about 30, and in some embodiments, from about 7 to about 20. Although the anode is shown having a "D-shape" in FIG. 2, it should also be understood that the anode may have any other desired shape, for example square, rectangular, circular, oval, triangular , 15 etc. Polygonal shapes having more than four (4) sides (e.g., hexagon, octagon, heptagon, pentagon, etc.) are particularly desirable because of their relatively high surface area.
    [0008] The anode also contains a dielectric formed by anodic oxidation ("anodization") of the sintered anode such that a dielectric layer is formed on and / or inside the planar anode. For example, a tantalum anode (Ta) may be anodized to tantalum pentoxide (Ta2O5). Typically, the anodization is carried out by initial application of a solution to the anode, for example by immersing the anode in the electrolyte. Aqueous solvents (e.g., water) and / or non-aqueous solvents (e.g., ethylene glycol) can be used. To improve the conductivity, a compound can be used which is capable of dissociating in the solvent to form ions. Examples of these compounds include, for example, acids, such as those described below with respect to the electrolyte. For example, an acid (eg, phosphoric acid) can be from about 0.01% by weight to about 5% by weight, in some embodiments from about 0.05% by weight to about 0% by weight. , 8% by weight, and in some embodiments, from about 0.1% by weight to about 0.5% by weight of the anodizing solution. If desired, acid mixtures can also be used. A current is passed through the anodizing solution to form the dielectric layer. The value of the formation voltage determines 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. After this, the power supply can switch to a potentiostatic mode to ensure that the desired dielectric thickness is formed over the entire surface of the anode. Of course, other known methods may also be employed, such as pulse or step potentiostatic methods. The voltage at which anodic oxidation occurs is typically high to obtain a capacitor capable of operating in a high voltage range. In other words, the voltage range is typically from about 100 volts to about 300 volts, in some embodiments from about 170 volts to about 280 volts, and in some embodiments from about 30 volts to about 300 volts. 200 volts at about 250 volts. The temperature of the anodization solution may be in the range of about 10 ° C to about 200 ° C, in some embodiments from about 20 ° C to about 150 ° C, and in some embodiments from about 30 ° C to about 90 ° C. The resulting dielectric layer may be formed on a surface of the anode and within its pores. When used, the specific nature of the powder can allow the resulting anode to reach a high specific charge even at the high forming voltages often used in the present invention. II. Working Electrolyte The working electrolyte may be in electrical communication with the anode and the cathode. The electrolyte is a fluid that can be impregnated into the anode, or that can be added to the capacitor at a later stage of production. The fluid electrolyte 20 generally uniformly humidifies the dielectric on the anode. Various suitable electrolytes are disclosed in U.S. Patent Nos. 5,369,547 and 6,594,140 issued to Evans, et al. Typically, the electrolyte is ionically conductive in that it has an electrical conductivity of from about 0.1 to about 20 Siemens per centimeter ("S / cm"), in some embodiments from about 0.2 to about 15 S / cm, and in some embodiments from about 0.5 S / cm to about 10 S / cm, determined at a temperature of about 23 ° C using a known conductivity meter (e.g., Oakton Con Series 11). The fluid electrolyte is generally in the form of a liquid, for example a solution (for example aqueous or non-aqueous), a colloidal suspension, a gel, etc. For example, the electrolyte may be in the form of an aqueous solution of an acid (eg, sulfuric acid, phosphoric acid, or nitric acid), a base (for example, potassium hydroxide) or a salt (for example, an ammonium salt, such as a nitrate), as well as any other suitable electrolyte known in the art, such as a salt dissolved in an organic solvent ( for example, an ammonium salt dissolved in a glycol-based solution). Various other electrolytes are described in U.S. Patent Nos. 5,369,547 and 6,594,140 to Evans, et al.
    [0009] The desired ionic conductivity can be attained by selecting the ionic compound (s) (eg, acids, bases, salts, and so forth) within certain ranges of concentrations. In a particular embodiment, the weak organic acid salts may be effective in achieving the desired electrolyte conductivity. The cation of the salt may comprise monoatomic cations, for example alkali metals (e.g., Li +, Na +, K +, Rb +, or Cs +), alkaline earth metals (e.g., Be2 +, Mg2 +, Ca2 +, Sr2 + or Ba2 +), transition metals (eg, Ag +, Fe2 +, Fe3 +, etc.), as well as poly-atomic cations, such as NH4 +. Monovalent ammonium (NH4 +), sodium (K +), and lithium (L1 are cations particularly suitable for use in the present invention.) The organic acid used to form the salt anion may be in the sense that it typically has a first acid dissociation constant (pK, I) of from about 0 to about 11, in some embodiments from about 1 to about 10, 5 and in some embodiments from about 2 to about 10, determined at about 23 ° C. Any suitable weak organic acid can be used in the present invention, for example, carboxylic acids, such as acrylic acid, methacrylic acid, malonic acid, succinic acid, salicylic acid, sulfosalicylic acid, adipic acid, maleic acid, malic acid, oleic acid, gallic acid, tartaric acid (e.g. , dextotartaric acid, mesotartaric acid, etc.), citric acid, Acetic acid, glycolic acid, oxalic acid, propionic acid, phthalic acid, isophthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid, glutamic acid, itaconic acid, trifluoroacetic acid, barbituric acid, cinnamic acid, benzoic acid, 4-hydroxybenzoic acid, aminobenzoic acid, and the like. ; mixtures of these, and so on. Polyprotic acids (for example, diprotic, triprotic, etc.) are particularly desirable for their use in salt formation, such as adipic acid (pKaI of 4.43 and pI, of 5.41), α-tartaric acid (pKaI of 2.98 and pI <", 2 of 4.34), meso-tartaric acid (pKaI of 3.22 and pI <", 2 of 4.82), oxalic acid (pKaI of 1.23 and pI <", 2 of 4.19), lactic acid (pKaI of 3.13 and pI of 2.76, and p1 of 6.40), etc. While the actual amounts may vary depending on the particular salt used, its solubility in the solvent (s) used in the electrolyte, and the presence of other components, these acid salts The low organic levels are typically present in the electrolyte in an amount of from about 0.1 to about 25 percent by weight, in some embodiments from about 0.2 to about 20 percent by weight, in some embodiments. from about 0.3 to about 15% by weight, and in some embodiments from about 0.5 to about 5% by weight. The electrolyte is typically aqueous in that it contains an aqueous solvent, such as water (e.g., deionized water). For example, water (e.g., deionized water) can be from about 20% by weight to about 95% by weight, in some embodiments from about 30% by weight to about 90% by weight. and in some embodiments from about 40% by weight to about 85% by weight of the electrolyte. A secondary solvent may also be used to form a solvent mixture. Secondary solvents may include, for example, glycols (e.g., ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, polyethylene glycols, ethoxydiglycol, dipropylene glycol, etc. .); glycol ethers (e.g., methyl glycol ether, ethyl glycol ether, isopropyl glycol ether, etc.); alcohols (for example, methanol, ethanol, n-propanol, isopropanol, and butanol); ketones (for example, acetone, methyl ethyl ketone, and methyl isobutyl ketone); esters (e.g., ethyl acetate, butyl acetate, diethylene glycol ether acetate, methoxypropyl acetate, ethylene carbonate, propylene carbonate, etc. ); amides (for example, dimethylformamide, dimethylacetamide, dimethylcaprylic / capric fatty acid amide and N-alkylpyrrolidones); sulfoxides or sulfones (for example, dimethylsulfoxide (DMSO) and sulfolane); And so on. These solvent mixtures typically contain water in an amount of from about 40% by weight to about 80% by weight, in some embodiments from about 50% by weight to about 75% by weight, and in some embodiments embodiments, from about 55% by weight to about 70% by weight and one or more secondary solvents in an amount of about 20% by weight to about 60% by weight, in some embodiments of about 25% by weight. from about 50% by weight to about 50% by weight, and in some embodiments from about 30% by weight to about 45% by weight. The secondary solvent (s) may, for example, be from about 5% by weight to about 45% by weight, in some embodiments from about 10% by weight to about 40% by weight, and in some embodiments from about 15% by weight to about 35% by weight of the electrolyte. If desired, the electrolyte may be relatively neutral and have a pH of from about 4.5 to about 8.0, in some embodiments from about 5.0 to about 3029006, and in some embodiments from about 5.5 to about 7.0. One or more pH adjusting agents (eg, acids, bases, etc.) may also be used to help achieve the desired pH. In one embodiment, an acid is used to lower the pH to the desired range. Suitable acids include, for example, organic acids as described above; inorganic acids, such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boric acid, boronic acid, and the like. ; and mixtures thereof. Although the total concentration of pH adjusting agents may vary, these are typically present in an amount of about 0.01% by weight to about 10% by weight, in some embodiments of about 0% by weight. From about 5% by weight to about 5% by weight, and in some embodiments from about 0.1% by weight to about 2% by weight of the electrolyte.
    [0010] The electrolyte may also contain other components that help improve the electrical performance of the capacitor. For example, a depolarizer may be used in the electrolyte to help inhibit the evolution of hydrogen gas at the cathode of the electrolytic capacitor, which could otherwise result in swelling of the capacitor and eventually failure. When used, the depolarizer is typically from about 1 to about 500 parts per million ("ppm"), in some embodiments from about 10 to about 200 ppm, and in some embodiments, 3029006 From about 20 ppm to about 150 ppm of the electrolyte. Suitable depolarizers may include nitroaromatic compounds, for example 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2-nitrobenzonic acid, 3-nitrobenzonic acid, 4-nitrobenzonic acid, 2-nitroacetophenone , 3-nitroacetophenone, 4-nitroacetophenone, 2-nitroanisole, 3-nitroanisole, 4-nitroanisole, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 2-nitrobenzyl alcohol, 3-nitrobenzyl alcohol, 4-nitrobenzyl alcohol, 2-nitrophthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, and so on. Nitroaromatic depolarizers particularly suitable for use in the present invention are nitrobenzoic acids, their anhydrides or their salts, substituted with one or more alkyl groups (eg, methyl, ethyl, propyl, butyl, etc.). Specific examples of such alkyl-substituted nitrobenzoic compounds include, for example, 2-methyl-3-nitrobenzoic acid; 2-methyl-6-nitrobenzoic acid; 3-methyl-2-nitrobenzoic acid; 3-methyl-4-nitrobenzoic acid; 3-methyl-6-nitrobenzoic acid; 4-methyl-3-nitrobenzoic acid; Their anhydrides or their salts; And so on. III. Cathode A. Metal Substrate The cathode typically contains a metal substrate, which may optionally serve as a housing for the capacitor. The substrate may be formed from a variety of different metals, such as tantalum, niobium, aluminum, nickel, hafnium, titanium, copper, silver, steel (e.g. Stainless), alloys thereof, composites thereof (e.g., an electroconductive oxide coated metal), and so on. The geometrical configuration of the substrate may generally vary as known to those skilled in the art, for example in the form of an aluminum foil, a sheet, a screen, a container, a bottle, etc. The metal substrate may form all or part of the housing, or it may simply be applied to the housing. Independently, the substrate may have a variety of shapes, for example, generally cylindrical, D, rectangular, triangular, prismatic, etc. If desired, a surface of the substrate may be roughened to increase its surface area and increase the degree to which a material may be able to adhere thereto. In one embodiment, for example, a surface of the substrate is chemically etched, for example by applying a solution of a corrosive substance (e.g., hydrochloric acid) to the surface. Mechanical roughening can also be used. For example, a surface of the substrate may be abrasive blasted by propelling a stream of abrasive medium (eg, sand) against at least a portion of its surface.
    [0011] B. Conductive Coating 3029006 A conductive coating may also be disposed on a surface of the metal substrate (e.g., an interior surface) to serve as an electrochemically active material for the capacitor.
    [0012] Any number of layers may be used in the coating. The materials used in the coating may vary. For example, the conductive coating may contain a noble metal (eg, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, etc.), an oxide , (eg ruthenium oxide), carbon materials, conductive polymers, etc. In one embodiment, for example, the coating may comprise one or more conductive polymers which are typically n-conjugated and which have electrical conductivity after oxidation or reduction. Examples of such n-conjugated conductive polymers include, for example, polyheterocycles (eg, polypyrroles, polythiophenes, polyanilines, etc.), polyacetylenes, poly-p-phenylenes, polyphenolates, and so on. after. The substituted polythiophenes are particularly suitable for use as conductive polymers in that they exhibit particularly good mechanical strength and electrical performance. In a particular embodiment, the substituted polythiophene has 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 tertbutyl, 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 C 5 -C 18 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 from 0 to 8, in some embodiments, from 0 to 2, and in one embodiment, 0; and n is from 2 to 5,000, in some embodiments from 4 to 2,000, and in some embodiments from 5 to 1,000. Examples of substituents for radicals "D" or "R7" include, for example, 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, carboxylamide, and so on. 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) having the following general structure: (R7) Processes for forming the conductive polymers as described above are well known in art. For example, U.S. Patent No. 6,987,663 to Merker, et al. describes various techniques for forming substituted polythiophenes from a monomeric precursor. The monomer precursor may, for example, have the following structure: wherein T, D, R7, and q are defined above. Particularly suitable thiophene monomers are those in which "D" is an optionally substituted C2 to C3 alkylene radical. For example, optionally substituted 3,4-alkylenedioxythiophenes may be used which have the following general structure: wherein R7 and q are as defined above. In a particular embodiment, "q" is 0. A commercially available example of 3,4-ethylenedioxythiophene is available from Heraeus 30 Clevios under the designation Clevios ™ M. Other suitable monomers are also described in US Pat. U.S. Patent No. 5,111,327 issued to Blohm, et al. and 6,635,729 issued to Groenendaal, et al. Derivatives of these monomers may also be used which are, for example, dimers or trimers of the aforementioned monomers. Higher molecular derivatives, in other words, tetramers, pentamers, etc. monomers are suitable for use in the present invention. The derivatives may consist of identical or different monomeric units and used in pure form and in a mixture with each other and / or with the monomers. Oxidized or reduced forms of these precursors may also be used. The thiophene monomers can be chemically polymerized in the presence of an oxidation catalyst. The oxidation catalyst typically comprises a transition metal cation, such as iron (III), copper (II), chromium (VI), cerium (IV), manganese (IV), manganese (VII), ruthenium (III), etc. A dopant may also be used to provide excess charge to the conductive polymer and stabilize the conductivity of the polymer.
    [0013] The dopant typically comprises an inorganic or organic anion, such as an ion of a sulfonic acid. In some embodiments, the oxidation catalyst used in the precursor solution has both catalytic and dopant functionality in that it comprises a cation (e.g., a transition metal) and an anion (e.g. sulfonic acid). For example, the oxidation catalyst may be a transition metal salt that includes iron (III) cations, such as iron (III) halides (e.g., FeCl3) or iron (III) salts. and other inorganic acids, such as Fe (C104) 3 or Fe2 (SO4) 3 and iron (III) salts of organic acids and inorganic acids including organic radicals. Examples of iron (III) salts of inorganic acids with organic radicals include, for example, iron (III) salts of monoesters of sulfuric acid of C 1 -C 20 alkanols (e.g. iron (III) lauryl sulphate). Similarly, examples of iron (III) salts of organic acids include, for example, (III) salts of C 1 -C 20 alkanesulphonic acids (eg methane, ethane, propane). butane, or dodecane sulfonic acid); iron (III) salts of perfluorosulfonic aliphatic acids (e.g., trifluoromethanesulfonic acid, perfluorobutane sulfonic acid, or perfluorooctane sulfonic acid); iron (III) salts of C1-C20 aliphatic carboxylic acids (for example 2-ethylhexylcarboxylic acid); iron (III) salts of aliphatic perfluorocarboxylic acids (e.g., trifluoroacetic acid or perfluorooctane acid); iron (III) salts of aromatic sulfonic acids optionally substituted by (C1-C20) alkyl groups (e.g., benzene sulfonic acid, o-toluenesulfonic acid, p-toluenesulphonic acid, or dodecylbenzene sulphonic acid); iron (III) salts of cycloalkanesulphonic acids (e.g., camphorsulfonic acid); And so on. 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 available example of iron (III) -ptoluene sulfonate is available from Heraeus Clevios as Clevios ™ C. Various methods can be used to form the conductive layer. In one embodiment, the oxidation catalyst and the monomer are applied, sequentially or at the same time, so that the polymerization reaction occurs in situ on the substrate. Suitable application techniques may include screen printing, dipping, electrophoretic coating, and sputtering, and may be used to form a conductive polymer coating. As an example, a monomer may initially be mixed with the oxidation catalyst to form a precursor solution. Once the mixture is formed, it can be applied to the substrate and then allowed to polymerize so that the conductive layer is formed. Alternatively, the oxidation catalyst and the monomer may be applied sequentially. In one embodiment, for example, the oxidation catalyst is dissolved in an organic solvent (eg, butanol) before being applied as an immersion solution. The substrate can then be dried to remove the solvent therefrom. After this, the substrate may be immersed in a solution containing the monomer. Polymerization is typically 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. used and the desired reaction time. Suitable polymerization techniques as described above can be described in more detail in US publication No. 2008/232037 to Biler. While chemical polymerization techniques can be used in some embodiments, it is often desired to minimize the use of oxidation catalysts in the capacitor since these materials can often lead to the formation of iron radicals (e.g. These radicals can, in turn, lead to a degradation of the dielectric at the high voltages often used during the use of the wet capacitor, thus electrochemical anodic polymerization techniques can be used in certain modes of operation. These techniques generally employ a colloidal suspension which is generally free of iron-based oxidation catalyst For example, the colloidal suspension typically contains less than about 0.5% by weight, in particular some embodiments, less than about 0.1% by weight, and in this Some embodiments are less than about 0.05% by weight (eg, 0% by weight) of these iron based oxidation catalysts.
    [0014] The colloidal suspension may be in the form of a macroemulsion, a microemulsion, a solution, etc. depending on the particular nature of the components of the suspension. Independently, the slurry generally contains a solvent which serves as a continuous phase within which the precursor monomer is dispersed. Any solvent of a variety of different solvents can be used in the colloidal suspension, such as alcohols, glycols, water, etc. In a particular embodiment, the colloidal suspension is of an aqueous nature. If desired, other additives may also be used in the suspension to facilitate polymerization, such as surfactants (e.g., nonionic, anionic or cationic surfactants), dopants (e.g. anti-foam agents, and so on. The solvents (eg water) can comprise from about 50% by weight to about 99% by weight, in some embodiments from about 70% by weight to about 98% by weight and in some embodiments from about 80% by weight to about 95% by weight. The remaining components of the colloidal suspension (e.g., precursor monomers, surfactants, and sulfonic acids) may likewise be from about 1% by weight to about 50% by weight, in some embodiments of the invention. from about 2% by weight to about 30% by weight and in some embodiments from about 5% by weight to about 20% by weight of the colloidal suspension.
    [0015] To apply the colloidal suspension, any application technique among a variety of suitable application techniques may be used, for example, screen printing, immersion, electrophoretic coating, spraying, and the like. Regardless of the mode of application, the monomer within the colloidal suspension may undergo anodic electrochemical polymerization to form the conductive polymer layer. In one embodiment, for example, the metal substrate is immersed in a bath containing the colloidal suspension of the present invention. A pair of electrodes may be disposed in the bath for electrolysis. An electrode may be connected to the positive terminal of a current source and also in contact with the metal substrate. The other electrode can be connected to the negative terminal of the current source and an additional inert metal. During operation, the power source supplies power to the electrodes in the electrochemical cell, thereby inducing electrolysis of the electrolyte and oxidative polymerization of the monomer in the colloidal suspension, or solution, on the metal substrate. . The anodic electrochemical polymerization is generally carried out at ambient temperature to ensure that the colloidal suspension does not undergo phase separation. For example, the colloidal suspension can be maintained at a temperature of about 15 ° C to about 80 ° C, in some embodiments, from about 20 ° C to about 75 ° C, and in some embodiments, from about 30 ° C to about 50 ° C. The time during which the metal substrate is in contact with the colloidal suspension during the electrochemical anodic polymerization can vary. For example, the metal substrate may be immersed in a solution for a time in the range of about 10 seconds to about 10 minutes. Multiple polymerization steps can be repeated until the desired thickness of the coating is obtained. In one embodiment, for example, a chemically polymerized layer may be formed directly on the noble metal layer and an electrochemically polymerized layer may be disposed thereon, or vice versa. Independently, the total target thickness of the conductive polymer layer (s) can generally vary depending on the desired properties of the capacitor. Typically, the resulting conductive polymer layer (s) has a thickness of about 0.2 micrometer ("pm") to about 50 pm, in some embodiments from about 0.5 pm to about 20 pm, and in some embodiments, from about 1 μm to about 5 μm. It should be understood that the thickness of the layers is not necessarily the same at all locations on the substrate. Nevertheless, the average thickness on the substrate is generally in the ranges noted above. The particular manner in which the components are incorporated in the capacitor is not critical and can be accomplished using a variety of techniques. In most embodiments, however, the anode is positioned within a housing. Referring to FIGS. 1 and 4, for example, one embodiment of a capacitor 10 is shown which includes the anode 200 shown in FIGS. 2 and 3. Although only one anode is shown, it should be understood that multiple anodes (eg, a stack) may be used as described, for example, in US Pat. No. 7,483,260 issued to Ziarniak et al. In the illustrated embodiment, the anode 200 may be positioned within a housing 12 formed by a first housing member 14 and a second housing member 16. The first housing member 14 has a front wall 18 joined 15 to a peripheral wall 20, which extends to an edge 22. The second housing member 16 may likewise contain a second front wall 24 having a peripheral edge 26. In the illustrated embodiment, the second housing member 16 is thus in the form of a plate which serves as a cover for the housing 10. The housing elements 14 and 16 can be hermetically sealed to one another by welding (for example, laser welding) edges 22 and 26 where they contact each other. The housing members 14 and / or 16 may be analogous to the metal substrate described above so that a conductive polymer coating (not shown) may be deposited on the inside of its surface. Alternatively, a separate metal substrate may be adjacent to the housing member 14 and / or 16 and the conductive polymer coating may be applied thereto.
    [0016] Although not illustrated, one or more separators may be used between the anode and the cathode (for example between the anode 200 and the first housing element 14, between the anode 200 and the second element housing 16, or between the anode and the two housing elements) which help to isolate the anode and the conductive polymer-coated cathode from each other. Examples of suitable materials for this purpose include, for example, porous polymeric materials (e.g., polypropylene, polyethylene, etc.), porous inorganic materials (e.g., fiberglass mats, porous glass, etc.), ion exchange resin materials, etc. Particular examples include ionic perfluorinated membranes of sulfonic acid polymers (e.g., NafionTM from DuPont de Nemours & Co.), fluorocarbon polymer sulfonated membranes, polybenzimidazole (PBI) membranes, and polyether membranes. ether ketone (PEEK). Even though it prevents direct contact between the anode and the cathode, the separator allows the flow of ionic current from the electrolyte to the electrodes. A bushing 30 (FIG. 1) can also be used which electrically insulates the anode wire 200 from the housing 12. The bushing 30 extends from the inside of the housing 12 to its outside. A hole 34 may be provided in the peripheral side wall 20 of the housing member 14 having the passage 30. The passage 30 may for example be a glass-on-metal ("GTMS") seal which contains a ferrule (not shown) with an internal cylindrical bore of constant inner diameter 3029006. An insulating glass can thus provide a hermetic seal between the bore and the anode wire 200 therethrough. After assembly and sealing (eg welding), the electrolyte may optionally be introduced into the housing through a fill port. Filling can be accomplished by placing the capacitor in a vacuum chamber so that the fill port extends into a reservoir of the electrolyte. When the chamber is evacuated, the pressure is reduced inside the capacitor. When the vacuum is released, the pressure inside the capacitor rebalances, and the electrolyte is drawn through the fill port into the capacitor.
    [0017] Regardless of its particular configuration, the capacitor of the present invention can exhibit excellent electrical properties. For example, the capacitor may have a high volumetric efficiency, e.g. from about 50,000 pF * V / cm3 to about 300,000 pF * V / cm3, in some embodiments of about 60,000 pF * V / cm3. at about 200,000 pF * V / cm3, and in some embodiments, from about 80,000 pF * V / cm3 to about 150,000 pF * V / cm3, determined at a frequency of 120 Hz and at room temperature ( for example, 25 ° C). The volumetric efficiency is determined by multiplying the forming tension of a part by its capacity, then by dividing the product by the volume of the part. For example, a forming voltage may be 175 volts for a portion having a capacity of 520 pF, resulting in a product of 91,000 pF * V. If the portion occupies a volume of about 0.8 cm3, this results in a volumetric efficiency of about 113,750 pF * V / cm3. The capacitor may also have a high energy density which makes it suitable for use in high pulse applications. The energy density is generally determined according to the equation E = 1/2 * CV 2, where C is the capacity in farads (F) and V is the working voltage of the capacitor in volts (V). The capacitance may, for example, be measured using a capacitance meter (for example, the Keithley 3330 Precision LCZ measuring instrument with Kelvin wires, 2 volt polarization and 1 volt signal) at operating frequencies of 10 volts. at 120 Hz (for example, 120 Hz) and at a temperature of 25 ° C. For example, the capacitor may have an energy density of about 2.0 joules per cubic centimeter (J / cm 3) or more, in some embodiments of about 3.0 J / cm 3, in some embodiments. about 3.5 J / cm 3 to about 10.0 J / cm 3, and in some embodiments, about 4.0 to about 8.0 J / cm 3. The capacity may similarly be about 1 millifarad per square centimeter ("mF / cm 2") or more, in some embodiments of about 2 mF / cm 2 or more, in some embodiments. from about 5 to about 50 mF / cm 2, and in some embodiments from about 8 to about 20 mF / cm 2. The capacitor may also have a relatively high "breakdown voltage" (voltage at which the capacitor becomes faulty), for example about 180 volts or more, in embodiments of about 200 volts or more, and in some embodiments, from about 210 volts to about 260 volts. Equivalent series resistance ("ESR") - the degree to which the capacitor acts as a resistor when charging and discharging in an electronic circuit - can also be less than about 15,000 milliohms, in some embodiments less than about 10 000 milliohms, in some embodiments less than about 5,000 milliohms, and in some embodiments, from about 1 to about 4,500 milliohms, measured with a 2 volt bias and a 1 volt signal at a frequency of 120 Hz. In addition, the leakage current, which generally refers to the current flowing from a conductor to an adjacent conductor by an insulator, can be maintained at relatively low levels. For example, the numerical value of the normalized leakage current of a capacitor of the present invention is, in some embodiments, less than about 1 pA / pF * V, in some embodiments less than about 0.5 pA. In some embodiments, less than about 0.1 pA / pF * V, where pA is microamperes and pF * V is the product of capacity and rated voltage. Leakage current can be measured using a leak test instrument (for example, MC 190 Leakage test, Mantracourt Electronics LTD, UK) at a temperature of 25 ° C and at a certain rated voltage after a charging time of 30 minutes. about 60 to about 300 seconds. Such values of RSE and normalized leakage current may even be maintained after aging for a significant period of time at elevated temperatures. For example, these values may be maintained for about 100 hours or more, in some embodiments for about 300 hours to about 2500 hours, and in some embodiments, for about 400 hours to about 1500 hours (e.g. 500 hours, 600 hours, 700 hours, 800 hours, 900 hours, 1000 hours, 1100 hours, or 1200 hours) at temperatures in the range of about 100 ° C to about 250 ° C, and in some embodiments from about 100 ° C to about 200 ° C (e.g., 100 ° C, 125 ° C, 150 ° C, 175 ° C, or 200 ° C) The electrolytic capacitor of the present invention may be used in a variety of applications including, but not limited to, implantable medical devices, such as implantable defibrillators, pacemakers, cardiovers, neural stimulators, drug delivery devices, and the like. In one embodiment, for example, the capacitor may be used in an implantable medical device configured to provide high voltage therapeutic treatment (e.g., between approximately 500 volts and approximately 850 volts, or desirably approximately 600 volts. volts and approximately 900 volts) to a patient. The device may contain a container or housing that is hermetically sealed and biologically inert. One or more wires are electrically coupled between the device and the patient's heart via a vein. Cardiac electrodes are provided to detect cardiac activity and / or provide tension to the heart. At least a portion of the leads (e.g., an end portion of the leads) may be provided adjacent or in contact with at least one of a ventricle and atrium of the heart. The device may also contain a capacitor bank that typically contains two or more capacitors connected in series and coupled to a battery that is internal or external to the device and provides power to the capacitor bank. In part because of the high conductivity, the capacitor of the present invention can achieve excellent electrical properties and thus be adapted for use in the capacitor bank of the implantable medical device. The present invention will be better understood by reference to the following example.
    [0018] Test procedure Capacitance ("CAP"), equivalent series resistance ("ESR") and leakage current ("DCL") were tested in a neutral electrolyte at a temperature of 37 ° C ± 0.5 ° vs.
    [0019] Capacitance ("CAP") Capacitance can be measured with a Keithley 3330 Precision LCZ measuring instrument with Kelvin wires with a DC bias of 2.2 volts and a peak-to-peak sinusoidal signal of 0.5 volts.
    [0020] The operating frequency can be 120 Hz. Equivalent Series Resistance ("ESR") 3029006 The equivalent series resistance can be measured with a Keithley 3330 Precision LCZ measuring instrument with Kelvin wires with a DC bias of 2.2 volts and sinusoidal signal peak to peak of 0.5 volts.
    [0021] The operating frequency can be 120 Hz. Leakage current ("DCL") Leakage current can be determined by charging at 250 V for 300 seconds without series resistance.
    [0022] EXAMPLE Anodes were formed from a reduced magnesium tantalum nodule powder (H.C. Starck) and a tantalum lamellar powder (Global Advanced Metals). Samples of each powder were compressed at a density of 5.3 g / cm 3 using 4% stearic acid lubricant. After the delubrication, a suspension crucible was then vacuum sintered at 1400 ° C for 10 minutes in a crucible suspended from 20 samples of each powder. During sintering, the pellets were anodized in a solution containing 50% glycol / water with phosphoric acid at a temperature of 85 ° C and a conductivity of 1 mS / cm. The formation current density was 45 mA / g for each sample. The 220 volt anodizing voltage was tested. The resulting anodes had a D-shape in which the length was about 32 millimeters, the width was about 23 millimeters, and the thickness was about 2 millimeters. The anodes were then joined with two cathodes prepared from Pd / PEDT coated titanium sheets 46 (0.1 mm thick) separated with two plastic threads (0.2 mm thick). The resulting capacitors were then tested as described above. The results are shown below.
    [0023] CAP powder [F] CSR [Ohm] DCL [A / g] CV / cc CV / g tantal [F / cm3] [F / g] NODULAR 465 1.42 33 93 238 15 761 LAMELLAR 360 1.40 116 As illustrated, the nodular powder was able to achieve comparatively high capacity and comparatively lower DCL. Using the obtained capacitance values and assuming an operating voltage, the energy density (E = 0.5 * CV2) indicated that the nodular powder also had a significantly higher energy density.
    [0024] These 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. In addition, it should be understood that aspects of the various embodiments may be modified in whole or in part. In addition, those skilled in the art will appreciate that the foregoing description is provided by way of example only, and is not intended to limit the invention further described in the appended claims.
    权利要求:
    Claims (26)
    [0001]
    REVENDICATIONS1. A wet electrolytic capacitor (10) comprising: a planar anode (200) which comprises an anodically oxidized pellet formed from a compressed and sintered valve metal powder, wherein the valve metal powder is formed by reaction of an oxide of a valve metal compound with a reducing agent which contains a metal having an oxidation state of 2 or more; a cathode which comprises a metal substrate coated with a conductive coating; and a working fluid electrolyte in communication with the anode (200) and the cathode.
    [0002]
    2. The capacitor (10) of claim 1, wherein the metal is an alkaline earth metal, aluminum, or a combination thereof.
    [0003]
    The capacitor (10) of claim 2, wherein the metal is magnesium.
    [0004]
    4. The capacitor (10) of claim 1, wherein the oxide is tantalum pentoxide.
    [0005]
    The capacitor (10) of claim 1, wherein the valve metal powder comprises tantalum.
    [0006]
    The capacitor (10) of claim 1, wherein the valve metal powder contains particles having an aspect ratio of about 4 or less. 3029006 48
    [0007]
    The capacitor (10) of claim 6, wherein the particles are nodular or angular particles.
    [0008]
    8. The capacitor (10) of claim 1, wherein the valve metal powder contains particles having an average size of about 5 to about 1000 nanometers.
    [0009]
    9. The capacitor (10) of claim 1, wherein the powder has a specific surface area of about 1 square meter per gram or more.
    [0010]
    The capacitor (10) of claim 1, wherein the powder has a specific charge of about 15,000 pF * V / g or more
    [0011]
    11. The capacitor (10) of claim 1, wherein the powder has not more than about 50 ppm alkali metals.
    [0012]
    The capacitor (10) of claim 1, wherein the anode (200) is about 5 millimeters thick or less in thickness. 20
    [0013]
    The capacitor (10) of claim 1, wherein an output wire extends from the planar anode (200).
    [0014]
    The capacitor (10) of claim 1, wherein the anode (200) is D-shaped.
    [0015]
    The capacitor (10) of claim 1, wherein the metal substrate comprises titanium or stainless steel.
    [0016]
    16. The capacitor (10) of claim 1, wherein the conductive coating comprises a substituted polythiophene. 3029006 49
    [0017]
    The capacitor (10) of claim 1, wherein the electrolyte has a pH of about 5.0 to about 7.5.
    [0018]
    The capacitor (10) of claim 1, wherein a separator is positioned between the anode (200) and the cathode.
    [0019]
    19. The capacitor (10) according to claim 1, wherein the capacitor (10) contains a housing (12) which contains a first housing element (14) and a second housing element (16) between which the anode ( 200) and the working fluid electrolyte, wherein the metal substrate forms at least a portion of the first housing member (14), the second housing member (16), or both.
    [0020]
    The capacitor (10) of claim 19, wherein the first housing member (14) contains a front wall (18) and a peripheral side wall (20) extending to an edge (22), and further wherein the second housing member (16) is in the form of a cover which is sealed to the edge (22) of the side wall (20).
    [0021]
    An implantable medical device comprising the capacitor (10) according to claim 1.
    [0022]
    A wet electrolytic capacitor (10) comprising: a planar anode (200) which comprises an anodically oxidized pellet formed from a compressed and sintered tantalum powder, wherein the powder is nodular or angular and has a charge specific of about 15,000 pF * V / g or more; A cathode which comprises a metal substrate coated with a conductive coating; and a working fluid electrolyte in communication with the anode (200) and the cathode. 5
    [0023]
    The capacitor (10) of claim 22, wherein the tantalum powder is formed by reacting a tantalum oxide with a reducing agent that contains magnesium, strontium, barium, cesium, calcium, aluminum, or a combination thereof.
    [0024]
    The capacitor (10) of claim 22, wherein the powder has a specific surface area of from about 4 to about 30 square meters per gram.
    [0025]
    25. The capacitor (10) of claim 22 wherein the powder has not more than about 50 ppm alkali metals.
    [0026]
    26. A method of forming a wet electrolytic capacitor (10), the method comprising: compressing the tantalum powder into a pellet form, wherein the tantalum powder is formed by reacting an oxide of tantalum with a reducing agent that contains magnesium, calcium, strontium, barium, cesium, aluminum, or a combination thereof; Sintering the pellet; the anodic oxidation of the sintered pellet to form a dielectric layer which covers the anode (200); and positioning the anode (200) and a working fluid electrolyte within a housing (12).
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    同族专利:
    公开号 | 公开日
    US20160148757A1|2016-05-26|
    HK1219561A1|2017-04-07|
    CN105632766A|2016-06-01|
    US10290430B2|2019-05-14|
    DE102015220954A1|2016-05-25|
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    CN112735830A|2021-04-30|
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    法律状态:
    2016-10-17| PLFP| Fee payment|Year of fee payment: 2 |
    2017-10-18| PLFP| Fee payment|Year of fee payment: 3 |
    2017-12-01| PLSC| Publication of the preliminary search report|Effective date: 20171201 |
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    2021-10-25| PLFP| Fee payment|Year of fee payment: 7 |
    2022-03-04| CD| Change of name or company name|Owner name: KYOCERA AVX COMPONENTS CORPORATION, US Effective date: 20220125 |
    优先权:
    申请号 | 申请日 | 专利标题
    US14/551,183|US10290430B2|2014-11-24|2014-11-24|Wet Electrolytic Capacitor for an Implantable Medical Device|
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