The present invention generally relates to a capacitor, and more particularly, to a capacitor having a cathode spaced from an anode. The cathode is of an active material supported on a casing sidewall or a conductive substrate/partition in contact with the casing sidewall. The anode is typically in the form of a sintered valve metal pellet, such as a sintered tantalum pellet that has been anodized. The anode and cathode are kept from direct physical contact with each other by a separator. A working electrolyte filled into the casing serves as an ionic transport for charging and discharging the capacitor.
The present invention is directed to a capacitor having at least two anodes, each preferably in the form of a tantalum pellet housed inside a casing compartment. The casing preferably includes two shallow-drawn casing portions, each housing one of the anode pellets and each in the shape of a clamshell having their annular rims facing each other. Unlike conventional capacitor designs, the two casing clamshells do not contact each other. Instead, an intermediate partition in the shape of a wall or lid is provided between the casing clamshell portions. The intermediate partition is sized and shaped so that the clamshell rims butt-up to its opposite sides. Further, major face walls of the clamshells as well as opposed major surface of the intermediate partition support cathode active material thereon. The clamshell rims are hermetically secured to the intermediate partition by a perimeter weld to thereby seal the casing. Preferably, the main body of the intermediate partition serving as a cathode current collector supporting cathode active material is perforated while the surrounding perimeter frame of the partition welded to the spaced apart clamshells is not.
The casing is filled with electrolyte thru a port and hermetically sealed. Preferably, the anode pellets have their own feedthrough, which electrically isolate the respective anode leads from the casing. The feedthrough leads are electrically connected in parallel outside the casing to provide one terminal for the capacitor. The casing serves as the other terminal.
These and other objects of the present invention will become increasingly more apparent to those skilled in the art by reference to the following detailed description and the appended drawings.
The present invention will be described in connection with preferred embodiments, however, it will be understood that there is no intent to limit the invention to the embodiments described. On the contrary, the intent is to cover all alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
As shown in
Casing 18 is of metal material comprising first and second clamshell portions 20 and 22. As will be described in detail hereinafter, a novel aspect of the present invention is that the clamshells 20 and 22 do not contact each other, but, instead, contact the opposite sides of an intermediate partition or lid serving as a cathode current collector 24 supporting cathode active materials 16 thereon.
The casing clamshells 20, 22 and the electrically conductive intermediate partition serving as the cathode current collector 24 are made of a conductive metal selected from the group consisting of tantalum, titanium, nickel, niobium, stainless steel, aluminum, zirconium, and mixtures and alloys thereof. Regardless the metal, the clamshells 20, 22 have a thickness of about 0.015 to about 0.5 millimeters and together with the current collector 24 serves as one terminal or contact for making electrical connection between the capacitor and its load.
In greater detail, the first clamshell 20 comprises a face wall 26 joined to a surrounding sidewall 28 extending to an outwardly extending rim 30 having a rim outer edge 30A. Similarly, the second clamshell 22 comprises a face wall 32 joined to a surrounding sidewall 34 extending to an outwardly extending rim 36 having a rim outer edge 36A. The clamshells 20, 22 are sized so that their rims 30, 36 butt-up to opposite sides of the intermediate partition serving as the cathode current collector 24. While not shown in the drawings, the clamshell rims 30, 36 are hermetically secured to the cathode current collector 24 by a perimeter weld to thereby seal the casing 18. Preferably, the main body of the current collector 24 is perforated while a surrounding perimeter frame 24A (
Accordingly, the cathode current collector 24 is sized and shaped so that an outer perimeter edge 24B of the unperforated perimeter frame 24A is substantially coincident with the outer edges 30A, 36A of the clamshell rims 30, 36. It should be understood, however, that the present invention is not limited to the outer rim edges 30A and 36A being precisely aligned one above the other with respect to the outer perimeter edge 24B of the current collector. Instead, the respective edges are aligned one above the other to a degree that is sufficient to weld completely around the perimeter of the rims and current collector edge to thereby secure the clamshells 20, 22 together, sandwiching the current collector 24 therebetween in a hermetically sealed manner. This weld is provided by any conventional means; however, a preferred method is by laser welding.
The active material of the anodes 12 and 14 is typically of a metal in the form of a pellet. The anode metal is selected from the group consisting of tantalum, aluminum, titanium, niobium, zirconium, hafnium, tungsten, molybdenum, vanadium, silicon, germanium, and mixtures thereof. As is well known by those skilled in the art, the anode metal in powdered form, for example tantalum powder, is compressed into a pellet having an anode lead 38 (
A preferred tantalum material and method of manufacturing an anode pellet for the present capacitor 10, which is well suited for implantable cardiac device capacitor applications, is described in U.S. Pat. No. 9,312,075 to Liu et al., which is assigned to the assignee of the present invention and incorporated herein by reference. Other suitable capacitor grade tantalum powders are described in U.S. Pat. No. 9,312,075 to Liu et al., which is assigned to the assignee of the present invention and incorporated herein by reference.
Before pressing, the tantalum powder is typically, but not necessarily, mixed with approximately 0 to 5 percent of a binder such as ammonium carbonate. This and other binders can be used to facilitate metal particle adhesion and die lubrication during anode pressing. The powder and binder mixture are dispended into a die cavity and pressed to a density ranging from about 4 grams/cc3 to about 8 grams/cc3. The binder is then removed from the anode pellets 12, 14 either by washing in warm deionized water or by heating at a temperature sufficient to decompose the binder. Complete binder removal is desirable since residuals may result in high leakage current. The washed anode pellets with extending leads 38 are then vacuum-sintered at between about 1,350° C. to about 1,600° C. to permanently bond the metal anode particles.
An oxide is formed on the surface of the sintered anode pellets 12, 14 and their leads 38 by immersing them in an electrolyte and applying a current. The electrolyte includes constituents such as water and phosphoric acid and perhaps other organic solvents. The application of current drives the formation of an oxide film that is proportional in thickness to the targeted forming voltage. A pulsed formation process may be used wherein current is cyclically applied and removed to allow diffusion of heated electrolyte from the internal pores of the anodes. Intermediate washing and annealing steps may be performed to facilitate the formation of a stable, defect free, oxide. Preferably, the anode pellets 12, 14 and extending leads 38 are anodized to a formation voltage that is greater than zero up to 550 V.
Cathode active material 16 having a thickness of about a few hundred Angstroms to about 0.1 millimeters is directly coated on the inner surface of the clamshell face walls 26, 32 or, the cathode active material is coated on a conductive substrate (not shown) in electrical contact with the inner surface of the face walls, spaced from the respective sidewalls 28, 34. Another portion of the cathode active material 16 is supported on the opposed perforated major surfaces of the current collector 24, but spaced from the unperforated perimeter frame 24A.
These coatings are accomplished by providing the conductive face walls 26, 32 and the perimeter current collector frame 24A with a masking material in a known manner so that only intended areas of the clamshell face walls 26, 32 and cathode current collector 24 are contacted with active material. The masking material is removed from the face walls 26, 32 and current collector frame 24A prior to capacitor fabrication. Preferably, the cathode active material 16 is substantially aligned in a face-to-face, but spaced apart relationship with the major faces of the anodes 12, 14.
As disclosed in U.S. Pat. No. 7,116,547 to Seitz et al., a preferred coating process is by pad printing. This patent is assigned to the assignee of the present invention and incorporated herein by reference. An ultrasonically generated aerosol, as described in U.S. Pat. Nos. 5,894,403, 5,920,455, 6,224,985, and 6,468,605, all to Shah et al., is also suitable for making a coating of the active materials. These patents and the Seitz et al. patent are assigned to the assignee of the present invention and incorporated herein by reference. In that manner, the ultrasonically generated active material contacted to the conductive surfaces of the clamshell face walls 26, 32 and current collector 24 has a majority of its particles with diameters of less than about 10 microns. This provides an internal surface area for the active material of about 10 m2/gram to about 1,500 m2/gram.
In various embodiments, the face walls 26, 32 and the current collector 24 may be of an anodized-etched conductive material, have a sintered active material with or without oxide contacted thereto, be contacted with a double layer capacitive material, for example a finely divided carbonaceous material such as graphite, carbon, activated carbon or platinum black, a redox, pseudocapacitive or an under potential material, or be an electroactive conducting polymer such as polyaniline, polypyrrole, polythiophene, and polyacetylene, and mixtures thereof.
According to one preferred aspect of the present invention, the redox or cathode active material 16 includes an oxide of a first metal, the nitride of the first metal, the carbon nitride of the first metal, and/or the carbide of the first metal, the oxide, nitride, carbon nitride and carbide having pseudocapacitive properties. The first metal is preferably selected from the group consisting of ruthenium, cobalt, manganese, molybdenum, tungsten, tantalum, iron, niobium, iridium, titanium, zirconium, hafnium, rhodium, vanadium, osmium, palladium, platinum, nickel, and lead.
The cathode active material 16 may also include a second or more metals. The second metal is in the form of an oxide, a nitride, a carbon nitride or carbide, and is not essential to the intended use of the conductive face walls 26, 32 and the intermediate current collector 24 as a capacitor electrode. The second metal is different than the first metal and is selected from one or more of the group consisting of tantalum, titanium, nickel, iridium, platinum, palladium, gold, silver, cobalt, molybdenum, ruthenium, manganese, tungsten, iron, zirconium, hafnium, rhodium, vanadium, osmium, and niobium. In a preferred embodiment of the invention, the cathode active material 16 includes an oxide of ruthenium.
The cathode active material 16 may also be selected from graphitic or glassy carbon on titanium carbide, carbon and silver vanadium oxide on titanium carbide, carbon and crystalline manganese dioxide on titanium carbide, platinum on titanium, ruthenium on titanium, barium titanate on titanium, carbon and crystalline ruthenium oxide on titanium carbide, carbon and crystalline iridium oxide on titanium carbide, silver vanadium oxide on titanium, and activated carbon.
A separator (not shown) of electrically insulative material is provided between the anodes 12 and 14 and the cathode active materials 16 to prevent an internal electrical short circuit between the electrodes. The separator is chemically unreactive with the anode and cathode active materials and both chemically unreactive with and insoluble in the electrolyte. In addition, the separator material has a degree of porosity sufficient to allow flow therethrough during charging and discharging of the capacitor 10.
Illustrative separator materials include woven and non-woven fabrics of polyolefinic fibers including polypropylene and polyethylene, or fluoropolymeric fibers including polyvinylidene fluoride, polyethylenetetrafluoroethylene, and polyethylenechlorotrifluoroethylene laminated or superposed with a polyolefinic or fluoropolymeric microporous film, non-woven glass, glass fiber materials and ceramic materials. Suitable microporous films include a polyethylene membrane commercially available under the designation SOLUPOR®, (DMS Solutech); a polytetrafluoroethylene membrane commercially available under the designation ZITEX®, (Chemplast Inc.) or EXCELLERATOR®, (W.L. Gore and Associates); a polypropylene membrane commercially available under the designation CELGARD®, (Celgard LLC); and a membrane commercially available under the designation DEXIGLAS®, (C. H. Dexter, Div., Dexter Corp.). Cellulose based separators also typically used in capacitors are contemplated by the scope of the present invention. Depending on the electrolyte used, the separator can be treated to improve its wettability, for example with a surfactant, as is well known by those skilled in the art.
As shown in
As shown in
An insulative glass 52 provides a hermetic seal between the inside of the ferrule 44 and the anode feedthrough lead 42. The glass is, for example, ELAN® type 88 or MANSOL™ type 88. Alternatively, member 52 is not a glass, but, instead, a synthetic polymeric material such as elastomeric materials that are capable of sealing between feedthrough lead 42 and the inner surface of ferrule 44. A suitable polymeric material for the layer 52 is, for example Master-Sil 151 made by Master Bond. While such a seal structure using only a synthetic polymeric material is not necessarily hermetic, acceptable isolation of the electrolyte from inside of the casing 18 to the outside thereof is provided by the polymer layer 52.
The anode lead 38 and feedthrough lead 42 preferably comprise the same material as the anode active material. In that manner, the portion of the feedthrough lead 42 extending outside the capacitor 10 is hermetically sealed from the interior of the capacitor and insulated from the mating casing portions 20, 22 serving as the terminal for the cathode electrode.
The capacitor 10 illustrated in
A fill opening or port in the casing 16 is provided for filing a working electrolyte (not shown) into the capacitor 10, after which this opening is sealed with a closure member 66, which is preferably welded in place. A suitable working electrolyte for the capacitor 10 is described in U.S. Pat. No. 6,219,222 to Shah et al., which includes a mixed solvent of water and ethylene glycol having an ammonium salt dissolved therein. U.S. Pat. No. 6,687,117 and U.S. Patent Application Pub. No. 2003/0090857, both to Liu et al., describe other electrolytes that are useful with the present capacitor 10. The electrolyte of the latter publication comprises water, a water-soluble inorganic and/or organic acid and/or salt, and a water-soluble nitro-aromatic compound while the former relates to an electrolyte having de-ionized water, an organic solvent, isobutyric acid and a concentrated ammonium salt. These patents and publications are assigned to the assignee of the present invention and incorporated herein by reference.
Filling is accomplished by placing the capacitor 10 in a vacuum chamber such that the electrolyte fill port extends into a reservoir of electrolyte. When the chamber is evacuated, pressure is reduced inside the capacitor. When the vacuum is released, pressure inside the capacitor re-equilibrates, and electrolyte is drawn through the fill port into the capacitor.
The capacitor 10 is now connectable to a load (not shown) as a power source. That is done by connecting the load to a negative polarity casing terminal pin 64 and the common positive terminal 62.
Capacitor 10 of the present invention is not limited to dual anode designs. Instead, the capacitor may comprise additional anodes and cathode current collectors including cathode active material on the current collector faces thereof. Moreover, while not shown in the drawings, a molded polymeric cradle or restraint is preferably provided for containing the anodes 12, 14 in the desired position should the capacitor 10 experience high shock and vibration conditions. Suitable restraints are described in U.S. Pat. No. 7,085,126 to Muffoletto et al. and U.S. Pat. No. 7,092,242 to Gloss et al., which are assigned to the assignee of the present invention and incorporated herein by reference.
Although several embodiments of the invention have been described in detail, for purposes of illustration, various modifications of each may be made without departing from the spirit and scope of the invention. Accordingly, the invention is not to be limited, except as by the appended claims.
This application claims priority to U.S. provisional patent application Ser. No. 62/248,842, filed on Oct. 30, 2015.
Number | Date | Country | |
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62248842 | Oct 2015 | US |