|Publication number||US6979513 B2|
|Application number||US 10/798,875|
|Publication date||27 Dec 2005|
|Filing date||12 Mar 2004|
|Priority date||28 Jun 2002|
|Also published as||US20040191632, US20050191555, WO2005096418A1, WO2005096418B1|
|Publication number||10798875, 798875, US 6979513 B2, US 6979513B2, US-B2-6979513, US6979513 B2, US6979513B2|
|Inventors||Kurtis Chad Kelley, John J. Votoupal|
|Original Assignee||Firefly Energy Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (111), Non-Patent Citations (7), Referenced by (60), Classifications (39), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part of U.S. application Ser. No. 10/183,471 filed on Jun. 28, 2002, which is incorporated herein by reference.
This invention relates generally to current collectors for a battery and, more particularly, to carbon foam current collectors for a battery.
Electrochemical batteries, including, for example, lead acid and nickel-based batteries, among others, are known to include at least one positive current collector, at least one negative current collector, and an electrolytic solution. In lead acid batteries, for example, both the positive and negative current collectors are constructed from lead. The role of these lead current collectors is to transfer electric current to and from the battery terminals during the discharge and charging processes. Storage and release of electrical energy in lead acid batteries is enabled by chemical reactions that occur in a paste disposed on the current collectors. The positive and negative current collectors, once coated with this paste, are referred to as positive and negative plates, respectively. A notable limitation on the durability of lead-acid batteries is corrosion of the lead current collector of the positive plate.
The rate of corrosion of the lead current collector is a major factor in determining the life of the lead acid battery. Once the electrolyte (e.g., sulfuric acid) is added to the battery and the battery is charged, the current collector of each positive plate is continually subjected to corrosion due to its exposure to sulfuric acid and to the anodic potentials of the positive plate. One of the most damaging effects of this corrosion of the positive plate current collector is volume expansion. Particularly, as the lead current collector corrodes, lead dioxide is formed from the lead source metal of the current collector. Moreover, this lead dioxide corrosion product has a greater volume than the lead source material consumed to create the lead dioxide. Corrosion of the lead source material and the ensuing increase in volume of the lead dioxide corrosion product is known as volume expansion.
Volume expansion induces mechanical stresses on the current collector that deform and stretch the current collector. At a total volume increase of the current collector of approximately 4% to 7%, the current collector may fracture. As a result, battery capacity may drop, and eventually, the battery will reach the end of its service life. Additionally, at advanced stages of corrosion, internal shorting within the current collector and rupture of the cell case may occur. Both of these corrosion effects may lead to failure of one or more of the cells within the battery.
One method of extending the service life of a lead acid battery is to increase the corrosion resistance of the current collector of the positive plate. Several methods have been proposed for inhibiting the corrosion process in lead acid batteries. Because carbon does not oxidize at the temperatures at which lead-acid batteries generally operate, some of these methods have involved using carbon in various forms to slow or prevent the detrimental corrosion process in lead acid batteries. For example, U.S. Pat. No. 5,512,390 (hereinafter the '390 patent) discloses a lead acid battery that includes current collectors made from graphite plates instead of lead. The graphite plates have sufficient conductivity to function as current collectors, and they are more corrosion resistant than lead. Substituting graphite plates for the lead current collectors may, therefore, lengthen the life of a lead-acid battery.
While the battery of the '390 patent may potentially offer a lengthened service life as a result of reduced corrosion at the positive plate, the graphite plates of the '390 patent are problematic. For example, the graphite plates of the '390 patent are dense, flat sheets of material each having a relatively small amount of surface area. Unlike lead electrode plates of a conventional lead-acid battery, which are generally patterned into a grid-like structure to increase the available surface area of the plates, the graphite plates of the '390 patent are smooth sheets with no patterning. In lead acid batteries, an increase in surface area of the current collector may increase the specific energy and power of the battery and, therefore, may translate into improved battery performance. More surface area on the current collectors may also lead to a reduction in the time required for charging and discharging of the battery. The relatively small surface area of the graphite plates of the '390 patent results in poorly performing batteries that have slow charging speeds.
Additionally, the graphite plates of the '390 patent lack the toughness of lead current collectors. The dense, graphite plates of the '390 patent are brittle and may fracture when subjected to physical shock or vibration. Such physical shock and vibration commonly occur in vehicular applications, for example. Any fracturing of the graphite plates would lead to the same problems caused by volume expansion of ordinary lead current collectors. Therefore, despite offering an increased resistance to corrosion compared to conventional lead current collectors, the brittle nature of the graphite plates of the '390 patent could actually result in battery service lives shorter than those possible through use of ordinary lead current collectors.
The present invention is directed to overcoming one or more of the problems or disadvantages existing in the prior art.
One embodiment of the present invention includes an electrode plate for a battery. The electrode plate includes a carbon foam current collector that has a network of pores. A chemically active material is disposed on the carbon foam current collector such that the chemically active material penetrates into the network of pores.
A second embodiment of the present invention includes a method of making an electrode plate for a battery. This method includes forming a current collector from carbon foam. The carbon foam current collector includes a protruding tab and a network of pores. An electrical connection may be formed at the protruding tab of the current collector. The method also includes applying a chemically active material to the current collector such that the chemically active material penetrates the network of pores in the carbon foam.
A third embodiment of the present invention includes a method of making an electrode plate for a battery. The method includes supplying a wood substrate and carbonizing the wood substrate to form a carbonized wood current collector. Chemically active material may be disposed on the carbonized wood current collector.
A fourth embodiment of the present invention includes a battery. This battery includes a housing, and positive and negative terminals. Within the housing is at least one cell that includes at least one positive plate and at least one negative plate connected to the positive terminal and negative terminal, respectively. An electrolytic solution fills a volume between the positive and negative plates. The at least one positive plate includes a carbon foam current collector including a network of pores, and a chemically active material disposed on the carbon foam current collector such that the chemically active paste penetrates the network of pores.
Each cell 13 may be composed of alternating positive and negative plates immersed in an electrolytic solution. The electrolytic solution composition may be chosen to correspond with a particular battery chemistry. For example, while lead acid batteries may include an electrolytic solution of sulfuric acid and distilled water, nickel-based batteries may include alkaline electrolyte solutions that include a base, such as potassium hydroxide, mixed with water. It should be noted that other acids and other bases may be used to form the electrolytic solutions of the disclosed batteries.
The positive and negative plates of each cell 13 may include a current collector packed or coated with a chemically active material. The composition of the chemically active material may depend on the chemistry of battery 10. For example, lead acid batteries may include a chemically active material including, for example, an oxide or salt of lead. Further, the anode plates (i.e., positive plates) of nickel cadmium (NiCd) batteries may include cadmium hydroxide (Cd(OH)2) material; nickel metal hydride batteries may include lanthanum nickel (LaNi5) material; nickel zinc (NiZn) batteries may include zinc hydroxide (Zn(OH)2) material; and nickel iron (NiFe) batteries may include iron hydroxide (Fe(OH)2) material. In all of the nickel-based batteries, the chemically active material on the cathode (i.e., negative) plate may be nickel hydroxide.
The current collector shown in
While the type of plate, whether positive or negative, does not depend on the material selected for current collector 20, the current collector material and configuration affects the characteristics and performance of battery 10. For example, during the charging and discharging processes, each current collector 20 transfers the resulting electric current to and from battery terminals 12. In order to efficiently transfer current to and from terminals 12, current collector 20 must be formed from a conductive material. Further, the susceptibility of the current collector material to corrosion will affect not only the performance of battery 10, but it will also impact the service life of battery 10. In addition to the material selected for the current collector 20, the configuration of current collector 20 is also important to battery performance. For instance, the amount of surface area available on current collector 20 may influence the specific energy, specific power, and the charge/discharge rates of battery 10.
In an exemplary embodiment of the present invention, current collector 20, as shown in
The disclosed foam material may include any carbon-based material having a reticulated pattern including a three-dimensional network of struts and pores. The foam may comprise either or both of naturally occurring and artificially derived materials.
Regardless of the average pore size, a total porosity value for the carbon foam may be at least 60%. In other words, at least 60% of the volume of the carbon foam structure may be included within pores 41. Carbon foam materials may also have total porosity values less than 60%. For example, in certain embodiments, the carbon foam may have a total porosity value of at least 30%.
Moreover, the carbon foam may have an open porosity value of at least 90%. Therefore, at least 90% of pores 41 are open to adjacent pores such that the network of pores 41 forms a substantially open network. This open network of pores 41 may allow the active material deposited on each current collector 20 to penetrate within the carbon foam structure. In addition to the network of pores 41, the carbon foam includes a web of structural elements 42 that provide support for the carbon foam. In total, the network of pores 41 and the structural elements 42 of the carbon foam may result in a density of less than about 0.6 gm/cm3 for the carbon foam material.
Due to the high conductivity of the carbon foam of the present invention, current collectors 20 can efficiently transfer current to and from the battery terminals 12, or any other conductive elements providing access to the electrical potential of battery 10. In certain forms, the carbon foam may offer sheet resistivity values of less than about 1 ohm-cm. In still other forms, the carbon foam may have sheet resistivity values of less than about 0.75 ohm-cm.
In addition to carbon foam, graphite foam may also be used to form current collector 20. One such graphite foam, under the trade name PocoFoam™, is available from Poco Graphite, Inc. The density and pore structure of graphite foam may be similar to carbon foam. A primary difference between graphite foam and carbon foam is the orientation of the carbon atoms that make up the structural elements 42. For example, in carbon foam, the carbon may be at least partially amorphous. In graphite foam, however, much of the carbon is ordered into a graphite, layered structure. Because of the ordered nature of the graphite structure, graphite foam may offer higher conductivity than carbon foam. Graphite foam may exhibit electrical resistivity values of between about 100 μΩ-cm and about 2500 μΩ-cm.
The carbon and graphite foams of the present invention may also be obtained by subjecting various organic materials to a carbonizing and/or graphitizing process. In one exemplary embodiment, various wood species may be carbonized and/or graphitized to yield the carbon foam material for current collector 20. Wood includes a natural occurring network of pores. These pores may be elongated and linearly oriented. Moreover, as a result of their water-carrying properties, the pores in wood form a substantially open structure. Certain wood species may offer an open porosity value of at least about 90%. The average pore size of wood may vary among different wood species, but in an exemplary embodiment of the invention, the wood used to form the carbon foam material has an average pore size of at least about 20 microns.
Many species of wood may be used to form the carbon foam of the invention. As a general class, most hardwoods have pore structures suitable for use in the carbon foam current collectors of the invention. Exemplary wood species that may be used to create the carbon foam include oak, mahogony, teak, hickory, elm, sassafras, bubinga, palms, and many other types of wood. Optionally, the wood selected for use in creating the carbon foam may originate from tropical growing areas. For example, unlike wood grown in climates with significant seasonal variation, wood from tropical regions may have a less defined growth ring structure. As a result, the porous network of wood from tropical areas may lack certain non-uniformities that can result from the presence of growth rings.
To provide the carbon foam, wood may be subjected to a carbonization process to create carbonized wood (e.g., a carbon foam material). For example, heating of the wood to a temperature of between about 800° C. and about 1400° C. may have the effect of expelling volatile components from the wood. The wood may be maintained in this temperature range for a time sufficient to convert at least a portion of the wood to a carbon matrix. This carbonized wood will include the original porous structure of the wood. As a result of its carbon matrix, however, the carbonized wood can be electrically conductive and resistant to corrosion. During the carbonization process, the wood may be heated and cooled at any desired rate. In one embodiment, however, the wood may be heated and cooled sufficiently slowly to minimize or prevent cracking of the wood/carbonized wood. Also, heating of the wood may occur in an inert environment.
The carbonized wood may be used to form current collectors 20 without additional processing. Optionally, however, the carbonized wood may be subjected to a graphitization process to create graphitized wood (e.g., a graphite foam material). Graphitized wood is carbonized wood in which at least a portion of the carbon matrix has been converted to a graphite matrix. As previously noted, the graphite structure may exhibit increased electrical conductivity as compared to non-graphite carbon structures. Graphitizing the carbonized wood may be accomplished by heating the carbonized wood to a temperature of between about 2400° C. and about 3000° C. for a time sufficient to convert at least a portion of the carbon matrix of the carbonized wood to a graphite matrix. Heating and cooling of the carbonized wood may proceed at any desired rate. In one embodiment, however, the carbonized wood may be heated and cooled sufficiently slowly to minimize or prevent cracking. Also, heating of the carbonized wood may occur in an inert environment.
In an exemplary embodiment of the present invention, current collector 20 may be made from either carbon foam or from graphite foam. In certain battery chemistries, however, either the current collector of the positive plate or the current collector of the negative plate may be formed of a material other than carbon or graphite foam. For example, in lead acid batteries, the current collector of the negative plate may be made of lead or another suitable conductive material. In other battery chemistries (e.g., nickel-based batteries), the current collector of the positive plate may be formed of a conductive material other than carbon or graphite foam.
The process for making an electrode plate for a battery according to one embodiment of the present invention can begin by forming current collector 20. In one embodiment of the invention, the carbon foam material used to form current collector 20 may be fabricated or acquired in the desired dimensions of current collector 20. Alternatively, however, the carbon foam material may be fabricated or acquired in bulk form and subsequently machined to form the current collectors.
While any form of machining, such as, for example, band sawing and waterjet cutting, may be used to form the current collectors from the bulk carbon foam, wire EDM (electrical discharge machining) provides a method that may better preserve the open-cell structure of the carbon foam. In wire EDM, conductive materials are cut with a thin wire surrounded by de-ionized water. There is no physical contact between the wire and the part being machined. Rather, the wire is rapidly charged to a predetermined voltage, which causes a spark to bridge a gap between the wire and the work piece. As a result, a small portion of the work piece melts. The de-ionized water then cools and flushes away the small particles of the melted work piece. Because no cutting forces are generated by wire EDM, the carbon foam may be machined without causing the network of pores 41 to collapse. By preserving pores 41 on the surface of the current collector, chemically active materials may penetrate more easily into current collector 20.
As shown in
Once a carbon-metal interface has been established at tab 21, a second conductive material may be added to the tab 21 to complete the electrical connection. For example, a metal such as lead may be applied to tab 21. In an exemplary embodiment, lead wets the silver-treated carbon foam in a manner that allows enough lead to be deposited on tab 21 to form a suitable electrical connection.
A chemically active material, in the form of a paste or a slurry, for example, may be applied to current collector 20 such that the active material penetrates the network of pores in the carbon foam. It should be noted that the chemically active material may penetrate one, some, or all of the pores in the carbon foam. One exemplary method for applying a chemically active material to current collector 20 includes spreading a paste onto a transfer sheet, folding the transfer sheet including the paste over the current collector 20, and applying pressure to the transfer sheet to force the chemically active paste into pores 41. Pressure for forcing the paste into pores 41 may be applied by a roller, mechanical press, or other suitable device. Still another method for applying a chemically active material to current collector 20 may include dipping, painting, or otherwise coating current collector 20 with a slurry of active material. This slurry may flow into pores 41 to coat internal and external surfaces of current collector 20.
As noted above, the composition of the chemically active material used on current collectors 20 depends on the chemistry of battery 10. For example, in lead acid batteries, the chemically active material that is applied to the current collectors 20 of both the positive and negative plates may be substantially the same in terms of chemical composition. Specifically, this material may include lead oxide (PbO). Other oxides and salts of lead, however, may also be suitable. The chemically active material may also include various additives including, for example, varying percentages of free lead, structural fibers, conductive materials, carbon, and extenders to accommodate volume changes over the life of the battery. In certain embodiments, the constituents of the chemically active material for lead acid batteries may be mixed with sulfuric acid and water to form a paste, slurry, or any other type of coating material that may be disposed within pores 41 of current collector 20.
The chemically active material used on current collectors of nickel-based batteries may include various compositions depending on the type of battery and whether the material is to be used on a positive or negative plate. For example, the positive plates may include a cadmium hydroxide (Cd(OH)2) active material in NiCd batteries, a lanthanum nickel (LaNi5) active material in nickel metal hydride batteries, a zinc hydroxide (Zn(OH)2) active material in nickel zinc (NiZn) batteries, and an iron hydroxide (Fe(OH)2) active material in nickel iron (NiFe) batteries. In all nickel-based batteries, the chemically active material disposed on the negative plate may be nickel hydroxide. For both the positive and negative plates in nickel-based batteries, the chemically active material may be applied to the current collectors as, for example, a slurry, a paste, or any other appropriate coating material.
Independent of battery chemistry, depositing the chemically active material on the current collectors 20 forms the positive and negative plates of the battery. While not necessary in all applications, in certain embodiments, the chemically active material deposited on current collectors 20 may be subjected to curing and/or drying processes. For example, a curing process may include exposing the chemically active materials to elevated temperature and/or humidity to encourage a change in the chemical and/or physical properties of the chemically active material.
After assembling together the positive and negative plates to form the cells of battery 10 (shown in
By incorporating carbon into the electrode plates of the battery 10, corrosion of the current collectors may be suppressed. As a result, batteries consistent with the present invention may offer significantly longer service lives.
Additionally, the large amount of surface area associated with the carbon foam or graphite foam materials forming current collectors 20 may translate into batteries having both large specific power and specific energy values. Specifically, because of the open cell, porous network and relatively small pore size of the carbon foam materials, the chemically active material of the positive and negative plates is intimately integrated with the current collectors 20. The reaction sites in the chemically active paste are close to one or more conductive, carbon foam structural elements 42. Therefore, electrons produced in the chemically active material at a particular reaction site must travel only a short distance through the paste before encountering one of the many highly conductive structural elements 42 of current collector 20. As a result, batteries with carbon foam current collectors 20 may offer both improved specific power and specific energy values. In other words, these batteries, when placed under a load, may sustain their voltage above a predetermined threshold value for a longer time than batteries including traditional current collectors made of lead, graphite plates, etc.
The increased specific power values offered by batteries consistent with the present invention also may translate into reduced charging times. Therefore, the disclosed batteries may be suitable for applications in which charging energy is available for only a limited amount of time. For instance, in vehicles, a great deal of energy is lost during ordinary braking. This braking energy may be recaptured and used to charge a battery of, for example, a hybrid vehicle. The braking energy, however, is available only for a short period of time (i.e., while braking is occurring). Thus, any transfer of braking energy to a battery must occur during braking. In view of their reduced charging times, the batteries of the present invention may provide an efficient means for storing such braking energy.
Additionally, the disclosed carbon foam current collectors may be pliable, and therefore, they may be less susceptible to damage from vibration or shock as compared to current collectors made from graphite plates or other brittle materials. Batteries including carbon foam current collectors may perform well in vehicular applications, or other applications, where vibration and shock are common.
Further, by including carbon foam current collectors having a density of less than about 0.6 g/cm3, the battery of the present invention may weigh substantially less that batteries including either lead current collectors or graphite plate current collectors. Other aspects and features of the present invention can be obtained from a study of the drawings, the disclosure, and the appended claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US1285660||4 Apr 1918||26 Nov 1918||Bruce Ford||Secondary or storage battery.|
|US2620369||2 Aug 1950||2 Dec 1952||Arthur F Daniel||Plastic-cased dry cells|
|US2658099||11 Oct 1949||3 Nov 1953||Basset Lucien Paul||Microporous carbon and graphite articles, including impregnated battery electrodes and methods of making the same|
|US2843649||30 Nov 1956||15 Jul 1958||Myron A Coler||Moldable miniature battery|
|US3021379||21 Apr 1960||13 Feb 1962||Roland D Jackel||Ceramic separators for primary batteries|
|US3188242||13 Jul 1962||8 Jun 1965||Union Carbide Corp||Fuel cell battery containing flat carbon electrodes|
|US3442717||1 Oct 1965||6 May 1969||Varta Ag||Process for enveloping battery electrode plates in separators|
|US3565694||17 Mar 1969||23 Feb 1971||Yardney International Corp||Bipolar electrode and method of making same|
|US3597829||18 Mar 1969||10 Aug 1971||Us Army||Method of making a nickel hydroxide electrode|
|US3635676||5 Nov 1969||18 Jan 1972||Atomic Energy Commission||Method for increasing the strength of carbon foam|
|US3832426||19 Dec 1972||27 Aug 1974||Atomic Energy Commission||Syntactic carbon foam|
|US3833424||27 Mar 1973||3 Sep 1974||Licentia Gmbh||Gas fuel cell battery having bipolar graphite foam electrodes|
|US3857913||13 Oct 1972||31 Dec 1974||Atomic Energy Commission||Method for the manufacture of carbon foam|
|US3960770||25 Jul 1974||1 Jun 1976||The Dow Chemical Company||Process for preparing macroporous open-cell carbon foam from normally crystalline vinylidene chloride polymer|
|US4011374||2 Dec 1975||8 Mar 1977||The United States Of America As Represented By The United States Energy Research And Development Administration||Porous carbonaceous electrode structure and method for secondary electrochemical cell|
|US4084041 *||22 Mar 1977||11 Apr 1978||Ford Motor Company||Secondary battery or cell with polysulfide wettable electrode - #2|
|US4086404||7 Apr 1977||25 Apr 1978||The United States Of America As Represented By The United States Department Of Energy||Electrode including porous particles with embedded active material for use in a secondary electrochemical cell|
|US4098967||20 Jan 1975||4 Jul 1978||Gould Inc.||Electrochemical system using conductive plastic|
|US4125676||15 Aug 1977||14 Nov 1978||United Technologies Corp.||Carbon foam fuel cell components|
|US4134192||12 Oct 1976||16 Jan 1979||Gould Inc.||Composite battery plate grid|
|US4152825||10 Jun 1974||8 May 1979||Polaroid Corporation||Method of making a flat battery|
|US4188464||31 Jul 1978||12 Feb 1980||Hooker Chemicals & Plastics Corp.||Bipolar electrode with intermediate graphite layer and polymeric layers|
|US4224392||16 Dec 1977||23 Sep 1980||Oswin Harry G||Nickel-oxide electrode structure and method of making same|
|US4275130||27 Sep 1979||23 Jun 1981||California Institute Of Technology||Bipolar battery construction|
|US4339322||21 Apr 1980||13 Jul 1982||General Electric Company||Carbon fiber reinforced fluorocarbon-graphite bipolar current collector-separator|
|US4363857||16 Oct 1981||14 Dec 1982||General Motors Corporation||Laminated metal-plastic battery grid|
|US4374186||29 Apr 1981||15 Feb 1983||The United States Of America As Represented By The Secretary Of The Navy||Polymer packaged cell in a sack|
|US4485156||13 Apr 1984||27 Nov 1984||Japan Storage Battery Company Limited||Pasted type lead-acid battery|
|US4566877||9 Apr 1984||28 Jan 1986||Institut De Recherches De La Siderurgie Francaise||Carbon foam usable as blast-furnace fuel and method of making same|
|US4717633||25 Nov 1985||5 Jan 1988||Eric Hauser||Electrode structure for lightweight storage battery|
|US4722875 *||18 Sep 1986||2 Feb 1988||501 Lilliwyte Societe Anonyme||Electrochemical cell|
|US4749451||5 Feb 1987||7 Jun 1988||Basf Aktiengesellschaft||Electrochemical coating of carbon fibers|
|US4758473||20 Nov 1986||19 Jul 1988||Electric Power Research Institute, Inc.||Stable carbon-plastic electrodes and method of preparation thereof|
|US4865931||4 Dec 1984||12 Sep 1989||The Dow Chemical Company||Secondary electrical energy storage device and electrode therefor|
|US4900643||8 Apr 1988||13 Feb 1990||Globe-Union Inc.||Lead acid bipolar battery plate and method of making the same|
|US4975343 *||24 May 1989||4 Dec 1990||Lilliwyte Societe Anonyme||Electrochemical cell|
|US5017446||24 Oct 1989||21 May 1991||Globe-Union Inc.||Electrodes containing conductive metal oxides|
|US5106709||20 Jul 1990||21 Apr 1992||Globe-Union Inc.||Composite substrate for bipolar electrode|
|US5162172||14 Dec 1990||10 Nov 1992||Arch Development Corporation||Bipolar battery|
|US5200281||18 Nov 1991||6 Apr 1993||Westinghouse Electric Corp.||Sintered bipolar battery plates|
|US5208003||13 Oct 1992||4 May 1993||Martin Marietta Energy Systems, Inc.||Microcellular carbon foam and method|
|US5223352||7 Jan 1992||29 Jun 1993||Rudolph V. Pitts||Lead-acid battery with dimensionally isotropic graphite additive in active material|
|US5229228||24 May 1991||20 Jul 1993||Sorapec S.A.||Current collector/support for a lead/lead oxide battery|
|US5260855||17 Jan 1992||9 Nov 1993||Kaschmitter James L||Supercapacitors based on carbon foams|
|US5268395||16 Feb 1993||7 Dec 1993||Martin Marietta Energy Systems, Inc.||Microcellular carbon foam and method|
|US5300272||13 Sep 1993||5 Apr 1994||Martin Marietta Energy Systems, Inc.||Microcellular carbon foam and method|
|US5348817||2 Jun 1993||20 Sep 1994||Gnb Battery Technologies Inc.||Bipolar lead-acid battery|
|US5374490||19 May 1993||20 Dec 1994||Portable Energy Products, Inc.||Rechargeable battery|
|US5393619||18 Apr 1994||28 Feb 1995||Regents Of The University Of California||Cell separator for use in bipolar-stack energy storage devices|
|US5395709||18 Oct 1993||7 Mar 1995||Westinghouse Electric Corporation||Carbon bipolar walls for batteries and method for producing same|
|US5402306||4 May 1993||28 Mar 1995||Regents Of The University Of California||Aquagel electrode separator for use in batteries and supercapacitors|
|US5411818||18 Oct 1993||2 May 1995||Westinghouse Electric Corporation||Perimeter seal on bipolar walls for use in high temperature molten electrolyte batteries|
|US5426006||16 Apr 1993||20 Jun 1995||Sandia Corporation||Structural micro-porous carbon anode for rechargeable lithium-ion batteries|
|US5429893||4 Feb 1994||4 Jul 1995||Motorola, Inc.||Electrochemical capacitors having dissimilar electrodes|
|US5441824||23 Dec 1994||15 Aug 1995||Aerovironment, Inc.||Quasi-bipolar battery requiring no casing|
|US5474621||19 Sep 1994||12 Dec 1995||Energy Conversion Devices, Inc.||Current collection system for photovoltaic cells|
|US5498489||14 Apr 1995||12 Mar 1996||Dasgupta; Sankar||Rechargeable non-aqueous lithium battery having stacked electrochemical cells|
|US5508131||7 Apr 1994||16 Apr 1996||Globe-Union Inc.||Injection molded battery containment for bipolar batteries|
|US5510359||14 Apr 1993||23 Apr 1996||Merck Sharp & Dohme Ltd.||Heteroaromatic 5-hydroxytryptamine receptor agonists|
|US5512390||21 Jul 1994||30 Apr 1996||Photran Corporation||Light-weight electrical-storage battery|
|US5529971||25 Mar 1993||25 Jun 1996||Regents Of The University Of California||Carbon foams for energy storage devices|
|US5538810||7 Jun 1995||23 Jul 1996||Kaun; Thomas D.||Corrosion resistant ceramic materials|
|US5543247||17 Oct 1994||6 Aug 1996||Northrop Grumman Corporation||High temperature cell electrical insulation|
|US5563007||11 Jan 1995||8 Oct 1996||Entek Manufacturing Inc.||Method of enveloping and assembling battery plates and product produced thereby|
|US5569563||2 Sep 1994||29 Oct 1996||Ovshinsky; Stanford R.||Nickel metal hybride battery containing a modified disordered multiphase nickel hydroxide positive electrode|
|US5580676||11 Sep 1995||3 Dec 1996||Sony Corporation||Rectangular battery|
|US5593797||24 Feb 1993||14 Jan 1997||Trojan Battery Company||Electrode plate construction|
|US5595840||27 Nov 1995||21 Jan 1997||Gnb Technologies, Inc.||Method of manufacturing modular molded components for a bipolar battery and the resulting bipolar battery|
|US5626977||21 Feb 1995||6 May 1997||Regents Of The University Of California||Composite carbon foam electrode|
|US5636437||12 May 1995||10 Jun 1997||Regents Of The University Of California||Fabricating solid carbon porous electrodes from powders|
|US5643684||2 Jun 1995||1 Jul 1997||Sumitomo Electric Industries, Ltd.||Unwoven metal fabric|
|US5667909||23 Jun 1995||16 Sep 1997||Power Conversion, Inc.||Electrodes configured for high energy density galvanic cells|
|US5677075||28 Sep 1995||14 Oct 1997||Fujita; Kenichi||Activated lead-acid battery with carbon suspension electrolyte|
|US5705259||25 Oct 1995||6 Jan 1998||Globe-Union Inc.||Method of using a bipolar electrochemical storage device|
|US5712054||3 Jan 1996||27 Jan 1998||Electrion, Inc.||Rechargeable hydrogen battery|
|US5723232||1 Apr 1996||3 Mar 1998||Sharp Kabushiki Kaisha||Carbon electrode for nonaqueous secondary battery and nonaqueous battery using the same|
|US5738907||4 Aug 1995||14 Apr 1998||Eltech Systems Corporation||Conductive metal porous sheet production|
|US5766789 *||28 Dec 1995||16 Jun 1998||Energetics Systems Corporation||Electrical energy devices|
|US5766797||27 Nov 1996||16 Jun 1998||Medtronic, Inc.||Electrolyte for LI/SVO batteries|
|US5882621||9 May 1997||16 Mar 1999||Sandia Corporation||Method of preparation of carbon materials for use as electrodes in rechargeable batteries|
|US5888469||3 Jul 1997||30 Mar 1999||West Virginia University||Method of making a carbon foam material and resultant product|
|US5898564||2 Dec 1996||27 Apr 1999||Regents Of The University Of California||Capacitor with a composite carbon foam electrode|
|US5932185||23 Aug 1993||3 Aug 1999||The Regents Of The University Of California||Method for making thin carbon foam electrodes|
|US5955215||21 Jul 1997||21 Sep 1999||Dornier Gmbh||Bipolar electrode-electrolyte unit|
|US5972538 *||14 May 1997||26 Oct 1999||Nisshinbo Industries, Inc.||Current collector for molten salt battery, process for producing material for said current collector, and molten salt battery using said current collector|
|US5993996||16 Sep 1997||30 Nov 1999||Inorganic Specialists, Inc.||Carbon supercapacitor electrode materials|
|US6001761||19 May 1997||14 Dec 1999||Nippon Shokubai Co., Ltd.||Ceramics sheet and production method for same|
|US6033506||2 Sep 1997||7 Mar 2000||Lockheed Martin Engery Research Corporation||Process for making carbon foam|
|US6037032||8 Jun 1998||14 Mar 2000||Lockheed Martin Energy Research Corp.||Pitch-based carbon foam heat sink with phase change material|
|US6045943||4 Nov 1997||4 Apr 2000||Wilson Greatbatch Ltd.||Electrode assembly for high energy density batteries|
|US6060198||29 May 1998||9 May 2000||Snaper; Alvin A.||Electrochemical battery structure and method|
|US6077464||14 Nov 1997||20 Jun 2000||Alliedsignal Inc.||Process of making carbon-carbon composite material made from densified carbon foam|
|US6077623||11 Jun 1998||20 Jun 2000||Grosvenor; Victor L.||Bipolar lead-acid battery plates and method of making same|
|US6103149||12 Jul 1996||15 Aug 2000||Ultramet||Method for producing controlled aspect ratio reticulated carbon foam and the resultant foam|
|US6117592||27 Apr 1998||12 Sep 2000||Mitsubishi Materials Corporation||Porus metallic material having high specific surface area, method of producing the same, porus metallic plate material and electrode for alkaline secondary battery|
|US6127061||26 Jan 1999||3 Oct 2000||High-Density Energy, Inc.||Catalytic air cathode for air-metal batteries|
|US6146780||24 Jan 1997||14 Nov 2000||Lynntech, Inc.||Bipolar separator plates for electrochemical cell stacks|
|US6183854||22 Jan 1999||6 Feb 2001||West Virginia University||Method of making a reinforced carbon foam material and related product|
|US6193871||9 Dec 1998||27 Feb 2001||Eagle-Picher Industries, Inc.||Process of forming a nickel electrode|
|US6217841||20 Jul 1994||17 Apr 2001||Pechiney Recherche||Process for the preparation of metal carbides having a large specific surface from activated carbon foams|
|US6241957||11 Jun 1998||5 Jun 2001||West Virginia University||Method of making a carbon foam material and resultant product|
|US6245461||24 May 1999||12 Jun 2001||Daimlerchrysler||Battery package having cubical form|
|US6248467||23 Jul 1999||19 Jun 2001||The Regents Of The University Of California||Composite bipolar plate for electrochemical cells|
|US6258473||10 Feb 1999||10 Jul 2001||Wilson Greatbatch Ltd.||Electrochemical cell having multiplate electrodes with differing discharge rate regions|
|US6656640 *||9 Nov 2000||2 Dec 2003||Alcatel||Non-sintered electrode with three-dimensional support for a secondary electrochemical cell having an alkaline electrolyte|
|US6670039 *||6 Apr 2000||30 Dec 2003||Dennis C. Nagle||Carbonized wood and materials formed therefrom|
|US6869547 *||9 Oct 2001||22 Mar 2005||Valence Technology, Inc.||Stabilized electrochemical cell active material|
|US6899970 *||25 Jun 2001||31 May 2005||Touchstone Research Laboratory, Ltd.||Electrochemical cell electrodes comprising coal-based carbon foam|
|US20030165744 *||17 Dec 2002||4 Sep 2003||Schubert Mark A.||Flexible thin printed battery and device and method of manufacturing same|
|US20040002006 *||28 Jun 2002||1 Jan 2004||Caterpillar Inc.||Battery including carbon foam current collectors|
|US20040121238 *||23 Dec 2002||24 Jun 2004||Kelley Kurtis C.||Battery having carbon foam current collector|
|1||Blood et al., "Electrodeposition of Lead Dioxide on Carbon Substrates From a High Internal Phase Emulsion (HIPE)," Journal of Applied Electrochemistry, vol. 34, pp. 1-7, (2004).|
|2||Czerwinski et al., "Electrochemical Behavior of Lead Dioxide Deposited on Retuculated Vitreous Carbon (RVC)," Journal of Power Sources, vol. 64, pp. 29-34, (1997).|
|3||http:www.powertechnologyonline.com/progress.html, Power Technology, Inc, Jan. 15, 2002.|
|4||International Search Report and Written Opinion of the International Searching Authority for PCT/US2004/042286, dated Jul. 29, 2005.|
|5||U.S. Appl. No. 10/183,471, filed Jun. 28, 2002.|
|6||U.S. Appl. No. 10/324,068, filed Dec. 20, 2002.|
|7||U.S. Appl. No. 10/326,257, filed Dec. 23, 2002.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US7709139||22 Jan 2007||4 May 2010||Physical Sciences, Inc.||Three dimensional battery|
|US7732098||17 Nov 2008||8 Jun 2010||Eliot Gerber||Lead acid battery having ultra-thin titanium grids|
|US7766981||26 Jun 2008||3 Aug 2010||Corning Incorporated||Electrode stack for capacitive device|
|US7838146||16 Nov 2006||23 Nov 2010||Graftech International Holdings, Inc.||Low conductivity carbon foam for a battery|
|US7933114||31 Aug 2007||26 Apr 2011||Corning Incorporated||Composite carbon electrodes useful in electric double layer capacitors and capacitive deionization and methods of making the same|
|US7993779||18 Oct 2010||9 Aug 2011||Graftech International Holdings Inc.||Low conductivity carbon foam for a battery|
|US8017273||13 Sep 2011||Ut-Battelle Llc||Lightweight, durable lead-acid batteries|
|US8048572||3 May 2010||1 Nov 2011||Eliot Samuel Gerber||Long life lead acid battery having titanium core grids and method of their production|
|US8142522||9 Jun 2010||27 Mar 2012||Corning Incorporated||Electrode stack for capacitive device|
|US8232005||10 Sep 2011||31 Jul 2012||Eliot Gerber||Lead acid battery with titanium core grids and carbon based grids|
|US8277974||24 Apr 2009||2 Oct 2012||Envia Systems, Inc.||High energy lithium ion batteries with particular negative electrode compositions|
|US8300385||17 Mar 2011||30 Oct 2012||Corning Incorporated||Composite carbon electrodes useful in electric double layer capacitors and capacitive deionization and methods of making the same|
|US8399134 *||20 Nov 2007||19 Mar 2013||Firefly Energy, Inc.||Lead acid battery including a two-layer carbon foam current collector|
|US8445138||19 Jul 2011||21 May 2013||Ut-Battelle Llc||Lightweight, durable lead-acid batteries|
|US8617492||8 Jan 2008||31 Dec 2013||Carbonxt Group Limited||System and method for making low volatile carboneaceous matter with supercritical CO2|
|US8617747||24 Feb 2009||31 Dec 2013||Firefly Energy, Inc.||Electrode plate for a battery|
|US8628707||8 Jan 2008||14 Jan 2014||Carbonxt Group Limited||System and method for making carbon foam anodes|
|US8673490||12 Sep 2012||18 Mar 2014||Envia Systems, Inc.||High energy lithium ion batteries with particular negative electrode compositions|
|US8691166||6 Oct 2008||8 Apr 2014||Carbonxt Group Limited||System and method for activating carbonaceous material|
|US8709663||10 May 2010||29 Apr 2014||Xiaogang Wang||Current collector for lead acid battery|
|US9012073||14 Jul 2009||21 Apr 2015||Envia Systems, Inc.||Composite compositions, negative electrodes with composite compositions and corresponding batteries|
|US9065144 *||9 Aug 2011||23 Jun 2015||Cardiac Pacemakers, Inc.||Electrode including a 3D framework formed of fluorinated carbon|
|US9083048||9 Aug 2011||14 Jul 2015||Cardiac Pacemakers, Inc.||Carbon monofluoride impregnated current collector including a 3D framework|
|US9139441||19 Jan 2012||22 Sep 2015||Envia Systems, Inc.||Porous silicon based anode material formed using metal reduction|
|US9178217 *||5 Jan 2010||3 Nov 2015||Joey Chung Yen JUNG||Multiply-conductive matrix for battery current collectors|
|US9190694||3 Nov 2010||17 Nov 2015||Envia Systems, Inc.||High capacity anode materials for lithium ion batteries|
|US20060165876 *||8 Apr 2006||27 Jul 2006||Elod Gyenge||Current Collector Structure and Methods to Improve the Performance of a Lead-Acid Battery|
|US20060292448 *||27 Jun 2006||28 Dec 2006||Elod Gyenge||Current Collector Structure and Methods to Improve the Performance of a Lead-Acid Battery|
|US20070248887 *||21 Apr 2006||25 Oct 2007||Eskra Technical Products, Inc.||Using metal foam to make high-performance, low-cost lithium batteries|
|US20080118832 *||16 Nov 2006||22 May 2008||Artman Diane M||Low Conductivity Carbon Foam For A Battery|
|US20080176139 *||22 Jan 2007||24 Jul 2008||Physical Sciences Inc.||Three dimensional battery|
|US20080274407 *||3 May 2007||6 Nov 2008||Roy Joseph Bourcier||Layered carbon electrodes for capacitive deionization and methods of making the same|
|US20080297980 *||31 May 2007||4 Dec 2008||Roy Joseph Bourcier||Layered carbon electrodes useful in electric double layer capacitors and capacitive deionization and methods of making the same|
|US20090172998 *||8 Jan 2008||9 Jul 2009||Carbonxt Group Limited||System and method for refining carbonaceous material|
|US20090175779 *||6 Oct 2008||9 Jul 2009||Harris Randall J||System and Method for Activating Carbonaceous Material|
|US20090175780 *||8 Jan 2008||9 Jul 2009||Carbonxt Group Limited||System and method for making low volatile carboneaceous matter with supercritical CO2|
|US20090176130 *||8 Jan 2008||9 Jul 2009||Carbonxt Group Limited||System and method for making carbon foam anodes|
|US20090291368 *||18 Aug 2008||26 Nov 2009||Aron Newman||Carbon Foam Based Three-Dimensional Batteries and Methods|
|US20090305131 *||24 Apr 2009||10 Dec 2009||Sujeet Kumar||High energy lithium ion batteries with particular negative electrode compositions|
|US20090320253 *||26 Jun 2008||31 Dec 2009||Corning Incorporated||Electrode Stack For Capacitive Device|
|US20100009262 *||11 Jul 2008||14 Jan 2010||Eliot Gerber||Non-lead grid cores for lead acid battery and method of their production|
|US20100009263 *||17 Nov 2008||14 Jan 2010||Eliot Gerber||Lead acid battery having ultra-thin|
|US20100119942 *||14 Jul 2009||13 May 2010||Sujeet Kumar||Composite compositions, negative electrodes with composite compositions and corresponding batteries|
|US20100124702 *||17 Nov 2008||20 May 2010||Physical Sciences, Inc.||High Energy Composite Cathodes for Lithium Ion Batteries|
|US20100216025 *||26 Aug 2010||Firefly Energy, Inc.||Electrode plate for a battery|
|US20100306979 *||9 Dec 2010||Roy Joseph Bourcier||Electrode stack for capacitive device|
|US20110027654 *||18 Oct 2010||3 Feb 2011||Graftech International Holdings Inc.||Low Conductivity Carbon Foam For A Battery|
|US20110033744 *||10 Feb 2011||Gerber Eliot S||Long life lead acid battery having titanium core grids and method of their production|
|US20110083966 *||9 Jun 2008||14 Apr 2011||Commissariat A L 'energie Atomique Et Aux Energies Alternatives||Electrode for lead-acid battery and method for producing such an electrode|
|US20110085962 *||14 Dec 2010||14 Apr 2011||Carbonxt Group Limited||System and method for making low volatile carbonaceous matter with supercritical co2|
|US20110111294 *||3 Nov 2010||12 May 2011||Lopez Heman A||High Capacity Anode Materials for Lithium Ion Batteries|
|US20110163273 *||7 Jul 2011||Adra Smith Baca||Composite carbon electrodes useful in electric double layer capacitors and capacitive deionization and methods of making the same|
|US20110287314 *||5 Jan 2010||24 Nov 2011||Jung Joey Chung Yen||Multiply-conductive Matrix for Battery Current Collectors|
|US20120041507 *||9 Aug 2011||16 Feb 2012||Francis Wang||Electrode including a 3d framework formed of fluorinated carbon|
|DE102013019309A1||4 Nov 2013||15 May 2014||Technische Universität Bergakademie Freiberg||Casting porous cellular metal parts, comprises mixing preform of space-holding salt granules with binder, adding starch to mixture, introducing mixture into mold, and curing mold by flowing carbon dioxide/hot air to form preform|
|DE102013019309B4 *||4 Nov 2013||24 Jul 2014||Technische Universität Bergakademie Freiberg||Verfahren zum Gießen von offenporigen zellularen Metallteilen|
|WO2008064052A2 *||15 Nov 2007||29 May 2008||Graftech Int Holdings Inc||Nonconductive carbon foam for battery|
|WO2009089357A1 *||8 Jan 2009||16 Jul 2009||Carbonxt Group Ltd||System and method for making carbon foam anodes|
|WO2010088755A1 *||5 Jan 2010||12 Aug 2010||Evt Power, Inc.||Multiply-conductive matrix for battery current collectors|
|WO2012116200A2||23 Feb 2012||30 Aug 2012||Firefly Energy, Inc.||Improved battery plate with multiple tabs and mixed pore diameters|
|U.S. Classification||429/121, 429/233, 429/236|
|International Classification||H01M4/56, H01M4/58, H01M4/04, C01B31/02, H01M4/52, B05D5/12, H01M4/48, H01M10/30, H01M10/06, H01M4/02, H01M4/64, H01M2/26, H01M10/18, H01M8/00, H01M4/14, H01M2/28, H01M4/20, H01M, H01M10/20, C01B31/00, H01M4/66, H01M4/80|
|Cooperative Classification||Y02P70/54, H01M4/808, H01M10/30, H01M4/663, H01M4/20, H01M10/06, Y02E60/126, H01M4/14, Y02T10/7016|
|European Classification||H01M4/20, H01M4/66C, H01M4/66A, H01M4/14, H01M4/80D|
|8 Jun 2004||AS||Assignment|
Owner name: FIREFLY ENERGY INC., ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KELLEY, KURTIS CHAD;VOTOUPAL, JOHN J.;REEL/FRAME:015443/0299;SIGNING DATES FROM 20040311 TO 20040319
|29 Jun 2009||FPAY||Fee payment|
Year of fee payment: 4
|11 Mar 2010||AS||Assignment|
Owner name: PNC BANK, NATIONAL ASSOCIATION (AS SUCCESSOR IN IN
Free format text: SECURITY AGREEMENT;ASSIGNOR:FIREFLY ENERGY INC.;REEL/FRAME:024066/0258
Effective date: 20070907
|17 Jun 2013||FPAY||Fee payment|
Year of fee payment: 8