CA2509961A1

CA2509961A1 - Composite material and current collector for battery

Info

Publication number: CA2509961A1
Application number: CA002509961A
Authority: CA
Inventors: Kurtis C. Kelley; Matthew J. Maroon; Charles F. Ostermeier
Original assignee: Firefly Energy Inc.; Kurtis C. Kelley; Matthew J. Maroon; Charles F. Ostermeier; Caterpillar, Inc.; City Of Peoria; County Of Peoria; Firefly International Energy Co.
Current assignee: Firefly International Energy Co
Priority date: 2002-12-20
Filing date: 2003-11-10
Publication date: 2004-07-22
Anticipated expiration: 2023-11-10
Also published as: US20060151756A1; ATE355623T1; CN100352088C; EP1573836B1; EP1573836A2; AU2003291420A1; CN1729587A; KR101061971B1; KR20050091738A; RU2005121126A; JP2006511917A; WO2004062005A2; US7033703B2; DE60312217T2; JP5005886B2; WO2004062005A3; RU2325007C2; DE60312217D1; CA2509961C; US20040121237A1

Abstract

A composite material (10) including two sheets of carbon foam (11, 13) laminated together using a bonding material (12), which may permeate pores (14) of both sheets of carbon foam. The bonding material may include an insulating material or a conductive material. The composite material can be configured to serve as a current collector (20) for battery (100). To form the positive and negative plates of a battery, chemically active paste is disposed on the composite current collector. The carbon foam composite material resists corrosion and exhibits a large amount of surface area.

Description

Description COMPOSITE MATERIAL AND CURRENT COLLECTOR FOR BATTERY
Technical Field This invention relates generally to a composite material and, more particularly, to a composite material current collector for an energy storage device.
Bacl~ rg ound Lead acid batteries are known to include at least one positive current collector, at least one negative current collector, and an electrolytic solution including, for example, sulfuric acid (HZSO~) and distilled water.
Ordinarily, both the positive and negative current collectors in a lead acid battery 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 sulfuric acid electrolyte 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. This lead dioxide

-2-coiTOSion 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 four percent (4%) to seven percent (7%), the current collector may fracture. As a result, battery capacity drops, a~ld 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 can 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. Patent 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 cunent 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

-3-acid battery, which are generally patterned into a grid-life 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 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 lacy the toughness of lead current collectors. The dense graphite plates of the '390 patent are brittle and may fracture when subjected to physical shoclc 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.
Suxmnary of the Invention One aspect of the present invention includes a composite material.
The composite material includes a first carbon foam layer including a networl~
of pores and a second carbon foam layer including a networlc of pores. An intermediate bonding layer is disposed between the first and second carbon foam layers.
A second aspect of the present invention includes a method of mal~ing a composite material. This method includes providing a first sheet of

-4-carbon foam including a network of pores and applying a layer of bonding material to the first sheet of carbon foam. A second sheet of carbon foam material, which includes a network of pores, is then placed on the layer of bonding material to form a stacked structure.
A third aspect of the present invention includes a current collector for a battery. The current collector includes a first carbon foam layer having a network of pores, and a first electrical connection element provided on the first carbon foam layer. An intermediate bonding layer is provided on the first electrical connection element and the first carbon foam layer, and a second carbon foam layer, including a network of pores, is provided on the intemnediate bonding layer.
Brief Description of the Drawings The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and, together with the written description, serve to explain the principles of the invention. In the drawings:
Fig. 1 is a cross-sectional view of a composite material in accordance with an exemplary embodiment of the present invention;
Fig. 2A is a plan view of a current collector in accordance with an exemplary embodiment of the present invention;
Fig. 2B is a cross-sectional view of the current collector of Fig. 2A
talcen along the line 2A;
Fig. 3 illustrates an electrical connection element according to an exemplary embodiment of the present invention;
Fig. 4A is a plan view of another current collector in accordance with an exemplary embodiment of the present invention;
Fig. 4B is a cross-sectional view of the current collector of Fig. 4A
taken along the line 4A;

5 PCT/US2003/035722 Fig. 5 is a diagrammatic cut-away representation of a battery in accordance with an exemplary embodiment of the present invention.
Detailed Descri tp ion In the following description, reference is made to the accompanying drawings that form a part thereof, and in which is shown by way of illustration specific exemplary embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those slcilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that changes may be made without departing from the scope of the present invention. The following description is, therefore, not to be talcen in a limited sense. Wherever possible, the same reference numbers are used throughout the drawings to refer to the same or life parts.
As shown in Fig. l, composite material 10 includes two layers of porous carbon foam 11, 13. A intermediate layer of bonding material 12 is 1 S disposed between carbon foam layers 11 and 13. Bonding material 12 attaches carbon foam layers 11 and 13 together and provides structural support for composite material 10.
The carbon foam used to form carbon foam layers 11 and 13 of composite material 10 is electrically conductive. In certain forms, the carbon foam may offer sheet resistivity values of less than about 1 ohmlcm. In still other forms, the carbon foam may have sheet resistivity values of less than about 0.75 olun/cm. The electrical conductivity of carbon foam layers 11 and 13 allows composite material 10 to be used in a variety of applications such as, for example, current collectors in batteries.
The carbon foam used to form carbon foam layers 11 and 13 of composite material 10 is also resistant to corrosion. In general, carbon oxidizes only at very high temperatures and will resist corrosion even in corrosive enviromnents. The carbon foam used in composite material 10 retains this

-6-corrosion resistance, and therefore, composite material 10 may be used, for example, in the corrosive environment of a lead acid battery.
Additionally, carbon foam layers 11 and 13 are lightweight due to the presence of a networlc of pores 14. The carbon foam of the present invention may include a total porosity value of at least 60%. In other words, at least 60%
of the volume of carbon foam layers 11 and 13 is included within pores 14.
Moreover, the carbon foam may have an open porosity value of at least 90%. In other words, at least 90% of pores 14 are open to adjacent pores such that the networlc of pores 14 forms a substantially open network. This open network of pores 14 may result in a density of less than about 0.6 gm/cm3 for each of carbon foam layers 11 and 13. Further, the average pore size of the carbon foam may be between about 0.25 mm and about 2.0 mm.
In addition to carbon foam, graphite foam may also be used to form composite material 10. One such graphite foam, tinder the trade name PocoFoamTM, 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 of the foam. For example, in carbon foam, the carbon may be primarily amorphous. Tn 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 offers higher conductivity than carbon foam. PocoFoamTM graphite foam exhibits electrical resistivity values of between about 100 :Efcm and about 400 :Elcm.
In composite material 10, bonding material 12 is disposed between carbon foam layers 11 and 13. Bonding material 12 attaches carbon foam layers 11 and 13 together by permeating at least some of pores 14 of carbon foam layer 11 and at least some of pores 14 of carbon foam layer 13. In an exemplary embodiment, bonding material 12 permeates the pores of carbon foam layer 11 by a depth equal to or greater than an average pore size of layer 11.
Similarly, in the exemplary embodiment, bonding material 12 may permeate the pores of carbon foam layer 13 by a depth equal to or greater than an average pore size of layer 13. The depth of permeation of bonding material 12 into carbon foam layers 11 and 13 is not limited to depths of at least the average pore size of layers 11 and 13. Rather, a suitable bond may be created with a penetration depth sufficient to include at least one carbon structure (e.g., elements bordering a pore) within foam layers 1 l and 13. The permeation of bonding material 12 into carbon foam layers 11 and 13 is represented in Fig. 1 by permeation zones 15 and 16, respectively.
A variety of materials may be used as bonding material 12.
Bonding material 12 may include an electrically insulating material including a polymer. For example, in one embodiment, bonding material 12 may include polypropylene. I1i yet another embodiment, bonding material 12 may include any of a wide range of epoxies. In still another embodiment, an electrically conductive material may be used as bonding material 12. Such electrically conductive materials may include, for example, various metals and electrically conductive polymers.
To make the composite material of the present invention, a layer of bonding material is applied to a sheet of carbon foam material. Next, a second sheet of carbon foam material is placed on the layer of bonding material to form a stacked structure. If the bonding material is applied as a solid, such as in the case of most polymers and metals, then heat may be applied to the staclced structure to soften and/or melt the bonding material. Softening and/or melting of the bonding material encourages permeation of the bonding material into the pores of the carbon foam. In addition to heat, pressure can also be applied to the stacked structure. The application of external pressure may aid in forcing the bonding material to permeate the pores of the carbon foam. In an exemplary embodiment of the present invention, heat and pressure are applied simultaneously. In certain situations, however, heat may be applied exclusive of pressure. In still other _g_ situations, the application of heat may occur separate from the application of pressure.
In instances where the bonding material is applied as a liquid, such as an epoxy, for example, the bonding material may permeate the pores of each of the two sheets of carbon foam without the need for applying heat or pressure.
Nevertheless, even in the case of bonding materials applied as a liquid, the application of heat and pressure may facilitate permeation of the bonding material into the pores of the carbon foam by reducing the viscosity of the bonding material.
Figs. 2A and 2B illustrate a current collector 20 that includes the composite material of the present invention. As shown in Figs. 2A and 2B, current collector 20 includes carbon foam layers 11 and 13 bonded together by a conductive bonding material 22. Bonding material 22 permeates at least some of the pores of the carbon foam layers 11 and 13. Further, bonding material 22 may permeate the pores of carbon foam layers 11 and 13 by a depth equal to or greater than an average pore size of layers 11 and 13, respectively.
An electrical connection element 21 is disposed within bonding material 22 and provides an external, electrical connection for current collector 20. Electrical connection element 21 includes a tab 31 that extends beyond an edge of either or both of carbon foam layers 1 l and 13. Electrical connection element 21 also includes at least one electrically conductive portion 33 (Fig.
3) that extends within current collector 20.
In the exemplary embodiment shown in Figs. 2A and 2B, bonding material 22 of current collector 20 is an electrically conductive material.
For example, bonding material 22 may include a metal or an electrically conductive polymer. Because bonding material 22 is electrically conductive, an external electrical connection to current collector 20 may be made using only one electrical connection element 21. Particularly, tab 31 can male electrical contact to both carbon foam layers 11 and 13 through bonding material 22.

Fig. 3 illustrates an electrical connection element 21 according to an exemplary embodiment of the present invention. Electrical connection element 21 includes tab 31 and at least one electrically conductive portion 33 that extends away from tab 31. While tab 31 and the at least one electrically conductive portion 33 may be made from metal, in the exemplary embodiment shown in Fig. 3, both tab 31 and the electrically conductive portion 33 are formed from a plurality of carbon fibers. Specifically, tab 31 may be formed by a plurality of carbon fibers arranged adjacent to one another and bonded together.
Extending from tab 31, the plurality of carbon fibers may be spread apart to form electrically conductive portion 33. Spreading the fibers, as shown in Fig. 3, provides a relatively even distribution of carbon fibers throughout current collector 20, for example. Such a distribution helps to maintain good electrical contact between tab 31 and carbon foam layers 11 and/or 13.
Tab 31 may also include a coating 32 that can be used to form certain types of electrical connections to tab 31. For example, where carbon fibers are used to male tab 31, coating 32 may include a metal. Such a metal coating may improve the durability of tab 31 and promote good electrical contact between tab 31 and external circuitry.
Figs. 4A and 4B illustrate another current collector 40 including the composite material of the present invention. As shown in Figs. 4A and 4B, current collector 40 includes carbon foam layers 11 and 13 bonded together by a bonding material 42. Similar to the bonding material of composite material 10, bonding material 42 permeates at least some of the pores of the carbon foam layers 11 and 13. Further, bonding material 42 may permeate the pores of carbon foam layers 11 and 13 by a depth equal to or greater than an average pore size of layers 11 and 13, respectively.
In the exemplary embodiment shown in Figs. 4A and 4B, bonding material 42 is an electrically insulating material. Because bonding material 42 is electrically insulating, an external electrical connection to current collector 40 may be made using two electrical connection elements 21. Particularly, when making current collector 40, a first electrical connection element 21 may be disposed on, for example, carbon foam layer 11. Then, bonding material 42 is applied to both the first electrical connection element and to carbon foam layer 11. Because electrically insulating bonding material 42 coats the first electrical connection element 21, an additional electrical comlection element may be required to make contact with carbon foam layer 13, which is applied to the bonding material 42 to create a stacked structure. Therefore, prior to placing carbon foam layer 13 on bonding material 42, a second electrical connection element 21 may be placed on bonding material 42. The second electrical comlection element 21 provides an external electrical contact with carbon foam layer 13.
Accordingly, two electrical connection elements 21 are shown in Fig. 4B. Each resides at an original interface (i.e. prior to permeation of bonding material 42 into either of carbon foam layers 11 or 13) between bonding material 42 and carbon foam layers 11 and 13, respectively. Electrical connection elements 21, which may be configured as shown in Fig. 3, for example, do not interfere with permeation of bonding material 42 into the pores of the respective carbon foam layers.
While the exemplary embodiment of the present invention illustrated in Fig. 4B includes two electrical connection elements 21, electrical connections to the carbon foam layers 1 l and 13 may be accomplished through alternative configurations. For example, a single electrical connection element 21 may be configured such that electrically conductive portions 33 malce electrical contact to both carbon foam layers 11 and 13. For example, conductive portions 33 may be arranged such that some of the conductive portions contact foam layer 11 and other conductive portions contact foam layer 13. Alternatively, electrical connection element 21 may be sized with a sufficient thickness relative to the tluckness of bonding material 42 such that a single connection element 21 may contact both foam layers 11 and 13. In these exemplary instances, one electrical connection element 21 would be sufficient.
Fig. S illustrates a battery 100 in accordance with an exemplary embodiment of the present invention. Battery 100 includes a housing 110 and terminals 120, which are external to housing 110. At least one cell 130 is disposed within housing 110. While only one cell 130 is necessary, multiple cells may be connected in series to provide a desired total potential of battery 100.
Each cell 130 may be composed of alternating positive and negative plates immersed in an electrolytic solution including, for example, sulfuric acid and distilled water. Both the positive and negative plates include a current collector packed with a paste material, including, for example, an oxide of lead. As noted above, Figs. 2A, 2B, 4A, and 4B illustrate current collectors and 40 according to exemplary embodiments of the present invention that may be used to form the positive and/or negative plates of battery 100. Chemical reactions in the paste disposed on the current collectors of the battery enable storage and release of energy. The composition of this paste, a~ld not the material selected for the current collector, determines whether a given current collector functions as either a positive or a negative plate.
To create the positive and negative plates of battery 100, a chemically active paste is applied to current collectors 20, 40 such that the chemically active paste penetrates the network of pores in the carbon foam of the current collector. Initially, the chemically active paste that is applied to the current collectors 20, 40 of both the positive and negative plates may be substantially the same in terms of chemical composition. For example, the paste may include lead oxide (Pb0). Other oxides of lead may also be suitable. The paste 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. Irl practice, the constituents of the chemically active paste may be mixed with a small amount of sulfuric acid and water to form a paste that may be disposed within pores 14 of the current collectors 20, 40.
Once the paste has been deposited on current collectors 20, 40 the positive and negative plates are formed. To create a positive plate, current collectors 20, 40 including lead oxide paste, for example, are subjected to a curing process. This curing process may include exposing the pasted current collectors 20, 40 to elevated temperature and humidity to encourage growth of lead sulfate crystals within the paste. To create the negative plate, current collectors 20, 40 including the lead oxide paste may be left "as is", with the exception of an optional step of drying.
When the positive and negative plates have been assembled together to form the cells of a battery 100 (shown in Fig. 5), battery 100 is subjected to a charging (i.e., formation) process. During this charging process, the cured paste of the positive plate is electrically driven to lead dioxide (Pb02), and the paste of the negative plate is converted to sponge lead. Conversely, during subsequent discharge of the battery 100, the pastes of both positive and negative plates convert toward lead sulfate.
Industrial Applicability The composite material of the present invention is useful in any of a wide variety of applications where materials with corrosion resistance, high surface area, electrical conductivity, or low weight would be desirable. In one possible application, the composite material of the present invention may serve as a current collector in a battery, such as a lead acid battery, for example.
Current collectors may support the chemically active components of the battery and promote the flow of current between terminals of the battery.
Because current collectors 20, 40 include carbon foam, these current collectors resist corrosion even when exposed to sulfuric acid and to the anodic potentials of the positive plate in a lead acid battery. As a result, the battery may offer a significantly longer service life as compared to batteries without carbon foam current collectors.
The carbon foam includes a network of pores, which provides a large amount of surface area for each current collector 20, 40. Current collectors composed of carbon foam may exhibit more than 2000 times the amount of surface area provided by conventional lead current collectors. The large amount of surface area associated with current collectors 20, 40 translates into batteries having large specific energy values. For example, because of the open cell, porous network and relatively small pore size of the carbon foam materials, the chemically active paste of the positive and negative plates is intimately integrated with the conductive carbon material of current collectors 20, 40. Therefore, electrons produced in the chemically active paste at a particular reaction site must travel only a short distance through the paste before encountering the conductive carbon foam of current collectors 20, 40. This current may then be carried by the electrically conductive portion 33 of the electrical connection element 21, for example.
As a result, batteries with carbon foam current collectors 20, 40 may offer improved specific energy and power 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 either lead current collectors or graphite plate cmTent collectors. Also, these batteries may discharge more quiclcly than batteries including either lead current collectors or graphite plate current collectors.
The increased specific power values offered by batteries of the present invention also translate into reduced charging times. Therefore, the 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 braying is occurring). In view of their reduced charging times, the batteries of the present invention may provide an efficient means for storing such braying energy.
The porous nature of the carbon foam current collectors also creates an improved substrate for retaining the chemically active paste of the energy storage device. By impregnating the paste into pores of the carbon foam current collectors, the paste is less lilcely to separate from the current collectors.
This property is important in vehicle and other applications where vibration is common.
Further, by including carbon foam current collectors having a density of less than about 0.6 g/cm3, a battery 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.

Claims

1. A composite material (10), comprising:
a first carbon foam layer (11) including a network of pores (14);
a second carbon foam layer (13) including a network of pores; and an intermediate bonding layer (12) disposed between the first and second carbon foam layers.

2. The composite material of claim 1, wherein the intermediate bonding layer permeates at least some of the pores of the first carbon foam layer and at least some of the pores of the second carbon foam layer.

3. The composite material of claim 2, wherein the intermediate bonding layer permeates the pores of the first carbon foam layer by a depth equal to or greater than an average pore size of the first carbon foam layer and permeates the pores of the second carbon foam layer by a depth equal to or greater than an average pore size of the second carbon foam layer.

4. The composite material of claim 1, wherein the intermediate bonding layer includes an electrically insulating material.

5. The composite material of claim 1, wherein the intermediate bonding layer includes an electrically conductive material.

6. The composite material of claim 1, wherein each of the first and second carbon foam layers has an average pore size of between about 0.25 mm and about 2.0 mm.

7. A current collector (2) for a battery (100), comprising:
the composite material of claim 1, and at least one electrical connection element (21) disposed between the first carbon foam layer and the second carbon foam layer.

8. A battery (100) comprising:
a housing (110);
a positive terminal (120) and a negative terminal (120) external to the housing;
at least one cell (130) disposed within the housing and including at least one positive plate and at least one negative plate connected to the positive terminal and negative terminal, respectively, the at least one positive plate including the current collector of claim 7 having a chemically active paste disposed on the first and second carbon foam layers such that the chemically active paste penetrates at least some of the pores of both the first and second carbon foam layers; and an electrolytic solution filling a volume between the positive and negative plates.

9. A method of making a composite material (10), comprising:
providing a first sheet of carbon foam (11) including a network of pores (14);
applying a layer of bonding material (12) to the first sheet of carbon foam; and placing a second sheet of carbon foam material (13), which includes a network of pores, on the layer of bonding material to form a stacked structure.

10. The method of claim 9, further including:
applying heat to the stacked structure and softening the layer of bonding material to facilitate permeation of the bonding material into the pores of the first and second sheets of carbon foam; and applying pressure to the stacked structure.