1. Field of the Invention
The present invention relates to polymer-based films and improved film surface characteristics thereof. More particularly, the present invention relates to relatively thin polymer-based films that have conductive characteristics. The conductive polymer-based films possess sufficient conductivity and certain film surface characteristics such that they may be used as a component for electrodes used in batteries or capacitors. The invention includes the process for making such films.
2. Description of the Prior Art
Resins suitable for blown and cast polymer film manufacture and loaded with conductive carbon particles have been available for many years. Commercially available resins suitable for film making and including carbon loading, such as in the form of carbon powder, have been limited to the inclusion of 25% by weight or less of carbon. The typical volume resistance values of films in the thickness range of about 2-25 mils made using such resins are greater than 100 ohms and are not suitable as components for electrodes used in batteries or capacitors. Resin compounders have increased the conductive carbon loading to 50%, which works well for injection molding of polymeric products but are too thick and weigh too much to be a commercially reasonable option as a component in an electrode in a battery or a capacitor. This filled resin makes the extrusion of a film with desirable physical characteristics very difficult. For purposes of the description of this invention, the resistance of a film means the resistance measured in ohms through the thickness of the film for a specified film thickness or film thickness range, which is sometimes referred to as volume resistance, and not the resistance across the surface of the film, which is sometimes referred to as surface resistance.
Conductive carbon nanotubes have also been used with polymer resins to produce polymer-based products of sufficiently thin dimensions with resistance values of less than 100 ohms. Unfortunately, carbon nanotubes are difficult to disperse uniformly throughout the resin such that any resultant film, to the extent it can be manufactured at a uniform desired thickness, will have non-uniform characteristics, including non-uniformity of resistance of the film product, and may have non-uniform resistances through the film thickness. While they may provide suitable resistance characteristics in a polymer film, they reduce the overall structural characteristics of the film. Further, they are relatively costly and therefore make conductive films which are more costly than is desired.
As noted above, resins exist with as much as 50% by weight of carbon loading. However, attempts by the present inventors to produce a polymeric film with a fully 50% conductive carbon loaded polymer resin on a blown film extruder and a cast film extruder met with unsuitable results. In that effort, blends of low density polyethylene, high density polyethylene and polypropylene were used. The blown film attempt failed due to the existence of numerous pinholes that caused the resin bubble to burst prior to desired expansion. The cast film met with some success in that a film sheet was made; however, attempts to reach desired relatively thin film thicknesses were unsuccessful in that numerous pinholes were created and film tearing occurred.
It was determined that in the course of attempting to make a polymer-based conductive film with resistance values of less than 100 ohms that the resin required extensive drying as carbon-loaded resins are very hydroscopic. Any absorbed moisture in the resin will cause outgassing in the heated extrusion process. This causes gels and imperfections throughout the film to be formed, resulting in pinholes in the final film product. Typical drying times for a 25% carbon loaded resin is 6 hours at 150° F. in a desiccant carousel dryer. The 50% carbon loaded resin requires longer drying time. For example, a 50% carbon-filled resin required 12 hours of drying at 150° F. before reaching a satisfactory moisture content. It was also determined in the course of attempting to make the polymer-based conductive film with a resistance less than 100 ohms that the resin loaded with 50% by weight of conductive carbon did not have acceptable puncture and tear strength. The larger loading of conductive carbon produce areas of conductive carbon clusters that produce pinholes in the extruded film. Based on that effort, it was determined that a polymeric film with a resistance below 100 ohms, desired thickness and sufficient structural integrity has not been made available prior to the development of the present invention. It was also determined that it would be desirable to provide a thin polymer film with physical integrity and a resistance through its thickness of less than 100 ohms and preferably below 10 ohms. Such a film could be used in a range of applications, including, but not limited to, batteries and capacitors.
It is an object of the present invention to provide a thin polymer film with physical integrity and a resistance of less than 100 ohms, and preferably below 10 ohms, through its thickness. It is also an object of the present invention to provide a process for making such a conductive film. The film includes a structural material, such as a polymer. The polymer may be a polyolefin, such as polyethylene, polypropylene, or blends thereof. The polyethylene may be a high density polyethylene or a low density polyethylene. The structural material is blended with one or more additives to produce desired characteristics. One additive of the film of the present invention is a conductive additive, such as a carbon filler. The carbon filler may be a carbon powder, for example. The structural material and the one or more additives are combined together to produce a resin, such as in pellet form, that may be extruded and processed into the conductive film, or blown and processed into the conductive film.
In one embodiment, the conductive film of the present invention is a conductive carbon filled polyolefin blend that is flexible and sealable, less than about 6 mils thick and with a resistance of less than about 50 ohms. In a second embodiment, the conductive film is a conductive carbon filled polyolefin blend that is flexible and sealable, about 2 mils thick and with a resistance of less than about 10 ohms. This second embodiment of the film may be inert, with minimum oxidation to material. It further provides little to no danger of overcharge of electrons. In a third embodiment, the conductive film is a conductive carbon filled polymer blend that is flexible and sealable, less than about 6 mils thick, with a resistance of less than about 10 ohms and selectively coated with vapor deposition of metals, semiconductors and/or dielectrics so that the film can be sealed where the materials are not deposited. In a fourth embodiment, the conductive film is a conductive carbon filled polyolefin blend that is flexible and sealable, less than about 2 mils thick, with a resistance of less than about 10 ohms, selectively coated with vapor deposition of metals, semiconductors and/or dielectrics so that the film can be sealed where the materials are not deposited. As noted, one or more of the indicated film embodiments may include a metal, such as aluminum, copper or tin, applied to one or both sides thereof. The metal may be applied to the film such as by vacuum metallization. One or more of the indicated film embodiments may include a non-metallic material applied to one or both sides thereof. The non-metallic material may be chemically or mechanically joined to the conductive film, either permanently or removably.
One or more of the one or more embodiments of the conductive film of the present invention may be used as an electrical current collector and pathway for electrons to flow through. Such conductive film may be used as an electrical current collector and pathway for electrons to flow to other connected films, whether conductive or non-conductive. The film may be used for unidirectional electron flow or bidirectional electron flow. The conductive film of the present invention may be used as an anode or a cathode in the construction of batteries or capacitors. It may be used as a bipolar electrode for a capacitor. The film may be used as a laminate to an anode material and/or a cathode material. The film may be laminated to the anode and/or cathode material by a heat lamination process or through the use of a conductive binder. The conductive film may be used as a barrier to block electrolyte transfers. The conductive film may be used as a replacement for any battery metallized electrode conductor whether used with acidic, basic or organic electrolyte solutions. The conductive film in any of the variations described herein including the polymeric structural material can be heat sealed to another non-conductive polymer.
The present invention includes a process of combining and blending a plurality of resins with different conductive carbon loading to produce a thin film with acceptable physicals, no pinholes and a resistance through its thickness of less than about 10 ohms. The resins may include the same or different structural materials. An embodiment of the process of combining and blending includes the process of combining and blending low density polyethylene, high density polyethylene or polypropylene with about 50% conductive carbon loading with a low density polyethylene, high density polyethylene or polypropylene with about a 25% conductive carbon loading to produce a thin conductive film with acceptable physical characteristics, no pinholes and a resistance of less than about 10 ohms.
Another embodiment of the process of combining and blending includes the process of combining and blending about a 40% blend of about 50% loaded conductive carbon polymer with about a 60% blend of about 25% loaded conductive carbon polymer to form a thin conductive film with acceptable physicals, no pinholes and a resistance of about 30 ohms. Another embodiment of the process of combining and blending includes the process of combining and blending about a 50% blend of about 50% loaded conductive carbon polymer with about a 50% blend of about 25% loaded conductive carbon polymer to form a thin conductive film with acceptable physicals, no pinholes and a resistance of less than about 15 ohms. Another embodiment of the process of combining and blending includes the process of combining and blending about a 60% blend of about 50% loaded conductive carbon polymer with about a 40% blend of about 25% loaded conductive carbon polymer to form a thin conductive film with acceptable physicals, no pinholes and a resistance of less than about 10 ohms. Another embodiment of the process of combining and blending includes the process of combining and blending about a 66% blend of about 50% loaded conductive carbon polymer with about a 34% blend of about 25% loaded conductive carbon polymer to form a thin conductive film with acceptable physical characteristics, no pinholes and a resistance of less than about 5 ohms.
The present invention includes an optional process and associated apparatus for treating the surface of the film to enhance its surface energy, also referred to as dyne level, and thus improve its ability to bond to other materials. The process is preferably a corona treatment process known to those of skill in the art of fabricating non-metallic materials such as polymeric film materials. This optional process enhances the ability of the film of the present invention to bond to various other materials including, but not limited to, inks, coatings, metals, other non-metallic materials, semiconductor structures, dielectrics and electrolytes, as well as to form laminates, if that is of interest.
The films of the present invention are particularly suited for use as the conductive media for both anode and cathode electrodes in batteries. A known problem in the art was the difficulty of finding an electrode material of suitable thinness and resistance that does not react with active materials and that can be sealed to form a leak proof containment. Each of these problems is overcome by the films of the present invention. The films of the present invention are also suitable for use as the conductive media in electrodes in desalination and deionization systems. These and other advantages will become apparent upon reviewing the following detailed description, the accompanying figures and the appended claims.
A conductive film of the present invention is fabricated in a single layer or a plurality of layers. It includes a structural material blended with a conductive material into a form suitable for extrusion or blow molding as those processes are generally understood by those of ordinary skill in the art of polymer film fabrication. The structural material may be polyethylene, polypropylene and variants and blends thereof. The conductive material is carbon. The film may include other additives as desired. The structural material and additives are selected and processed to establish desired physical and electrical characteristics, and optional visual characteristics. The physical characteristics include, but are not limited to, a thickness of less than 12 mils, preferably less than five mils, and preferably about two mils. The film surface may include a certain dyne level that acts as a catalyst for the film to bond with various electrolytes. The physical characteristics may also include flexibility, sealability, tensile and tear strength and others of interest. The electrical characteristics include a resistance less than about 100 ohms, preferably less than about 50 ohms, and more preferably less than about 10 ohms. The physical and electrical characteristics of the films of the present invention make them particularly suited for use as the conductive media for cathode and anode electrodes in batteries or in desalination and deionization systems. Embodiments of the structural material and conductive material blends used to make the conductive film have been described hereinabove.
The process of making any of the blends described into the conductive film of the present invention involves steps in which a blended resin, such as in pellet form, is first created and then processed in a fabrication system 10 of the type represented as an example in
The two resins in pellet form are directed to mixer 20 and mixed together to form a conductive resin mix that is transferred to a desiccant carousel dryer 22, where the resin pellet mixture is dried to a selected moisture content. For the embodiment of the conductive film described herein, the conductive resin mixture is dried in the dryer 22 for about 12 hours at about 150° F. The mixer 20 and the dryer 22 are of the type known to those of ordinary skill in the art of manufacturing polymeric films. An example of a suitable mixer for initial formation of the conductive resin is a TrueBlend® model no. TB1800 series mixer available from Conair of Hartford, Conn. An example of a suitable desiccant carousel dryer for making the conductive resin pellets is a carousel dryer model no. W600 available from Conair of Hartford, Conn. The present invention is not limited to the use of that specific equipment.
With reference to
With continuing reference to
In the film-stabilization unit 42, the film 34 is maintained in tension after the chilling process. The film-stabilization unit 42 includes a plurality of rollers arranged and operated to minimize or eliminate film wrinkling and to generally maintain the uniform passage of the film 34 through the system 10. With reference to
Finally, the conductive film 34 is wound onto either one of wind-up rolls 48 and 50 for storage or delivery to users, wherein the rolls 48 and 50 are arranged such that the film 34 winds on one of the two until full and then transfers to the other of the two rolls as the full roll pivots out of the process line.
The present invention also encompasses products which make use of the conductive films of the present invention, as well as methods of making such products. For example, one application of the present invention is as the conductive medium of an electrode in a battery cell.
As can be seen in
The conductive film 52 of the present invention has a unique property that allows it to be very effective and useful in batteries, and especially lithium batteries. This property is called Positive Temperature Coefficient Resistance (PTCR). Specifically, when the temperature of the conductive film 52 gets to a specific level, caused by an increase in current density, the film 52 starts to limit current flow. At a high enough level of power, the resistance of the film 52 goes very high, and protects the battery cell from short circuit. Currently, circuits must be protected from short circuits or surges by incorporating another device into the circuit, such as a PolySwitch, which is known to those of skill in the art. The PTCR properties of the conductive film 52 of the present invention can be seen in
Another application of the present invention is as the conductive medium for an electrode for use in desalination and deionization. Present desalination processes require expensive equipment and materials and still fail to provide sufficient, affordable water to people who cannot obtain clean drinking water without great difficulty, if at all. The conductive film of the present invention can be used to meet this need as a desalinization and/or deionization device. In this application, the conductive film is laminated to a thin aluminum sheet. The aluminum sheet is then laminated to a dry process electrode (such as from Maxwell Technologies of San Diego, Calif.). The laminating can be carried out using any suitable method known in the art, including heat lamination or by conductive binder. Producing a multilayer electrode such as this requires little energy and no solvents, which is a dramatic improvement over traditional wet manufacturing processes. This type of electrode can be modified into low, medium, and high voltage designs and can reduce both energy use and costs associated with desalination processes, and similarly for deionization processes. An example desalination system employing electrodes using the conductive film of the present invention includes a holding tank with a charcoal filter and three desalination tanks. A voltage of approximately 0.5 volts would be applied to the conductive film configured electrodes in the first desalination tank to reduce the concentration of sodium chloride (NaCl) in the water from around 35,000 ppm to below 5000 ppm. The second and third tank would be arranged and operated similarly, but using higher voltages each time, resulting in a decrease in NaCl to less than 100 ppm after treatment in the third tank.
Electrodes made including the conductive film of the present invention have several advantages over traditional electrodes used in desalination. For example, electrodes using the conductive film of the present invention are more energy and cost efficient than traditional expensive coated metal electrodes, and have a longer lifespan because the polyolefin does not corrode, in contrast to traditional electrodes. A side benefit of using the conductive film in electrodes is based on selective site activation of the carbon, which allows for “mining” certain anions and cations from the source, thus acting as a deionization device.
It is to be understood that the specific films and methods described herein are but representations of options for making the conductive films of the present invention. This description is not intended to limit the principle concept of the present invention, and it is to be understood that various modifications may be made without departing from the spirit and scope of the invention. All equivalents are deemed to fall within the scope of this description of the invention.
The present application claims the priority benefit of U.S. provisional patent application Ser. No. 61/103,788, filed on Oct. 8, 2008, entitled “CONDUCTIVE FILM AND PROCESS FOR MAKING SAME.” The entire contents of that prior application are incorporated herein by reference.
Number | Date | Country | |
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61103788 | Oct 2008 | US |