For the past one hundred years or so, scientists have been making Carbon/Zinc portable power sources for various applications. In the early days of portable power, these power sources were very large compared to today's standards. For example, the very popular “Ignitor Cell” made by Eveready was about 3″ diameter and about 9″ tall and was used in many applications such as radios, buzzers, Xmas lighting, etc. These large cells, as well as some smaller versions, such as the famous Eveready #6 (about 2″ dia.×6″ tall) and the smallest unit cell of the day, the #950 (D size), were commonly made into battery packs with voltages exceeding 40 volts in some applications. These were similar in size, and even larger, than today's car batteries, for uses in lighting devices, radios and car ignition systems. In the mid 1900's, with the advent of advanced electronics such as the transistor, the electrical requirements for portable power sources were drastically reduced. Consequently, cell sizes could also be reduced to include C's, AA's, and AAA's, and even small button cells. This power reduction has continued into the twenty-first century, where applications such as smart labels, smart credit cards, sensors, data loggers, novelty devices such as greeting cards and badges, etc., now require a maximum current of several milliamperes, with many applications requiring as little as a few microamperes at about 1.5-3.0 volts. These applications also have the requirement that the power sources be flat and very thin to maintain their low profiles and portability.
In the past twenty-five years, various approaches for making thin, flat cells and batteries were attempted by numerous scientists and corporations. These include the widely known instant film battery pack developed by Polaroid. This battery pack was used in each package of Polaroid instant film. This allowed Polaroid to have a fresh battery in the camera each time the user placed a new pack of film in the camera. This high cost battery with multiple layers and a metal foil laminate package is a high voltage, high current battery, capable of igniting flash bulbs and powering motors, for example, and is not a realistic competitor of the new thin low cost batteries that are needed. In addition to Polaroid, others have tried to develop thin batteries in various electrochemical systems.
Co-pending U.S. application Ser. Nos. 11/110,202 filed on Apr. 20, 2005 and 11/378,520 filed on Mar. 17, 2006, incorporated herein by reference, discuss new designs and methods of manufacture of a flat cell and battery.
With the growing market needs for low cost, low capacity thin flat cells, it would be beneficial to produce a thin, flat, printable flexible cell that is versatile and inexpensive to mass-produce. Printable, disposable thin cells that are well suited for low-power and high-production volume applications would be useful, especially if they offer adequate voltage, sufficient capacity, and low-cost solutions. Conventional low-profile batteries typically have few of these attributes, if any.
In recent years there has been a growing interest for active skin patches that deliver medication and/or cosmetics by means of Iontophoresis. Initially these patches used large power sources such as generated by household currents or large batteries which meant the patients had to be tethered to these large power sources. However, with the development of lower current devices, the Iontophoresis devices could be powered by smaller and/or portable power sources such as small alkaline cells/batteries and more recently the smaller coin cells could be used. Still, such devices may require expensive hand assembly of cells/batteries with these devises and/or extra hardware to make the connections with the smaller dry cells (alkaline cells and or batteries, and/or coin cells). In addition to the manufacturing problems, the patient may have to contend with a large bulky non flexible patch that probably confined the patient to his or her home. Therefore, a method for allowing manufacturers to integrate the printing of the desired Iontophoresis components while mating components to a battery to power the components would be useful. For example, it would be beneficial to apply both an Iontophoresis device and its power source to a single substrate. In other words, the Iontophoresis device and its power source can share a single substrate to simplify the manufacturing process to provide reduced costs, greater efficiency, and increased economies of scale.
As a result, integrating the printing and assembly of cells and/or batteries with the printing of the Iontophoresis device would also be useful to realize such increased economies of scale. Furthermore, a method of manufacture for integrated devices that would help reduce or eliminate expensive assembly of cells/batteries with these applications would be useful.
Provided are a plurality of embodiments for the invention, including, but not limited to, an Iontophoresis device, including: a base substrate having a first side, an Iontophoresis device on the base substrate, and an electrochemical cell and/or battery on the base substrate that is electrically connected to the Iontophoresis device by means of circuitry, wherein the cell or battery is for providing electrical energy for the Iontophoresis process.
In accordance with one aspect of the present invention, a method of manufacturing an Iontophoresis device including a flat electrochemical cell for generating an electrical current is provided. The method including the steps of providing a first substrate and a second substrate. At least one of the first and second substrates includes a plurality of layers. A plurality of electrodes are provided on the first substrate. A cathode layer is provided on the first substrate, and an anode layer is provided on the first substrate. An electrolyte layer is provided including a viscous liquid in contact with the cathode layer and also in contact with the anode layer. A frame is provided on the first side of the first substrate to form an inner space containing the electrolyte, and also containing at least a major portion of the cathode layer and at least a major portion of the anode layer within the inner space. The cathode layer, anode layer, and the plurality of electrodes are electrically coupled, and the second substrate is connected to the first substrate to substantially seal the inner space containing the cathode layer, the anode layer, and the electrolyte layer.
In accordance with another aspect of the present invention, a method of manufacturing an Iontophoresis device including a flat electrochemical cell for generating an electrical current is provided. The method includes the steps of providing a first substrate and a second substrate. At least one of the first and second substrates includes a web having a plurality of layers. A plurality of electrodes are provided on the first substrate. A cathode collector layer is printed on the first substrate. A cathode layer is printed on the first substrate and includes hydroxyethyl cellulose, and an anode layer is laminated on the first substrate. An electrolyte layer is provided including a viscous liquid in contact with the cathode layer and also in contact with the anode layer. A paper separator is provided over each of the anode layer and cathode layer and is adapted to absorb at least a portion of the electrolyte layer. A frame is provided on the first side of the first substrate to form an inner space containing the electrolyte, and also containing at least a major portion of the cathode layer and at least a major portion of the anode layer within the inner space. The cathode layer via the cathode collector layer, the anode layer, and the plurality of electrodes are electrically coupled, and the second substrate is connected to the first substrate to substantially seal the inner space containing the cathode layer, the anode layer, and the electrolyte layer.
In accordance with yet another aspect of the present invention, an Iontophoresis device is provided including a flat electrochemical cell for generating an electrical current. The Iontophoresis device includes a first substrate including of a plurality of laminated layers, and a second substrate. A cathode layer is provided on the first substrate, and an anode layer is provided on the first substrate. A plurality of electrodes are provided on the first substrate and are spaced a distance from the cathode layer and the anode layer. An electrolyte layer includes a viscous liquid in contact with the cathode layer and also in contact with the anode layer. A frame is interposed between the first and second substrate to connect and seal the first substrate to the second substrate to form an inner space containing the electrolyte, and also containing at least a major portion of the cathode layer and at least a major portion of the anode layer within the inner space. At least one of the anode layer and the cathode layer include a cured or dried ink. An electrical coupler assembly provides electrical communication between the cathode layer, the anode layer, and the plurality of electrodes.
In accordance with still yet another aspect of the present invention, a method of manufacturing an Iontophoresis device including a flat electrochemical cell for generating an electrical current is provided. The method includes the steps of providing a first substrate, providing a plurality of Iontophoresis electrodes on said first substrate, providing a cathode collector layer on said first substrate, providing a cathode layer on said first substrate, and providing an anode layer on said first substrate. The method further includes the steps of providing an electrolyte layer in contact with said cathode layer and also in contact with said anode layer, and electrically coupling the cathode layer via the cathode collector layer, the anode layer, and the plurality of Iontophoresis electrodes by a printed, conductive ink.
The foregoing and other features and advantages of the present invention will become apparent to those skilled in the art to which the present invention relates upon reading the following description with reference to the accompanying drawings, in which:
Generally, the invention is an electronic device and method of manufacturing said electronic device by integrating an electrical circuit, skin patch electrodes with one or more cells/batteries to power the device. In one example, the method applies both an electronic device and its power source to a single substrate. In other words, the electronic device and its power source can share a single substrate or even two substrates could be laminated to together to simplify the manufacturing process to provide reduced costs, greater efficiency, and increased economies of scale. The circuit and a battery are typically printed and/or laminated on a continuous, flexible substrate web, and may be formed into a roll or the like. The individual devices can be removed from the roll, such as one at a time. For example, the devices can be cut from the roll, and/or perforations of the flexible substrate roll can be provided for easy tear off. The apparatus can include one or more electrical components, such as electrodes and/or control circuitry, for example. The multiple facets of this invention could be used in the total package described and/or they could be used individually or in any combination.
As used herein, unless otherwise explicitly indicated, all percentages are percentages by weight. Also, as used herein, when a range such as “5-25” (or “about 5-25”) is given, this means, for at least one embodiment, at least about 5 and, separately and independently, not more than about 25, and unless otherwise indicated, ranges are not to be strictly construed, but are given as acceptable examples. Also herein, a parenthetical range following a listed or preferred value indicates a broader range for that value according to additional embodiments of the invention.
The present invention relates to thin, printed electrochemical cells and/or batteries comprising a plurality of such cells. Such cells each typically include at least a first electrode including a first electrochemical layer (e.g., a cathode), a second electrode including a second electrochemical layer (e.g., an anode), and an electrolyte that interacts with the electrodes to create an electrical current. All of the first and second electrodes and the electrolyte are typically contained within some structure which provides an external electrical access to the electrodes for providing an electrical current supply to some device.
One method of mass-producing such cells includes depositing aqueous and/or non-aqueous solvent inks and/or other coatings in a pattern on a special substrate, such as a laminated polymeric film layer, for example. The depositing can be by means of, for example, printing conductive and/or electrochemical inks and/or laminating a metallic foil, such as a zinc foil, for example, on one or more high-speed web printing presses with rotary screen and/or flexographic printing stations, especially if the desired volumes are very high. If volumes are relatively lower, say in the quantities of only about several million or less, then relatively slower methods such as web printing with flat bed screens could be appropriate. If the volumes are even lower, such as hundreds or thousands, then a sheet-fed flat bed printing press may be utilized, for example. Still, various printing methods can be used for various desired quantities.
After the inks are printed and/or the solids have been properly placed, the cells can be completed (e.g., sealed, die cut, stacked and/or perforated and wound into a roll, or stacked if sheets are used on a printing press). This cell manufacturing process can also be utilized for integrating one or more individual cells with an actual electronic application, or into batteries comprising multiple cells connected in series or parallel, or some combination of the two. Examples of such devices and corresponding processes will be described later, but many additional embodiments are also contemplated.
As discussed above, the invention may be described as a printed, flexible, and thin electrochemical cell integrated with an electronic device. Such a cell can include, for example, a lower film substrate that can utilize a special polymer laminate that has special features, possibly including, for example, a high moisture barrier layer in the center that is surrounded by polymer films on both sides. Furthermore, one or both outside surfaces can be made to be print receptive for printing information, logos, instructions, identifications, serial numbers, graphics, or other information or images, as desired.
Depending on which construction of this invention is used, the inner ply of the substrate could also feature a heat-sealing layer that might be co-extruded on the side opposite the barrier coating.
In addition, a portion of the inner surface of a lower substrate layer of a cell of at least some embodiments could utilize a cathode current collector, such as carbon, for example, printed or coated or otherwise applied on a portion of the film substrate. At an outside contact area of this collector can also be printed a layer of a relatively highly conductive ink, such as silver, nickel, or tin, for example, to improve the conductivity to the application connection, if desired. However, if the battery application is used for relatively low current requirements, then the higher conductive layer material, or even the current collector, may not be utilized for one or both electrodes.
For at least some embodiments, a water-based ink electrochemical layer is printed as the cathode. Such a cathode layer can include, for example, manganese dioxide (MnO2), carbon, and a polymer binder. Other formulations for the cathode layer can also be utilized with or without any of these materials. If a cathode collector layer is used, which may or may not form a portion of the cathode layer, the cathode electrochemical layer will be printed on at least a portion of the cathode current collector, which is printed or otherwise applied first to the substrate.
In some embodiments, adjacent to the cathode collector, at a spacing of about 0.050″, can be placed a narrow strip of zinc foil as the anode. Other anode compositions are also possible, such as an ink layer including zinc or some other proper material, for example.
Prior to this anode placement, in an off-line operation, a dry-film adhesive layer, possibly using a release liner, can be applied to the zinc foil. The zinc foil can then be laminated to the base substrate.
Optionally, printed over one or both the anode and cathode, is a starch ink or similar material. The starch ink can act as an electrolyte absorber to keep the electrodes “wet” after an aqueous electrolyte solution is added to the cell. This starch ink could also include the electrolyte salts and the water used for the cell reaction. A paper layer over the anode and cathode could be used in place of the printed starch.
For some embodiments, before or after the two electrodes are in place, with or without the starch layer(s), a cell “picture frame” can be added. This could be done using a number of different methods. One method is to print this cell picture frame with a dielectric ink, for example. Another method is to utilize a polymer sheet or a laminated polymer sheet that includes adhesive layers, that is stamped, die cut, laser cut or similar methods to form the appropriate “pockets” (inner space or spaces) to house materials of each unit cell.
To ensure good sealing of the picture frame to the substrates, and to provide good sealing of the contact feed-throughs (providing an electrical pathway from the cell inside to the cell exterior), a sealing or caulking adhesive could be printed on the substrate and on top of the zinc foil and cathode collector, such as in the same pattern as the cell frame, for example, prior to the frame being printed or prior to the polymer sheets being inserted, for example.
This sealing or caulking material could be pressure sensitive, and/or heat sensitive, for example, such as Acheson Colloids' PM040, for example, or any other type of material that would facilitate sealing to both surfaces.
After the dielectric picture frame is printed and dried and/or cured, a heat sensitive sealing adhesive can be printed on top of the frame to allow good sealing of the top substrate to the cell frame. This cell picture frame could also comprise a polymer film or a laminated film of about 0.015″ thick (range of about 0.003″-0.050″) that is pre-punched and then laminated in registration to match the preprinted caulking adhesive layer described above.
Zinc chloride (ZnCl2) can be chosen as the electrolyte, for at least some embodiments, in the concentration range of about 18%-45% by weight, for example. In one example, about 27% may be preferred. The electrolyte can be added, for example, to the open cell. To facilitate processing on the line, this electrolyte, or a different electrolyte, could be thickened with, for example, CMC at about a level of about 0.6 wgt % (range of about 0.05%-1.0%).
Other useful electrolyte formulations, such as ammonium chloride (NH4Cl), mixtures of zinc chloride (ZnCl2) and ammonium chloride (NH4Cl), zinc acetate (Zn(C2H2O2)), zinc bromide (ZnBr2), zinc fluoride (ZnF2), zinc tartrate (ZnC4H4O6.H2O), zinc per-chlorate Zn(ClO4)2.6H2O), potassium hydroxide, sodium hydroxide, or organics, for example, could also be used.
Zinc chloride may be the electrolyte of choice, providing excellent electrical performance for ordinary environmental conditions normally encountered. Likewise, any of the above mentioned alternative electrolytes, among others, could be used in concentrations (by weight), for example, within the range of about 18%-45%, with the range of about 25%-35% used for at least some other embodiments. Such compositions could also provide acceptable performance under ordinary environmental conditions.
The use of electrolytes other than of zinc chloride can provide improved cell/battery electrical performance under some differing environmental conditions. For example, about 32% by weight zinc acetate (F.P.—freezing point—about 28° C.) exhibits a lower freezing point than about 32% by weight zinc chloride (F.P. about −23° C.). Both of these solutions exhibit a lower freezing point than of about 27% zinc chloride (F.P. about −18° C.). Other zinc acetate concentrations, e.g. about 18-45 or about 25-35 weight percent, also exhibit reduced freezing points.
Use of such electrolyte formulations as substitutes for zinc chloride, or in various mixtures used in cells, can allow for improved performance at low temperatures. For example, it has been found that the use of an about 32% zinc acetate electrolyte substantially improves low temperature (i.e. below about −20° C.) performance of a voltaic cell. This type of electrochemical cell performance improvement at low temperature can be utilized in various transient (transportable) electrically operated devices, such as Iontophoresis, for example, which may be used, stored, and/or transported in relatively cold environments. For example, many products that are shipped today, such as food products pharmaceuticals, blood, etc, may require low temperature storage and shipping conditions, or even low temperature operation. These devices might require electrochemical cells and/or batteries to operate effectively at temperatures at, or even below, −20° C., such as at about −23° C., about −27° C., or even at about −30° C. or less.
When zinc acetate is used to achieve improved low temperature performance for low temperature applications, the zinc acetate concentration in the range of about 31-33, is often acceptable, although ranges of about 30-34, about 28-36, about 26-38, and even about 25-40, weight percent, could also be utilized.
In at least one embodiment, the construction of the printed starch layer with the addition of the aqueous electrolyte could be replaced, for example, by a printable viscous liquid (which could include a gel, or some other viscous material) that effectively covers at least a portion of each electrode. One such printable gel is described in United States Patent Publication 2003/0165744A1, published on Sep. 4, 2003, and incorporated herein by reference. These viscous formulations could, for example, utilize the electrolyte formulas and concentrations previously discussed.
The upper substrate of a cell package could utilize a special laminated polymeric film, which has an edge that extends beyond the internal cell/battery components onto the cell frame. The upper layer is sealed around the edges of the cell frame by means of a pressure sensitive adhesive (PSA), and/or with the heat sensitive sealing adhesive that was previously printed, thus confining the internal components within the cell frame.
The above-described constructions can be wet cell constructions; however, using a similar cell construction, the present invention could be also be made into a reserve cell construction, which has the benefit of providing extended shelf life prior to the application of a liquid. The printable, flexible, zinc chloride thin cell can be made environmentally friendly. Such a construction could be utilized which does not require the use of harmful components, such as mercury or cadmium, for example. Old and/or depleted cells of this design could thus be disposed using regular waste removal procedures.
The devices for which this technology can be used are extensive. Devices that utilize relatively low power or a limited life of one to three years, and possibly longer, could function utilizing a thin cell/battery according to the invention. The cell of the invention, as explained in the above paragraphs and below, can often be inexpensively mass-produced so that it can be used in a disposable product, for example. The low cost allows for applications that previously were not cost effective.
The electrochemical cell/battery according to the invention might have one or more of the following advantages:
The above was a general description of various cell constructions according to some embodiments of the invention, and further details utilizing drawings follow below. Cell and battery production processes for cell printing and assembly also will be described as well.
Generally, Iontophoresis is related generally to the transdermal delivery of therapeutic agents by the use of an applied electro motive force (emf). The therapeutic agents can include various compounds, such as medication and/or cosmetics, or the like. The process of iontophoresis was described by LeDuc in 1908 and has since found commercial use in the delivery of ionically charged therapeutic agent molecules such as pilocarpine, lidocaine and dexamethasone, though various other therapeutic agents may also be used. In this delivery method, ions bearing a positive charge are driven across the skin at the site of an electrolytic electrical system anode, while ions bearing a negative charge are driven across the skin at the site of an electrolytic system cathode. An Iontophoresis device may include a therapeutic agent, a power source, and electrodes for delivering the therapeutic agent to a patient via the electro-motive force provided by the power source. However, an Iontophoresis device can also include additional elements (analog and/or digital) to provide various additional features, such as control circuitry, computational circuitry, storage circuitry (memory), switches, wired or wireless communication, etc. In other examples, an Iontophoresis device can be remotely controlled, such as by wireless radio frequency transmissions received by an antenna or the like, and may even be capable of transmitting information.
Prior to discussing an example method of manufacturing the Iontophoresis device, various components for use in the manufacturing process will be discussed in greater detail. Turning now to
Depending on the cell construction, the cell application, and/or the cell environment, it may be advantageous to have different barrier properties for the substrate. Due to the wide range of available vapor transmission rates available, the barrier layer can be chosen for each specific application and construction, as desired. In some cases, for example where the cell by design has a higher gassing rate short life cycle, it may be appropriate and desirable to use a film with a higher transmission rate to allow for a larger amount of gas to escape, so as to minimize cell bulging. Another example would be an application that is in a hot dry environment such as a desert. In such cases, it may be desirable to have a barrier film with low transmission rates to prevent excessive moisture loss from the batteries.
The use of a thicker substrate, by increasing any or all of the polymer thicknesses, may have some advantages: These may include one or both of the following:
In addition to the above specifications, both the outside and the inside layers could include the addition of a print-receptive surface for the inks. The inside layer is used for the functional inks (such as the collector and/or electrochemical layers) while the outside layer can be used for graphical inks, if desired. Flat cell constructions having a sealed system might utilize a laminated structure that includes metallized films and/or a very thin metal foil or foils as a moisture barrier. Although such structures using a metal layer might have better moisture barrier properties than the constructions used for some of the above described embodiments, it might also have some disadvantages. These may include one or more of the following:
The various substrates of
Alternately, a very thin aluminum foil could be laminated within the structure of the film layer, or even in a different position. Such a modification could reduce already low water loss to practically nil. On the other hand, if the application is for a relatively short shelf life and/or a short operating life, a more expensive barrier layer could be replaced with a less efficient one that would be of a lower cost and still allow the cell to function for the desired lifetime.
In applications where only an extremely short life is desired, the cell package could instead use a film layer of a low cost polymer substrate such as polyester or polyolefin. It is possible that the pressure sensitive adhesives for coupling and/or sealing the various substrates together could be replaced with a heat sealing system on the laminates. For example, a heat sealing coating or the like could be used, such as amorphous polyester (APET or PETG), semi crystalline polyester (CPET), polyvinyl chloride (PVC), or a polyolefin polymer etc. on polymer film such as polyester. One such example material is the Ovenable Lidding (OL) films made by Dupont and designated as their OL series such as OL, OL2 or OL13.
Similar to
An example method of manufacturing the Iontophoresis device will now be discussed. In one example, such as where relatively high speed, high output manufacturing is contemplated, such as 50 linear feet per minute or another relatively high speed, the invention can utilize multiple webs. It is to be understood that the multiple webs can be generally continuous, and can be utilized with known web manufacturing equipment. A first web can be relatively thin, such as ˜0.002″-0.010″ and preferably about 0.003-0.006″, flexible base substrate including a multi-ply laminated structure or single ply material. In one example, the multi-ply structure can include five layers. Alternatively, the single ply material can include various materials, such as Kapton or polyester. A second web can be a relatively thick laminated structure including a PVC or Polyester film that is about 0.005-0.030″ thick, and preferably about 0.010-0.015″ thick. The second web can have a layer of pressure sensitive adhesive at about 1-5 mils thick on one side. After this laminated structure of the second web is completed, it can be applied to the first web. In addition or alternatively, the second web can be pattern cut using any type of mechanical means to allow for cavities for the cells active materials as well as an optional cavity for the cell/battery contacts. A third web can be a relatively thin laminated structure the same and/or similar to the first web. The completed three web structure may have a pressure sensitive adhesive on either side to allow the individual device assembly to be applied as a label. The cell/battery may be of the thin cell type, such as disclosed in co-pending application Ser. No. 11/110,202, filed on Apr. 20, 2005 and incorporated herein by reference, and/or the cells disclosed in co-pending application Ser. No. 11/378,520, filed on Mar. 17, 2006, and also incorporated herein by reference.
The various conductive inks described herein could be based on many types of conductive materials such as carbon, silver, nickel, silver coated copper, copper, silver chloride, zinc and/or mixtures of these. For example, one such material that shows useful properties in terms of conductivity and flexibility is Acheson Colloids (Port Huron, Mich.) PM046. Furthermore, various components of the Iontophoresis device, such as the printed electrodes, circuitry, etc. can be made by etching aluminum, copper or similar type metallic foils that are laminated on a polymer such as Kapton substrate. This could be done with many types (sizes and frequencies) of components whether they are etched or printed. As described herein, a 3 volt battery is obtained by connecting two 1.5 volt unit cells in series, although other voltages and/or currents can be obtained by using unit cells with different voltages and/or by combining different numbers of cells together either in series and/or in parallel. Thus, applications using greater voltages can connect unit cells in series, whereas applications using greater currents can connect unit cells in parallel, and applications using both can utilize various groups of cells connected in series further connected in parallel. Thus, a variety of applications that use different voltages and currents can be supported using a variety of unit cell and/or battery configuration.
To make the manufacturing process of a cell/battery more efficient and/or achieve greater economies of scale, such as via production at high speeds and low cost, the processing and assembly could be integrated with the manufacture of an electronic component (for example, one to be powered by the battery or cell). In other words, the completed electronic application with the power source can be manufactured at the same time. An example of an integrated procedure is illustrated in the flow diagram of
According to available printing presses, the cells could be made with one pass, or multiple passes, on a given press, for example. The various drawings illustrate, as an example, two rows of cells to make a 3 volt battery on the web; however, the number of rows is limited only to the size of the unit cells and the maximum web width that the press can process. Because there may be numerous steps, thereby likely utilizing a long and complicated press, some of these steps, as well as some of the materials, could be modified and/or multiple passes of a press or multiple presses could be used. Some modified process summaries will be shown after the initial discussion is completed. Moreover, any or all of the printing steps can be performed by screen printing, such as by flat bed screens or even rotary screen stations. Additionally, one skilled in the art would realize that one printing and converting on a press with more than ten stations could be difficult to find and or to operate, and thus the following discussion of the process could occur on one or more presses or even multiple passes through one press.
However, before the cell/battery is processed as shown in
One skilled in the art would realize that there are many methods, materials, and sequences of operations that could be used to accomplish this invention, and that more or less, similar or different, numbers of stations could also be utilized. For purposes of brevity, the example integrated process 8000 will be discussed with the manufacture of an Iontophoresis device 999 and/or other power-assisted medication dispersal device. Still, it is to be understood that the following process 8000 can also be utilized for the manufacture of various other integrated electronic devices. Further, for the purposes of clarity only one column of devices 999 will be described and illustrated with the understanding that such description can similarly apply to other columns. Moreover, it is to be understood that any or all of the following elements can include any of the various materials, chemical compositions, etc. described throughout this document. Additionally, the various steps as shown in the process 8000 of
As discussed above, the integrated process 8000 shown in
The process 8000 includes the first step 8002 at the first station 6001, which can be optional, of printing various indicia, such as graphics, letters, symbols, etc. on the first substrate 1000. For example, an outline 102 of the Iontophoresis device can be printed. In addition or alternatively, polarity indicators 101, instructions (not shown), or the like can similarly be printed. The indicia can be printed using various materials, such as commercial graphic inks and/or any of the inks described herein.
Next, in step 8004 at the second station 6002, the cathode collector 201 is printed onto the first substrate 1000 with a highly conductive carbon ink. The cathode collectors 201 and 202 can include various materials, such as a highly conductive carbon ink (e.g., PM024) such as manufactured by Acheson Colloids of Port Huron, Mich. The cathode collectors 201 and 202 can be printed on the lower laminate by commercial means such as screen printing, for example using a very coarse screen of about 61 mesh (about 20-100 mesh for some embodiments) to allow for a dry deposit of about 1 mil (about 1.2-0.4 mils respectively). A cell with a size of about 2″×2″ would thus have a resistance of about 60 ohms (about 40-100 ohms). To further reduce this resistance, a highly conductive contact could be printed at the external contact area of the positive electrode. The material used in this example construction is a silver filled conductive ink (SS479) manufactured by Acheson Colloids of Port Huron, Mich. which can be screen printed.
Other useable conductive materials, such as gold, tin, copper, nickel and/or mixtures of two or more conductive materials, along with other materials, could also be used for acceptable embodiments. Any of these conductive inks might be applied by means of, for example, a printing method, such as flat bed screen, rotary screen, flexography, and gravure, as well as with ink jet printing techniques, for example. Additionally, manufactured foils of graphite and/or mixtures including one or more of conductive resins, metals, and graphite could be inserted and used, instead of printing an ink cathode collector. In applications where only very low currents are used, a highly conductive positive contact may not be utilized, and/or if somewhat higher currents are desired, the circuit contact might instead be used as the high conductivity contact.
Next, in step 8006 at the third station 6003, a continuous strip of zinc foil/PSA laminate 1200 (i.e., see
In the example embodiments, strips of zinc foil can be continuous; however, they are illustrated broken off at the edges of the individual stations to better identify the unit stations. In another embodiment (not shown), a precut anode strip foil 301, 302, which can be a laminate (and of possible dimensions of about: 1.75″×0.20″33 0.002″, for example), is inserted onto the lower substrate adjacent to the cathode collector at a gap of about 0.050″ (about 0.010″-0.100″) from the cathode collector. Prior to its lamination for high speed and high volume applications or insertion onto substrate 1000 for lower speed and volume applications, the 2 mil thick battery grade zinc foil can be laminated to a dry film adhesive with a release liner, such as #2180, IB1190 or IB2130 manufactured by Morgan Adhesive Co. of Stow, Ohio. After this lamination is completed, for example on a wide roll of zinc (e.g., about 3-12′ wide), this laminated structure can be slit into narrow rolls with a width of about 0.200″ (about 0.170″-0.230″) for an about 1 sq. inch cathode cell. Cells with other sizes of cathodes can utilize different slit widths for the anode laminate. In another construction, the lamination could be done with a printed adhesive on the substrate prior to applying the zinc foil strip, for example. Still, in other examples, the anode can be provided by a printing process. For example, the anode can be printed about 0.20″ wide and about 0.002″ (about 0.0003-0.005″) thick, though various other widths and thicknesses are contemplated. Moreover, to make the printed anode even more conductive, an anode collector (not shown) can be printed under the anode, such as in a conductive pattern or the like.
Next, in step 8008 at the fourth station 6004 illustrated in
Next, in step 8010 at the fifth station 6005, a second Iontophoresis electrode 501 can be provided onto the first substrate 1000. In one example, the second electrode 501 can be printed onto the first substrate 1000 using various inks, such as zinc or silver chloride ink. Indeed, where both of the first and second electrodes 401, 501 are printed using the same ink, both can be printed generally simultaneously. Still, various other inks can also be used, such as zinc ink. For example, use of one silver chloride electrode and one zinc electrode can facilitate medicine delivery. As before, the second electrode 501 can be a negative electrode (as shown), though it can also be a positive electrode depending upon the construction of the device. Moreover, either or both of the first and second electrodes 401, 501 can have various geometries, such as circular, triangular, square, rectangular, other polygonal shape, random, etc. Either or both of the first and second electrodes 401, 501 can have also have various sizes. For example, the first electrode 401 (i.e., positive) can be generally smaller than the second electrode 501 (i.e., negative) so as to facilitate application of medicated pads having positively charged medication and negatively charged medication, which can have similar size differences.
Next, in step 8012 at the sixth station 6006 illustrated in
Next, in step 8014 at the seventh station 6007, a frame sealant 700 (i.e., shaded area 702, 703, 704, 705), which can be an adhesive, can be printed around the perimeter of both unit cells 1501 and 1502 to form a “picture frame.” The frame sealant 700 can be provided on top of the zinc anode 1200 and over the cathode collector 201, 202 in the seal area, as well as along a top 702, bottom 704, sides 703, and the centerpost 705. The frame sealant 700 can generally bound an inner space 230 that will define an interior volume of the battery cells 1501, 1502.
The frame sealant 700 can be provided as one frame surrounding both cells of the 3 volt battery package, though it can also be provided as separate elements. Though described as being printed, the frame sealant 700 could also be formed from a pre-punched polymer sheet, such as polyvinyl chloride, polyester, or various other dielectric or electrically-neutral material. Additionally, though shown as having a generally rectangular geometry, the frame sealant 700 can have various other geometries so as to bound the battery cells 1501, 1502. In addition or alternatively, the frame sealant 700 can have an adhesive layer, such as a PSA layer or the like.
Next, in step 8016 at the eighth station 6008, the cathode layer 801, 802 can be screen-printed over part of the cathode collector 201, 202 for both cells 1501 and 1502. In an example embodiment, the cathode layer 801, 802, shown as a partial cut-away for clarity, can be printed on a portion of the previously printed and dried cathode collector layer 201, 202 with an aqueous based ink that has a wet composition, for example, of about 43.4% of battery grade Manganese Dioxide (about 20%-60%), about 14.4% of KS-6 graphite (about 2%-25%), about 29.5% of about 6.5% (about 0.5%-15%) aqueous solution of polyvinylpyrrolidone (PVP) (about 20%-60%); and about 9.65% of De-ionized or distilled water (about 0.1%-20%). Such an ink can be printed with about a 46 mesh (about 10-65 mesh) fiberglass screen so as to allow a nominal dry lay down weight of about 0.10 grams per square inch (about 0.03-0.25 g/sq. in.). The amount of dry print would typically be dictated by the desired cell capacity, using more material when a higher capacity is desired, for example. By using this unconventional printing method utilizing a very coarse mesh screen instead of multiple hits of a finer mesh screen, the number of printing stations can be reduced and the cell performance can be increased. In addition or alternatively, the cathode layer 801, 802 can be printed on a portion of the previously printed and dried cathode collector layer 201, 202 with another aqueous based ink that replaces the above-described polyvinylpyrrolidone (PVP) component with Dow Cellosize hydroxyethyl cellulose (HEC) in about 0.93 to 1.08% (weight percent) solutions in deionized water solutions that represent about 40% (weight percent) of the wet cathode. Various HEC's can be used, such as type HEC-25 or type QP100 MH.
The cathode layer 801, 802 material used in this example construction includes, for example, an electrolytic manganese dioxide of high purity battery grade. The material particle size range for this embodiment is, for example, about 1 to 100 microns with an average size of about 40 microns. If additional fineness of the material is desired to facilitate the application to the collector, the material can be milled to achieve a particle size range of about 1 to 20 microns, with an average of about 4 microns, if desired. Other usable electro-active cathode materials that may be used in conjunction with the zinc anode in the subject construction, are silver oxides Ag2O and/or AgO, mercuric oxide HgO, nickel oxide NiOOH, oxygen O2 (as in the form of an air cell, for example), and Vanadium oxide VO2, for example. Cathodic materials that may be used with different anodic materials include one or more of NiOOH with Cd, NiOOH with metal hydrides of the AB2 and the AB3 types, and NiOOH with Fe and FES2, for example.
A binder used in the cathode layer 801, 802 of an example embodiment includes a class of high molecular weight binders that exceed about 950,000-grams/mole. One such polymer that can be used is polyvinylpyrrolidone, about K 85-95 or about K 120 (higher molecular weight). Other classes of materials that can be used include one or more of the following: polyvinyl alcohol; classes of starches and modified starches, including rice, potato, corn, and bean varieties; ethyl and hydroxy-ethyl celluloses (HEC); methyl celluloses; polyethylene oxides; polyacryamides; as well as mixtures of these materials. Additional binding may be derived, if desired, from the use of Teflon solutions or Teflon fibrillated during the blending process.
Next, in step 8018 at the ninth station 6009 in
Next, in step 8020 at the tenth station 6010, “paper separator” 1801, 1802 or another type of soak-up material can be inserted on top of the anode and the cathode. Alternatively, a “starch ink” or the electrolyte could be flowed or printed over the anode and cathode that are inside the picture frame.
Next, in step 8022 at the eleventh station 6011, when a paper separator 1801, 1802 is used, an electrolyte 1901, 1902, such as an aqueous ZnCl2 electrolyte, is added to the top of the paper separator 1801, 1802 which was placed over the cathode 801, 802 and anode 1200. In addition or alternatively, a starch ink or similar material could be used to act as an electrolyte absorber to keep the electrodes “wet” after an aqueous electrolyte solution is added to the cell. This starch ink could also include the electrolyte salts and the water used for the cell reaction.
As an alternative to the aforedescribed eleventh station 6011, an alternative electrolyte configuration (not shown) can be used when a paper separator is not used. For example, the electrolyte can be provided in the form of a viscous liquid (such as a flowable-gel) is added on the inside area of each unit cell. Due to its flow-ability, the electrolyte will generally spread out to uniformly to cover the anode and cathode. A printed electrolyte (e.g., using an ink or flowable gel) could be substituted for the liquid electrolyte and paper separator of the above referenced application.
Next, in step 8024 at the twelfth station 6012 in
Turning now to
In one example, as shown in
Turning now to
Another possible embodiment of the invention is illustrated in
Turning now to
Also in step 8028 (or even in step 8030 below), the fourth layer 1400 (i.e., the foam web) of the Iontophoresis devices 999 can be “kiss cut” to define a shaped element, such as a desired shape of the devices 999. It can be beneficial to perform the “kiss cut” operation(s) prior to the above-described perforating and/or slitting operations, though either operation can precede the other. It is to be understood that the “kiss cut” can provide various shapes of the Iontophoresis devices 999. As used herein, the phrase “kiss cut” is intended to generally refer to a separation by a cut (i.e., provided by a knife cut, a linear die cut, a rotary die cut, etc.) through at least a face material (though can also be through various layers) without removing a matrix between remaining layers. In other words, a “kiss-cut” is a controlled depth cut that extends only through a predetermined number of layers. For example, in the shown example only the bottom release liner is not cut, though various numbers of layers can be cut. Thus, as shown in
Turning now to
Next, at the final step 8032 illustrated in
rolled onto a roll 400 for storage, transport. It is to be understood that the devices 999 are illustrated schematically for clarity. Still, the devices 999 can be stored in various other manners. In one example, instead of perforations, the devices 999 can be complete separated from each other along the transverse perforation line 1430, and the devices 999 can be stored as generally flat units. In addition or alternatively, any or all of the four substrates 1000, 1100, 3000, 1400 can be slit on the outside edge thereof to alter a width thereof. Turning now to
The manufacturing process 5000 can include various other stages, steps, etc. For example, prior to the printing station 5008, the web 5004 can pass through a preliminary station 5006 wherein various additional elements of the Iontophoresis device 999 can be provided. Moreover, any or all of the various layers, substrates, etc. can be provided by supplemental rolls along the process. For example, a portion of the Iontophoresis devices 999 can be provided by a first supplemental roll 5012 via a supplemental web 5014. In another example, either or both of the second, third, or fourth substrates 1100, 3000, 1400 can be provided by a second supplemental roll 5016 via another supplemental web 5018. Though illustrated near the beginning of the printing station 5008, it is to be understood that any or all of the supplemental webs 5014, 5018 can be provided at various locations along the manufacturing process 5000. Further, the Iontophoresis devices 999 can be “kiss cut” at station 5030. In addition or alternatively, waste material, such as release layers or the like, or even the waste portion matrix from the “kiss cut”, can be removed from as a waste web 5020 and taken-up by a waste roll 5022 or the like. Various other pre-processing and/or post-processing stations, steps, etc. can also be included. It is to be understood that the various stations, rolls, etc. of the described process 5000 can be utilized in various orders, and additional equipment may even be provided (e.g., idler rollers, tension rollers, turn-bars, slit or perforators, etc.) to facilitate the “reel-to-reel” process.
Various other additional steps (not shown) can be utilized to provide additional structure, features, etc. to the completed Iontophoresis devices 999. In one example, an outer portion of the device 999, such as the second substrate 3000 “top cover”, can be provided with a method of attaching the device 999 to another object, surface, etc. For example, the second substrate 3000 can include a pressure sensitive adhesive, another adhesive layer, a hook-and-loop style fastener, a liquid or hot-melt adhesive, etc. In another example, an outer portion of the device 999, such as the second substrate 3000 “top cover”, can be provided with printed indicia or even a label or the like.
In addition or alternatively to the foregoing description, as illustrated in
In addition or alternatively, as illustrated in
In addition or alternatively to the foregoing description, though not illustrated, it is to be understood that the Iontophoresis structure and the battery power supply can be provided on different substrates. For example, the battery power source 1530 can be manufactured on a first side of the first substrate 1000, while the Iontophoresis structure (i.e., the electrodes 401, 501, circuitry 602, 603, 606, and 607 can be provided on the first side of a substrate which can be a low cost polymer film such as at about 0.003″ thick. Then in process 5000 these rolls of medical devices are fed through the process on web 5004, then on web 5014 from reel 5012 rolls of completed batteries 1530 are inserted as discrete batteries and attached onto web 5004 and structurally fastened to substrate and electrically connected to the electrodes in station 5006. In another method the batteries on substrate 1000 which were assembled with the same registration as the Iontophoresis device, thus two rolls could be laminated in registration. In both cases various structures can be provided to electrically couple the battery to the electrodes. In one example, apertures or through holes can extend through the first substrate 1000. The through holes can be located in registration generally with the electrodes 401, 501. Various numbers of through holes can be provided for each contact, such as between one and five holes. The number, location, and/or spacing of the various holes may depend on the application and materials of construction. The holes could be made by several methods such as punching, laser cutting, etc. Moreover, it is to be understood that various other alternatives to the holes can be employed. For example, via, electrical jumpers, or the like can also be used together with, or as alternatives to, the holes. The various holes, etc. can be provided at various times in the manufacturing process 8000, though it can be beneficial to provide the holes prior to printing and prior to the lamination of the foam substrate 1400, etc. Substrate 4000 with its precut holes is laminated to the substrates in station 5008 of process 5000. Substrate 4000 is fed into station 5008 by means of reel 5016 and web 5018. After the lamination of the three webs to complete the assembly of the medical device 999, the assembled roll is kiss cut and the excess matrix material is removed, the rolls are slit and/or perforated as required and finally, the completed Iontophoresis devices 999 on the generally continuous web 5004 can be collected at a take-up station 5010, which can include a collection roll, such as the roll 400 previously described herein.
Further, the manufacturing process for this integrated assembly of this medical device could have a different approach which is easily understood to those skilled in the art. The device with its electrodes 401 and 501 and circuitry 602, 603, 606, and 607 is printed on substrate 1000 as previously described. Then in process 5000 these rolls of devices are fed through the process on web 5004, then on web 5014 from reel 5012 rolls of completed batteries 1530 are inserted and attached onto web 5004 and electrically connected to the electrodes in station 5006.
Thin printed flexible batteries can have many potential applications, which can include one or more of the following generally categories as examples:
1. Skin patches that apply Iontophoresis or other electrical function for the purpose of drug delivery, wound care, pain management and/or cosmetics;
2. Advertising and promotion;
3. Toys, novelties, books, greeting cards, and games;
4. Inventory tracking and control such as (smart RFID tags);
5. Security tags;
6. Condition indicators such as temperature, humidity, etc.;
7. RFID assemblies; and
8. Healthcare products such as smart diapers, incontinence products, etc.
The invention has been described hereinabove using specific examples and embodiments; however, it will be understood by those skilled in the art that various alternatives may be used and equivalents may be substituted for elements and/or steps described herein, without deviating from the scope of the invention. Modifications may be performed to adapt the invention to a particular situation or to particular needs without departing from the scope of the invention. It is intended that the invention not be limited to the particular implementations and embodiments described herein, but that the claims be given their broadest interpretation to cover all embodiments, literal or equivalent, disclosed or not, covered thereby.
This application claims the benefit of U.S. provisional application Ser. No. 60/953,391, filed on Aug. 1, 2007, which is incorporated herein in its entirety by reference thereto.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US08/71549 | 7/30/2008 | WO | 00 | 1/14/2010 |
Number | Date | Country | |
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60953391 | Aug 2007 | US |