The present application relates to a fuel cell, and more particularly a membraneless fuel cell wherein a flow of reductant and oxidant are provided to a transport zone in which ions are exchanged and the reductant and oxidant undergo oxidation and reduction, respectively.
If fuel cells are to become viable portable power sources in the future, solutions to a number of difficult, persistent technical problems are needed. Many of these problems are associated with the presence of the proton exchange membrane, which is highly sensitive to various factors, such as operating temperatures and membrane humidity. Efforts in portable applications have largely focused on reducing the size of proton exchange membrane (PEM) fuel cells. By portable power sources, this is generally referring to substitutes for batteries that power portable electronic devices. This approach carries all the cost and efficiency issues associated with larger scale PEM fuel cells. Moreover, the reduction in size exaggerates some of these problems, and introduces even further problems that require resolution for a commercially viable product.
One approach has been to deliver parallel co-laminar flows of oxidizer and fuel saturated electrolytes into a single channel with a cathode on one side and an anode on another. See, e.g., Membraneless Vanadium Redox Fuel Cell Using Laminar Flow, Ferrigno et al., J. Amer. Chem. Soc. 2002, 124, 12930-12931; Fabrication and Preliminary Testing of a Planar Membraneless Microchannel Fuel Cell, Cohen et al., J. Power Sources, 139, 96-105; and Air-Breathing Laminar Flow-Based Microfluidic Fuel Cell, Jayashree et al., J. Am. Chem. Soc., 2005, 127, 16758-16759. See also, U.S. Pat. Nos. 7,252,898 and 6,713,206. Each of these is incorporated into the present application by reference in their entirety for background teachings.
This approach has various shortcomings. First, the fuel and oxidizer will mix downstream of the entry point, wasting the majority of the fuel. Second, the diffusivity of many oxidizers leads to mixed potentials at the anode due to oxidizer cross-over to the anode. This takes energy away from the circuit and also leads to inefficiency of the overall cell. Third, a mass transport boundary layer builds up on the electrodes which generates mass transport losses in the fuel cell and decreases performance. Fourth, the architecture of the cell is restricted to the geometries, length scales, and electrolytes where laminar flow is ensured.
U.S. Patent Publication Nos. 2003/0165727 and 2004/0058203 disclose mixed reactant fuel cells where the fuel, oxidant and electrolyte are mixed together and then flow through the anode and cathode. These publications are incorporated herein by reference. According to these publications, the anode is allegedly selective for fuel oxidation and the cathode is allegedly selective for oxidizer reduction. The designs in these publications have significant shortcomings. First, the amount of some oxidizers that can be typically carried by an electrolyte is relatively low (e.g., the oxygen solubility in an electrolyte is typically quite low relative to fuel solubility). This means that a relatively high flow rate is required for the mixed reactants to ensure that an ample amount of oxidizer is flowing through the cell. That is, a relatively high flow rate is required to maximize oxidizer exposure and reaction at the cathode. But increasing the flow rate requires increased work, thus detracting from the overall power efficiency of the cell. Increasing the flow rate also advects the reactants downstream before they can fully react, resulting wasted reactants. Moreover, electrodes that are selective by virtue of their material properties tend to have lower reaction activity rates than non-selective electrodes. Because the designs in these two publications rely primarily on the use of selective electrodes for both the cathode and anode, this further detracts from the efficiency of the cell.
The present application addresses the aforementioned challenges without a proton exchange membrane.
According to an aspect of the present invention, there is provided a method for generating electrical current using a fuel cell comprising an anode, a cathode, a first flow channel associated with the anode, a second flow channel associated with the cathode, and a plurality of spaced apart exchange zones wherein the first and second flow channels are open to one another. The method includes flowing a first flow comprising a fuel and a first electrolyte through the first channel. The fuel is oxidized at the anode to generate electrons for conduction to a load and oxidation products in the first flow. The method includes flowing a second flow that includes an oxidizer and a second electrolyte through the second channel. The cathode receives electrons from the load and the oxidation products, and the oxidizer forms reduction products to complete an electrochemical circuit. The plurality of exchange zones are positioned and the flows are oriented within their respective first and second channels such that the first and second flows contact one another intermittently at the exchange zones to enable transport of the reduction and oxidation products to the anode and the cathode.
According to an aspect of the invention, there is provided a fuel cell that includes an anode configured to be connected to a load, a cathode configured to be connected to the load; and a first flow channel associated with the anode, and configured to receive a flow of a fuel and a first electrolyte so that, in use, the fuel is oxidized by the anode to generate electrons for conduction to the load and oxidation products in the first electrolyte. The fuel cell also includes a second flow channel associated with the cathode, and configured to receive a flow of an oxidizer and a second electrolyte so that, in use, the oxidizer is reduced by its reaction with the oxidation products and incoming flux of electrons from the load to form reduction products, and a plurality of spaced apart exchange zones wherein the first and second flow channels are open to one another. The first and second flow channels are oriented such that the flow of the fuel and first electrolyte and the flow of the oxidizer and the second electrolyte within their respective first and second channels contact one another intermittently.
Other aspects, features, and advantages of the present invention will become apparent from the following detailed description, the accompanying drawings, and the appended claims.
Embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts, and in which:
The Figures illustrate several embodiments of various aspects of the inventions claimed. These embodiments are in no way intended to be limiting, and are intended only as an example for facilitating an understanding of the principles of the claimed inventions. In some instances, various components are illustrated schematically, as it is understood many different structures may be used.
In the illustrated embodiment of
The fuel source 16 is connected to a first fluid passageway 22 and is configured to supply the fuel to the first fluid passageway 22. The fuel may be fed to the first fluid passageway 22 by gravity, surface forces, such as surface tension or electroosmotic flow, or a fuel flow generator, such as a pump, may be used to generate flow of the fuel through the first fluid passageway 22.
Similarly, the oxidizer source 18 is connected to a second fluid passageway 26 and is configured to supply the oxidizer to the second fluid passageway 26. The oxidizer may be fed to the second fluid passageway 26 by gravity, surface forces, such as surface tension or electroosmotic flow, or an oxidizer flow generator, such as a pump, may be used to generate flow of the oxidizer through the first fluid passageway 26.
The first fluid passageway 22 may be defined by a channel or conduit that is in contact with or defines the anode 12. The anode 12 may comprise a catalyst that is configured to catalyze the fuel so that the fuel is oxidized into at least oxidized fuel ions and electrons for conduction by the anode 14 to the load L. An oxidation product is an ionic or molecular byproduct of the fuel's oxidation that has donated at least one electron. An oxidation product may also be referred to as a cation because the loss of an electron may result in a positive charge. However, the cations may be supported in the electrolyte by negative ions. Non-limiting examples of catalysts that may be used include platinum, ruthenium, palladium, nickel, gold, and carbon or alloys of the aforementioned. The first fluid passageway 22 is preferably designed so that the flow of the fuel and electrolyte, which may be referred to as an anolyte, in the passageway 22 is a laminar flow.
Similarly, the second fluid passageway 26 may be defined by a channel or conduit that is in contact with or defines the cathode 14. The cathode 14 receives electrons from the load L and may comprise a catalyst that is configured to catalyze the oxidizer so that the oxidizer is reduced into at least reduced products. A reduced product is an ionic or molecular byproduct of the oxidizer that has gained at least one electron. A reduced product may also be referred to as an anion because the gain of an electron may result in a negative charge. However, the anions may be supported in the electrolyte by positive ions. Non-limiting examples of catalysts that may be used include platinum, ruthenium, palladium, nickel, gold, and carbon or alloys of the aforementioned. Like the first fluid passageway 22, the second fluid passageway 26 is preferably designed so that the flow of the oxidizer and electrolyte, which may be referred to as a catholyte, in the passageway 26 is a laminar flow. The fuel cell 10 also includes an insulator 28, as schematically shown in
As illustrated in
The exchange zone may have a relatively large area to facilitate reaction of the ions so that the resistance of the electrochemical circuit may be reduced, which may maximize potential at each electrode (i.e., at the anode 12 and the cathode 14). Having an area that is too high, however, may result in more diffusive mixing at the intersection 30, as well as flow instabilities, which may disrupt the laminar flows within the first and second fluid passageways 22, 26 or allow cross-over of the reactants.
As illustrated in
In the illustrated embodiment, six intersections or exchange zones are provided. Of course, more or less intersections may be provided, depending on the application. The intersections or exchanges zones are arranged so that there is intermittent contact between the respective flows within the first and second fluid passageways 22, 26. By arranging the first fluid passageway 22 and the second fluid passageway 26 in this way, the contact area between the two streams (i.e., of anolyte and catholyte) flowing through the passageways 22, 26 may be minimized, but the instances or frequency of contact between the two streams may be increased. This may reduce the overall diffusive mixing effects, maintain a stable flow pattern in each of the passageways 22, 26, and allow for an overall large area for ion exchange. This arrangement may also allow essentially no cross-over of un-reacted fuel and oxidizer from one fluid passageway to the other fluid passageway.
In the embodiment illustrated in
In an embodiment, the fuel may be hydrogen saturated sulfuric acid and the oxidant may be oxygen saturated sulfuric acid. For an acidic cell using such reactants, oxidation of the fuel at the anode 12 may be generally represented by the following equation:
H2→2H++2e− (1)
and reduction of the oxidant (oxidizer) at the cathode 14 may be represented by the following equation:
0.5O2+2e−+2H1→H2O (2)
and the net reaction of the system is:
H2+0.5O2→H2O (3)
Thus, the byproduct of these reactions is water.
For an alkaline fuel cell, oxidation of the fuel at the anode 12 may be generally represented by the following equation:
H2+2OH−→2H2O+2e− (4)
and reduction of the oxidant (oxidizer) at the cathode 14 may be represented by the following equation:
O2+2H2O+4e−→4OH− (5)
and the net reaction of the system is:
H2+0.5O2→H2O (6)
which is the same net reaction described above in reference to an acidic fuel cell in equation (3).
For either type of fuel cell (i.e., acidic or alkaline), other possible reactions may occur, including various intermediary reactions, or different reactions when different reactants are used. The system generates an open circuit voltage based on the potentials of its respective half cell reactions. When current is drawn through the load L, this voltage will generally decrease in value to zero, the point of maximum extractable current, or short circuit voltage.
As shown in
The slots 116, 118 of the flow guides 104, 106 create flow channels when the fuel cell is assembled, and may be configured to allow the catholyte 105 and the anolyte 107, respectively, to flow from one end of the slot 116, 118 to the other end of the slot 116, 118 in such a manner that the flows are laminar. In other embodiments, instead of having unitary plate-like structures or grids for the flow guides 104, 106, the slots 116, 118 could be defined by individual members positioned in spaced apart relation.
As illustrated in
Similarly, a delivery manifold 130, also shown schematically in
In the embodiment illustrated in
The flow channels created by the slots 116, 118 may span the microfluidic to millifluidic range, i.e., the smallest dimension, such as the depth of the channel, may be in the range of about 1 μm to about 10 mm. The lengths of the channels may be designed so that the most efficient reactant utilization may be achieved, and may depend on the concentrations of the particular reactants in the catholyte and the anolyte. In an embodiment, the length of the channels may be selected within an aspect ratio that is based upon the Peclet number (Pe), as specified by equation (4) below:
Pc=UH/D (4)
where U is the average velocity of the catholyte or anolyte in the channel, which may be controlled by the flow rate, H is the characteristic dimension of the channel (such as the width or height), and D is the diffusion coefficient of the catholyte or anolyte that is flowing in the channel. Preferably, the channel geometry and flow rates are selected so that a high Peclet number, such as greater than 10 is achieved, so as to substantially prevent intermixing of the catholyte and the anolyte at the intersection points, (contact zones).
The cathode 102 may be made out of a catalyst material so that when the cathode 102 is connected to the anode 108 via the load L, the cathode reduces the oxidizer. In an embodiment, the cathode 102 may include a catalyst material that is only on the portions of the surface of the cathode 102 that form walls of the channels defined by the slots 116 and come into contact with the oxidizer and electrolyte (catholyte). Similarly, the anode 108 may be made out of a suitable catalyst material so that when the anode 108 is connected to the cathode 102 via the load L and is in contact with the fuel and electrolyte, the anode 108 oxidizes the fuel. In an embodiment, the anode 108 may include a catalyst material that is only on portions of the surface of the anode 108 that form walls of the channels defined by the slots 118 and come into contact with the fuel and the electrolyte (anolyte).
The electrodes (i.e., anode and cathode) can be made up of any electrically conductive material that is coated with a suitable catalyst. In an embodiment, each electrode comprises a porous material that is the catalyst itself, including but not limited to a catalyst coated carbon cloth, a porous foam, a packed bed of catalyst particles, and/or colloidal crystals.
In addition to any fuel, oxidant, electrolyte or catalyst material mentioned above, any of the following in various combinations may be used in any of the embodiments described above, as well as in any other embodiment within the scope of any aspect of the invention.
Electrodes/Catalysts: Platinum, Platinum black, Platinized metal (any), Nickel, Nickel Hydroxide, Manganese, Manganese Oxides (all states), Palladium, Platinum Ruthenium alloys, Nickel Zinc alloys, Nickel Copper alloys, Gold, Platinum black supported on metal oxides, Platinum Molybdenum alloys, Platinum Chromium alloys, Platinum Nickel alloys, Platinum Cobalt alloys, Platinum Titanium alloys, Platinum Copper alloys, Platinum Selenium alloys, Platinum Iron alloys, Platinum Manganese alloys, Platinum Tin alloys, Platinum Tantalum alloys, Platinum Vanadium alloys, Platinum Tungsten alloys, Platinum Zinc alloys, Platinum Zirconium alloys, Silver, Silver/Tungsten Carbide, Iron tetramethoxyphenyl porphorin, Carbon or Carbon Black.
Fuels: Formic acid, Methanol, Ethanol, 1-proponal, 2-proponal, Cyclobutanol, Cyclopentanol, Cyclohexanol, Benzyl alcohol, Lithium, Zinc, Aluminum, Magnesium, Iron, Cadmium, Lead, Acetaldehyde, Propionaldehyde, Benzaldehyde, Ethylene glycol, Glyoxal, Glycolic acid, Glyoxylic acid, Oxalic acid, 1,2-propanediol, 1,3-propanediol, Glycerol, Hydrogen, Vandium(II)/Vanadium(III), Carbon Monoxide, Sodium Borohydride, Other Borohydrides (e.g. Potassium), and other metal redox systems e.g.: Iron/chromium, Nickel/cadmium.
Oxidants: Air, Oxygen gas, Dissolved Oxygen, Hydrogen Peroxide, Potassium Permanganate, Vanadium(IV)/Vanadium(V) and Manganese Oxide.
Electrolytes: Potassium Hydroxide, Sodium Hydroxide, Sulfuric acid, Nitric acid, Formic acid, Phosphoric acid, Trifluoromethanesulfonic acid (TFMSA), Ionic liquids (all types), Acetimide, Fluoroalcohol emulsions, and Perflourocarbon emulsions (e.g. Flourinert®).
The foregoing illustrated embodiment(s) have been provided solely for illustrating the structural and functional principles of the present invention and are not intended to be limiting. To the contrary, the present invention is intended to encompass all modifications, substitutions, alterations, and equivalents within the spirit and scope of the following appended claims.
This application claims the benefit of priority from U.S. Provisional Patent Application No. 61/193,157, filed Oct. 31, 2008, the entire content of which is incorporated herein by reference.
Number | Date | Country | |
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61193157 | Oct 2008 | US |