Patent Application
20080160382
The present disclosure relates generally to an electrochemical cell system, and especially relates to a compartmentalized storage tank for use with an electrochemical cell system capable of operating in a low gravity environment.
Electrochemical cells are energy conversion devices, usually classified as either electrolysis cells or fuel cells. An electrolysis cell functions as a hydrogen generator by electrolytically decomposing water to produce hydrogen and oxygen gases, and functions as a fuel cell by electrochemically reacting hydrogen with oxygen to generate electricity.
Referring to
The same configuration as is depicted in
A typical electrochemical cell system includes a one or more individual cells arranged in a stack, with the working fluid directed through the cells via input and output conduits formed within the stack structure. The cells within the stack are sequentially arranged, each including a cathode, a proton exchange membrane, and an anode. In certain conventional arrangements, the anode, cathode, or both, are gas diffusion electrodes that facilitate gas diffusion to the membrane. Each cathode/membrane/anode assembly (hereinafter “membrane electrode assembly”, or “MEA”) is typically supported on both sides by flow fields comprising screen packs or bipolar plates. Such flow fields facilitate fluid movement and membrane hydration and provide mechanical support for the MEA. Since a differential pressure often exists in the cells, compression pads or other compression means are often employed to maintain uniform compression in the cell active area, that is, the electrodes, thereby maintaining intimate contact between flow fields and cell electrodes over long time periods.
In certain arrangements, the electrochemical cells can be employed to both convert electricity into hydrogen, and hydrogen back into electricity as needed. Such systems are commonly referred to as regenerative fuel cell systems.
Electrochemical cell systems are generally operated within a gravitational field. Gravity aids in pulling water away from the electrode surface when the electrochemical cell is used in fuel cell mode, whereas in the electrolysis mode, gas and water exit the cell stack together thereby necessitating gravity-induced phase separation.
It is sometimes desirable to operate electrochemical cell systems in a low gravity environment, or even in a zero gravity environment. However, in typical configurations, water may collect on an electrode thereby inhibiting oxygen access to the electrode in the fuel cell mode, and alternative water/gas separation methods would be needed in the electrolysis cell mode. Solutions addressing each of these requirements would necessitate excess equipment costs, add to system complexity, and consume electricity.
While existing electrochemical cell systems are suitable for their intended purposes, there still remains a need for improvements, particularly regarding operation of electrochemical cell systems in low gravity or zero gravity environments.
Embodiments of the invention includes a compartmentalized storage tank having a housing, a first fluid storage section disposed within the housing, a second fluid storage section disposed within the housing, the first and second fluid storage sections being separated by a movable divider, and a constant force spring. The constant force spring is disposed between the housing and the movable divider to exert a constant force on the movable divider to cause a pressure P1 in the first fluid storage section to be greater than a pressure P2 in the second fluid storage section, thereby defining a pressure differential.
Embodiments of the invention also include an electrochemical cell system having at least one electrochemical cell having a hydrogen electrode and an oxygen electrode with a proton exchange membrane disposed therebetween and in intimate contact therewith. The system also includes a compartmentalized storage tank having a housing, a first fluid storage section disposed within the housing, a second fluid storage section disposed within the housing, the first and second fluid storage sections being separated by a movable divider, and a constant force spring disposed between the housing and the movable divider to exert a constant force on the movable divider to cause a pressure P1 in the first fluid storage section to be greater than a pressure P2 in the second fluid storage section, thereby defining a substantially constant pressure differential. The compartmentalized storage tank is in fluid communication with the at least one electrochemical cell.
These and other advantages and features will be more readily understood by those skilled in the art from the following detailed description of preferred embodiments of the invention that is provided in connection with the following accompanying drawings.
Referring now to the drawings, which are meant to be exemplary and not limiting, and wherein like elements are numbered alike in the several Figures:
An embodiment of the invention, as shown and described by the various figures and accompanying text, provides an electrochemical cell and an electrochemical cell system. The system has one or more electrochemical cells and a compartmentalized storage tank that enable the system to be used in a low or zero gravity environment. Upon application of a load or electricity to the system, the system operates statically, eliminating the need for both external pumps and the external electrical supply needed for the operation of those pumps. As used herein, “low gravity” means a gravity less than that of the surface gravity of the earth, that is, less than about 9.78 m/s2 (meters per squared), and preferably from about zero to about 9.5 m/s2, more preferably from about 0.1 to about 9.0 m/s2. Of course, it is to be understood that while useful in low gravity environments, the system may also be used at normal gravity.
It should be noted that although the present invention will be described in relation to a proton exchange membrane electrochemical cell employing hydrogen, oxygen, and water, it is readily understood that this invention can be employed with all types of electrochemical cells. Additionally, all types of electrolytes may be used, including, but not limited to the following: phosphoric acid, solid oxide, and potassium hydroxide, and the like. Various reactants can also be used, including, but not limited to, the following: hydrogen bromine, oxygen, air, chlorine, and iodine. Upon the application of different reactants and/or different electrolytes, the flows and reactions are understood to change accordingly, as is commonly understood in relation to that particular type of electrochemical cell.
Referring to
Storage tank 54 and compartmentalized storage tank 42 can be made out of any conventional material that can withstand the required pressures and the exposure to reactants, and preferably comprise a sufficient capacity to hold the desired amount of fluids for the given application. Lines 50, 52, and 56 can also be any material that can withstand the required pressures and the exposure to reactants. The movable divider 48, which separates the oxygen storage section 44, that is, the first fluid storage section, from the water storage section 46, that is, the second fluid storage section, comprises any material that is compatible with the stored gas and in any shape that allows the volume of the oxygen storage section 44 to change inversely with the volume of the water storage section 46, while effectively preventing the mixing of the two stored fluids. Possible compartmentalized storage tanks 42 include bladder tanks, bellows tanks, piston tanks, and diaphragm tanks, among others, with a stainless steel vessel having an elastomeric bladder typically preferred for low or zero gravity applications.
During operation in electrolyzer mode, stored water is converted to hydrogen gas and oxygen gas. The hydrogen produced hereby can be stored as high pressure gas, or alternatively, in a solid form, such as a metal hydride, a carbon based storage (for example, particulates, nanofibers, nanotubes, or the like), or others, and combinations comprising at least one of the foregoing storage mediums.
As oxygen gas is produced, it passes through line 50 to oxygen storage section 44, increasing the pressure of the oxygen therein and placing pressure on the movable divider 48. The pressure on the movable divider 48 increases the pressure of the water storage section 46, and forces the water through line 52 to the water flow field 38 of electrochemical cell 30.
In all cases, however, the oxygen pressure is greater than the water pressure, with the difference between the oxygen pressure and the water pressure being below the bubble pressure of the porous media divider 40. In fuel cell mode, the operation of the movable divider 48 reverses as stored oxygen converts into water and the pressure in the oxygen storage section 44 decreases. In this mode, the water generated by the reaction flows back to the water storage section 46.
Although
Turning now to
The membrane 62 can be of any material typically employed for forming the membrane in electrochemical cells. The electrolytes are preferably solids or gels under the operating conditions of the electrochemical cell. Typically, the thickness of the membrane 62 is up to about 0.05 inches (1.27 millimeters, “mm”), with about 0.001 (0.0254 mm) to about 0.015 inches (0.381 mm) preferred. Useful materials include proton conducting ionomers and ion exchange resins. Proton conducting ionomers comprise complexes of an alkali metal, allcali earth metal salt, or a protonic acid with one or more polar polymers such as a polyether, polyester, or polyimide, or complexes of an alkali metal, alkali earth metal salt, or a protonic acid with a network or crosslinked polymer containing the above polar polymer as a segment. Useful polyethers include polyoxyalkylenes, such as polyethylene glycol, polyethylene glycol monoether, polyethylene glycol diether, polypropylene glycol, polypropylene glycol monoether, and polypropylene glycol diether, and the like; copolymers of at least one of these polyethers, such as poly(oxyethylene-co-oxypropylene) glycol, poly(oxyethylene-co-oxypropylene) glycol monoether, and poly(oxyethylene-co-oxypropylene) glycol diether, and the like; condensation products of ethylenediamine with the above polyoxyalkylenes; esters, such as phosphoric acid esters, aliphatic carboxylic acid esters or aromatic carboxylic acid esters of the above polyoxyalkylenes. Copolymers of, e.g., polyethylene glycol with dialkylsiloxanes, polyethylene glycol with maleic anhydride, or polyethylene glycol monoethyl ether with methacrylic acid are known in the art to exhibit sufficient ionic conductivity to be useful. Useful complex-forming reagents can include alkali metal salts, alkali metal earth salts, and protonic acids and protonic acid salts. Counterions useful in the above salts can be halogen ion, perchloric ion, thiocyanate ion, trifluoromethane sulfonic ion, borofluoric ion, and the like. Representative examples of such salts include, but are not limited to, lithium fluoride, sodium iodide, lithium iodide, lithium perchlorate, sodium thiocyanate, lithium trifluoromethane sulfonate, lithium borofluoride, lithium hexafluorophosphate, phosphoric acid, sulfuric acid, trifluoromethane sulfonic acid, tetrafluoroethylene sulfonic acid, hexafluorobutane sulfonic acid, and the like.
Ion-exchange resins useful as proton conducting materials include hydrocarbon-and fluorocarbon-type resins. Hydrocarbon-type ion-exchange resins can include phenolic or sulfonic acid-type resins; condensation resins such as phenol-formaldehyde, polystyrene, styrene-divinyl benzene copolymers, styrene-butadiene copolymers, styrene-divinylbenzene-vinylchloride terpolymers, and the like, that are imbued with cation-exchange ability by sulfonation, or are imbued with anion-exchange ability by chloromethylation followed by conversion to the corresponding quaternary amine.
Fluorocarbon-type ion-exchange resins can include hydrates of a tetrafluoroethylene-perfluorosulfonyl ethoxyvinyl ether or tetrafluoroethylene-hydroxylated (perfluoro vinyl ether) copolymers. When oxidation and/or acid resistance is desirable, for instance, at the cathode of a fuel cell, fluorocarbon-type resins having sulfonic, carboxylic and/or phosphoric acid functionality are preferred. Fluorocarbon-type resins typically exhibit excellent resistance to oxidation by halogen, strong acids, and bases. One family of fluorocarbon-type resins having sulfonic acid group functionality is the NAFION® resins (Dupont Chemicals, Wilmington, Del.).
The electrodes 58, 60 can be conventional electrodes composed of materials such as platinum, palladium, rhodium, iridium, ruthenium, osmium, carbon, gold, tantalum, tin, indium, nickel, tungsten, manganese, and the like, as well as mixtures, oxides, alloys, and combinations comprising at least one of the foregoing materials. Additional possible catalysts, which can be used alone or in combination with the above, include graphite and organometallics, such as pthalocyanines and porphyrins, and combinations thereof, and the like. Some possible catalysts are disclosed in U.S. Pat. Nos. 3,992,271, 4,039,409, 4,209,591, 4,707,229, and 4,457,824, which are incorporated herein by reference. This catalyst can comprise discrete catalyst particles, hydrated ionomer solids, fluorocarbon, other binder materials, other materials conventionally utilized with electrochemical cell catalysts, and combinations comprising at least one of the foregoing. Useful ionomer solids can be any swollen (i.e. partially disassociated polymeric material) proton and water conducting material. Possible ionomer solids include those having a hydrocarbon backbone, and perfluoroionomers, such as perfluorosulfonate ionomers (which have a fluorocarbon backbone). Ionomer solids and catalysts therewith are further described in U.S. Pat. No. 5,470,448 to Molter et al., which is incorporated herein by reference.
In order to allow transport of the electrons, the electrodes electrically connect to an electrical load and/or power source. The electrical connection can comprise any conventional electrical connector such as wires, a truss/bus rod, bus bars, combinations thereof, or another electrical connector.
The oxygen flow field 34 and the hydrogen flow field 32 are located on either side of the MEA 36, and typically comprise material that is porous and also electrically conductive. The porous, electrically conductive material is capable of providing structural integrity for supporting the membrane assembly, allowing passage of system fluids to and from the appropriate electrodes 58 or 60, and conducting electrical current to and from the appropriate electrodes 58 or 60.
The oxygen flow field 34 preferably comprises a porous material 64 that is disposed adjacent to and in intimate contact with the MEA 36. This porous material 64 enables dual-directional flow of gas and water, promoting water flow to and from the membrane by acting as a wick to remove liquid water from the MEA 36, and serves as an electrode support. Preferably, a flow field member (for example, one or more screen layers, bipolar plates, or other type of support structures) is disposed adjacent to and in intimate contact with the porous material 64 at a surface of porous material 64 that is opposite the electrode 58.
The water flow field 38, which is disposed adjacent to and in electrical contact with the electrically conductive porous media divider 40, can comprise a similar or different porous conductive material as the other flow fields 32, 34. The material used in the water flow field 38 should allow the flow of water to and from the porous media divider 40.
The flow fields 32, 34, 38 may each comprise support structures such as screen packs, bipolar plates with grooves or other flow features formed therein, other type of support structure, or combinations of at least one of the foregoing support structures. Suitable screen packs comprise electrically conductive material, such as woven metal, expanded metal, perforated or porous plates, fabrics (woven and non-woven), ceramic (e.g., particulate filled ceramic), polymers or other material, or a combination thereof, which provide structural integrity to the membrane assembly while forming an appropriate flow field for the various fluids and establishing an electron transport to and from the electrodes. Typically the screen packs are composed of material such as niobium, zirconium, tantalum, titanium, steels such as stainless steel, nickel, and cobalt, among others, as well as mixtures, oxides, and alloys comprising at least one of the foregoing materials. The geometry of the openings in the screens can range from ovals, circles, and hexagons to diamonds and other elongated and multi-sided shapes. The particular porous conductive material employed is dependent upon the particular operating conditions on that side of the membrane assembly. Examples of suitable screen packs are disclosed in commonly assigned U.S. application Ser. No. 09/464,143, and U.S. patent Ser. No. 09/102,305, which are both incorporated herein by reference in their entireties. The size and geometry of the flow fields 32, 34, 38 should be sufficient to enable the desired fluid control. Typically, the thickness is up to about 10 inches (254 mm), with about 0.001 (0.0254 mm) to about 0.1 (2.54 mm) inches preferred.
The porous media divider 40 is typically disposed between and in electrical contact with the oxygen flow field 34 and the water flow field 38. The porous media divider 40 can be any material that provides a barrier to oxygen passage and enables the flow of water between the oxygen flow field 34 and the water flow field 38, while also allowing electron flow to and from the electrodes 58, 60, as described further herein.
In an alternative embodiment, the media divider 40 can be disposed in electrical contact with the hydrogen flow field 32. In this embodiment, water is either produced on the hydrogen electrode and moved through the media divider 40 to the compartmentalized tank 42, or from the compartmentalized tank 42 to the hydrogen electrode 60, through the membrane 62, to the oxygen electrode 58 where it reacts to form oxygen and hydrogen ions.
The porous media divider 40 can comprise any electrically conductive material compatible with the electrochemical cell environment (for example, the desired pressure differential, preferably up to or exceeding about 4,000 psi, temperatures up to about 250° C., and exposure to hydrogen, oxygen, and water). Some possible materials include carbon, nickel and nickel alloys (e.g., Hastelloy®, which is commercially available from Haynes International, Kokomo, Ind., and Inconel®, which is commercially available from INCO Alloys International Inc., Huntington, W. Va., among others), cobalt and cobalt alloys (e.g., MP35N®, which is commercially available from Maryland Specialty Wire, Inc., Rye, N.Y., Haynes 25, which is commercially available from Haynes International, and Elgiloy®, which is commercially available from Elgiloy® Limited Partnership, Elgin, Ill., among others), titanium, zirconium, niobium, tungsten, carbon, hafnium, iron and iron alloys (e.g., steels such as stainless steel and the like), among others, and oxides, mixtures, and alloys comprising at least one of the foregoing materials.
The particular form of the porous media divider 40 includes forms such as fibrous (random, woven, non-woven, chopped, continuous, and the like), granular, particulate powder, preform, and the combinations comprising at least one or more of the foregoing forms. The size and geometry of the media divider 40 should be sufficient to enable the desired movement of water while inhibiting the flow of oxygen therethrough (or other appropriate fluid control). Typically, the thickness is up to about 0.5 inches (12.7 mm), with about 0.001 inches (0.0254 mm) to about 0.3 inches (7.62 mm) preferred, about 0.001 inches (0.0254 mm) to about 0.05 (1.27) inches more preferred, and about 0.001 inches (0.0254 mm) to about 0.03 inches (0.762 mm) most preferred. Furthermore, to attain the desired flow through the media divider 40, the bubble pressure should be greater than about 0.01 pounds per square inch (psi), with about 7.0 to about 8.0 psi preferred.
Prior to operation as a fuel cell, the stored gas, oxygen for example, in the compartmentalized storage tank is preferably at a pressure greater than that of the stored water (for example, up to about 2 psi greater, with about 1 psi to about 2 psi greater typically sufficient, with a pressure differential up to the bubble pressure of media divider 40 possible). This pressure differential causes the movable divider 48 to be initially biased toward the water storage section 46 of the compartmentalized storage tank 42, forcing water toward the water flow field 38. For example, a mechanical, hydraulic or similar force bias can be employed in the storage tank 42 to push the bellows open, with the bias preferably set at a pressure below the bubble pressure of media divider 40.
In order to utilize the electrochemical cell 30, it is preferably initially charged by an external power source (not shown). During charging, the cell 30 is operating as an electrolyzer, and water (or other liquid reactant such as hydrogen, bromine) is separated, for example, into hydrogen and oxygen. The hydrogen and oxygen are stored in their respective areas within the system (for example, hydrogen in storage tank 54 and oxygen in oxygen storage section 44), and, after reaching operating pressure, the system can be used as a fuel cell to produce electricity. That is, the external power source can be disconnected and an electrical load can be attached (for example, as in load 21 depicted in
The stored oxygen from the oxygen storage section 44 and hydrogen from the hydrogen storage tank 54 move to the respective active areas of the electrochemical cell 30. The hydrogen gas flows through the hydrogen flow field 32 and dissociates into hydrogen ions and free electrons at the hydrogen electrode 60. The hydrogen ions move across the proton exchange membrane 62 to the oxygen flow field 34 while the electrons travel through an external load to the oxygen electrode 58. At the oxygen electrode 58, the hydrogen ions combine with oxygen and electrons to form water. The newly formed water moves through the oxygen flow field 34 and is wicked away by the porous media divider 40 to the water flow field 38. From the water flow field 38, the water is piped into the water storage section 46 of the compartmentalized storage tank 42, and the movable divider 48 shifts toward the gas storage side 44 to accommodate the increased water volume.
When the pressure of the stored gases falls below the level needed to operate the fuel cell 30, an external power supply can be attached to the system. The cell 30 is then operated in reverse, as an electrolyzer, and the stored water, which is biased to a pressure below that of the oxygen gas, is fed into the water flow field 38. The porous media divider 40 wicks the water from the water flow field to the oxygen flow field 34. Not intending to be limited by theory, it is believed that the water, in the form of water vapor, moves through the oxygen flow field 34 to the oxygen electrode 58 where it forms oxygen gas, hydrogen ions, and electrons. Again, the hydrogen ions pass through the membrane 62 and the electrons move through the external load, to the hydrogen electrode 60, where they combine to form hydrogen.
To facilitate a substantially constant pressure differential, such as the aforementioned 2 psi, between the oxygen storage section 44 and the water storage section 46 for controlling the feed and removal of water to and from the proton exchange membrane, a compartmentalized storage tank 42 of a particular structure is employed, which will now be described with reference to
Referring to
In an embodiment, and referring now to
In an embodiment, the tongue 86 of the first spring 85 is disposed to exert a force parallel to but off-axis from an axis 95 of the movable divider 48, and the tongue 91 of the second spring 90 is disposed to exert a force parallel to but off-axis from the axis 95 of the movable divider 48. The two off-axis forces are disposed on opposing sides of the movable divider axis 95 to neutralize a side force on the movable divider 48.
As illustrated in
In an embodiment, the first fluid storage section 44 is in fluid communication with a first port 100 proximate the top of housing 70, and the second fluid storage section 46 is in fluid communication via a flexible line 105 with a second port 110 proximate the top of housing 70, the flexible line 105 being in fluid communication between the movable divider 48 and the second port 110.
In an embodiment, the electrochemical cell 30 can be operated in low gravity or even zero gravity environments, such as extraterrestrial environments, without the need for an external electrical supply that would be required in a conventional system to power pumps, fans, and other supporting equipment. Cell 30 is effective with or without the compartmentalized storage tank. The electrochemical cell system may be charged in electrolyzer mode by photovoltaic cells attached to the outside of an orbiting space station, for example, and used as a fuel cell to provide electricity thereafter. Since the system is regenerative and does not require the use of pumps, it can serve as a stand-alone system for electrical needs. Additionally, the electrochemical cell system has increased reliability relative to conventional systems because it has fewer moving components. Embodiments of the invention can operate in both low gravity and zero gravity environments, as the need arises. Finally, since embodiments of the invention uses fewer parts and integrates others, it is more compact than conventional electrochemical cell systems.
While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best or only mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
This invention was made with Government support under contract NNC04CA12C awarded by NASA, and under contract HQ0006-04-C-7081 awarded by the Missile Defense Agency. The Government has certain rights in this invention.
