WO2006059239A2 - Direct liquid fuel cell and method of preventing fuel decomposition in a direct liquid fuel cell - Google Patents

Direct liquid fuel cell and method of preventing fuel decomposition in a direct liquid fuel cell Download PDF

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Publication number
WO2006059239A2
WO2006059239A2 PCT/IB2005/004083 IB2005004083W WO2006059239A2 WO 2006059239 A2 WO2006059239 A2 WO 2006059239A2 IB 2005004083 W IB2005004083 W IB 2005004083W WO 2006059239 A2 WO2006059239 A2 WO 2006059239A2
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WO
WIPO (PCT)
Prior art keywords
fuel cell
fuel
anode
membrane
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2005/004083
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English (en)
French (fr)
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WO2006059239A3 (en
Inventor
Gennadi Finkelshtain
Yuri Katsman
Ilan Sadon
Mark Estrin
Alexander Litvinov
Boris Ilyushin
Alexander Chinak
Alexander Bluvstein
Michael Lerner
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More Energy Ltd
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More Energy Ltd
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Filing date
Publication date
Application filed by More Energy Ltd filed Critical More Energy Ltd
Priority to AU2005310973A priority Critical patent/AU2005310973A1/en
Priority to BRPI0515310-7A priority patent/BRPI0515310A/pt
Priority to MX2007003028A priority patent/MX2007003028A/es
Priority to EA200700645A priority patent/EA200700645A1/ru
Priority to EP05850784A priority patent/EP1810356A4/en
Priority to JP2007531878A priority patent/JP2008513942A/ja
Priority to CA002580045A priority patent/CA2580045A1/en
Publication of WO2006059239A2 publication Critical patent/WO2006059239A2/en
Anticipated expiration legal-status Critical
Publication of WO2006059239A3 publication Critical patent/WO2006059239A3/en
Ceased legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/065Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023Porous and characterised by the material
    • H01M8/0232Metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04186Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201Reactant storage and supply, e.g. means for feeding, pipes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/06Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0637Direct internal reforming at the anode of the fuel cell
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1009Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/22Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/22Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • H01M8/225Fuel cells in which the fuel is based on materials comprising particulate active material in the form of a suspension, a dispersion, a fluidised bed or a paste
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/30Fuel cells in portable systems, e.g. mobile phone, laptop
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0002Aqueous electrolytes
    • H01M2300/0014Alkaline electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0271Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0271Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028Sealing means characterised by their material
    • H01M8/0284Organic resins; Organic polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/08Fuel cells with aqueous electrolytes
    • H01M8/083Alkaline fuel cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B90/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02B90/10Applications of fuel cells in buildings
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • the present invention relates to a Direct Liquid Fuel Cell (DLFC) which uses a hydride fuel and also relates to specifically preventing or at least substantially reducing the generation of hydrogen caused by a decomposition of the hydride fuel at the anode of the fuel cell when the DLFC is under no or only a low load.
  • DLFC Direct Liquid Fuel Cell
  • a hydride fuel decomposition reaction at the anode of the fuel cell generates hydrogen during the period where the fuel cell is under no or only a low load.
  • the invention thus also provides a method which uses the generated hydrogen to provide a separation layer between the anode and the liquid fuel. In this way, the fuel is substantially prevented from contacting the anode, whereby decomposition of the fuel is prevented to at least a substantial extent.
  • DMFCs Direct Methanol Fuel Cells
  • the main problem associated with hydride and borohydride fuels is a spontaneous decomposition of the fuel on the (active layer of the) anode surface which is accompanied by a generation of hydrogen, usually in the form of microbubbles, e.g., bubbles of from about 0.01 to about 2 mm in size. This process is particularly significant in a DLFC open circuit regime and in a stand-by (low current) regime.
  • Hydride and borohydride decomposition at the anode of a DLFC results in several technical problems, in particular, energy loss, destruction of the anode active layer, and decreasing safety characteristics. As a result, there is a need to develop ways to substantially prevent the fuel from decomposing while the DLFC is under no or no substantial load.
  • the present invention provides a liquid fuel cell for use with a liquid fuel that is prone to undergo decomposition on the surface of the anode and generates gas in the course of this decomposition.
  • the fuel cell comprises a cathode, an anode, an electrolyte chamber which is arranged between the cathode and the anode, a fuel chamber which is arranged on that side of the anode which is opposite to the side which faces the electrolyte chamber, and at least one membrane which is arranged on that side of the anode which faces the fuel chamber.
  • the at least one membrane is structured and arranged to allow gas which is formed, as a result of the fuel decomposition, on or in the vicinity of the surface of the anode that faces the fuel chamber to accumulate adjacent to the anode at least to a point where the gas substantially prevents a direct contact between the anode and the liquid fuel when liquid fuel is present in the fuel chamber.
  • the fuel may comprise a metal hydride and/or borohydride compound and/or the gas may comprise hydrogen.
  • the at least one membrane may comprise a single layer of material and/or the at least one membrane may comprise a hydrophilic material.
  • the hydrophilic material may comprise a metal and/or a metal alloy.
  • the hydrophilic material may comprise stainless steel.
  • the at least one membrane may comprise a hydrophobic material, for example, an organic polymer such as, e.g., a polyolefin (for example, homo- and copolymers of ethylene and propylene), a polyamide and polyacrylonitrile.
  • the at least one membrane may comprise one or more of a non-wove ⁇ material, a composite material, a laminate material, a composite/laminate material, a foam material, a porous paper material, a cloth material, a carbon material (e.g. graphite), a sintered metal material, a ceramic material, and a polymer material.
  • a non-wove ⁇ material e.g., a composite material, a laminate material, a composite/laminate material, a foam material, a porous paper material, a cloth material, a carbon material (e.g. graphite), a sintered metal material, a ceramic material, and a polymer material.
  • the at least one membrane may comprise a foam and/or a mesh, for example, a stainless steel micromesh.
  • the micromesh may comprise cells which have a size of up to about 0.5 mm, e.g., of from about 0.06 ⁇ m to about 0.05 mm.
  • the at least one membrane (mesh) may have a thickness of from about 0.01 mm to about 5 mm, for example, form about 0.03 mm to about 3 mm, or from about 0.05 mm to about 0.3 mm.
  • the at least one membrane may comprise a polymer mesh and/or a porous polymer layer.
  • the polymer mesh or porous polymer layer may have a thickness of from about 0.02 mm to about 2 mm and/or a cell size of from about 0.01 mm to about 0.1 mm or a pore size of from about 0.01 ⁇ m to about 0.1 mm.
  • the at least one membrane may be in contact with the surface of the anode which faces the fuel chamber.
  • the at least one membrane may be attached and/or bonded to the surface of the anode (e.g., rolled onto the anode).
  • the fuel cell may further comprise a free space and/or a spacer structure that is arranged between the at least one membrane and the anode.
  • the spacer structure may comprise a spacer material having free space therein.
  • the spacer structure may comprise a layer of spacer material having a thickness of up to about 3 mm and/or at least about 0.1 mm.
  • the layer of spacer material may have a thickness of from about 0.5 mm to about 1.5 mm.
  • the spacer material may comprise a hydrophobic material
  • the hydrophobic material may comprise one or more of an olefin homopolymer (e.g., polyethylene, polypropylene, polytetrafluoroethylene), an olefin copolymer, ABS, polymethyl methacrylate, polyvinyl chloride, and a polysulfone.
  • an olefin homopolymer e.g., polyethylene, polypropylene, polytetrafluoroethylene
  • an olefin copolymer e.g., polymethyl methacrylate, polyvinyl chloride, and a polysulfone.
  • the spacer structure may comprise a net such as, e.g., a wattled net.
  • the net may, for example, comprise openings of from about 1 mm to about 50 mm.
  • the spacer structure may comprise, instead of or in addition to the spacer material that has free space therein, a frame seal which is arranged on the surface of the anode which faces the fuel chamber.
  • the frame seal may comprise a hydrophobic material, for example, a polymer such as, e.g., a fluorinated polymer (e.g., polytetrafluoroethylene).
  • the frame seal preferably has a thickness of up to about 0.1 mm, e.g., a thickness of from about 0.02 mm to about 0.05 mm.
  • the fuel cell of the present invention may further comprise a pressure relief device which is arranged to allow the gas to escape from a space between the anode and the at least one membrane.
  • the pressure relief device may be arranged to allow the gas to escape into the fuel chamber.
  • the pressure relief device may comprise a small diameter tube.
  • the at least one membrane and the spacer structure together may form an integral structure.
  • the fuel cell may comprise at least a first membrane adjacent to the anode and a second membrane on the side of the first membrane that faces the fuel chamber. At least the first membrane is structured and arranged to allow gas which is formed on or in the vicinity of the surface of the anode which faces the fuel chamber to accumulate adjacent to the anode at least to a point where the accumulated gas substantially prevents a direct contact between the anode and the liquid fuel.
  • the second membrane may be structured and arranged to filter solids from the liquid fuel and/or protect the first membrane.
  • the first membrane and the second membrane may form an integral structure.
  • the second membrane may comprise a material that is different from that of the first membrane and/or may have a thickness that is different from that of the first membrane and/or may have a pore size or cell size that is different from that of the first membrane.
  • the second membrane may comprises a material that is substantially the same as that of the first membrane and/or may have a thickness that is substantially the same as that of the first membrane and/or may have a pore size or cell size that is substantially the same as that of the first membrane.
  • the fuel cell may be the same as the fuel cell set forth above that has (at least) one membrane.
  • the first membrane may comprise a polymer mesh or porous polymer layer that has a thickness of between about 0.02 mm and 2 mm and a cell size of from about 0.01 mm to about 0.1 mm or a pore size of from about 0.01 ⁇ m to about 0.1 mm, or at least the first membrane may comprise a stainless steel mesh having a thickness of from about 0.01 mm to about 5 mm.
  • the first membrane may be bonded to and/or in contact with the surface of the anode that faces the fuel chamber.
  • the fuel cell may further comprise a free space and/or a spacer structure arranged between the first membrane and the anode.
  • the spacer structure may be the same as the spacer structure described above, including the various aspects thereof.
  • the anode may be fixed within the fuel cell (case) and/or in sealing engagement with the fuel cell (case).
  • the fuel chamber may comprise at least a first part that is adjacent to the at least one membrane and at least one second part that is connected to the first part by one or more liquid passageways.
  • the at least one second part of the fuel chamber may comprise an (optionally disposable) liquid fuel cartridge.
  • the fuel cell of the present invention may comprise a case which accommodates at least the anode, at least one part of the fuel chamber may be arranged outside the case, and the case may be connected to the at least one part of the fuel chamber that is arranged outside the case through one or more liquid passageways.
  • the at least one part of the fuel chamber that is arranged outside the case may comprise an (optionally disposable) cartridge.
  • the at least one membrane may be arranged in one or more of the following locations: (a) at or in a vicinity of one or more locations of the case where liquid fuel from the at least one part of the fuel chamber that is arranged outside the case can enter the case, (b) at or in a vicinity of one or more locations of the at least one part of the fuel chamber that is arranged outside the case where liquid fuel can leave the at least one part of the fuel chamber that is arranged outside the case, and (c) at one or more locations inside the one or more liquid passageways.
  • the present invention further provides a method for reducing or substantially preventing decomposition of a fuel in a direct liquid fuel cell at an anode of the fuel cell when the fuel cell is under substantially no load and wherein a gas is generated as a result of the fuel decomposition.
  • the method comprises causing gas that is generated by the initial decomposition of the fuel to form a barrier that restricts or substantially prevents further contact between the fuel and the anode.
  • the barrier may comprise a substantially continuous layer of gas across substantially the entire surface of the anode that faces the fuel chamber of the fuel cell.
  • the gas may comprise hydrogen and/or the fuel may comprise at least one of a hydride compound and a borohydride compound, e.g., an alkali metal (e.g., sodium) borohydride that is dissolved and/or suspended in a liquid carrier.
  • a hydride compound e.g., an alkali metal (e.g., sodium) borohydride that is dissolved and/or suspended in a liquid carrier.
  • a borohydride compound e.g., an alkali metal (e.g., sodium) borohydride that is dissolved and/or suspended in a liquid carrier.
  • the fuel decomposition may be substantially stopped within not more than about 5 minutes, e.g., not more than about
  • the method may comprise limiting or substantially preventing the ability of the gas that is generated by the initial fuel decomposition to flow away from the anode. This may be accomplished, for example, by at least one membrane that is arranged on the side of the anode that faces the fuel chamber of the fuel cell.
  • the present invention further provides a method for reducing or substantially preventing fuel decomposition at an anode of a direct liquid fuel cell which uses a fuel that generates a gas when undergoing said decomposition.
  • the method comprises arranging, between the fuel chamber of the fuel cell and the anode, one or more of at least one porous structure, at least one mesh structure, and at least one membrane, and allowing the gas to be formed during an initial decomposition of the fuel in the fuel cell, whereby the gas restricts or substantially prevents contact between the fuel and the anode.
  • the forming of gas may further comprise substantially preventing, with the gas, the fuel from contacting the anode. In another aspect, it may further comprise the formation of a substantially continuous layer of gas across substantially the entire surface of the anode that faces the fuel chamber of the fuel cell. In yet another aspect, it may further comprise a substantial confinement of the gas between the anode and the at least one porous structure, the at least one mesh structure and/or the at least one membrane.
  • the gas may comprise hydrogen
  • the method may further comprise placing the fuel cell under substantially no load so as to cause fuel decomposition.
  • the method may further comprise substantially stopping the initial fuel decomposition within not more than about 3 minutes.
  • the method may further comprise providing a space between the anode and the at least one porous structure, the at least one mesh structure and/or the at least one membrane, the space being capable of being substantially filled with the gas.
  • the present invention also provides a method of preventing or reducing fuel decomposition in the fuel cell set forth above, including the various aspects thereof.
  • the method comprises generating electrical energy with the fuel cell, substantially preventing the fuel cell from further generating electrical energy, whereby fuel decomposition is caused at the anode of the fuel cell with generation of a gas;
  • the invention also provides a fuel cell that comprises a cathode, an anode and an electrolyte chamber which is arranged between the cathode and the anode.
  • a cartridge comprising a fuel chamber can be connected and/or removably connected to the fuel cell housing (case) having the cathode, anode and electrolyte chamber.
  • the fuel chamber is arranged on that side of the anode which is opposite to the side which faces the electrolyte chamber.
  • At least one membrane (and possibly also a spacer material) can be arranged between the gas accumulation space adjacent the anode and the fuel chamber.
  • the at least one membrane is structured and arranged to allow gas which is formed, as a result of the fuel decomposition, on or in the vicinity of the surface of the anode that faces the fuel chamber to accumulate adjacent to the anode at least to a point where the gas substantially prevents a direct contact between the anode and the liquid fuel.
  • Fig. 1 shows a schematic cross section view of a prior art fuel cell
  • Fig. 2 shows a cross section of a fuel cell according to one embodiment of the invention
  • FIG. 3 shows an enlarged portion of Fig. 2
  • Fig. 4 presents a chart illustrating hydrogen productivity in a fuel cell of the type shown in Fig. 1;
  • Fig. 5 presents a chart illustrating hydrogen productivity in a fuel cell of the type shown in Fig. 2;
  • Fig. 6 shows a partial view of one non-limiting weave pattern for the wattled spacer material
  • Fig. 7 shows a partial view of another non-limiting weave pattern for the wattled spacer material
  • Fig. 8 shows a cross section of a fuel cell according to another embodiment of the invention.
  • Fig. 9 shows a cross section of a fuel cell according to still another embodiment of the invention.
  • Fig. 10 shows a cross section of a fuel cell according to yet another embodiment of the invention.
  • Fig. 11 shows a cross section of a fuel cell according to yet another embodiment of the invention.
  • This embodiment uses a cartridge containing the fuel chamber (or at least a part thereof) which can be connected and/or removably mounted to the housing of the fuel cell;
  • Fig. 12 shows an enlarged view of the embodiment shown in Fig. 11 and illustrates how the membrane and/or spacer material can have the form of small screen filter member. This figure also illustrates how the tubes of the cartridge are sealed relative to openings in the wall of the housing via o-rings; and
  • Fig. 13 shows a cross section of a fuel cell according to the embodiment of Fig. 11 with the cartridge separated and/or unconnected with the housing of the fuel cell.
  • a conventional DLFC utilizes a case or container body 1 which contains therein a fuel chamber 2 and an electrolyte chamber 5.
  • the case 1 is typically formed of, e.g., a plastic material.
  • the fuel chamber 2 contains liquid fuel in the form of, e.g., a hydride or borohydride fuel.
  • the electrolyte chamber 5 contains liquid electrolyte in the form of, e.g., an aqueous alkali metal hydroxide.
  • An anode 3 is arranged within the case 1 and separates the two chambers 2 and 5.
  • the anode 3 will usually comprise a porous material that is pervious to gaseous and liquid substances.
  • a cathode 4 is also arranged in the case 1 and, together with the anode 3, defines the electrolyte chamber 5. At the anode 3 an oxidation of the liquid fuel takes place. At the cathode 4 a substance, typically oxygen in the ambient air, is reduced.
  • the DLFC differs from the fuel cell illustrated in Fig. 1 at least in that it additionally comprises, arranged inside the case 1, a frame seal 6, a special membrane 8, a spacer material 9, and an optional pressure bleeding device having the form of, e.g., a capillary needle 7.
  • the generated gas usually hydrogen and usually in the form of micro-bubbles of a size of from about 0.01 to about 2 mm, accumulates into a space between a surface of the anode 3 and the special membrane 8.
  • the bubbles will usually coalesce and/or unite to form a layer of gas which fills essentially all of the volume between the anode 3 and the special membrane 8. This, in turn, causes the liquid fuel to be separated from the anode 3.
  • the special membrane 8 substantially prevents any further contact between the liquid fuel and the anode 3.
  • the space between the anode 3 and the membrane 8 will usually be from about 0.1 mm to about 3.0 mm thick, and preferably has a thickness of from about 0.5 mm to about 1.5 mm, and most preferably about 0.5 mm.
  • Any extra gas which exceeds the volume of the space between the anode 3 and the special membrane 8 vents or bleeds out and into the fuel chamber 2 through the optional capillary needle 7. This bleeding process stops essentially automatically when the pressure in the volume between the anode 3 and the special membrane 8 equals the pressure in the fuel chamber 2.
  • the frame seal 6 extends around the perimeter of the anode 3 and is arranged between the anode 3 and the special membrane 8.
  • the frame seal 6 preferably has the form of a thin (non-porous) film and is utilized to prevent fuel from escaping in the area of the borders or outer edges of the anode perimeter.
  • the material of the frame seal 6 will usually be hydrophobic (at least on the surface thereof which faces the fuel chamber) and can be formed from a material such as, e.g., polytetrafluoroethylene, although other hydrophobic materials such as, e.g., olefin polymers like polyethylene and polypropylene may also be used for this purpose.
  • the frame seal 6 will be made of or at least include a fluorinated polymer such as, e.g., a fluorinated or perfluorinated polyolefin.
  • the frame seal 6 may also be made of a material that is not hydrophobic as such but has been rendered hydrophobic on the surface thereof by way of, e.g., coating with a hydrophobic material, or any other procedure which affords hydrophobicity.
  • the frame seal 6 has a thickness of not more than about 0.1 mm. It will usually have a thickness of at least about 0.02 mm. A thickness of about 0.05 mm is particularly preferred for the frame seal 6 for use in the present invention.
  • the frame seal 6 may be mounted on the anode 3 in many ways, e.g., with application of pressure and/or by using an adhesive. A preferred way of mounting the frame seal 6 comprises insert molding.
  • the frame seal 6 can also be replaced by fixing and/or sealingly attaching a perimeter frame of the anode 3 to anode 3 by, e.g., friction welding.
  • the spacer material 9 is arranged between the anode 3 and the special membrane 8.
  • the spacer material 9 also extends to the inside perimeter of the case 1 and, in the perimeter area, is also arranged between the frame seal 6 and the special membrane 8.
  • the purpose of the spacer material 9 is to create a separation distance between the special membrane 8 and the surface of the anode 3. This separation distance forms space or volume for the gas layer. As the gas is generated, it accumulates within and fills this space.
  • the spacer material 9 will permit the essentially free flow of gas across the surface of the anode 3, and may be in the form of a net such as, e.g., a wattled net material.
  • the spacer material 9 must be able to withstand the chemical attack by the components of the liquid fuel and will usually be hydrophobic, at least on the outer surfaces thereof.
  • the spacer material 9 may also be a hydrophilic material which has been made hydrophobic on the other surfaces thereof by any process suitable for this purpose such as e.g., coating with a hydrophobic material.
  • Preferred spacer materials for use in the present invention include organic polymers such as, e.g., olefin homopolymers and olefin copolymers. Specific examples thereof include materials which may also be used for the frame seal 6 such as, e.g., homo- and copolymers of ethylene and propylene, polytetrafluoroethylene, and the like.
  • the spacer material 9 can also be made of other materials such as, e.g., ABS, polymethylmethacrylate, polyvinyl chloride, polysulfone and similar organic polymers.
  • the spacer material 9 will usually have a thickness of not more than about 5 mm, preferably not more than about 3 mm, more commonly a thickness of not more than about 1.5 mm.
  • the spacer material 9 will usually have a thickness of at least about 0.1 mm, preferably at least about 0.5 mm. In a preferred embodiment of the present invention, the spacer material 9 has a thickness of about 0.5 mm.
  • the spacer material 9 can also be dispensed with (its function being performed by another structure and/or the special membrane 8 itself) as is the case with other embodiments that will be described below.
  • the special membrane 8 separates the gas layer which has formed at the anode surface from liquid fuel in the fuel chamber 2.
  • the special membrane 8 is made of a material which can withstand the chemical attack by the components of the liquid fuel and will not catalyze a decomposition of the fuel or a component thereof to any appreciable extent. This material may be hydrophilic or hydrophobic.
  • the hydrophilic material can also be a hydrophobic material which has been rendered hydrophilic on the outer surface thereof by any suitable process, such as coating, surface treatment (e.g., oxidation) and the like.
  • suitable hydrophilic materials for the special membrane 8 include metals, as such or in the form of alloys.
  • Particularly preferred materials include corrosion-resistant metals (e.g., nickel) and corrosion-resistant alloys such steel, in particular, stainless steel, etc.
  • suitable hydrophobic materials for the special membrane 8 include organic polymers such as, e.g., polyolefins (for example, homo- and copolymers of, e.g., ethylene or propylene), polyamides and polyacrylonitrile.
  • the hydrophilic or hydrophobic material will preferably be present in the form of a foam, a mesh and the like.
  • the special membrane 8 may be or at least include a metal mesh such as, e.g., a stainless steel micromesh.
  • the cells of the mesh may, for example, have a size of up to about 0.5 mm, e.g., up to about 0.1 mm, or up to about 0.06 mm.
  • a preferred mesh cell size is from about 0.05 ⁇ m to about 0.06 mm, a size of about 0.05 mm being particularly preferred.
  • the metal mesh preferably has a thickness of from about 0.01 mm to about 5 mm, e.g., from about 0.03 mm to about 3 mm.
  • the special membrane 8 include a polymer mesh or a porous polymer layer.
  • the polymer mesh or porous polymer layer will have a thickness of from about 0.02 mm to about 2 mm.
  • the cell size or pore size thereof will preferably be from about 0.01 mm to about 0.1 mm and from about 0.01 ⁇ m to about 0.1 mm, respectively.
  • the membrane 8 may also comprise other hydrophilic and/or hydrophobic materials, e.g., composites and/or laminates of hydrophilic materials, hydrophobic materials and combinations of hydrophilic and hydrophobic materials.
  • the membrane 8 can also comprise, e.g., a non-woven material, foam materials (polymeric or metallic) and other porous materials such as porous papers, cloths and carbon (e.g., in the form of graphite), sintered metals, and ceramic materials.
  • the capillary needle 7 is secured to the special membrane 8 and can be arranged at a convenient position thereon such as, e.g., centrally located (and, preferably, substantially perpendicular to the membrane 8).
  • the purpose of the needle 7 is to balance the pressure between gas layer and liquid fuel in the fuel chamber 2.
  • the balance pressure range will usually be from about 1 atm to about 1.5 atm (absolute).
  • the needle 7 is made of a material which can withstand the chemical attack by the components of the liquid fuel and does not catalyze a decomposition thereof to any appreciable extent. This material will usually be selected from the materials which are suitable for making the special membrane 8, but may also be made of other materials, e.g., polymeric materials. Non-limiting examples of polymeric materials include polyolefins such as polytetrafluoroethylene and polypropylene.
  • the needle 7 is a stainless steel needle.
  • the needle 7 While a suitable length of the needle 7 may vary over a wide range (depending, in part on the dimensions of the spacer 9, the membrane 8, etc.) the needle 7 will often have a length of up to about 2 cm, or even longer.
  • the inner diameter of the needle 7 will usually not exceed about 2 mm, preferably not exceed about 1 mm, or not exceed about 0.5 mm.
  • the needle 7 may be attached to the membrane 8 by any suitable method, e.g., by using a thermoadhesive, welding and mechanical attachment (the latter being a preferred method).
  • the needle 7 is not essential for the operation of the fuel cell of the present invention and can also be dispensed with, as in the case of the other embodiments that will be described below. [0062] Fig.
  • FIG. 8 shows another non-limiting embodiment of the fuel cell of the present invention that differs from the fuel cell illustrated in Fig. 1 at least in that it additionally comprises, arranged inside the case 1 , an anode 3 having a frame, a special membrane 8a, an optional second membrane 8b, and an optional spacer material 9.
  • This embodiment eliminates the need for the frame seal 6 and also does not comprise the capillary needle 7.
  • the perimeter frame of the anode 3 can be fixed to the anode 3 by, e.g., friction welding.
  • the materials and thicknesses of the devices 3, 4, 9, 8a and 8b can be the same as the corresponding devices described above with regard to the embodiment shown in Fig. 2.
  • the membranes 8a and 8b may be of the same material, types and/or thicknesses as described above or may be different in anyone or more of these respects.
  • Fig. 9 shows another non-limiting embodiment of the fuel cell of the present invention that differs from the fuel cell illustrated in Fig. 1 at least in that it additionally comprises, arranged inside the case 1 , an anode 3, a special membrane 8a, an optional second membrane 8b, an optional spacer material 9, and an optional frame seal 6.
  • This embodiment also does not comprise the capillary needle 7.
  • the materials and thicknesses of the devices 3, 4, 6, 9, 8a and 8b can be the same as the corresponding devices described above with regard to the embodiment shown in Fig. 2.
  • the membranes 8a and 8b may be of the same material, types and/or thicknesses as described above or may be different in anyone or more of these respects.
  • Fig. 10 shows another non-limiting embodiment of the fuel cell of the present invention that differs from the fuel cell illustrated in Fig. 1 at least in that it additionally comprises, arranged inside the case 1, an anode 3, and a special membrane 8a, and an optional second membrane 8b.
  • This embodiment eliminates the need for the spacer material 9 and the frame seal 6, and also does not comprise the capillary needle 7.
  • the materials and thicknesses of the devices 3, 4, 8a and 8b can be the same as the corresponding devices described above with regard to the embodiment shown in Fig. 2.
  • the membranes 8a and 8b may be of the same material, types and/or thicknesses as described above or may be different in anyone or more of these respects.
  • the membrane 8a is preferably in contact with the anode 3.
  • the membrane 8a can be rolled or otherwise attached or bound to the surface of the anode 3.
  • the voids and/or free space in the membrane 8a provide the empty space that can be occupied by the generated gas to thereby form a barrier that substantially prevents the fuel from contacting the anode.
  • the first membrane 8a can function in the manner described above with regard to the space and/or spacer material whereas the second membrane 8b can serve a different function such as, e.g., filter solids and the like from the fuel in the fuel chamber 2 in order to protect the first membrane 8a and/or substantially prevent a clogging thereof.
  • the fuel chamber 2 may comprise one part that is adjacent to the at least one membrane 8 (e.g., adjacent to membrane 8b) and one or more other parts (e.g., one or more cartridges) that are arranged outside the housing or case of the fuel cell and are connected to the case through one or more liquid passageways.
  • the volume of the part of the fuel chamber that is arranged within the case, if any, may be small compared to the volume of the one or more parts that are arranged outside the case (e.g., not more than about 20 %, e.g., not more than about 10 %, not more than about 5 %, or not more than about 2 % of the latter volume).
  • the fuel chamber 2 may be arranged substantially completely outside the case, and may be connected to the case by one or more liquid passageways (e.g., in the form of small diameter tubes and the like).
  • the fuel chamber may be in the form of an (optionally disposable) cartridge that is connected to the case.
  • the at least one membrane 8 may be comprised by the case (e.g., at or in the vicinity of one or more points where liquid fuel can enter the case) and/or may be comprised by the fuel chamber 2 (e.g., the cartridge) (e.g., at or in the vicinity of one or more points where liquid fuel can leave the fuel chamber 2) and/or may be arranged somewhere in between the case and the fuel chamber 2 (e.g., within the one or more liquid passageways that connect the fuel chamber 2 and the case).
  • the at least one membrane 8 may comprise at least a first membrane 8a and a second membrane 8b.
  • Figs. 11-13 show one non-limiting embodiment of a fuel cell 1 having a cathode 4, an anode 3, an electrolyte chamber 5 which is arranged between the cathode 4 and the anode 3.
  • a cartridge CA having a fuel chamber 2 is connected and/or removably connected to the fuel cell housing having the cathode 4, anode 3 and electrolyte chamber 5.
  • the fuel chamber 2 is arranged on that side of the anode 3 which is opposite to the side which faces the electrolyte chamber 5.
  • At least one membrane 8 is arranged between the gas accumulation space adjacent the anode 3 and the fuel chamber 2.
  • the width of this space can be approximately 1 mm, but may be considerably larger or smaller.
  • the at least one membrane 8 is structured and arranged to allow gas which is formed, as a result of the fuel decomposition, on or in the vicinity of the surface of the anode 3 that faces the fuel chamber 2 to accumulate adjacent to the anode 3 at least to a point where the gas substantially prevents a direct contact between the anode 3 and the liquid fuel in the fuel chamber 2.
  • the membrane 8 (which can also include an additional layer of spacer material 9) can have the form of small screen filter member that is fixed to the inner surface of a wall of the housing.
  • the filter element can also be arranged on the opposite end of the tubes so as to be arranged in the cartridge CA without leaving the scope of the invention.
  • a filter element can be arranged on both sides of the tubes.
  • the inside of the tubes can include the membrane/spacer material, which can have the form of a cigarette filter of sufficient length.
  • the tubes (the numbers and sizes of which can vary as desired and can be similar to that described with regard to tube 7) of the cartridge CA are sealed relative to openings in the wall of the housing via one or more o-rings.
  • any number of sealing techniques or methods may also be employed in providing sealing between the tubes and the openings on the wall of the housing.
  • the tubes can instead be coupled to the fuel cell housing while openings are arranged in the wall of cartridge CA.
  • Fig. 13 shows the cartridge CA being separated and/or unconnected from the housing of the fuel cell 1.
  • valves can be utilized to stop and/or regulate flow from and to the cartridge CA and the housing of the fuel cell 1.
  • Thickness or width of electrolyte chamber 4 mm
  • Thickness or width of fuel chamber 20 mm
  • volume of fuel in the fuel chamber 90 cm 3 .
  • Thickness or width of fuel chamber 20 mm
  • Thin film Teflon frame-seal thickness 50 ⁇ m
  • the time until the space between the anode 3 and the special membrane 8 was filled was 45 seconds.
  • the generation of hydrogen began to decrease after about 45 seconds, and stopped after about 3 minutes, i.e., the fuel decomposition stopped after about 3 minutes.
  • the exemplary and preferred dimensions of the various elements of the DLFC described above apply particularly to fuel cells for portable devices, e.g., for fuel cells which have dimensions of an order of magnitude which is suitable for portable devices (e.g., laptops, cell phones etc.). Examples of corresponding dimensions are given in the Examples herein.
  • a "hydrophilic" material is a material that has an affinity for water. The term includes materials which can be wetted, have a high surface tension value and have a tendency to form hydrogen-bonds with water. It also includes materials which have high water vapor permeability.
  • a "hydrophobic" material is a material which repels water.

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PCT/IB2005/004083 2004-09-15 2005-09-15 Direct liquid fuel cell and method of preventing fuel decomposition in a direct liquid fuel cell Ceased WO2006059239A2 (en)

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AU2005310973A AU2005310973A1 (en) 2004-09-15 2005-09-15 Direct liquid fuel cell and method of preventing fuel decomposition in a direct liquid fuel cell
BRPI0515310-7A BRPI0515310A (pt) 2004-09-15 2005-09-15 célula de combustìvel e métodos de reduzir ou substancialmente prevenir a decomposição de um combustìvel em uma célula de combustìvel e em um anodo de uma célula de combustìvel
MX2007003028A MX2007003028A (es) 2004-09-15 2005-09-15 Celda directa de combustible liquido y metodo para evitar la descomposicion del combustible en un celda directa de combustible liquido.
EA200700645A EA200700645A1 (ru) 2004-09-15 2005-09-15 Жидкостной топливный элемент прямого действия и способ предотвращения разложения топлива в жидкостном топливном элементе прямого действия
EP05850784A EP1810356A4 (en) 2004-09-15 2005-09-15 DIRECT LIQUID FUEL CELL AND METHOD FOR PREVENTING FUEL DECOMPOSITION IN A DIRECT LIQUID FUEL CELL
JP2007531878A JP2008513942A (ja) 2004-09-15 2005-09-15 直接液体燃料電池および直接液体燃料電池における燃料分解防止方法
CA002580045A CA2580045A1 (en) 2004-09-15 2005-09-15 Direct liquid fuel cell and method of preventing fuel decomposition in a direct liquid fuel cell

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US10/941,020 US20060057435A1 (en) 2004-09-15 2004-09-15 Method and apparatus for preventing fuel decomposition in a direct liquid fuel cell
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CN101432922A (zh) 2009-05-13
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WO2006059239A3 (en) 2009-04-16
EP1810356A2 (en) 2007-07-25
JP2008513942A (ja) 2008-05-01
KR20070053346A (ko) 2007-05-23
EP1810356A4 (en) 2009-12-30
MX2007003028A (es) 2008-10-24
BRPI0515310A (pt) 2008-07-15
EA200700645A1 (ru) 2008-06-30
US20060057437A1 (en) 2006-03-16
AU2005310973A1 (en) 2006-06-08
KR100853021B1 (ko) 2008-08-20
US20060057435A1 (en) 2006-03-16

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