Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
  • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
• • Y—GENERAL 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• This invention relates to porous electrodes for fuel cells and similar cells such as air-metal cells, and alkaline zinc/manganese dioxide cells (particularly secondary cells), or other primary or secondary alkaline cells, and to the methods of making the present electrodes.
• the invention relates to porous electrodes which may be used as fuel cell cathodes or as auxiliary gas recombining or transfer electrodes in alkaline cells, wherein a catalytically active layer is formed on a porous conductive substrate, and the catalytically active layer is derived from non-noble metals.
• a further small amount of a noble metal is included in the catalytically active layer.
• electrodes according to the present invention have a lower loading of catalytically active layer in terms of weight of catalyst per unit area of geometric electrode surface than heretofore, but with operating characteristics that compare favourably with prior art electrodes having noble metal catalysts, but being available at much reduced costs.
• the present invention teaches several alternative methods for producing electrodes according to the present invention; whereby the electrode, once produced, will in all events have a catalytically active layer on a porous conductive substrate.
• Electrodes of the present invention may comprise a porous metal current collector, and a further gas diffusion layer, with the current collector being situated or embedded in the porous conductive substrate or within the gas diffusion layer.
• KORDESCH et al United States Patent 3,405,010 dated October 8, 1968 has included KORDESCH United States Patent 3,310,434, dated March 21, 1967.
• the former patent relates to the catalyzing of porous electrodes, using a heavy metal salt, an aluminum salt, and a ruthenium salt.
• the latter patent is particularly related to the use of noble metals as catalysts on a porous electrode.
• KORDESCH patent relating to the use of wet proofed conductive substrates having an active conductive layer with a surface-deposited noble metal catalyst is United States Patent 3,899,354 issued August 12, 1975.
• the catalyzed electrodes of the present invention are specifically adapted for use in fuel cells and metal-air cells; and especially useful as auxiliary gas recombining electrodes in alkaline zinc/manganese dioxide cells (particularly secondary cells), or other primary or secondary alkaline cells.
• the porous catalyzed electrodes of the present invention have particular utility as oxygen reduction electrodes in alkaline cells as noted above.
• the present invention comprises the provision of a porous electrode which comprises a porous conductive substrate and a porous catalytically active layer on the porous conductive substrate; the porous conductive substrate being chosen from the group consisting of carbon, graphite, and metal; and the porous catalytically active layer being chosen from the group consisting of a catalytically active non-noble metal, an oxide of a catalytically active non-noble metal, carbon, carbon together with a catalytically active non-noble metal, and carbon together with an oxide of a catalytically active non-noble metal.
• the electrode of the present invention is as described above, together with a further additional smaller amount of a catalytically active noble metal or carbon together with a catalytically active noble metal.
• Catalytically active non-noble metals that are particularly contemplated for use in the present invention include iron, cobalt, nickel, manganese, chromium, copper, and vanadium; and catalytically active noble metals there particularly intended for use in the present invention, in anodes according to this invention, include platinum, palladium, rhodium, iridium, osmium, gold, silver, and ruthenium.
• a porous electrode according to the present invention may include the porous active layer chosen from the group consisting of carbon together with a catalytically active non-noble metal, and carbon together with an oxide of a catalytically active non-noble metal; and very often, the porous active layer may further comprise polytetraf luoroethylene (PTFE), as a binder.
• PTFE polytetraf luoroethylene
• the carbon may be graphite.
• fuel cells may be considered to be galvanic cells, with the basic reaction being the electrochemical oxidation of a fuel and the electrochemical reduction of an oxidant (e.g., oxygen).
• oxidant e.g., oxygen
• fuel cells differ from ordinary primary cells such as commercially available dry cells, in that the fuel and oxidant are generally introduced continuously into the cell electrodes during the production of electricity.
• the electrodes and electrolyte of fuel cells should maintain a constant value, during the time when the fuel and the oxidant are reacted electrochemical ly within the fuel cell, and electricity and the product of reaction -- usually water — are removed from the fuel cell.
• the present invention provides a major step in the required direction, by providing catalyzed porous conductors having relatively low production costs, and with excellent characteristics as to their efficiency, power density, performance, and life.
• the characteristics of electrodes according to the present invention compare most favourably with the characteristics of certain higher efficiency prior art fuel cell electrodes which, however, contained noble metals in all instances and which therefore were costly to produce.
• electrodes of the present invention When used as a catalyzed porous electrodes in fuel cells or alkaline zinc/manganese dioxide cells, electrodes of the present invention may comprise a porous gas diffusion layer adhered to the porous conductive substrate spoken of above, at one side thereof. In fuel cells, electrodes according to the present invention may also generally include porous metal current collectors, as a convenient way of conducting electrical current produced in the fuel cell out of the fuel cell.
• the catalyst provided by the present invention is insoluble within the operating voltage and the operating condition range of the electrode, thereby contributing to the life of the electrode.
• catalyzed porous electrodes according to the present invention may be used with such electrolytes as alkaline electrolytes, for example potassium hydroxide as used in zinc/manganese dioxide cells. It also makes the use of catalyzed porous electrodes according to the present invention in metal-air batteries and cells more attractive.
• a metal or metal oxide from the group consisting of iron, cobalt, nickel, manganese, chromium, copper, and vanadium -- all non-noble metals -- to a porous electrode provides an electrode having a service life and performance characteristics comparable to those of platinum catalyzed electrodes.
• the cost of electrodes according to the present invention when compared to the cost of a platinum, catalyzed electrode, may be considerably lower.
• platinum catalyzed electrodes may have significant carbon corrosion of the carbon within the porous substrate structure, whereas the use of metals and metal oxides according to the present invention significantly decreases the risk of carbon corrosion.
• the porous conductive substrate of electrodes may be carbon, graphite, or metal; or, indeed, any other suitable conductive material.
• the porous active layer may comprise a catalytically active non-noble metal as discussed above, an oxide of a catalytically active non-noble metal, carbon, carbon together with a catalytically active non- noble metal, and carbon together with a oxide of catalytically active non-noble metal.
• the porous active layer consists of carbon together with a catalytically active non-noble metal or carbon together with an oxide of catalytically active non-noble metal; and in either case, it may further comprise a binder, usually PTFE.
• a typical porous electrode according to the present invention would consist of an electrochemical ly active layer which may be typically from 50 to 500 microns thick, and it may further include a gas diffusion layer which may also be 50 to 500 microns thick. If used in a fuel cell, the electrode would usually also have a metal screen current collector (a porous metallic current collector) embedded in an electrode layer -- unless a bipolar construction method is applied.
• the electrochemically active layer as noted, would contain the electrocatalyst as described above, supported on a carbon, graphite or metal porous substrate, and is located on the electrolyte side of the electrode.
• a gas diffusion layer when used, may typically consist of PTFE bonded carbon, and would normally have a higher degree of hydrophobicity than the active layer.
• a pore builder such as ammoniumbicarbonate, may be used.
• the current collector when used, may be embedded in either the gas diffusion layer or the active layer; and when electrodes according to the present invention are used in bipolar cells, no current collector is required.
• the total electrode thickness of an electrode comprising an active layer, a gas diffusion layer, and a current collector may range from 100 to 750 microns.
• porous electrodes according to the present invention may comprise a porous conductive substrate, and a porous gas diffusion layer adhered to one side thereof.
• the porous active layer is at a first side of the porous conductive substrate, and the porous gas diffusion layer is at the side of the porous conductive substrate opposite to that of the active layer.
• the porous active layer may permeate the porous conductive substrate, and in any event the porous gas diffusion layer is adhered to one side thereof.
• electrodes according to the present invention may also be used as anodes in fuel cells, in which case a further additional smaller amount of a catalytically active noble metal or carbon together with a catalyticall active noble metal is added to the catalytically active layer of the electrode.
• a catalytically active noble metal or carbon together with a catalyticall active noble metal is added to the catalytically active layer of the electrode.
• the concentration of catalyst within the porous catalytically active layer is generally in the range of from 0.1 to 10 mg per square centimeter of the geometrical electrode surface area. Typically, the concentration of catalyst within the porous catalytically active layer is in the range of from 1 to 5 mg per square centimeter of the geometrical electrode surface area.
• cathodes for hydrogen/oxygen fuel cells may have a service life well in excess of two thousand hours at a current density of 100 milliamperes per square centimeter, at a voltage above 0.85 volts versus RHE (Reversible Hydrogen Electrode). Similar electrodes, using non-noble metal oxide catalysts, can be run at up to 300 milliamperes per square centimeter on oxygen and air, with potentials of about 0.8 volts and 0.79 volts versus RHE, respectively.
• RHE Reversible Hydrogen Electrode
• the electrodes may be successfully subjected to current densities up to 750 mA/sq. cm. at low temperatures.
• the present invention provides three generally related but distinct processes for the production of porous electrodes in keeping herewith. Those three general methods may be characterized as follows:
• the compound used in step (a) of Process I is a metal salt solution of the chosen catalytically active metal.
• the formation process of step (b) of the Process I may be the chemical formation of the porous active layer, or the thermal formation of the porous active layer.
• the chosen active material that is used in step (a) of the Process II may further be mixed with carbon and PTFE.
• the Process III is carried out at least 600 degrees C, and the gas atmosphere may be steam, carbon dioxide, carbon monoxide, ammonia, nitrogen, argon, or hydrogen.
• a typical embodiment of the present invention when used as an auxiliary electrode as an oxygen gas recombining electrode in an alkaline zinc/manganese dioxide cell is shown in the single Figure of drawing which accompanies the following discussion.
• the Figure shows a typical embodiment of an alkaline zinc/manganese dioxide cell having an auxiliary porous oxygen gas recombining electrode in keeping with the present invention.
• the cell comprises a steel can 10 having a conventional metal oxide cathode 12 which is typically formed cylindrically around an anode 14.
• the cathode 12 may comprise finely divided manganese dioxide and graphite, and the anode may comprise zinc powder.
• an electrolyte permeable separator 16 Between the cathode and the anode is an electrolyte permeable separator 16.
• the electrolyte may be an aqueous solution of potassium hydroxide.
• a boss or a pip 18 is formed at the base of the can 10, to give the cathode or positive contact for the cell.
• the electrolyte permeable separator 16 is typically formed of rayon/polyvinyl alcohol.
• the anode may have at its upper end an auxiliary porous gas recombining electrode 20, which is arranged so as to be wetted by the electrolyte. At its lower end, the anode may be provided with an insulated disc or basket 22, to preclude anode contact with the cathode pip 18.
• a current collector nail 24 projects into the anode 14 through a casing cover 26, with the head 28 of the collector nail 24 being on the outside of the cover 26 to form the anode contact for the cell.
• the cover 26 seals the can 10 by crimping formed around its edge.
• An additional anode cover 30 is provided to give the anode or negative contact for the cell.
• the cathode may be provided with auxiliary cathode material to catalyze the reabsorption of hydrogen as set forth in KORDESCH and TOMANTSCHGER United States Patent 4,925,747 issued May 15, 1990.
• the auxiliary electrode 20 may have the characteristics set forth in TOMANTSCHGER and KORDESCH United States Patent 4,900,642 issued February 13, 1990.
• a graphite felt for example, a graphite product available commercially as PANEXTM CFP 30-10) was impregnated with manganese nitrate solution and pressed into a layer which comprised a mixture of carbon available commercially as SHAWINIGAN BLACKTM and PTFE.
• the carbon/PTFE layer comprised 62.5% carbon, 37.5% PTFE.
• the catalyst was thermally formed at 300 degrees C, in air, and resulted in an electrode having catalyst loading of 1.5 mg. of manganese per square centimeter of geometrical electrode surface area.
• the following table demonstrates the electrode performance, as a cathode at the oxygen side of an oxygen/hydrogen fuel cell system having 9 N KOH electrolyte, at 65 degrees C.
• an active layer of nickel FIBREXTM felt was impregnated with manganese nitrate solution, and again pressed into a carbon/PTFE layer as in Example I.
• the catalyst was thermally formed at 300 degrees C in air, with a catalyst loading of 7.6 mg. of manganese per square centimeter of geometrical electrode surface area.
• activated carbon plus an active catalyst was used, in a multi-layer PTFE bonded carbon electrode.
• the gas diffusion layer was a carbon/PTFE layer as described above in Examples I and II.
• the active layer comprised carbon black available commercially as VULCANTM XC 72R which was activated to 30% weight loss in the presence of cobalt-aluminum spinel (5
• SUBSTITUTESHEET mmol cobalt, 10 mmol aluminum pe. 100 grams of carbon), in the amount of 67% together with graphite in the amount of 22%, and PTFE in the amount of 11%.
• the catalyst loading was 5 mg. of manganese dioxide per square centimeter of geometrical electrode surface area, which may also be expressed as 3.2 mg. of manganese per square centimeter of geometrical electrode surface area.
• the electrode was operated for 220 hours at 100 milliamperes per square centimeter at 65 degrees C in 12 N KOH.
• the oxygen and air operation, both, of the electrode are set forth in the following table:
• the electrode was also operated at 150 milliamperes per square centimeter, over a varying range of temperatures, with air operation being observed as set forth in the following table.
• oxygen long term performance in 12 N KOH at 65 degrees C operating at 100 milliamperes per square centimeter, was determined as follows:
• VULCANTM XC 72R carbon was activated in the presence of 5 mmol of cobalt per 100 grams of carbon in the gas phase, in a carbon dioxide gas atmosphere, at 1000 degrees C. This resulted in an active layer consisting of carbon activated at 1000 * C in carbon dioxide atmosphere, in the amount of 95.2% containing cobalt oxide; with PTFE in the amount of 4.8%
• the catalyst loading was determined to be 1.3 mg. of cobalt per square centimeter of geometrical electrode surface area.
• the electrode performance was determiner in 9 N KOH, at 20 degrees C with oxygen, as follows:
• anode was fabricated, as follows:
• the gas diffusion layer comprised carbon (SHA INIGAN BLACK) in the amount of 50%, with 50% PTFE.
• the active layer comprised superconductive carbon black available commercially as BLACK PEARLSTM activated to 30% weight loss in the presence of cobalt-aluminum spinel (5 mmol cobalt, 10 mmol aluminum per 100 grams of carbon), together with ruthenium (0.2 grams Ru per 100 grams of carbon) all in the amount of 80%; with 20% PTFE.
• superconductive carbon black available commercially as BLACK PEARLSTM activated to 30% weight loss in the presence of cobalt-aluminum spinel (5 mmol cobalt, 10 mmol aluminum per 100 grams of carbon), together with ruthenium (0.2 grams Ru per 100 grams of carbon) all in the amount of 80%; with 20% PTFE.
• electrodes that are intended for use as cathodes in fuel cells (or metal -air cells), or as auxiliary gas recombining electrodes in sealed alkaline cells, which electrodes have excellent operating characteristics and which are produced without the requirement for use of noble metals.
• the electrodes are suitable for use as anodes in fuel cells, with equally good operating characteristics and comparatively low costs of production.
• electrodes according to the present invention may be used as gas recombining electrodes in rechargeable alkaline zinc/manganese dioxide cells, as well as in other primary or secondary alkaline cells.
• electrodes such as those described above in Examples I to IV have utility as gas recombining electrodes such as for oxygen recombination in alkaline cel ls. The ability of such auxiliary porous electrodes to function at low temperatures and high current densities has been demonstrated.

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• 1991
  • 1991-05-31 WO PCT/CA1991/000192 patent/WO1991020102A1/en not_active Ceased
  • 1991-05-31 EP EP91910310A patent/EP0533711A1/de not_active Withdrawn
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