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WO2000036677A1 - Electrode oxydoreductrice fournissant une haute densite de courant pour accumulateurs metal-air - Google Patents

Electrode oxydoreductrice fournissant une haute densite de courant pour accumulateurs metal-air Download PDF

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Publication number
WO2000036677A1
WO2000036677A1 PCT/US1999/027997 US9927997W WO0036677A1 WO 2000036677 A1 WO2000036677 A1 WO 2000036677A1 US 9927997 W US9927997 W US 9927997W WO 0036677 A1 WO0036677 A1 WO 0036677A1
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WIPO (PCT)
Prior art keywords
cathode
active layer
current collector
thermoplastic
coating
Prior art date
Application number
PCT/US1999/027997
Other languages
English (en)
Inventor
Jonathan Goldstein
Oleg Abramzon
Robert B. Dopp
Jonathan Sassen
Original Assignee
Electric Fuel Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Electric Fuel Limited filed Critical Electric Fuel Limited
Priority to AU18316/00A priority Critical patent/AU1831600A/en
Publication of WO2000036677A1 publication Critical patent/WO2000036677A1/fr

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    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
    • H01M50/1385—Hybrid cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5033—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature used as charging means for another battery
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • 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
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/42—Grouping of primary cells into batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • 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

  • the present invention relates to electrochemical cells such as metal-air battery cells, fuel cells, and the like. More particularly it relates to the air cathodes of such cells in applications requiring high power output.
  • Secondary (rechargeable) batteries power most high-drain portable electronic appliances.
  • high-drain devices are cellular telephones, notebook computers, camcorders, and cordless hand-tools.
  • the reason primary (disposable) batteries are unattractive in such applications is that their service life is generally short, and the cost and weight are high.
  • a cellular telephone, with alkaline batteries would last about as long as a single charge of a nickel-metal hydride battery.
  • the cost per unit of energy of alkaline batteries is very high and, consequently, they are unattractive for that purpose.
  • the low energy to weight ratio also makes them unattractive - a businessperson would have to carry a substantial weight in primary batteries to remain self-sufficient on a long trip or flight.
  • USP 4,585,710 proposes an arrangement that reportedly prevents separator delamination and also helps prevent the air cathode from drying out.
  • a gelling agent such as a gelling agent commonly added to metal anodes, is applied between the cathode active layer and the separator layer to strengthen the adhesion between the separator and the cathode.
  • the cathode of a metal-air battery typically has an active layer of activated carbon, a catalyst, and a binder, which forms a network and holds the carbon together. Embedded within the active layer is a metal current collector.
  • a guard layer covers the surface of the active layer that faces the outside air, and an ionically conducting separator covers the surface that faces the anode. The guard layer keeps electrolyte from leaking out of the cell, and the separator separates the anode or an electrically conductive reaction product from the cathode active layer, thereby preventing an electrical short.
  • PTFE Polytetrafluoroethylene
  • a nickel screen is a commonly used current collector although an expanded metal sheet or an alternative conductive material can be used, instead.
  • the guard layer can be made of a sheet of porous PTFE, and the separator can be made of a semipermeable membrane or a porous material.
  • Another issue with regard to providing high current capacity is the various types of resistance in the battery.
  • One solution that has been proposed by various parties is to provide a polymer coating on the cathode current collector.
  • the coating has a conductive filler, such as carbon.
  • US patents 5,447,809 and 5,814,419 discuss this idea. This approach has been discussed in the high current per unit area environment of cylindrical cells (D, C, A, AN, ANN cells used widely in consumer electronics and toys), in which the current collector is a smooth cylindrical surface. Since the surface area is so small in this type of cell and the current demands typically so high, the smooth surface is a significant cause of resistance. But such coatings are not perfect.
  • the cathode current collector substrate is usually steel.
  • the coating is described as being applied directly over steel. This structure would invite corrosion and is unworkable for a practical battery.
  • the 419 patent which follows the '809 patent corrects this problem by proposing an additive in the coating or the steel substrate of silicic acid or sodium silicate, which, according the tests reported, improves performance. Also, at least one other reference discusses applying a polymer coating over nickel to prevent corrosion.
  • Another approach to ameliorating the current collector-to-cathode resistance is a higher surface area of the current collector.
  • a number of battery designs have employed rippled casing surfaces or wire mesh screens as current collectors.
  • polymer coatings have been demonstrated to provide an advantage.
  • batteries with mesh- type current collectors such coatings have not previously been demonstrated to provide an advantage, and further, formulations have not been optimized.
  • the chemistry and physics of air cathodes are not well understood and designing a cathode for a given level of power performance, manufacturability, durability, and other desired characteristics, in many ways, is a very unpredictable proposition. Many different techniques must be used to address the different problems that limit performance. Experimental results in the various environments are crucial.
  • the present invention results in a cathode that has a number of features that contribute to an improved performance within the constraints of this particular technical environment.
  • the invention provides a cathode for electrochemical cells with numerous advantages including high current output, ease of manufacture, reliable cell construction, and longevity in dry environments.
  • the invention provides an air cathode for an electrochemical cell.
  • the cathode has an active layer, which may include carbon and an oxygen-reducing catalyst.
  • the active layer may include a binding material such as a thermoplastic.
  • Incorporated in the cathode is a metallic current collector in electrical contact with the active layer.
  • the current collector is substantially covered in a conductive, non- metallic coating.
  • the coating may contain, in substantial proportion, carbon in the form of graphite or carbon black.
  • the coating may contain a non-conducting material combined with a conducting material, such that the coating forms a continuous hydrophobic layer.
  • a thermoplastic used in the coating may be fluorinated ethylene propylene copolymer (FEP).
  • the invention provides an air cathode for an electrochemical cell.
  • the cathode has an active layer, which may include carbon, a thermoplastic, and an oxygen-reducing catalyst.
  • an active layer which may include carbon, a thermoplastic, and an oxygen-reducing catalyst.
  • Incorporated in the cathode is a metallic current collector in electrical contact with the active layer.
  • the current collector is substantially covered in a conductive, non-metallic coating, which contains a thermoplastic and carbon.
  • the thermoplastic and the carbon may be present in substantially different proportions in the active layer as compared to the coating.
  • the invention provides an air cathode for an electrochemical cell.
  • the cathode has an active layer, which may include carbon and an oxygen-reducing catalyst.
  • Incorporated in the cathode is a metallic current collector in electrical contact with the active layer.
  • the current collector is substantially covered in a conductive, non-metallic coating, which is bonded to the current collector.
  • the coating may contain, in substantial proportion, a thermoplastic which bonds the coating to the current collector by sintering the thermoplastic to the current collector.
  • the thermoplastic in this case also may be a fluoropolymer, such as FEP.
  • the invention provides an air cathode that has an active layer that includes a mixture of a divided mass of carbon, a divided mass of PTFE and a divided mass of a hydrophilic material.
  • the hydrophilic material may be a cellulosic material, such as hydroxyethylcellulose.
  • the invention provides an air cathode for an electrochemical cell.
  • the cathode has an active layer that includes a mixture of a divided mass of carbon, a divided mass of thermoplastic and a divided mass of a hydrophilic material.
  • the thermoplastic may be a fluoropolymer and the hydrophilic material may be a cellulosic material.
  • the invention provides an air cathode for an electrochemical cell with an active layer containing a substantial quantity of carbon and an oxygen-reducing catalyst.
  • the cathode also has a separator sheet laminated to a primary surface of the active layer, which is effective to separate an anode from the active layer.
  • the average pore size of the separator is between 0.25 and 2.0 microns.
  • the separator can have an average pore size of at least 0.5 micron.
  • the invention provides an air cathode for an electrochemical cell.
  • the active layer of the cathode includes a substantial quantity of carbon and an oxygen-reducing catalyst.
  • the important feature is the average density of the active layer, which is not more than 1 g/cc. For better performance, the average density can be held to no more than 0.8 g/cc.
  • the cathode can have a metallic current collector in electrical contact with the active layer with the current collector being substantially covered in a conductive, non-metallic coating.
  • the coating may be bonded to the current collector.
  • the coating may contain, in substantial proportion, a thermoplastic with the coating being bonded by a sintering of the thermoplastic to the current collector.
  • the active layer and the coating may contain a thermoplastic in combination with carbon, with the thermoplastic and the carbon being present in substantially different proportions in the active layer as compared to the coating.
  • the invention provides an air cathode with an active layer containing at least an oxygen-reducing catalyst and carbon.
  • the cathode has a current collector in electrical contact with the active layer and a conducting hydrophobic material bonded to a surface of the current collector.
  • the conducting hydrophobic material may include a thermoplastic and the conducting hydrophobic material may be bonded to the current collector by the thermoplastic. At least a portion of the thermoplastic may be sintered to bond the coating to the current collector.
  • the thermoplastic may be a fluoropolymer, e.g., FEP, and the hydrophobic material may include carbon.
  • the active layer may have a surface that has a roughness of at least 10 micron pitch and depth to improve performance.
  • the invention provides a process for making an air cathode for an electrochemical cell.
  • the method includes the step of forming an active layer containing carbon, a binder, and an oxygen reducing catalyst so that at least one major surface of the active layer has a roughness of at least 10 micron pitch and depth.
  • the invention provides an air cathode for an electrochemical cell.
  • the cathode in this embodiment has an active layer that contains a substantial quantity of carbon and an oxygen-reducing catalyst.
  • the fluoropolymer sheet has an average porosity greater than 30% and a thickness of less than 100 microns. The porosity is preferably greater than 50%.
  • the invention provides an air cathode for a zinc-air battery.
  • the active layer contains at least an oxygen-reducing catalyst and carbon.
  • the cathode has a current collector in electrical contact with the active layer.
  • the current collector has a conducting hydrophobic material bonded to a surface thereof.
  • the conducting hydrophobic material preferably contains an insulating material that acts as a binder.
  • the insulating material may be sinterable or thermally meltable, and the insulating material may be bonded to the surface of the current collector by sintering or melting the insulating material onto the current collector.
  • the invention provides an air cathode for an electrochemical cell, comprising an active layer that includes carbon, and an oxygen-reducing catalyst.
  • the cathode has a current collector that is at least partly metallic with a conductive surface, whereby the current collector conducts electrical current from conductive material in contact with the surface.
  • the current collector is substantially covered in a conductive, non- metallic coating bonded to the surface.
  • the non-metallic coating is preferably bonded by means of a sintered thermoplastic, which forms a component of the composition of the coating.
  • the invention provides an air cathode for an electrochemical cell, comprising a laminated structure that includes an active layer.
  • the active layer includes carbon and an oxygen-reducing catalyst.
  • the cathode has a conductive current collector in electrical contact with the active layer, with the current collector being substantially coated in a conductive non-metallic coating.
  • the active layer includes a binding material.
  • the binding material is, preferably, a thermoplastic.
  • the coating may contain a non-conducting material combined with a conducting material, such that the coating forms a continuous hydrophobic layer.
  • the non-conducting material may include a thermoplastic which can be a fluoropolymer such as FEP.
  • the active layer and the coating may contain a thermoplastic in combination with carbon with the thermoplastic and the carbon being present in substantially different proportions in the active layer as compared to the coating.
  • the invention provides an air cathode, which has an active layer made of carbon and an oxygen-reducing catalyst, and a metallic current collector in electrical contact with the active layer.
  • the current collector is substantially covered in a conductive non-metallic coating containing a sinterable material that is bonded to the current collector by sintering.
  • the active layer has an average density of no more than 1 g/cc.
  • Fig. 1 is a schematic section view of a typical zinc-air battery cell that can make use of the air cathode of the present invention. The schematic is intended only to illustrate relationships between various components.
  • Fig. 2 is schematic section, partial perspective, view of an air cathode illustrating some of the embodiments of the invention.
  • the invention provides an air-electrode for use in metal-air batteries, fuel cells, or any device that requires an air electrode, provides high current density, relative ease of manufacture, good humidity tolerance, and a number of other benefits.
  • the cathode described herein is intended for use in electrochemical cells or fuel cells.
  • the cells may be any suitable shape and be arranged in a housing that is liberally supplied with openings to allow air gases to be exchanged between the ambient air and the enclosed cells.
  • the cells can have a housing of metal, plastic, or any other suitable material.
  • Each cell may have an array of air holes, such as used in zinc-air button cells, in such number and size as to allow oxygen to be supplied to a cathode inside the cell.
  • the air holes of each cell may face either a plenum or the casing wall.
  • the air holes are uniformly distributed, sized, and present in such number so as to insure that the cathode is not starved for oxygen, which could cause a drop in voltage.
  • the cell may use a semipermeable membrane or structure that permits the diffusion of gases through the membrane or structure.
  • each of the cells 5 contains at least one air cathode 20 and at least one zinc anode 25 with aqueous alkaline electrolyte (e.g., KOH).
  • the cathode 20 lies adjacent a cathode side of the cell casing 2 and may be separated from that side by a diffuser 50.
  • the diffuser 50 distributes oxygen from holes 60 in the cathode side of the cell 2 across the surface of the cathode 20 and keeps the cathode 20 at a fixed distance, equal to the diffuser's 50 thickness, from the cathode side 2 of the cell 5.
  • the diffuser 50 may be a porous material such as woven, knitted, or non-woven cloth or extended plastic mesh material.
  • the holes 60 in the cathode side of the cell 2 are uniformly distributed across the primary plane 70 of the cathode side of the cell.
  • the casing 1 / 2 of the cell may be formed in two halves, an anode side 1 and a cathode side 2 as in Fig. 1.
  • the cell casing 1 / 2 may be formed of any suitable material. If the casing 1 / 2 is made of metal or any other conductive material, the two halves 1 and 2 should be insulated from one another. In either case, to form a primary seal 80, the cathode 20 may be attached to, or sealed against, the cathode side 2 of the cell casing 1 / 2.
  • the primary seal 80 may be effected by pressure, adhesive, or any other suitable means to prevent liquid electrolyte from leaking into the space occupied by the diffuser 50.
  • the primary seal 80 prevents liquid electrolyte from seeping around the cathode 20 into the area exposed to the outside air.
  • a secondary seal 10 between the anode side of the cell 1 and the cathode side 2 prevents aqueous electrolyte from seeping around to the edge of the cathode 20 or leaking out of the cell 5.
  • the secondary seal 10 is formed by a grommet 90, which also serves to insulate the anode side 1 and cathode side 2 of the cell casing 1 / 2 from each other. Pressure, an adhesive, or flowing sealant, or other suitable means may be used to effect the secondary seal 10. Referring to Fig.
  • the cathode consists of multiple layers with the middle layer being an active layer 120 composed primarily of carbon, PTFE, and a catalyst for reducing oxygen.
  • the active layer 120 is the location where the oxygen reduction reaction takes place in the presence of the catalyst.
  • a separator layer 100 which may be prelaminated to the active layer 120 can be made from microporous hydrophilic polypropylene (PP), polyethylene, PVC, cellophane, nylon, Celgard®, or other materials exhibiting similar properties.
  • the pore size of the separator 100 is in the range of about 0.25 micron to 2 microns instead of the more typical average pore size of less than 0.25 micron used in other battery applications.
  • the larger pore size is sufficient to limit electrical shorts from crystallization of zinc oxide in the separator layer 100, and still permit enhanced wetting of the cathode active layer 120 with KOH solution.
  • Other types of separator materials that may provide better cathode performance include microporous polyethylene or polypropylene whose hydrophilicities are enhanced by radiation grafting.
  • Another class of suitable separator materials is semipermeable membranes based on cellophane, polyethylene, PVC, nylon, and polypropylene, for example, ZAMM-0 supplied by Pall RNI Corp.
  • An additional non- woven, absorbent material can be added between the air electrode and the microporous separator or between the microporous separator and the zinc. The purpose of this is to provide an electrolyte reservoir.
  • the following processes may provide the preferred composition of the electrode active layer 120.
  • the quantities are representative only and the quantities and proportions may be varied.
  • a current collector 140 commonly formed of a metal, for example, a nickel, screen. Nickel-plated or nickel-clad steel, gold-plated metal, or other materials could also be used. A plastic element coated or clad with a conductor could even be used. It is preferred that the current collector 140 of the cathode be treated or constructed in such a way as to provide high surface area and low electrical resistance. The formation of oxide on the surface of a metal mesh current collector or a thin film of electrolyte on the hydrophilic surface of the current collector may limit the power capacity of the battery cell. One way to deal with this is to coat the current collector with a coating of a non- corroding metal finish.
  • hydrophobic conductive paints have other advantages over metal finishes. Gold and silver are the only metals that can be coated on a cathode mesh and still provide reasonable conductivity. Both are very expensive. Moreover, a silver coating is slightly soluble in alkaline electrolytes, which may lead to an increased corrosion of the zinc anode.
  • This paint may be applied before the cathode active layer is combined with the current collector.
  • a preferred paint is a mixture of the following:
  • FEP Fluorinated ethylene propylene copolymer
  • Acetylene carbon (Shawinigan carbon black made by Chevron) or some other suitable form of carbon, preferably hydrophobic, such as graphite.
  • a representative batch of paint may be formed of 1400 cc isopropyl alcohol, 108 cc FEP and 20 g acetylene black.
  • the paint may be sprayed, or applied by any alternative suitable means, onto a mesh at a loading of 0.72 mg/cm 2 . This loading is only an example, and higher or lower loading values may also be used.
  • the coated mesh is then baked in an oven at 290-330°C to sinter the FEP and bond it to the metal current collector, e.g., woven nickel mesh.
  • the actual sintering temperature, in applications of the present invention, may depend upon the particular thermoplastic used.
  • a sinterable material such as FEP
  • materials that can be melted to form a coherent mass could also be used in replacement of the sinterable material to bond the coating in place.
  • the painted current collector may be heated by microwave, infrared, RF, or ultrasonic means instead of heating the coated mesh in an oven.
  • the sintered coating forms a continuous hydrophobic conducting coating that protects against the corrosion or the oxidation of the metal mesh material.
  • the sintering step also removes the surfactant in the FEP emulsion. It has been found that an air electrode with this coating laminated to a suitable separator and then incorporated into a zinc- air cell of area 10 cm 2 (2.5 cm. by 4 cm.) gave a steady state voltage 250 mV higher than an air electrode without this coating when discharged at a constant 0.47A.
  • the cathode should be fully saturated with electrolyte.
  • the cathode tends to dry out as a result of water evaporating from the cell and as a result of waters of hydration being drawn away from the cathode when zinc oxide forms during discharge of the cell.
  • hydrophilic agents to the cathode ameliorates this dryout effect.
  • cellulosic materials such as Natrosol ® 250 MBR hydroxyethylcellulose (HEC) may be added to the cathode material (finely divided and added to the active layer mixture).
  • MnO 2 powder (Aldrich Chemical Company, Milwaukee, WI) is ground finely in a mill for 24 hours. The MnO 2 is then poured into 2 liters of deionized (DI) water and heated to 85°C. Add 800 g. of Darco G-60 carbon (American Norit, Atlanta GA) while stirring. Then add 288cc of Dupont 30-N PTFE suspension. Continue stirring for one hour, and then filter and dry at 120°C for 5 hours. Slowly add 200g of the active mass made above to 5 liters of DI water stirred at 85°C. After all the carbon is in suspension, add 2 grams of Natrosol (grade 250MBR from Hercules). Continue stirring under heat until dry.
  • DI deionized
  • the active mass treated with the Natrosol® is spread evenly over a nickel mesh (40x40 mesh 0.005 mm dia. nickel from National Standard) and pressed to make an active layer of an air electrode. A porous PTFE sheet is then pressed on one side of the active layer.
  • the air electrode from above is then laminated with a microporous polypropylene film (grade 3501 from Celgard®) separator.
  • the air electrode and separator laminate is then assembled into a zinc-air cell of area 10cm 2 containing 3.1g zinc and 2.4g 8M KOH solution, and the complete cell closed by crimping.
  • the test cell and a control cell that does not contain the Natrosol® are exposed to a 25-30% relative humidity (RH) environment for a period of 7 days.
  • RH relative humidity
  • the cells are discharged under a load following a GSM profile, which is one of the standard profiles used by mobile communication devices for communicating with ground stations.
  • GSM is a galvanostatic square wave profile consisting of 1.3 A for 0.6 msec and 0.08 A for 4.0 msec.
  • the discharge cycle spans one hour (0.2 Ah).
  • the cells are then returned to the low humidity environment. This discharge cycle is repeated every 3-4 days until the cells fail. Failure is defined as the high current voltage falling below 0.9V.
  • a guard layer 160 preferably formed of a PTFE film, laminated to the side of the active layer facing the air holes.
  • the guard layer 160 allows oxygen to enter the cathode while preventing liquid electrolyte from leaking out.
  • This layer 160 is preferably unsintered and highly porous to gases.
  • the preferred porosity is at least 30%, but it is desirable to provide a guard layer that is even more porous. Porosity of 50% or more are even more preferable.
  • the preferred thickness of the guard layer is no more than 100 microns.
  • an uncompressed PTFE film 85 which is separate from the laminated structure of the cathode 20, is uncompressed by any laminating process used to form the cathode structure shown in Fig. 2.
  • the grommet 90 forces the cathode 20 against the cathode side of the cell 2, thereby compressing the previously uncompressed PTFE film 85. This helps to form the primary seal 80, which isolates the volume of the cell that is in communication with the outside air from the electrolyte as described above. Since the film 85 is initially uncompressed, it can act as a gasket to create or augment the secondary seal.
  • PTFE layers - the guard layer laminated to the cathode and the uncompressed layer - allow air to diffuse into the cathode while preventing liquid from leaking out.
  • the active layer 120, the separator sheet 100, and the guard layer 160 may be laminated together to form a single structure.
  • the dimensions of the active layer and the separator layers are 0.20-0.50 mm and 0.025-0.25 mm, respectively. The actual dimensions depend on the application and can be any suitable thickness. It is preferable that the final pressure used to laminate all the layers together not be too high.
  • an active layer density of less than 1 g/cc is a suitable for attaining high current densities. It has been found that an active layer density of 0.8 g/cc is achievable and provides even greater current density potential. It was found that a PTFE layer with a porosity greater than 50% and a thickness less than 100 microns and an active layer with a density less than 1 g/cc, and preferably less than 0.8 g/cc, exhibits a substantially higher limiting current than prior art cathodes. Together, these improvements produce an air electrode with a limiting current greater than 400mAJcm 2 with a voltage greater than -300mV as compared to a Hg/HgO reference electrode at room temperature.
  • Still another feature that has been found to result in higher performance is a roughened surface on the cathode active layer facing the separator.
  • a roughened surface can be obtained by pressing the surface with an irregularly surfaced mold to form an imprint.
  • various abrasion techniques such as brushing, air blasting, or sandblasting; or various heat treatments, such as partial oxidation, can be used.
  • the average roughness (R of the surface, as measured by ANSI B46.1-1978, should be on the order of 10-100 microns instead of the usual 0.1-1 microns.

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Abstract

Une électrode oxydoréductrice pour éléments électrochimiques produit une haute capacité de courant par rapport aux cathodes actuelles. L'électrode présente une couche active constituée d'une matrice en carbone ayant un catalyseur de réduction d'oxygène et un liant fluoropolymère. Un collecteur de courant intégré est revêtu d'un matériau conducteur contenant un agent de liaison polymère et un matériau conducteur, de préférence du carbone. Le collecteur de courant revêtu est cuit afin de fritter le liant et d'établir un revêtement conducteur hydrophobe continu sur le collecteur de courant. La couche active présente une faible densité, de préférence inférieure à 1 g/cc. L'électrode est une structure multicouches ayant un séparateur sur une face de la couche active et une couche de protection en Téflon ®* hautement poreuse sur l'autre face. La couche de protection a de préférence une porosité d'au moins 30 % et une épaisseur ne dépassant pas 100 microns.
PCT/US1999/027997 1998-12-15 1999-11-29 Electrode oxydoreductrice fournissant une haute densite de courant pour accumulateurs metal-air WO2000036677A1 (fr)

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US11229298P 1998-12-15 1998-12-15
US11950499P 1999-02-10 1999-02-10
US60/119,504 1999-02-10
US28656399A 1999-04-05 1999-04-05
US09/286,563 1999-04-05
US60/112,292 1999-04-15

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Cited By (15)

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US6593023B2 (en) 2001-04-27 2003-07-15 The Gillette Company Battery and method of making the same
WO2008073217A1 (fr) * 2006-12-08 2008-06-19 Eveready Battery Company, Inc. Pile électrochimique possédant une électrode de gaz déposée
WO2008085479A1 (fr) 2006-12-27 2008-07-17 Eveready Battery Company, Inc. Procédé de fabrication d'une électrode catalytique et cellule électrochimique utilisant ladite électrode
WO2009135030A1 (fr) * 2008-04-30 2009-11-05 Battelle Memorial Institute Accumulateur métal-air
WO2010138643A1 (fr) 2009-05-29 2010-12-02 Eveready Battery Company, Inc. Collecteur de courant pour électrode catalytique
WO2011094295A1 (fr) 2010-01-29 2011-08-04 Eveready Battery Company, Inc. Procede de production de cellule electrochimique a electrode catalytique comprenant du dioxyde de manganese
WO2012156639A1 (fr) 2011-05-19 2012-11-22 Electricite De France Accumulateur métal-air avec dispositif de protection de l'électrode à air
WO2013068694A1 (fr) 2011-11-09 2013-05-16 Electricite De France Electrolyte aqueux pour batterie lithium-air
DE102014218993A1 (de) 2014-09-22 2016-03-24 Robert Bosch Gmbh Separator-Kathodenstromkollektor-Element
US9972874B2 (en) 2013-11-22 2018-05-15 Electricite De France Battery with extractible air electrode
US10074877B2 (en) 2012-11-29 2018-09-11 Electricite De France Method for charging a zinc-air battery with limited potential
US10109902B2 (en) 2012-11-29 2018-10-23 Electricite De France Metal-air battery having a device for controlling the potential of the negative electrode
EP3671913A1 (fr) 2018-12-21 2020-06-24 Electricité de France Procédé de fabrication d'une électrode de zinc par voie aqueuse
CN113224318A (zh) * 2020-02-04 2021-08-06 三星电子株式会社 正极、包括其的锂-空气电池和制备所述正极的方法
US11764364B2 (en) 2020-02-04 2023-09-19 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode

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US6270921B1 (en) * 2000-01-19 2001-08-07 The Gillette Company Air recovery battery
US7147678B2 (en) * 2003-07-03 2006-12-12 The Gillette Company Alkaline cell with improved anode
US7179310B2 (en) * 2003-07-03 2007-02-20 The Gillette Company Zinc/air cell with improved anode
US7955755B2 (en) 2006-03-31 2011-06-07 Quantumsphere, Inc. Compositions of nanometal particles containing a metal or alloy and platinum particles
FR2931298B1 (fr) 2008-05-13 2010-09-03 Electricite De France Accumulateur fer-air a mediateur lithium

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6593023B2 (en) 2001-04-27 2003-07-15 The Gillette Company Battery and method of making the same
WO2008073217A1 (fr) * 2006-12-08 2008-06-19 Eveready Battery Company, Inc. Pile électrochimique possédant une électrode de gaz déposée
US7695840B2 (en) 2006-12-08 2010-04-13 Eveready Battery Co., Inc. Electrochemical cell having a deposited gas electrode
US8377149B2 (en) 2006-12-27 2013-02-19 Eveready Battery Company, Inc. Process for making a catalytic electrode and electrochemical cell using the electrode
WO2008085479A1 (fr) 2006-12-27 2008-07-17 Eveready Battery Company, Inc. Procédé de fabrication d'une électrode catalytique et cellule électrochimique utilisant ladite électrode
WO2009135030A1 (fr) * 2008-04-30 2009-11-05 Battelle Memorial Institute Accumulateur métal-air
US8541135B2 (en) 2009-05-29 2013-09-24 Eveready Battery Co, Inc. Current collector for catalytic electrode
WO2010138643A1 (fr) 2009-05-29 2010-12-02 Eveready Battery Company, Inc. Collecteur de courant pour électrode catalytique
WO2011094295A1 (fr) 2010-01-29 2011-08-04 Eveready Battery Company, Inc. Procede de production de cellule electrochimique a electrode catalytique comprenant du dioxyde de manganese
WO2012156639A1 (fr) 2011-05-19 2012-11-22 Electricite De France Accumulateur métal-air avec dispositif de protection de l'électrode à air
US9293757B2 (en) 2011-05-19 2016-03-22 Electricite De France Metal-air accumulator with air electrode protection device
WO2013068694A1 (fr) 2011-11-09 2013-05-16 Electricite De France Electrolyte aqueux pour batterie lithium-air
US10109902B2 (en) 2012-11-29 2018-10-23 Electricite De France Metal-air battery having a device for controlling the potential of the negative electrode
US10074877B2 (en) 2012-11-29 2018-09-11 Electricite De France Method for charging a zinc-air battery with limited potential
US9972874B2 (en) 2013-11-22 2018-05-15 Electricite De France Battery with extractible air electrode
DE102014218993A1 (de) 2014-09-22 2016-03-24 Robert Bosch Gmbh Separator-Kathodenstromkollektor-Element
EP3671913A1 (fr) 2018-12-21 2020-06-24 Electricité de France Procédé de fabrication d'une électrode de zinc par voie aqueuse
FR3091042A1 (fr) 2018-12-21 2020-06-26 Electricite De France Procédé de fabrication d’une électrode de zinc par voie aqueuse
US12027693B2 (en) 2018-12-21 2024-07-02 Electricite De France Method for production by aqueous route of a zinc electrode
CN113224318A (zh) * 2020-02-04 2021-08-06 三星电子株式会社 正极、包括其的锂-空气电池和制备所述正极的方法
EP3863095A3 (fr) * 2020-02-04 2021-12-08 Samsung Electronics Co., Ltd. Cathode, batterie lithium-air la comprenant et procédé de préparation de la cathode
US11658306B2 (en) 2020-02-04 2023-05-23 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode
US11764364B2 (en) 2020-02-04 2023-09-19 Samsung Electronics Co., Ltd. Cathode, lithium-air battery comprising the same, and method of preparing the cathode

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