WO2002009212A1 - Microcell electrochemical devices and assemblies, and method of making and using the same - Google Patents

Microcell electrochemical devices and assemblies, and method of making and using the same Download PDF

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Publication number
WO2002009212A1
WO2002009212A1 PCT/US2001/023220 US0123220W WO0209212A1 WO 2002009212 A1 WO2002009212 A1 WO 2002009212A1 US 0123220 W US0123220 W US 0123220W WO 0209212 A1 WO0209212 A1 WO 0209212A1
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WO
WIPO (PCT)
Prior art keywords
microcell
assembly
heat exchange
housing
potting
Prior art date
Application number
PCT/US2001/023220
Other languages
English (en)
French (fr)
Inventor
Ray Eshragui
Original Assignee
Microcell Corporation
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
Priority claimed from US09/625,218 external-priority patent/US6403517B1/en
Priority claimed from US09/624,070 external-priority patent/US6338913B1/en
Priority claimed from US09/625,219 external-priority patent/US6444339B1/en
Priority claimed from US09/621,228 external-priority patent/US6399232B1/en
Priority claimed from US09/624,303 external-priority patent/US6403248B1/en
Priority claimed from US09/621,713 external-priority patent/US6495281B1/en
Priority to AU8295301A priority Critical patent/AU8295301A/xx
Priority to KR10-2003-7001123A priority patent/KR20030038678A/ko
Priority to JP2002514817A priority patent/JP2004505417A/ja
Priority to AU2001282953A priority patent/AU2001282953B2/en
Application filed by Microcell Corporation filed Critical Microcell Corporation
Priority to EP01961707A priority patent/EP1316119A4/en
Priority to NZ523874A priority patent/NZ523874A/en
Priority to CA002417682A priority patent/CA2417682C/en
Publication of WO2002009212A1 publication Critical patent/WO2002009212A1/en
Priority to AU2004202981A priority patent/AU2004202981B2/en

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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/002—Shape, form of a fuel cell
    • H01M8/004—Cylindrical, tubular or wound
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H01M10/625—Vehicles
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/643—Cylindrical 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6556—Solid parts with flow channel passages or pipes for heat exchange
    • H01M10/6557—Solid parts with flow channel passages or pipes for heat exchange arranged between the 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6567—Liquids
    • 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
    • H—ELECTRICITY
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    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8846—Impregnation
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8864—Extrusion
    • H—ELECTRICITY
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    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
    • 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
    • H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
    • H—ELECTRICITY
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    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H01M50/469—Separators, membranes or diaphragms characterised by their shape tubular or cylindrical
    • H—ELECTRICITY
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    • 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
    • H01M6/44—Grouping of primary cells into batteries of tubular or cup-shaped cells
    • H—ELECTRICITY
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    • 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
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • 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
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2418—Grouping by arranging unit cells in a plane
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0472—Vertically superposed cells with vertically disposed plates
    • 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
    • H01M2004/022—Electrodes made of one single microscopic fiber
    • 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
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • H01M8/04074—Heat exchange unit structures specially adapted for fuel cell
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to microcell electrochemical devices and assemblies, methods of making same by various techniques, and use of such devices and assemblies.
  • electrochemical cells such as batteries and fuel cells are relatively simple, utilizing respective positive and negative electrodes separated in such manner as to avoid internal short circuiting, and with the electrodes being arranged in contact with an electrolyte medium.
  • the chemical energy of the reaction is converted into electrical energy with the flow of electrons providing power when the electrode circuit is coupled with an external load.
  • Battery cells may use separator plates between respective electrodes so that multiple sheet elements are arranged in successive face-to-face assemblies, and/or such sheets may be wound together in a (spiral) roll configuration.
  • the fuel cell is of significant current interest as a source of power for electrically powered vehicles, as well in distributed power generation applications.
  • a fuel is introduced to contact with an electrode (anode) and oxidant is contacted with the other electrode (cathode) to establish a flow of positive and negative ions and generate a flow of electrons when an external load is coupled to the cell.
  • the current output is controlled by a number of factors, including the catalyst (e.g., platinum in the case of hydrogen fuel cells) that is impregnated in the electrodes, as well as the kinetics of the particular fuel/oxidant electrochemical reaction.
  • Fuel cells also may be integrated with reformers, to provide an arrangement in which the reformer generates fuel such as hydrogen from natural gas, methanol or other feed stocks. The resulting fuel product from the reformer then is used in the fuel cell to generate electrical energy.
  • fuel such as hydrogen from natural gas, methanol or other feed stocks.
  • polymer electrolyte fuel cells in which the electrolyte is a fluorinated sulfonic acid polymer or similar polymeric material; alkaline fuel cells, using an electrolyte such as potassium hydroxide, in which the KOH electrolyte is retained in a matrix between electrodes including catalysts such as nickel, silver, metal oxide, spinel or noble metal;
  • molten salt fuel cells employing an electrolyte of alkali carbonates or sodium/potassium, in a ceramic matrix of lithium aluminate, operating at temperatures on the order of 600-700 degrees C, with the alkali electrolyte forming a high conductive molten salt;
  • solid oxide fuel cells utilizing metal oxides such as yttria-stabilized zirconia as the electrolyte and operating at high temperature to facilitate ionic conduction of oxygen between a cobalt-zirconia or nickel-zirconia anode, and a strontium-doped lanthanum manganate cathode.
  • metal oxides such as yttria-stabilized zirconia as the electrolyte and operating at high temperature to facilitate ionic conduction of oxygen between a cobalt-zirconia or nickel-zirconia anode, and a strontium-doped lanthanum manganate cathode.
  • LHV lower heating value
  • microcells small-sized electrochemical cells for battery, fuel cell and other electrochemical device applications.
  • the microcell technology is described in U.S. Patent Nos. 5,916,514; 5,928,808; 5,989,300; and 6,004,691, all to Ray R. Eshraghi.
  • the microcell structure described in these patents comprises hollow fiber structures with which electrochemical cell components are associated.
  • the aforementioned Eshraghi patents describe an electrochemical cell structure in which the single cell is formed of a fiber containing an electrode or active material thereof, a porous membrane separator, electrolyte and a second electrode or active material thereof.
  • Cell designs are described in the Eshraghi patents in which adjacent single fibers are utilized, one containing an electrode or active material thereof, the separator and electrolyte, with the second fiber comprising a second electrode, whereby the adjacent fibers constitute positive and negative electrodes of a cell.
  • the present invention embodies additional advances in the Eshraghi microcell technology.
  • Figures 1-4 are perspective views of fibrous element structures illustrating the fabrication of a microcell assembly.
  • Figure 5 is a perspective view of a connector for joining current collector or electrode elements of a •microcell fiber assembly.
  • Figure 6 is a microcell assembly according to one embodiment of the invention, with a terminal at one end of the assembly.
  • Figure 7 is an exploded perspective view of a microcell assembly showing series-connected microcell sheets.
  • Figure 8 is a schematic view of a layered arrangement of microcell sheets, joined in series relationship.
  • Figure 9 is a 3-dimensional perspective view of a series-connected arrangement of microcell layers.
  • Figure 10 shows a potted arrangement of microcell sheets.
  • Figure 11 is a perspective view of a duct that is perforated on the top surface, and optionally on the bottom surface for the fabrication of double stack bundles of electrochemical cells.
  • Figure 12 is a cross-sectional elevation view of a microcell fiber bundle potted in a vessel.
  • Figure 13 is a side elevation view of the vessel of Figure 12.
  • Figure 14 is an elevational cross-sectional view of a double stack of microcell sheets.
  • Figure 15 is a side elevation view of a double stack of microcell devices arranged in sheets, comprising a stack on each side of a perforated duct.
  • Figure 16 is a perspective view of potted fibers on one side of a perforated feed duct.
  • Figure 17 shows a vessel with fibers laid on both sides of the perforated feed duct.
  • Figure 18 is a side elevation view of an electrochemical cell device comprising an assembly of microcells.
  • Figure 19 shows a perforated feed tube used as a mandrel in forming microcell structures.
  • Figure 20 shows fibrous microcell and shell side current collector sheets that can be rolled or wound around the perforated tube of Figure 19, with the sheets being shown during rolling in Figure 21 and as finally rolled " into shape in Figure 22.
  • Figure 23 shows sheets of fibrous microcell elements and shell side current collectors, and an insulating sheet (e.g., of fiberglass or porous plastic material).
  • an insulating sheet e.g., of fiberglass or porous plastic material.
  • Figure 24 is a perspective view of a sheet assembly including two sheets of fibrous microcell elements and shell side current collectors.
  • Figure 25 is a side elevation view of a microcell assembly with off-set fiber layer sheets.
  • Figure 26 is a cross-sectional view of a microcell bundle.
  • Figure 27 is a side elevation view of series-connected microcell sub-bundles according to one embodiment of the invention.
  • Figure 28 is a perspective view of a connector that may be used to join component microcell sub- bundles in series.
  • Figure 29 is a cross-sectional elevation view of a multibundle assembly, wherein each bundle has a corresponding feed tube associated therewith.
  • Figure 30 is a cross-sectional elevation view of a multibundle assembly, wherein the respective bundles are connected in series.
  • Figure 31 is a cross-sectional view of a fuel cell module with multiple sub-bundles wherein blank seal elements provide closure members for the face sheet of the module enclosure.
  • Figure 32 is a side view of a fuel cell module with multiple sub-bundles of microcell elements, with a feed tube in a manifolded arrangement.
  • Figure 33 is a side elevation view in section, showing penetration of a feed tube into the interior volume of the housing of a module containing microcell sub-bundles according to one embodiment of the present invention.
  • Figure 34 is a cross-sectional view of a microcell assembly in which heat exchange fibers or tubes are provided in interspersed relationship to the microcell bundles.
  • Figure 35 is a cross-sectional elevation view of a fuel cell module, showing air/fuel passages and heat exchange passages, interspersed between the sub-bundles.
  • Figure 36 is a cross-sectional view of a microcell bundle wherein hollow fibers function as outer electrode elements and enable heat exchange.
  • Figure 37 is a side elevation in cross section of a fuel cell with heat exchange/current collector hollow fibers.
  • Figure 38 is a cross-sectional elevation view of a fuel cell module with heat exchange from current collectors by means of conduction.
  • Figure 39 is a schematic depiction of a fuel cell system, according to one embodiment of the invention.
  • Figure 40 is a cross-sectional view of a double membrane design with an electrically conductive perm- selective membrane on the anode or cathode element of the microcell.
  • Figure 41 is a cross-sectional view of a double separator design with perm-selective membranes protecting the anode or cathode elements of the microcell.
  • Figure 42 is a cross-sectional view of a double separator design with perm-selective membranes covering both anode and cathode elements of the microcell.
  • Figure 43 is a cross-sectional view of a double separator design with perm-selective membranes covering both anode and cathode elements of the microcell and with a porous, electrically conductive inner separator.
  • Figure 44 is a cross-sectional view of a double separator design with perm-selective membranes covering both anode and cathode elements of the microcell and with reformer catalyst on the inner wall of the inner separator.
  • Figure 45 is a schematic flowsheet of a solution impregnation system for impregnation of a membrane fiber with Nafion or electrocatalyst.
  • Figure 46 is an elevation view of a metallic fiber having a polymeric compound on its outer surface.
  • Figure 47 shows the corresponding fiber of Figure 46 after pyrolysis, with a pyrolyzed carbon coating on the outside surface thereof.
  • Figure 48 shows a fibrous carbon current collector laid along a coated metallic fiber.
  • Figure 49 shows the fiber assembly of Figure 48 after a disconnection break of the coated metallic fiber.
  • Figure 50 shows a cross-section of a hollow fiber and microcell tube bundle, in which the plane hollow fiber elements are used for channeling water from the assembly.
  • Figure 51 shows a vertically upward extending bundle of microcells, arranged so that water from the module drains to a lower plenum space for removal.
  • microcell refers to an electrochemical cell energy generation or conversion structure, including a porous membrane separator having electrolyte disposed in porosity thereof.
  • the porous membrane separator is in contact with electrically conductive fibers that in turn are in contact with or are coated with electrocatalyst forming positive and negative electrodes for the electrochemical cell.
  • a battery cell of course differs from a fuel cell in that the (electrode) active material in a battery is present and stored in the cell, as opposed to being externally furnished to the structure when electrochemical activity is desired.
  • the microcell when used in a battery cell, does not require a lumen at the center of the fiber, thereby correspondingly simplifying the bundling of fibers in modular assemblies for battery cell applications.
  • Microcells for battery cell applications thus have structural and operational differences from microcells used in fuel cells.
  • the microcell comprises an inner electrode active material, a microporous membrane separator in contact with the inner electrode active element, electrolyte in pores of the microporous membrane separator, and an outer electrode active element, wherein each of the inner and outer electrode active elements comprises at least one of electrode, current collector and electrocatalyst components.
  • the microcell may include a fibrous, inner electrode that is encapsulated by a microporous membrane separator with an electrolyte disposed in porosity of the microporous membrane separator, and with electrocatalyst impregnated or coated on the bore or shell side of the fiber (to form an inner or outer electrode, respectively) along with electrically conductive material.
  • the bore of the microcell hollow fiber defines a lumen for passage therethrough of gaseous or liquid feed (e.g., fuel or oxidant) components.
  • gaseous or liquid feed e.g., fuel or oxidant
  • electrolyte types can be used in the microcell fuel cell, depending on the specific application involved.
  • microcells are fabricated in a single fiber assembly.
  • the microcells can be of any predetermined length, typically with a length to diameter ratio significantly greater than 1, and are readily formed into microcell assemblies, including bundled forms as hereinafter described in greater detail.
  • Such microcell assemblies, or collections of such assemblies, may be aggregated to form a fuel cell module, similar in overall arrangement to a shell and tube heat exchanger.
  • the resulting compact unitary configuration provides high density energy output and enables minimization of the volume (and "footprint") of the fuel cell or other electrochemical cell apparatus fabricated from such bundles.
  • the microcell apparatus of the invention in one embodiment is fabricated with the inner electrode (or a multiplicity of current collector fibers) being encapsulated by a microporous membrane separator.
  • the electrocatalyst of the inner electrode in such embodiment is coated or impregnated on the inner wall of the membrane separator (or coated on the inner current collector fibers).
  • the electrocatalyst in one embodiment is impregnated onto the membrane separator wall from a catalyst solution.
  • a thin ink formulation of the catalyst is pumped through the bore of the membrane separator during the membrane spinning process.
  • One technique of forming porous separator membrane-electrode assemblies involves coating current collector fibers with an electrocatalyst formulation. Such coating in one embodiment is carried out in an extrusion process. In another embodiment, the current collector fibers are coated from a plating solution, hi yet another embodiment, the current collector fibers are coated by plasma deposition of a metal catalyst.
  • microcell fibers are bundled and potted in order to isolate and seal the bore side and the shell side of the cells.
  • microcells may be bundled around a perforated mandrel, such that the mandrel becomes the gas input structure for the shell side of the cells.
  • any suitable means and method for electrolyte impregnation or incorporation are usefully employed.
  • An illustrative and preferred technique for impregnation of the electrolyte is solution impregnation.
  • the porous membrane separator element itself can be of widely varying type and structure, and formed for a specific type of fuel cell or other electrochemical cell application.
  • an asymmetric channelized porous structure is preferred to provide a contiguous phase of the ion exchange polymer adjacent to the electrocatalyst layer.
  • a foam-like structure of the porous membrane element is desirable.
  • Fuel cells formed from microcells in accordance with a preferred aspect of the invention are monopolar and do not require bipolar flow field plates. Since the cells and current collectors are in fiber form, a high level of electrode surface area can be compacted in very small volumes. In parallel connection of individual bundled cells, wherein current is additive, very high current density per unit volume is achievable, allowing the microcell assembly to operate at high voltage and high efficiency.
  • inner electrodes of respective microcells are connected to form a first terminal of a microcell assembly, and current collectors on the outer shell of the fiber elements or on the outer shell of a bundle of such microcells, forms a second terminal.
  • fuel and oxidant are passed over electrodes on the corresponding respective shell and bore sides of the bundle.
  • the microporous membrane is impregnated with an appropriate electrolyte and forms a barrier or separator element.
  • the microporous matrix and electrolyte can combine to form a new structure in the form of a solid matrix or a liquid-solid matrix.
  • the size of the inner electrode element is selected to provide an appropriately dimensioned lumen on the bore side of the membrane separator containing the electrode.
  • Multiple fibers can also be positioned in the bore of a hollow fiber membrane separator to provide interstitial space forming a lumen in the hollow fiber. The formation of the lumen is important since the lumen allows (liquid or gaseous) fuel or oxidant to reach the inner electrode in the operation of the fuel cell.
  • an electrocatalyst and the electrically conductive material of a second electrode is coated, extruded or impregnated on the outer shell of the microporous membrane separator and electrolyte is disposed in the micropores of the membrane separator, to complete the microcell structure.
  • the microporous membrane separator may be formed of any suitable material of construction.
  • the microporous membrane separator is fabricated from a material selected from the group consisting of semi-permeable, ion-exchange membranes, and a porous membrane coated on a shell or bore side thereof with a penn-selective or an ion-exchange polymer.
  • the inner electrode or current collector is retained in a tightly-held manner in the bore of the separator and is contiguous to the inner wall of the fiber, for interfacial contact with the electrolyte or electrolyte/electrocatalyst layer.
  • the outer electrode or current collector also makes intimate contact with the shell side electrolyte, or with the electrolyte/electrocatalyst layer of adjacent cells, when the fibrous microcell structures are densely bundled with one another. Accordingly, the lumen of the microcell structure in fuel cell applications must be sufficiently "open” to allow passage of the gaseous feed (fuel or oxidant) through the lumen during normal operation.
  • the fuel cell apparatus desirably includes a pump, fan, blower, compressor, eductor, or the like. Since the flow rates required for fuel cell operation entail relatively low pressure differentials, pumping requirements (for gaseous feed flow through the lumen of the microcell hollow fiber) are readily accommodated by commercially available fluid driver devices of the above- mentioned types.
  • microcells are connected together in parallel.
  • Parallel connection of microcells for such purpose is readily effected by bundling the microcells in parallel relationship to one another and connecting the end portions of the current collectors at each extremity of the resulting microcell assembly.
  • microcells hi order to achieve high voltages, however, above the voltage afforded by a single microcell, it is necessary to connect microcells in series with one another. As described more fully hereinafter, various methods may be employed to effect series connection, depending on the geometry of the microcell assembly that is desired. For example, a rectangular configuration or a cylindrical configuration may be desired.
  • a sub-bundle of parallel fibrous microcells is first constructed to obtain the desired current.
  • the sub-bundles then are connected in series to achieve a desired voltage.
  • One preferred approach to forming a sub-bundle microcell assembly is to form a sheet arrangement of generally parallelly aligned microcell elements, wherein the microcells are in side-by-side relationship to one another, with the current collectors extending from one end of the generally planer sheet, in side-by-side register with one another (i.e., so that the current collector ends are generally arranged in a single plane with respect to one another, or otherwise so that the current collectors protruding from the microcells are generally coextensive in length relative to the face of the microcell sheet assembly from which they protrude).
  • the first layer of microcell elements is overlaid by a second layer comprising outer current collector elements, arranged so that the outer current collectors extend from an opposite side of the superimposed sheet from that from which the inner current collectors protrude.
  • the outer current collectors likewise extend outwardly to a generally same lengtli, so that the ends of the outer current collectors are in register with one another, residing generally in a single vertical plane relative to a flat, horizontal plane of the sheet assembly.
  • the constituent fibrous microcell elements in the first layer may be secured to one another to provide a unitary web or sheet form of such elements.
  • the outer current collectors overlaid on the fibrous microcell elements may be secured to one another to a sheet or web confirmation, such as by an inner connecting mesh or woven structure, transversely laid strips of adhesive tape, or other means by which a parallel assembly of current collector elements is provided.
  • any suitable means and methods may be employed to form the respective sheet-like layers of the microcell assembly just described.
  • Such layers can be pre-formed, for example, by weaving the microcell or current collector fibers into sheets or embedding them in a resinous matrix, or in any other suitable manner.
  • the composite structure then can be rolled into a cylindrical shape and potted at each of respective opposite ends, to form a sub-bundle assembly comprising a multiplicity of microcells.
  • Potting of such assembly can be carried out in any suitable manner, using methods conventionally employed to pot hollow fiber membranes, e.g., in the fabrication of hollow fiber filtration modules.
  • Each resultant potted sub-bundle thereby has a positive and negative terminal at each end, with one such terminal being formed by the inner current collector elements protruding from the microcell elements of the first-described layer, and the other terminal being formed by the outer current collector elements protruding from the opposite end of the sub-bundle.
  • Sub-bundles then are connected in series by connecting the positive terminal of a first sub-bundle to a negative terminal of a next sub-bundle, and so on in consecutive fashion.
  • the resulting long strand of connected sub-bundles then is re-bundled into a cylindrical shape, by folding each bundle in an alternating fashion at each end and at the connection between each succeeding microcell.
  • the resulting assembly of sub-bundles folded into parallel arrangement with one another then is potted again at each end thereof to form a bundle as a composite structure comprising a multiplicity of sub- bundles.
  • each sub-bundle may be covered or encased with a porous yet electrically insulating material. Accordingly, each sub-bundle may be sheathed or sleeved in a fiberglass or polymeric material encasement member, in to which the sub-bundle may be inserted or about which the encasement material may be wrapped.
  • Sub-bundles alternatively may be formed and the packed into a bundle by alternating each end so that a positive terminal end of a sub-bundle is in proximity to a negative terminal of another sub-bundle.
  • the sub-bundles in this alternative teclinique can first be potted and then connected in series, by connection of the positive terminal of a first sub-bundle to a negative terminal of a next adjacent sub- bundle.
  • the sub-bundles may be connected simply be maldng an electrical connection between each microcell.
  • an end plate having a mirror image of the location of sub-bundle connection nodes (where all the microcell fibers are connected in parallel in a sub-bundle) on its face, and an imprint of series connections of the terminals designed and built into the plate may be employed, so that electrical connection of the plate with each node of the bundle will automatically yield a series connection.
  • each sub-bundle may be fabricated with a sealed tube sheet member at each end. Each sub-bundle then can be inserted into a casing having openings at each end thereof that are the same size as the parameter (outer circumference) of the sub-bundle.
  • each sub-bundle may be sealed at each respective end of the housing, e.g., with O-ring seals or other sealing means, without the requirement of having to pot the sub-bundles again.
  • each sub-bundle can be removed from or introduced to the housing in a simple and readily affected manner, allowing for increase or reduction in power generation capacity of the overall microcell apparatus.
  • a sub-bundle article can be fabricated in a rectangular confi ⁇ nation by placing layers of microcells and outer current collectors over each other in alternating and repeating sequence to achieve a desired height and rectangular cross-section.
  • the constituent layers of microcell fibrous elements and outer current collectors can be preformed in sheet-like form, as previously described.
  • the current collector elements are generally of similar length characteristics to the fibrous microcell elements, such that respective fibrous microcell element and outer current collector layers are longitudinally off-set in relation to one another.
  • the outer current collector elements are longitudinally displaced beyond one end of the fibrous microcell element layer, and is correspondingly shorter at the opposite end so that the first layer (underlying layer) of fibrous microcell elements extends beyond the ends of the layer of outer current collectors.
  • a layer of porous, electrically insulating sheet material is placed, and a second sub-layer assembly then is formed on the porous, electrically insulating sheet, hi the second sub-layer assembly, a bottom layer is placed directly on the porous, electrically insulating sheet and overlaid with a layer of outer current collectors, off-set from one another, and arranged such that the positive tem ⁇ ial of the new sub-layer is on the same side of the overall assembly as the negative terminal of the first sub-layer.
  • This pattern of fabrication is continued until a desired sub-layer height is reached and a desired voltage is achieved.
  • the ends of the respective positive and negative current collectors from each end are then connected to each other with, for example, an electrically conductive rod or strip member, as hereinafter described.
  • the layered assembly may be fabricated, with electrical connection of the fiber sheets with positive and negative ends from adjoining sub-layers initially, prior to stacking of the respective sub-layers.
  • a final stack of sub-layers is then potted at both ends of the assembly, to isolate and seal the bore of the sub-layer assembly from the shell side.
  • the potted bundle of the fiber stack then can be placed on a perforated duct that will function as a feed inlet to the shell side of the hollow fibers in the assembly.
  • the fibrous microcell elements and the outer current collectors can alternatively be potted as the fibers are being layered, e.g., by depositing a line or bead of epoxy or other potting compound at both ends as the respective layers are being laid.
  • the viscosity of the potting material is suitably chosen so that complete wetting of the fibrous microcell elements takes place, to ensure leak- tightness of the resultant tube sheet.
  • the bundle or stack of microcell layers is placed in a housing such that the shell and bore of the microcell elements are sealed and isolated when a feed is introduced on either side (shell side or bore side).
  • the resulting unit has the confirmation of a rectangular shell and tube heat exchanger, and such unit is advantageously fabricated with at least one inlet to the housing for introducing feed to the bore side and at least one outlet in the housing for removing depleted feed from the bore side.
  • microcell elements When the microcell elements are provided in a stack of layers, such stack is placed on a duct perforated between the potting members at respective ends.
  • a non-perforated section of the duct extends through one end of the housing, e.g., with the feed inlet or outlet on the bore side of the microcell elements, as described, and with the duct extending sealingly tlirough the housing to provide a feed inlet to the shell side of the microcell elements.
  • the layered microcell stacks may be placed on both sides of a perforated feed duct to form a symmetric double stack, as hereinafter described in greater detail.
  • small sub-bundles of microcell assemblies can be electrically connected in series in the same cell housing, or smaller fuel cell modules can be electrically connected in series to increase the overall cell voltage.
  • One approach for achieving high voltage levels is to manifold fuel cell stacks (each comprising a plurality of microcell devices) to gas feeds in a parallel fashion, with the stacks themselves being series-connected assemblies of microcell bundles.
  • electrically conductive fibers are bundled with microcell devices, so that the electrically conductive fibers function as current collectors on the shell side of the fibers.
  • the shell side current collectors, or alternatively the outer electrodes coated with suitable electrocatalyst, are connected to a common plate to constitute a first terminal for the bundled assembly.
  • inner electrodes extending through the bore of the microcell fibers are connected to a plate forming a second terminal for the assembly.
  • fuel or oxidant is passed over the electrodes on the corresponding respective bore or shell side of the fibers, and the electiOlyte-incorporating membrane separator prevents migration of the fuel or oxidant to the other electrode.
  • the microcell fiber structures are usefully potted to form sub-bundles of a larger ultimate bundled structure, with the sub-bundles being connected in series or parallel (or, as discussed hereinafter, some structures or sub-bundles can be parallel connected, with the parallel- connected assembly of microcell elements then being series-connected to other sub-bundles; the converse arrangement, wherein series-connected microcell elements form sub-bundles that are parallel-connected to one another, also is usefully employed in some applications).
  • sub-bundles of the microcell fiber structures are fabricated, and then the sub-bundles are aggregated with other sub-bundles, and potted again to form the fuel cell module.
  • the potting medium advantageously used for such structural fixation of the microcell fiber structures or sub-bundles is any suitable potting or encapsulant medium, such as epoxy, urethane, silicone, EPDM rubber, or other encapsulant media.
  • the sub-bundles can be made with tube sheets at each end with O-ring seals, similar to the process employed in the final module assembly, and with the sub-bundles then inserted in a metal or polymeric sheet material having holes formed in it.
  • the fuel cell casing then will have two faces, one at each end, with holes cut into it the size of the outer diameter of the sub-bundled tube sheet.
  • sub-bundles can be added to or removed from the overall module to increase or decrease power (e.g., in a power source for stationary application, or alternatively for motive transport applications such as electrical vehicles, to provide adjustable vehicle power).
  • the holes in the faces can be sealed with blank sheets of the same size as the holes, if sub-bundles are removed from the module.
  • This feature also provides capability for servicing individual sub-bundles, by removing defective sub-bundles and replacing them with new sub-bundles.
  • the sub-bundles can themselves be potted units comprising smaller sub-bundles.
  • FIGS 1-4 are perspective views of fibrous element structures illustrating the fabrication of a microcell assembly.
  • a fibrous microcell element sheet 10 is formed of a plurality of fibrous microcell elements 12, laid side by side one another in parallel alignment.
  • the respective fibrous microcell elements 12 can be consolidated by a plurality of sewn seams 16 as shown, or by use of tape, adhesive bonding or other method of affixation to produce a unitary fibrous microcell element sheet.
  • the sheet 10 as illustrated is aligned with first ends 18 of the elements 12 being in transverse register with one another, i.e., the ends are generally coextensive in axial extent with one another, so that the ends 18 lie in a common vertical plane extending across the face of the sheet from which the internal current collectors 14 protrude.
  • the opposite ends 20 of the fibrous microcell elements 12 are in transverse register with one another, with the ends generally aligned with one another in a transversely extending vertical plane at the opposite face of the fibrous microcell elements 12.
  • the fibers are laid flat adjacent to one another and consolidated in a web structure, to form a sheet of fibers.
  • a plurality of external current collectors 24 are likewise secured together in parallelly aligned side by side arrangement, by a sewn seam 26, or alternatively, a tape, glue strip, or other consolidating means, to form a sheet 22 as shown in Figure 2.
  • the respective ends 28 and 30 of the constituent current collectors 24 are in register with one another so that all ends of the fibrous current collectors at each extremity of the web lie in a transversely extending vertical plane at such extremity.
  • the sheet 10 of fibrous microcell elements 12 and the sheet 22 of fibrous current collector elements 24 are stacked, with the current collector sheet 22 on top of the fibrous microcell elements sheet 10, to form a conjoint structure 32 as shown in Figure 3.
  • the respective sheets 10 and 22 are longitudinally off-set with respect to one another, so that the internal current collector elements 14 of sheet 10 extend beyond the ends of the external current collectors of sheet 22 as shown, and with the external current collectors of sheet 22 correspondingly extending beyond the ends of the internal current collectors 14 of sheet 10 at the opposite end of the conjoint structure.
  • the respective external current collectors of the overlying sheet 22 thus are in contact with associated fibrous microcell elements in the underlying sheet 10.
  • the conjoint structure 32 of Figure 3 is a bottom layer of an assembly that is formed by overlying the bottom layer with a second layer 36 including a parallely aligned arrangement of fibrous microcell elements 38 forming a corresponding sheet, and overlaid in the second layer by a sheet including external current collectors 48 secured together by a sewn seam 40 as shown.
  • the fibrous microcell elements 38 are in register with one another at their respective ends 42 and 44, and the sheet of external current collectors 48 is longitudinally displaced from the sheet of fibrous microcell elements 38.
  • the external current collectors 48 extend beyond the ends 42 of the fibrous microcell elements 38, and the internal current collectors 46 of the fibrous microcell elements 38 extend beyond the ends of the external current collectors 48.
  • the longitudinally protruding current collectors from the respective first and second layers at each of the ends of the assembly are coextensive in axial extent with one another.
  • a porous insulating layer of polymeric or fiberglass sheet 50 is placed between the layers 32 and 36, as shown in Figure 4.
  • Figure 5 is a perspective view of a comiector 52 for joining current collector or electrode elements of a microcell fiber assembly.
  • the connector 52 has two leaves 54 and 56 that are at a 90° angle in relation to one another, with the leaves being crimpable toward one another. When a group of current collector or electrode elements is placed between the leaves of the connector and the leaves are crimped together, the current collector or electrode elements then are secured in electrical contact with one another.
  • Figure 6 shows the microcell assembly of Figure 4, with the current collector elements at the right- hand portion of the drawing shown as being secured to the connector 52 so that the current collector elements are coupled in electrical contact with one another.
  • FIG. 7 is an exploded perspective view of a microcell assembly 70 showing series connected microcell sheet layers 60, 62, 64 and 66.
  • the bottom sheet layer 60 comprises internal current collector elements that are connected by connector 72, and the overlying sheet of external current collectors in such layer are in turn joined to connector 74.
  • the next upper layer in the assembly includes internal current collectors connected by connector 78, which is joined by interconnect 76 to connector 74, as well as external current collectors joined to connector 80.
  • Connector 80 is joined by interconnect 82 to connector 84 of the next upper layer in the assembly.
  • Connector 84 connects the internal current collectors of such next upper layer, and the connector 86 at the opposite end of the layer connects external current collectors of the layer to the connector 90 of the top layer in the assembly via interconnect 88.
  • Connector 90 connects the internal current collectors of the top layer in the assembly and the external current collectors at the opposite end of the top layer of the assembly are connected by connector 92.
  • Each of the constituent layers in the assembly is separated from an adjacent layer by a corresponding porous insulative sheet 94, 96 and 98, respectively.
  • each of the constituent layers in the assembly of Figure 7 is joined to a next adjacent layer in head-to-tail series relationship, as is evident from the indicated polarity of the respective connectors in the drawing.
  • Figure 8 is a schematic view of an assembly 100 comprising a layered arrangement of microcell layers joined in series relationship, including layers 102 and 104, separated by porous insulating sheet 110, layers 104 and 106, separated by porous insulating sheet 112, and 106 and 108, separated by porous insulating sheet 114.
  • Figure 9 is a three-dimensional perspective view of a series-connected arrangement 130 of microcell layers.
  • the lowermost layer is illustrative and comprises a sheet of fibrous microcell elements 122 from which internal current collector elements 124 protrude at the left-hand side of the layer, with overlying sheet of external current collector elements 126 completing the microcell layer.
  • the lowermost layer is shown as being electrically segregated from the next upper layer by a porous insulating layer 128, as schematically illustrated.
  • the other layers are analogously constructed.
  • the uppermost layer 130 as shown comprises three fibrous microcell elements arranged in side-by-side relationship, and the other sheets of fibrous microcell elements in the assembly are correspondingly constituted, hi this manner, a bundled microcell structure is fo ⁇ ned.
  • Figure 10 shows a potted arrangement 136 of microcell sub-bundles 138, in which component sub- bundles are connected by series connection of their respective opposite current collector elements 140 and 142, wherein adjacent sub-bundles are separated from electrical contact and potential short- circuiting by porous, insulative sheet 147.
  • the sub-bundles 138 are potted at their respective ends by potting members 144 and 146.
  • Figure 11 is a perspective view of a duct 150 that is perforated with openings 154 on the top surface 152, and optionally on the bottom surface (not shown in the view of Figure 11) for double stack bundles of the microcell layers.
  • Two retaining walls 156, 158 are on each side, to retain the fiber sheets in position. Fibers are stacked on top of each other on the perforated duct until the desired voltage is achieved.
  • a fluid ingress/egress conduit 160 is joined to the interior plenum chamber of the duct 150, as shown.
  • Fiber sheets can be potted with epoxy as they are laid.
  • the fiber sheets can be bundled and potted in the vessel to finish the procedure. Fibers are potted at each end such that the open end remains open.
  • the perforated duct will be the feed port to the shell side of the fibers.
  • Figure 12 shows a cross-sectional elevation view of a fiber bundle 162 potted in a vessel 150.
  • the fiber bundle comprises layers 164 and 166 of fibrous microcell elements, with an interposed sheet 168 of external current collector elements and with a separator sheet 170 of porous insulative material between adjacent current collector and fibrous microcell element sheets.
  • the bundle is potted by potting member 163.
  • Figure 13 is a side elevation view of the vessel of Figure 12, showing the retaining wall 156, and fluid ingress/egress conduit 160 of the housing, as well as the terminal connections at the respective faces 180 and 182 of the bundle.
  • Figure 14 shows a potted arrangement 186 of fibrous microcell element sheets, in two sub-bundles 188 and 190 on opposite sides of feed duct 196 receiving feed gas via inlet 198.
  • the feed duct has perforations on both top and bottom surfaces, and each of the constituent sub-bundles is potted with the top sub-bundle being potted by potting member 192 and the bottom sub-bundle being potted by potting member 194.
  • Figure 15 shows a side elevation view of a double stack arrangement 200, comprising a stack of microcell elements on either side of the perforated duct.
  • the gas feed 198 is shown in the drawing.
  • the arrangement shown in this drawing includes connector/terminal elements 202, 204 and 206 connecting the corresponding current collector elements.
  • Figure 16 is a perspective view of an assembly 210 of potted fibrous microcell elements on one side of a perforated feed duct including gas inlet 224 and retaining wall 216.
  • the potted rectangular bundle of microfibers is arranged with its respective ends potted by potting members 218 and 220.
  • FIG 17 shows a corresponding vessel 230 when fibers are laid on both sides of the perforated feed duct 238.
  • the vessel comprises a central section 232 with an outlet 242 for discharging gas from the shell side of the microcell assembly, end section 234 featuring outlet 248 for exhausting bore-side spent gas and end section 236 with inlet 246 for introducing bore-side gas into the housing.
  • the perforated feed duct is arranged to introduce feed gas into the central section 232 of the housing for flow on the shell side thereof.
  • Figure 18 is a sectional elevation view of system 250 including a microcell bundle 280 potted at respective ends thereof by potting members 266 and 268, which are leak-tightly secured to the inner surface of the housing 252 by O-ring elements 270 and 272.
  • the housing 252 has a flange element 256 joining the end section 258 of the housing with the central section.
  • the central section of the housing contains interior volume 252, which is separated from end volume 278 by potting member 268 and from end volume 282 by potting member 266.
  • Feed inlet 276 communicates with end volume 278 and end volume 282 communicates with spent gas outlet 284.
  • Spent gas outlet 264 communicates with the interior volume 262.
  • Feed tube 260 extends into the center of the microcell bundle 280 in the interior volume 262, and is perforate along its length to introduce feed gas to the shell side of the microcell bundle 280 in the interior volume, with the spent gas being discharged in outlet 264.
  • Feed introduced into end volume 278 from inlet 276 flows tlirough the bore side of the microcell elements in the bundle 280, and flows out of the bundle into end volume 282, following which it is discharged from the housing 252 in outlet 284.
  • the current collectors are joined to terminal 292 in the end volume 282, with the terminal structure extending exteriorly of the housing 252.
  • terminal structure extending exteriorly of the housing 252.
  • terminal 290 extends exteriorly of the housing.
  • Figure 19 shows a perforated feed tube 300 with open ends 302, having perforations 308 along a central part 306 of its length.
  • Figure 20 shows fibrous microcell and shell side current collector sheets 312, 314 that can be rolled or wound around the perforated tube 300 of Figure 19, with the sheets being shown during rolling in Figure 21 and as finally rolled into shape in Figure 22.
  • the sheets will be placed on top of each other such that the ends of the fibrous microcell sheet 312 extend farther than the shell side current collector sheet 314 on one side, and the shell side cunent collector sheet 314 extends farther on the other side.
  • the sheets 312, 314 then are wrapped tightly around the perforated tube 300 and then potted by potting members 322 and 324.
  • Figure 23 shows sheets 332, 334 of fibrous microcells and shell side current collectors, and an insulating sheet 330 (e.g., of fiberglass or porous plastic material).
  • Figure 24 is a perspective view of a sheet assembly 338, 340, 342, 344 and 346, including two sheets of fibrous microcells and shell side current collectors.
  • Figure 25 is a side elevation view of a microcell assembly 338, 340, 342, 344 and 346 with off-set fiber layers.
  • the electrically insulating sheet is placed between two layers of fibers forming a cell. If the sheets on either side of the insulator are extended beyond the edge of the insulator as shown in Figure 25, then the fiber layers can be connected to one another in series.
  • Figure 26 is a cross-sectional view of a microcell bundle 350 comprising an assembly of positive electrodes 354 interspersed with negative electrodes 352 in a bundled conformation.
  • Figure 27 is a side elevation view of series-connected microcell sub-bundles 360 including sub- bundles 362, 366, 370 and 374 interconnected by connectors 364, 368 and 372, respectively.
  • the connectors are desirably highly flexible and most preferably omnidirectionally flexible to accommodate accordion folding of the chain of sub-bundles, so that when folded back against a preceding sub-bundle or folded forwardly against the succeeding sub-bundle.
  • Figure 28 is a perspective view of a connector 376 that may be used to join component microcell sub- bundles in series.
  • the connector 376 comprises a spaced-apart pair of crimpable leaves 378, 380, each of which is crimpable by means of a pliers or similar tool, to compressively grip a protruberant group of current collectors of a sub-bundle.
  • the leaves are electrically conductive, and are themselves interconnected by a flexible yoke element 382, which may comprise wire or metal filament, etc. that serves to electrically interconnect the respective sub-bundles with which leaves 378 and 380 are coupled.
  • Figure 29 is a cross-sectional elevation view of a multibundle assembly 390, wherein each bundle 391 has a corresponding feed tube 394 associated therewith, and is mounted in a tubesheet 393 and leak- tightly sealed therein with an O-ring sealant element 392.
  • Figure 30 is a cross-sectional elevation view of the multibundle assembly of Figure 29, wherein the respective bundles are connected in series and are numbered correspondingly to Figure 29.
  • the respective adjacent bundles are interconnected by terminal elements 396 and 400 joined to one another by coupling wire 398 in series arrangement.
  • Figure 31 is a cross-sectional view of a fuel cell module with multiple sub-bundles, numbered correspondingly to Figure 29, and wherein blank seal elements 402 and 404 provide closure members for the tubesheet 393 of the module enclosure, when sub-bundles are removed.
  • Figure 32 is a side view of a fuel cell module 410 with multiple sub-bundles 460, 462 and 464 of microcell elements, with a feed tube 450 in a manifolded arrangement.
  • the module includes a housing 422 enclosing a central interior volume 424 bounded by the housing wall of the module and by tubesheets 472, to which the sub-bundles are leak-tightly secured by means of O-ring elements 438, and 474, to which the sub-bundles are leak-tightly secured by means of O-ring elements 434.
  • the end sections of the housing enclose respective end volumes 426 and 428.
  • the end volume 426 contains a manifold to which the feed tube 450 is joined in gas flow communication, for introduction of feed gas to each of the three sub-bundles 460, 462 and 464 by means of the manifold line 452 in communication with branch lines 454, 456 and 458 coupled to the respective sub-bundles.
  • connection line 440 interconnecting sub-bundles 460 and 462 and connection line 442 interconnecting sub-bundles 462 and 464.
  • connection line 442 interconnecting sub-bundles 462 and 464.
  • the exterior sub-bundles in such series are in turn joined respectively with terminals 444 and 446, as shown.
  • the right-hand end section of the housing is flangedly connected to the main central section of the housing by flange 430, with which mechanical fastener means may be coupled to leak-tightly secure the component sections of the housing to one another.
  • the housing is provided with a feed inlet 466 for introducing one of the fuel and oxidant streams into the end volume 426 for flow through the sub-bundles on the bore side thereof.
  • An outlet 468 is joined to the housing 422 at the left-hand section as shown, for discharge of spent feed gas from the end volume of the housing.
  • the spent gas outlet 470 is provided in the main central section of the housing, for discharge of spent feed from the shell side of the sub-bundle in the interior volume 424 of the housing.
  • Figure 33 is a side elevation view in section, showing penetration of a feed tube 514 into the interior volume 506 of the housing 515 of a module 480 containing microcell sub-bundles 494, 496, 489 and 498.
  • the sub-bundles are mounted in correspondingly sized receiving openings in tubesheets 500 and 502, leak-tightly secured in the housing by means of O-ring sealing elements 492.
  • the internal volume of the housing is divided into a central volume 506 and end volumes 526 and 528.
  • the housing is provided with feed gas inlet 510, spent gas outlet 508 and spent gas outlet 512.
  • Spent gas on the shell side of the sub-bundle is discharged from the housing in outlet 508, and feed gas introduced in inlet 510 is flowed through the bore side of the sub-bundle and discharged into end volume 528. From end volume 528 bore side spent gas is discharged from the housing in outlet 512.
  • the sub-bundles in the interior volume of housing 515 are joined in series relationship to one another by means of series connector lines 516, 518 and 520, and the outside sub-bundles in the series arrangement are in rum joined to terminals 522 and 524.
  • the housing 515 is openable at flange 443 to remove the right-hand end section, following which the respective sub-bundles can be accessed for repair or replacement.
  • microcell articles in accordance with the present invention may. be readily connected in series with one another, with successive adjacent articles (fibrous microcell sheet layers, sub-bundles) being insulated from each other by sheets or sheathing of porous insulating electrically non-conductive material, or in other manner ensuring the absence of electrical interference between such adjacent microcell articles.
  • successive adjacent articles fibrous microcell sheet layers, sub-bundles
  • sheets or sheathing of porous insulating electrically non-conductive material or in other manner ensuring the absence of electrical interference between such adjacent microcell articles.
  • a bundle or sheet-form assembly of microcells is fabricated. For example, if a design current of 200 amps is required, a number of fibrous microcell articles are connected in parallel to generate the necessary current.
  • the resultant microcell structure then is either bundled in a cylindrical shape or used to form a multi-layered assembly.
  • the positive and negative fibrous elements must be electrically insulated yet in intimate contact with each other.
  • the sheets or bundles are connected in series, i.e., the positive of one cell is connected to the negative of the next adjacent cell.
  • the cells, bundles or sheets connected in series with one another are then potted and sealed in the same housing to provide the desired high voltage electrochemical cell module.
  • the resulting electrochemical energy generation or energy conversion device When microcell elements are bundled or otherwise aggregated in a compact structural configuration to form modular electrochemical cell assemblies, the resulting electrochemical energy generation or energy conversion device generates significant heat in its operation.
  • heat exchange tubes are distributed in the microcell bundles, sub- bundles, or other aggregated microcell assembly.
  • such heat exchange tubes are aligned parallel with the fibrous microcell elements in the microcell assembly.
  • heat exchange tubes are placed between sub-bundles in the assembly, so that the heat exchange tubes extend at least from one end of a tubesheet face (in which the extremeties or outer portions of the sub-bundles are mounted) to the opposite end.
  • the number, size, and material of the heat exchange tubes are readily determined based on the amount of heat that must be recovered, the fuel cell operating temperature, the type of heat exchange fluid used, and the pumping requirement or flow rate of the fluid, as will be appreciated by those skilled in the art.
  • the length of the heat exchange tubes can be selected such that the heat exchange tubes extend beyond the tube sheet that seals the bore side of the microcell hollow fibers from the shell side.
  • the extended heat exchange tubes then are potted again to form a barrier between the bore of the heat exchange tubes and the bore of the microcell hollow fibers.
  • the final assembly of the fuel cell module with the heat exchange tubes preferably includes the formation of a first housing with an inlet for the introduction of heat exchange fluid in one end, a second housing between the two potted sections, i.e., the potted heat exchange tubes and the potted microcell elements, with an inlet for introduction of feed to the bore side of the microcell, and with the structure of the housing being correspondingly constructed at the opposite end, to provide corresponding respective outlets for discharge of the heat exchange fluid and the spent feed.
  • An alternative thermal management design for microcell electrochemical cell modules according to the present invention employs hollow, nonporous, electrically and thermally conductive tubes, as current collectors for either the bore side or the shell side or both the shell and bore side of the microcell structures.
  • the heat exchange current collector tube will be potted as described hereinabove, to separate the heat exchange fluid housing from the bore side/feed only at one end. At the opposite end the heat exchange tube is terminated at the tube sheet.
  • This arrangement allows the heat exchange fluid and feed to the bore to be mixed at the outlet.
  • the heat exchange fluid does not enter the bore of the microcell to contact the catalyst or the electrolyte.
  • the feed to the bore and the heat exchange fluid can be supplied to the module in the same direction, such that the heat exchange fluid and the feed to the bore can only mix at the feed outlet from the microcells.
  • the heat exchange fluid then is recovered in a separate unit, or a plenum in the housing can be provided to collect the heat exchange fluid for recycle.
  • the separation of heat exchange fluid from the feed can be readily achieved, e.g., in the case where the feed is air or hydrogen gas.
  • the heat exchange fluid and the feed to the bore are the same (for example, air)
  • the heat exchange fluid and the feed can be allowed to mix without further separation requirement.
  • heat is removed from the microcell module by conduction of heat from the current collectors on the shell side or bore side of the microcell elements.
  • the ends of the current collectors are extended and immersed in a heat exchange fluid in a plenum inside the housing containing the microcell module or in a heat exchange passage located within the housing, at the feed inlet to or outlet from the fiber bores.
  • the inlet and outlet of the heat exchange passage are leak-tightly segregated from the interior volume of the microcell module.
  • Figure 34 is a cross-sectional view of a microcell assembly 530 in which heat exchange fibers or tubes 538 are provided in interspersed (distributed) relationship to the microcell bundles 532, as shown.
  • each microcell bundle is mounted in a correspondingly sized opening in a tubesheet 536, with the microcell bundle being leak-tightly sealed in such opening by means of an O-ring sealing element.
  • the microcell bundles 532 and heat exchange tubes 538 are potted to form tube sheet 536.
  • Figure 35 is a sectional elevation view of a fuel cell module, showing air/fuel passages and heat exchange passages thereof.
  • the fuel cell module 540 comprises a housing 541 in which a microcell assembly 550 is mounted, by means of potting members 552 and 554, which are circumferentially sealingly engaged with the inner wall of the housing by means of O-ring sealing elements 556 and 558. In this manner, there is formed an interior volume 560 in the housing, bounded by the potting members 552 and 554.
  • a gas discharge outlet 586 is provided in the main central portion of the housing, in gas flow communication with the shell side of the microcell elements in the assembly 550.
  • the fuel cell module of Figure 35 also features respective tubesheets 562, sealingly engaged with the inner wall of the housing 541 by means of O-ring sealing element, and tubesheet 578, sealingly engaged with the inner wall of the housing by means of O-ring sealing element 580.
  • an intermediate volume 576 is provided between the potting 552 and tubesheet 578, and an end volume is provided at the extremity of the housing, in the left-hand portion in the view shown.
  • an intermediate volume 568 is fonned between the potting member 554 and the tubesheet 562, as well as an end volume at the right-hand end portion of the housing in the view shown in Figure 35.
  • Coolant inlet 582 is provided at the right-hand end volume portion of the fuel cell module housing, and a coolant outlet 590 is provided at the left-hand end portion of such housing.
  • a feed inlet 584 is provided in communication with the intermediate volume 568 of the module and a spent feed outlet 588 is provided in flow communication with the intermediate volume 576 at the opposite end of the module.
  • a central feed tube 592 enters the vessel from the right-hand side thereof and extends centrally into the microcell assembly 550.
  • the feed tube is of a perforate character, to provide feed to the shell side of the fibrous microcell elements in the microcell assembly.
  • the housing 541 is provided with a flange 570 connection, secured by suitable mechanical fasteners, whereby the right-hand intermediate volume and end volume portion of the housing is removable to access the interior elements of the fuel cell module.
  • the coolant medium (from an external source, not shown in Figure 35) is flowed into the end volume 566 and passes through the open-ended heat exchange tubes 604 and flows axially tlirough such tubes to the opposite end volume 565, from which the coolant is discharged through outlet 590, and may for example be subjected to heat recovery for re-circulation of coolant to the inlet 582 in a continuous loop fashion.
  • feed oxidant and fuel
  • feed are introduced to respective shell side and bore side of microcell elements in the microcell assembly 550 to effect electrochemical reaction generating power transmitted to an external load through the respective terminals 600 and 602, which are joined to appropriate circuitry and external load componentry, for such purpose.
  • Figure 36 is a cross-sectional view of a microcell bundle 610 incorporating hollow fibers 614 interspersed with fibrous microcell elements 612.
  • the hollow fibers function as outer electrode elements, as well as enabling heat exchange.
  • the hollow fibers may be coated, impregnated or extruded with electrocatalyst material or otherwise configured for functional use as electrode elements, in addition to providing a throughbore passage in the lumen thereof, for flow of a heat transfer medium, e.g., air, there tlirough, to effect heat removal from the bundle, incident to electrochemical reaction heat generation in the operation of the microcell assembly.
  • a heat transfer medium e.g., air, there tlirough
  • Figure 37 is a side elevation in section of a fuel cell module utilizing hollow fiber heat exchange elements.
  • the fuel cell module 620 of Figure 37 comprises a housing 625, which is flanged with flange structure 624, to allow separation of the right-hand portion of the housing to be removed from the main central portion, to access internal structures of the module.
  • the housing 625 contains a microcell bundle 626 which is potted by potting numbers 628 and 630, and leak-tightly sealed against the interior wall surface of the housing 625, by O-ring sealing elements 632 and 634, to define an interior volume 636 within the housing bounded by the interior walls and respective potting members 628 and 630.
  • a tubesheet 640 In axially spaced relationship to the potting number 630 is a tubesheet 640, thereby defining an intermediate volume 660, which is sealed by O-ring element 642 against the interior wall of the housing.
  • the heat exchange tubes constituting current collectors terminate at tube sheet 628, with heat exchange/current collector tubes communicating with end volume 662 of housing 622.
  • an end volume 658 Exterior of the tubesheet 640 within the housing is an end volume 658.
  • a central feed tube 641 extends through the end-wall 622 of the housing and is centrally extended in to the microcell assembly 626. Such central feed tube is perforate within the microcell assembly, to provide fuel to the shell side of the assembly.
  • the right-hand portion of the housing is removable at flange 624 to provide access to the interior elements of the module.
  • the intermediate volume 660 is provided with an inlet 646 for introduction of fuel thereto for flow through assembly 626 to volume 662, the latter being provided with outlet 648 for discharge of spent fuel therefrom.
  • the intermediate volume 636 of the housing is provided with outlet 638 for discharge of shell side spent feed.
  • the end volume 658 of the module is provided with inlet 644 for introduction of coolant for flow through hollow fiber elements extending in to such volume, for axial flow through the hollow fiber electrode elements to the opposite end volume 662.
  • the hollow fiber heat exchange passages in this embodiment are formed by hollow fiber electrodes, and such electrodes are coupled in the respective end volumes to the corresponding terminals 652 and 656, as illustrated.
  • FIG 38 is a sectional elevation view of a fuel cell module with heat exchange from current collectors by means of conduction.
  • the module 700 includes a housing 702 containing microcell assembly 704, potted by respective potting numbers 706, sealed by O-ring sealing element 710, and potting number 708, sealed by O-ring sealing element 712.
  • An interior volume 720 is thereby defined, communicating with the outlet 740 for discharge of spent feed from the interior volume 720.
  • a central feed tube 714 extends centrally in to the microcell assembly 704 and is perforate over its length within the microcell assembly, to provide feed to the shell side of the assembly.
  • the end volume 724 of the housing 702 is provided with an inlet 742 for introduction of feed for flow through bore passages of the microcell assembly 704 to the end volume 722 from wliich spent feed can be discharged from outlets 732.
  • a heat exchanger 746 is contained in end volume 724 and joined in heat exchange contact with current collector elements of the microcell assembly.
  • a heat exchange fluid (from a source not shown in Figure 38) is introduced to heat exchange or inlet 748 and circulated there through for discharge from outlet 750.
  • the opposite end volume 722 contains a heat exchanger 780 with an inlet 728 receiving heat exchange fluid for flow there through and discharge from the second heat exchanger 780 through outlet 730.
  • the current collector elements at respective ends are joined in electrically conductive relationship to terminals 738 and 736.
  • the left-hand portion of the housing 702 is flanged by flange 726, whereby the housing can be readily opened to access internal elements of the housing.
  • Figure 39 is a schematic representation of a fuel cell system, according to one embodiment of the invention.
  • the fuel cell system 780 includes a microcell module 782, which includes a housing 784 having joined thereto a coolant medium inlet 810, a coolant medium outlet 792, a fuel inlet 794, an oxidant inlet 799, a spent fuel outlet 786 and a spent oxidant outlet 804.
  • the feed outlet 786 is joined to a discharge line containing back pressure regulating valve 788 therein, hi like manner, the spent oxidant outlet 804 is joined to discharge line 806 containing back pressure regulating valve 808 therein.
  • the respective back pressure regulating valve 788 and 808 may be modulated to control the rate and extent of electrochemical reaction involving the fuel and oxidant species.
  • the system includes fuel supply tank 798 joined by fuel feed line 796 to the feed inlet tube 794.
  • an oxidant tank 802 is provided, joined to oxidant feed line 800 coupled to oxidant inlet 799.
  • the system involves a coolant recirculation arrangement, including recirculation line 816 joined to coolant outlet 792 and having dispose therein a pump 818 and heat exchanger 820.
  • Heat exchanger 820 effects heat removal from the warmed coolant medium, so that same is recycled to the surge tank 814 for return in feed line 812 to coolant inlet 810.
  • the coolant medium is flowed through hollow fiber heat exchange tubes in the housing and is continuously recirculated to the surge tank to provide a hold-up inventory of coolant for high rate electrochemical oxidation.
  • Microcell structures are usefully employed in specific applications of the invention in a double membrane configuration.
  • microcell structures of such type are readily formed using an inner hollow fiber separator having an inner current collector and electrocatalyst of the inner electrode on its shell side.
  • Such inner hollow fiber separator is encapsulated by an outer hollow fiber membrane.
  • the pores of the outer hollow fiber membrane are impregnated with an electrolyte and the electrocatalyst of the outer electrode is coated on the shell side of the outer hollow fiber membrane, to form a double membrane microcell structure.
  • This double membrane microcell structure is advantageous to enable the inner hollow fiber separator to be used as a membrane to selectively allow permeation of feed (e.g., hydrogen or oxygen), as desired. This may be effected, for example, by coating the inner wall or the outer shell of the inner separator with a penn-selective material that preferentially allows the desired gas to permeate to the electrode.
  • feed e.g., hydrogen or oxygen
  • This double membrane design thus is advantageous in reducing or eliminating the exposure of the electrocatalyst or the electrolyte to potential poisonous impurities in the feed.
  • Materials that may be used in the perm-selective membrane include cellulose esters, polyimides, polysulfones and palladium.
  • the inner wall of the inner separator may be impregnated or coated with a CO-H 2 0 sliift low temperature reforming catalyst.
  • the shell side of the inner separator is coated with an anode or cathode feed-selective material.
  • Another double membrane design involves coating both anode and cathode with a hydrogen- or oxygen-selective material.
  • the protective perm-selective material on the shell side of the outer hollow fiber membrane must be electrically conductive to allow electrical contact between the current collector of the outer electrode and the electrocatalyst on the shell side.
  • a perm-selective material such as palladium can be used for such purpose.
  • an electrically conductive perm-selective material can be applied only to one of the cathode and anode components, if desired.
  • Yet another design utilizing double membrane fabrication employs an electrically conductive imier hollow fiber separator.
  • Such electrically conductive hollow fiber separator may be formed of sintered metal, carbon or graphite, hi some embodiments of such double membrane design, an inner current collector may not be needed depending on the electrical conductivity of the imier hollow fiber.
  • the inner and outer hollow fiber membrane can be of any suitable commercially available membrane material, including, for example, polypropylene, polysulfones, polyacrylonitrile, etc.
  • the membrane is treated to impart perm-selective characteristics, e.g., to selectively allow permeation of the feed gases (fuel, oxidant) while remaining impermeable to other gases and components (such as fuel impurities) that may be present.
  • a protective hydrogen-permeable barrier layer can be deposited by solution deposition, electrolytic coating, etc., to provide a film of palladium on the membrane surface that allows passage of hydrogen therethrough, but occludes nitrogen and oxygen.
  • Figure 40 is a cross-sectional view of a double membrane design of a microcell 900 with an electrically conductive perm-selective membrane on the anode or cathode element of the microcell.
  • the microcell 900 comprises an outer electrocatalyst layer 912, the microporous membrane/electrolyte matrix 910, electrocatalyst 908, an inner hydrogen- or oxygen-selective membrane 906, and current collector or electrode elements 902 in the inner bore 904.
  • Figure 41 is a cross-sectional view of a double separator design of a microcell 914 with perm-selective membranes protecting the anode or cathode elements of the microcell.
  • the microcell 914 comprises an outer electrocatalyst layer 930, the microporous membrane/electrolyte matrix 928, electrocatalyst 926, current collector or electrode elements 922, inner porous separator 920, an inner hydrogen- or oxygen-selective membrane 918 and an inner bore 916.
  • Figure 42 is a cross-sectional view of a double separator design of a microcell 932 with perm-selective membranes covering both anode and cathode elements of the microcell.
  • the microcell 932 comprises an outer hydrogen- or oxygen-selective electrically conductive membrane 948, electrocatalyst layer 946, the microporous membrane/electrolyte matrix 944 electrocatalyst 942, current collector or electrode element 940, inner porous separator 938, an inner hydrogen- or oxygen-selective membrane 936 and an inner bore 934.
  • FIG 43 is a cross-sectional view of a double separator design of a microcell 950 with perm-selective membranes covering both anode and cathode elements of the microcell and with an electrically conductive inner separator.
  • the microcell 950 comprises an outer hydrogen- or oxygen-selective electrically conductive membrane 966, electrocatalyst layer 964, the microporous membrane/electrolyte matrix 962, electrocatalyst 960, electrically conductive porous current collector or electrode element 958, an inner hydrogen- or oxygen-selective membrane 956 and an inner bore 952.
  • Figure 44 is a cross-sectional view of a double separator design of a microcell 970 with perm-selective membranes covering both anode and cathode elements of the microcell and with reformer catalyst on the inner wall of the inner separator.
  • the microcell 970 comprises an outer electrocatalyst layer 986, the microporous membrane/electrolyte matrix 984, electrocatalyst 982, current collector or electrode elements 980, an inner hydrogen- or oxygen-selective membrane 978, inner porous separator 976, CO water shift/reforming catalyst 974, and an inner bore 972.
  • the microcell device with most of its components desirably is fabricated in a single extrusion step, at high rate.
  • a critical aspect of the high-volume fabrication process is encapsulating the inner electrode with the microporous membrane separator.
  • a strand or tow of electrically conductive fibers can be passed through the center of the bore former tube of an extrusion mold (spimierette).
  • the material that will form the backbone of the microporous membrane separator, referred to as a "dope,” is extruded around the bore former tube in continuous fashion onto the strand or tow of electrically conductive fiber(s).
  • An internal coagulant fluid e.g., a gas such as nitrogen or a liquid such as water, is passed tlirough the bore former tube along with the inner electrode fiber(s) or fibrous current collectors).
  • the size of the microcell fiber is determined by the size of the orifice of the extrusion mold.
  • Such orifice can be widely varied in size, e.g., from as small as 100 microns or smaller, with the membrane correspondingly being as thin as a few microns in thickness.
  • An electrocatalyst paste is simultaneously extruded through the bore if the method of microcell fabrication utilizes an ink paste. Extruded fiber is immersed in a quenching bath or an external coagulant medium, such as water.
  • the microporous membrane structure is instantaneously formed around the inner electrode as the water-soluble pore former compound is leached out in the coagulant/quenching medium.
  • Pore structure, porosity and pore size of the membrane separator thereby are accurately controlled by selection and corresponding control of parameters such as the membrane dope formulation, type of coagulant used, temperature of the spinning operation, etc. Specific conditions are readily determinable for such process by simple experiment without undue effort, by those skilled, in the art.
  • microporous membrane separator A wide variety of materials is useful to form the microporous membrane separator, including, without limitation, polysulfone, polyacrylonitrile, other high temperature polymers, glass and ceramic materials.
  • microcell articles can be fabricated at high rate on a continuous basis.
  • microporous membrane separator-encapsulated inner electrode structure After formation of the microporous membrane separator-encapsulated inner electrode structure, such encapsulated structure is coated or impregnated on the outside (shell side) with an ion exchange polymer in the case of polymer electrolyte fuel cells, and/or electrocatalyst of the outer electrode.
  • an ion exchange polymer in the case of polymer electrolyte fuel cells, and/or electrocatalyst of the outer electrode.
  • Such exterior coating can be advantageously performed by a similar extrusion process.
  • Figure 45 is a schematic flowsheet of a. solution impregnation system 988 for impregnation of a membrane fiber 992 with Nafion or electrocatalyst.
  • the membrane fiber 992 is dispensed from a fiber spool 990 and passes, by action of the roller 994, through a solution bath 996 in which the fiber is impregnated.
  • the impregnated fiber then passes over guide roll 998 and through the bank of heating elements 999 for final collection on take up winder 1000.
  • Additional applications for electrochemical cells of the invention include production of chemicals.
  • Chemical synthesis applications are advantageously effected utilizing microcells fabricated in accordance with the invention, which provide: high current density per unit volume, as necessary for chemical synthesis; low internal resistance due to minimal electrode membrane distance (thickness); and high efficiency due to low mass transfer resistance.
  • microcells fabricated in accordance with the present invention may be utilized to generate hydrogen and oxygen where other forms of electric power are available.
  • hydrogen (or other fuel gas) generated by the cell can be stored and used for generation of electricity.
  • the structure can be directly passed through a solution of aqueous polymeric electrolyte, such as a solution of Nafion (5% solids in water and alcohol) polymeric electrolyte, to impregnate the pores of the porous polymeric membrane with the polymeric electrolyte.
  • aqueous polymeric electrolyte such as a solution of Nafion (5% solids in water and alcohol) polymeric electrolyte
  • the amount of the impregnated polymeric electrolyte may be selectively varied depending on the residence time of the porous polymeric membrane in the electrolyte impregnant composition, and the number of times that the structure is repetitively exposed to the composition (i.e., in single-pass or multi-pass fashion) during processing.
  • the microcell fibers in one process embodiment are dried and impregnated with platinum as the electrocatalyst material, using a plating solution containing H 2 [PtCl 6 ], following which the fibers are passed through a bath of reducing agent, such as sodium borohydride (NaBH 4 ), to reduce the platinum composition to elemental platinum metal.
  • reducing agent such as sodium borohydride (NaBH 4 )
  • This continuous technique according to one embodiment of the invention is used to impregnate only the outer shell of the membrane with platinum.
  • the inner wall of the membrane is impregnated after the fibers have been potted in the vessel by pumping the platinum plating solution through the bore of the fibers.
  • both the shell and the bore side of the fibers are impregnated after the fibers have been potted.
  • the electrocatalyst is coated according to another aspect of the invention by using platinum loaded on activated carbon of suitable particle size.
  • the platinum loading on the activated carbon particles typically is in the range of from about 5 to about 10 percent by weight.
  • a paste is prepared consisting essentially of platinum loaded activated carbon, Nafion ionomer as the binder, and a Teflon® polytetrafluoroethylene emulsion. The paste then is coated, or alternatively extruded, on the shell side of the fibers.
  • Coating of the paste inside the fiber wall may be accomplished in various ways.
  • the paste is coextruded while the porous membrane separator element is being spun around the current collector.
  • a second approach is to pre-extrude the paste around the current collector before inserting the current collector into the membrane fiber.
  • a thin paste can be pumped into the bore of the porous membrane separator element after the cell assembly and potting has been completed.
  • the electrolyte is deposited inside the porous membrane separator element, and the catalyst is applied by electrodeposition from a solution containing platinum ions, by an electrolytic plating solution process, or by an electroless plating solution process.
  • current collectors In applications of conventional fuel cell technology, current collectors generally have been limited to the use of graphite type materials.
  • Current collectors formed of aluminum or titanium can be coated with corrosion-resistant coatings such as gold, but such coatings tend to peel and delaminate from the current collector element under the severe corrosive conditions and thermal cycles" that characterize the fuel cell operation.
  • microcell elements permits current collector materials of construction other than graphitic materials to be employed.
  • Metal fibers utilized in microcell structures in the electrochemical cell module can be coated by variety of techniques to achieve durable corrosion resistance.
  • Useful coating techniques for such purpose include, without limitation, electrochemical deposition, electroless coating, dipcoating, extrusion, etc., using corrosion resistant metal compositions or polymeric materials such as polyanaline.
  • a preferred approach for coating metal substrates for use as current collector involves use of amorphous metal compositions deposited by plasma coating techniques. In general, better corrosion resistance is attributable to the amorphous nature of the coating structure. Further, various amorphous metal compositions generate extremely high surface areas. Examples of such high surface area metal compositions include nickel metal hydride electrocatalyst materials. The use of such high surface metal compositions coupled with the inherently high surface area of the fibrous geometry of the microcells enables such amorphous metal coatings to be effectively utilized for hydrogen storage capability in the fuel cell, a potentially significant structural and operational advantage.
  • the metal fibers can be coated with a polymeric precursor or other organic coating, and the coating then is carbonized. Carbonization of the polymer to form graphitic material on metallic fibers yields a coating that is conOsion resistant, yet possesses electrical conductivity that is higher than that of carbon or graphite alone.
  • the metal fiber is advantageously coated with a compound such as a polymeric material, following which the coated fiber is subjected to pyrolysis conditions for the polymeric material.
  • the fiber coating material is pyrolyzed and converted to carbon using techniques that are conventionally employed to form carbon fibers perse.
  • Formation of a continuous layer of carbon on a metallic current collector fiber produces a fiber that is electrically conductive radially and longitudinally and at the same time is corrosion- resistant due to the surface layer protecting the underlying metal from corrosive attack.
  • Figure 46 is an elevation view of a conductor element 1002 including a metallic fiber 1004 having a polymeric compound coating 1006 on its outer surface.
  • the fiber is coated in any suitable manner, e.g., by spraying, dip-coating, roller coating, etc.
  • Figure 47 shows the corresponding fiber 1002 of Figure 46 after the pyrolysis step, as comprising a pyrolyzed carbon coating 1008 on the outside surface thereof.
  • the electrically conductive metal fibers of the microcell in one embodiment of the invention comprise copper, aluminum or titanium fibers, having a diameter in the range of from about 100 to about 10,000 microns, coated with a suitable thickness of corrosion-resistant material such as gold or platinum.
  • carbon/graphite fibers having diameter in the range of from about 100 to about 10,000 microns and having good electrical conductivity characteristics can be employed, and metallized with the electrocatalyst, e.g., platinum.
  • platinum metallization is advantageously effected by contacting the fibers with a plating solution contaimng H 2 [PtCl6j, followed by reduction of the platinum compound to elemental platinum metal via contact with sodium borohydride (NaBH 4 ).
  • NaBH 4 sodium borohydride
  • the presence of pinholes or coating defects causes accelerated corrosion of metallic current collectors. hi consequence of such corrosion, the fiber cell can disconnect (as a result of the continuity of the conductor being impaired) and become inoperable.
  • FIG 48 shows a conductor 1010 including a fibrous carbon current collector 1014 laid along a coated metallic fiber 1012. The carbon fiber 1014 will be in intimate contact with the coated fiber 1012, as shown in Figure 48.
  • Figure 49 shows the fiber assembly of Figure 48 after a disconnection break of the coated metallic fiber 1012.
  • the carbon fiber 1014 in contact with both sections of the corroded metal fiber 1012 provides continuity enabling the current to pass from one side to the other along the length of the carbon fiber/metallic fiber arrangement.
  • the microcell assembly desirably includes a water management system for addition and removal of excess water from the microcell assembly.
  • the high surface area of microcell structures, and lower mass transfer resistance mean that the removal of water from the microcell module is less problematic than in conventional planar fuel cell structures.
  • Various alternatives can be employed to further enhance the water management capacity of the microcell fuel cell module.
  • heat exchange tubes are employed in the fuel cell assembly, comprising hollow fiber membranes coated with Nafion or other ion-exchange polymer or material that will selectively allow water permeation, and if the heat exchange liquid is water, the heat exchange tubes can be used for water supply to the fuel cell and removal of heat from the fuel cell.
  • One approach for water removal from the fuel cell is to provide porous plane hollow fiber membranes in the microcell bundle, in distributed fashion therein, hi this structural arrangement, water will permeate through the membrane wall by a wicking action during operation of the fuel cell and will be channeled down the bore of the hollow fiber and away from the active surfaces. The resultingly channeled water then can be collected in a plenum provided in the housing containing the module, for discharge from the system.
  • hollow fiber membranes treated with a hydrophilic compound can be packed intermittently with fiber cells containing an electrode or current collector. Since these hollow fiber membranes are in intimate contact with the shell side of the cells and are open on the bore side, water produced in the fuel cell is absorbed by a wicking action and channeled down the bore of the membrane hollow fiber membrane away from the cells containing the electrode, thereby eliminating the water flooding in the cell.
  • Figure 50 shows a cross-section of a hollow fiber and microcell tube bundle 1020, in which the plane hollow fiber elements 1026 are interspersed with the microcell fiber elements 1022 and shell side electrodes 1024, and such hollow fiber elements are used for channeling water from the assembly.
  • Figure 51 is a sectional elevation view of a microcell fuel cell module 1030, including a housing 1032 containing a microcell assembly 1036 arranged vertically as shown. The housing 1032 has a flange 1034 by means of which the upper end of the housing can be removed to access the microcell assembly and other internal components of the module.
  • the microcell assembly 1036 is potted at its upper end by potting member 1040 leak-tightly sealed to the inner wall of the housing by O-ring sealing element 1042. In like manner, the microcell assembly 1036 is potted at its lower end by potting member 1044 leak-tightly sealed to the inner wall of the housing by O-ring sealing element 1046.
  • the microcell assembly 1036 engages a central feed tube 1080, which is perforate within the interior volume of the microcell assembly. Additionally, feed inlet 1060 provides feed to the bore side of the microcell elements in the assembly, from upper ehd volume 1048. Feed discharged at the lower end from the hollow fiber elements enters the lower end volume 1050 and is discharged from the housing from outlet 1072 or outlet 1070.
  • Outlet 1078 is provided for interior volume 1038 of the housing, for discharge of spent feed from the interior volume (shell side).
  • housing 1032 constitutes a plenum chamber 1076 which receives access water (condensate) gravitationally flowed to such lower end of the housing, and discharged by overflow through outlet 1072 or outlet 1070.
  • access water condensate
  • the current collector elements at respective ends of the microcell assembly are joined to respective terminals 1082 and 1084, as illustrated.
  • the hollow fiber tubular elements employed in the microcell assembly allow permeation of excess water in to the bore passages of such hollow fibers and drainage thereof to the plenum chamber, to readily remove excess water from the electrochemical fuel cell module.
  • any other suitable means or methods can be used to channel water from the microcell assembly, including elements or structures that utilize surface tension or capillarity effects to induce channelized flow of water from the microcell bundle to a collection vessel or locus.
  • the enhancement structure for film condensation apparatus that is described in U.S. Patent 4,253,519 issued March 3, 1981 to Leslie C. Kun and Elias G. Ragi is usefully employed as an overlay structure on the microcell fibers or bundles or sub-bundles comprising same, to effect channelized flow of liquid for recovery and discharge thereof from the fuel cell module.
  • the electrolyte/catalyst-impregnated coated fiber can be optionally coated with a Teflon ® polytetrafluoroethylene emulsion, to impart hydrophobicity to the membrane/electrode assembly.
  • a Teflon ® polytetrafluoroethylene emulsion to impart hydrophobicity to the membrane/electrode assembly.

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  • Electrochemistry (AREA)
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PCT/US2001/023220 2000-07-24 2001-07-23 Microcell electrochemical devices and assemblies, and method of making and using the same WO2002009212A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CA002417682A CA2417682C (en) 2000-07-24 2001-07-23 Microcell electrochemical devices and assemblies, and method of making and using the same
NZ523874A NZ523874A (en) 2000-07-24 2001-07-23 Microcell electrochemical devices and assemblies, and method of making and using the same
EP01961707A EP1316119A4 (en) 2000-07-24 2001-07-23 MICROCELL ELECTROCHEMICAL DEVICES AND ASSEMBLIES AND METHOD FOR THE PRODUCTION AND USE THEREOF
AU8295301A AU8295301A (en) 2000-07-24 2001-07-23 Microcell electrochemical devices and assemblies, and method of making and usingthe same
AU2001282953A AU2001282953B2 (en) 2000-07-24 2001-07-23 Series-connected microcell electrochemical devices and assemblies, and method of making and using the same
JP2002514817A JP2004505417A (ja) 2000-07-24 2001-07-23 マイクロセルによる電気化学的装置およびアセンブリならびにその作成方法および使用方法
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US09/625,218 US6403517B1 (en) 2000-07-24 2000-07-24 System and process for manufacturing microcell electrochemical devices and assemblies
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US09/621,713 US6495281B1 (en) 2000-07-24 2000-07-24 Microcell electrochemical devices assemblies with corrosion management subsystem, and method of making and using the same
US09/621,228 2000-07-24
US09/625,219 2000-07-24
US09/624,303 US6403248B1 (en) 2000-07-24 2000-07-24 Microcell electrochemical devices assemblies with water management subsystem, and method of making and using the same
US09/624,303 2000-07-24
US09/621,713 2000-07-24
US09/621,228 US6399232B1 (en) 2000-07-24 2000-07-24 Series-connected microcell electrochemical devices and assemblies, and method of making and using the same
US09/625,219 US6444339B1 (en) 2000-07-24 2000-07-24 Microcell electrochemical device assemblies with thermal management subsystem, and method of making and using the same
US09/624,070 US6338913B1 (en) 2000-07-24 2000-07-24 Double-membrane microcell electrochemical devices and assemblies, and method of making and using the same
US09/625,218 2000-07-24

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JP4945963B2 (ja) 2005-08-31 2012-06-06 トヨタ自動車株式会社 燃料電池
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WO2003005466A2 (de) * 2001-07-05 2003-01-16 Blum Stephan Ruediger Elektrodenanordnung
WO2003005466A3 (de) * 2001-07-05 2003-10-16 Stephan Ruediger Blum Elektrodenanordnung
US7306865B2 (en) 2001-07-05 2007-12-11 2S-Sophisticated Systems Limited Electrode arrangement for a fuel cell having sectored headplates
FR2840107A1 (fr) * 2002-05-23 2003-11-28 C3M Comm Procede de fabrication et d'assemblage des electrodes d'un generateur electrochimique primaire ou secondaire en source d'energie elementaire ultra mince souple et mecaniquement resistante
JP4783570B2 (ja) * 2002-07-02 2011-09-28 マイクロセル コーポレーション 耐食電流コレクタ付きのマイクロセル電気化学装置およびアセンブリ、ならびにその製造方法
JP2005531911A (ja) * 2002-07-02 2005-10-20 マイクロセル コーポレーション 耐食電流コレクタ付きのマイクロセル電気化学装置およびアセンブリ、ならびにその製造方法
EP1590157A1 (en) * 2002-12-23 2005-11-02 Microcell Corporation Substrate-supported process for manufacturing microfibrous fuel cells
US7648665B2 (en) 2002-12-23 2010-01-19 Microcell Corporation Substrate-supported process for manufacturing microfibrous fuel cells
EP1590157A4 (en) * 2002-12-23 2008-06-25 Microcell Corp SUBSTRATE BASED MANUFACTURING METHOD FOR MICROFIBER FUEL CELLS
JP2006520087A (ja) * 2003-03-07 2006-08-31 マイクロセル コーポレーション 燃料電池構造体および組立体
EP1805835A2 (en) * 2004-02-13 2007-07-11 Microcell Corporation Microfibrous fuel cell assemblies comprising fiber-supported electrocatalyst layers, and methods of making same
EP1805835A4 (en) * 2004-02-13 2009-10-21 Microcell Corp MICROFIBER FUEL CELL ASSEMBLIES CONTAINING FIBER ELECTROCATALYSIS LAYERS AND METHODS OF PRODUCING THE SAME
US7989114B2 (en) 2004-03-03 2011-08-02 White Fox Technologies Limited Fuel-cell comprising capillaries
WO2005086270A1 (de) * 2004-03-03 2005-09-15 White Fox Technologies Limited Brennstoffzelle bestehend aus kapillaren
US8741463B2 (en) 2004-06-11 2014-06-03 Toyota Jidosha Kabushiki Kaisha Fuel cell
WO2005122317A3 (en) * 2004-06-11 2006-08-17 Toyota Motor Co Ltd Fuel cell
CN100466357C (zh) * 2004-06-11 2009-03-04 丰田自动车株式会社 燃料电池
WO2005122317A2 (en) * 2004-06-11 2005-12-22 Toyota Jidosha Kabushiki Kaisha Fuel cell
WO2005122307A1 (en) * 2004-06-11 2005-12-22 Toyota Jidosha Kabushiki Kaisha Cell module and fuel cell
JP2005353494A (ja) * 2004-06-11 2005-12-22 Toyota Motor Corp 燃料電池
US7887973B2 (en) 2004-06-11 2011-02-15 Toyota Jidosha Kabushiki Kaisha Cell module and fuel cell having a water permeable hollow body
US8658228B2 (en) 2005-02-04 2014-02-25 Toyota Jidosha Kabushiki Kaisha Fuel cell module and fuel cell comprising fuel cell module
WO2006083037A1 (ja) * 2005-02-04 2006-08-10 Toyota Jidosha Kabushiki Kaisha 中空型燃料電池用膜電極複合体および中空型燃料電池
US8283084B2 (en) 2005-02-04 2012-10-09 Toyota Jidosha Kabushiki Kaisha Hollow-shaped membrane electrode assembly for fuel cell and hollow-type fuel cell
EP2662096A1 (en) 2005-08-24 2013-11-13 ImmunoGen, Inc. Process for preparing maytansinoid antibody conjugates
US7838064B2 (en) 2005-08-31 2010-11-23 Toyota Jidosha Kabushiki Kaisha Method for manufacturing tube-type fuel cell
JP4687406B2 (ja) * 2005-11-10 2011-05-25 トヨタ自動車株式会社 燃料電池
US7754366B2 (en) 2005-11-10 2010-07-13 Toyota Jidosha Kabushiki Kaisha Tubular fuel cell module and manufacturing method thereof
JP2007134180A (ja) * 2005-11-10 2007-05-31 Toyota Motor Corp 燃料電池
US8338056B2 (en) 2005-11-10 2012-12-25 Toyota Jidosha Kabushiki Kaisha Tubular fuel cell
WO2007068120A1 (en) * 2005-12-14 2007-06-21 Avestor Limited Partnership Electrochemical battery and method for making same
US8142523B2 (en) 2005-12-14 2012-03-27 Bathium Canada Inc. Electrochemical battery and method for making same
US8173295B2 (en) 2007-07-18 2012-05-08 Tesla Motors, Inc. Method and apparatus for battery potting
WO2009012036A1 (en) * 2007-07-18 2009-01-22 Tesla Motors, Inc. Method and apparatus for battery potting
US8216502B2 (en) 2008-12-02 2012-07-10 Tesla Motors, Inc. Method for the external application of battery pack encapsulant
US8293393B2 (en) 2008-12-02 2012-10-23 Tesla Motors, Inc. Apparatus for the external application of battery pack encapsulant
GB2579035A (en) * 2018-11-15 2020-06-10 Pab Coventry Ltd Battery
WO2021044345A1 (en) * 2019-09-06 2021-03-11 3M Innovative Properties Company Heat exchanger and battery system including same
SE2150185A1 (en) * 2021-02-22 2022-08-23 Myfc Ab Fuel cell power module and electric vehicle comprising such
SE544742C2 (en) * 2021-02-22 2022-11-01 Myfc Ab Fuel cell power module and electric vehicle comprising such
US20220393187A1 (en) * 2021-06-08 2022-12-08 Hyundai Motor Company Tube-shaped catalyst complex and catalyst slurry including same for fuel cell
US12100846B2 (en) * 2021-06-08 2024-09-24 Hyundai Motor Company Tube-shaped catalyst complex and catalyst slurry including same for fuel cell
CN114959758A (zh) * 2022-05-05 2022-08-30 中国科学院上海高等研究院 中空纤维电极阵列组装的复合电极系统、制备方法及应用
CN114959758B (zh) * 2022-05-05 2023-08-01 中国科学院上海高等研究院 中空纤维电极阵列组装的复合电极系统、制备方法及应用

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