WO2009017998A1 - Solid oxide fuel cell electrode systems and methods - Google Patents

Solid oxide fuel cell electrode systems and methods Download PDF

Info

Publication number
WO2009017998A1
WO2009017998A1 PCT/US2008/070605 US2008070605W WO2009017998A1 WO 2009017998 A1 WO2009017998 A1 WO 2009017998A1 US 2008070605 W US2008070605 W US 2008070605W WO 2009017998 A1 WO2009017998 A1 WO 2009017998A1
Authority
WO
WIPO (PCT)
Prior art keywords
molybdenum
sofc
metal
interconnect
matrix
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2008/070605
Other languages
French (fr)
Inventor
Brad L Kirkwood
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Boeing Co
Original Assignee
Boeing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Boeing Co filed Critical Boeing Co
Publication of WO2009017998A1 publication Critical patent/WO2009017998A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES, PROFILES OR LIKE SEMI-MANUFACTURED PRODUCTS OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C1/00—Manufacture of metal sheets, wire, rods, tubes or like semi-manufactured products by drawing
    • B21C1/003—Drawing materials of special alloys so far as the composition of the alloy requires or permits special drawing methods or sequences
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/20—Making alloys containing metallic or non-metallic fibres or filaments by subjecting to pressure and heat an assembly comprising at least one metal layer or sheet and one layer of fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0226—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture

Definitions

  • the present disclosure relates generally to solid oxide fuel cells and, more particularly, to a metal-matrix or in situ composite for use as an interconnect in a solid oxide fuel cell.
  • Interconnects may be made for example of stainless steel alloys.
  • Solid oxide fuel cell systems fabricated from heavy gage, dense materials such as this are less attractive for long endurance aircraft propulsion applications because of their weight.
  • stainless steel while heavy, has other materials characteristics which make it suited for use in fuel cells.
  • stainless steel has resistance to hydrogen embrittlement (formation of hydrides), good resistance to oxidation,with fair creep strength and conductivity at temperatures above 800 ° C.
  • a solid oxide fuel cell (SOFC) interconnect comprises a metal sheet with an air side and a fuel side.
  • the metal sheet comprises a metallic composite having a matrix.
  • the matrix comprises a first metal.
  • the metal sheet also comprises a plurality of discontinuous, elongated, directional reinforcement wires.
  • the reinforcement wires comprise a second metal that is immiscible in the first metal.
  • An oxidation protection layer is disposed on the air side of the metal sheet.
  • a solid oxide fuel cell comprises a plurality of individual fuel cells.
  • Each individual fuel cell comprises an anode layer, a cathode layer, and a catalyst layer between the anode layer and the cathode layer.
  • the SOFC also comprises a plurality of interconnects separating adjacent individual fuel cells.
  • Each one of the plurality of interconnects comprises a metal sheeta metallic composite.
  • the metallic composite has a matrix comprising copper or silver and a plurality of discontinuous, elongated, directional reinforcement wires dispersed in the matrix.
  • the reinforcement wires comprise molybdenum.
  • a method of fabricating an interconnect for a solid oxide fuel cell comprises melting a charge comprising copper and from 20 to 38 volume percent molybdenum and then cooling to form an ingot comprising a metallic composite.
  • the metallic composite has a copper matrix and spheroids dispersed within the matrix.
  • the method also includes forging the ingot followed by a first anneal to form a rough bar of metallic composite, swaging the rough bar followed by a second anneal to form a plurality of rods suitable for drawing, drawing the plurality of rods followed by a third anneal to form a plurality of wires of the metallic composite, bundling and canning to form a sheet of the metallic composite.
  • the sheet is suitable for use as an interconnect in an SOFC.
  • Fig. 1 shows a block diagram illustrating a detail of a portion of a solid oxide fuel cell in accordance with an embodiment.
  • FIG. 2 shows a cross-section of an interconnect of a solid oxide fuel cell in accordance with an embodiment.
  • FIG. 3 shows a flow diagram illustrating a method of fabricating a metal plate in accordance with an embodiment.
  • FIG. 4 shows a flow diagram illustrating a method of fabricating an interconnect for use in a solid oxide fuel cell.
  • FIGS. 5A, 5B and 5C show the thermal expansion coefficient, bulk thermal conductivity and RT electrical conductivity versus percent volume of molybdenum in a copper matrix in example embodiments.
  • FIG. 6 shows an interconnect of a solid oxide fuel cell in accordance with an embodiment.
  • Fig. 1 shows a detail view of a solid oxide fuel cell 100 in accordance with an embodiment of the present invention.
  • the solid oxide fuel cell 100 may include a plurality of individual solid oxide fuel cells 105. Each individual fuel cell may include an anode 106, an electrolyte 107 and a cathode 108.
  • the electrolyte 107 may comprise a partially stabilized zirconia (PSZ), for example an yttrium-stabilized zirconia (YSZ).
  • the anode 106 may comprise a surmet (sur-metal), for example nickel-PSZ.
  • the cathode 108 may comprise lanthanum chromite (LaCrO3).
  • the anode 106, catalyst 107 and cathode 108 may comprise any other suitable materials for use in a solid oxide fuel cell.
  • Each individual fuel cell may be separated from neighboring individual fuel cells by an interconnect 120.
  • the interconnect may seal neighboring individual fuel cells from one another, at least along the entire interface 122a,b where the interconnect and adjacent individual fuel cells face one another.
  • the interconnects 120 may have passages or channels 125 extending along the interface between the anode or cathode and the adjacent interconnects.
  • the passages or channels 125 may permit either fuel or air to pass through the opening, across the surface of one of either the anode or cathode, to permit operation of the solid oxide fuel cell.
  • the interconnect/anode interface 122a may have passages for fuel, for example H2.
  • the cathode/interconnect interface 122b may have passages 125 for air. The interaction of the air, individual fuel cell components and the hydrogen fuel generate a electrical current flow from the anode to the cathode.
  • the interconnects act as conductors to channel the generated power to the electrical load.
  • the channels 125 may be arranged to run at approximately 90 degree angles to each other, to facilitate the air inlet and outlet and the fuel inlet and outlet on various sides of the fuel cell.
  • the channels may be etched or machined.
  • the channels may be formed in a pressing or rolling process to have a smoother profile, for example an approximately sinusoidal or wave form, as shown in FIG. 6.
  • the interconnects 120 may comprise a composite, for example a metallic composite or in situ metallic composite.
  • the composite may include a reinforcement material, for example molybdenum or molybdenum alloy, dispersed in a matrix material, for example copper or silver.
  • a layer of rhenium or iridium disposed on the surface of the interconnect will provide protection against oxidation.
  • Molybdenum is used because for several reasons, for example, it does not form hydrides, is not soluble in either copper or silver, has good ductility, has a high tensile strength after wire drawing and maintains this strength to temperatures above 1000 degrees C, and has a moderate density when compared to other refractory or noble metal materials.
  • the metal plate 200 may comprise a composite 202, for example a metallic composite or in situ metallic composite.
  • the composite 202 may comprise a reinforcement material 204, for example molybdenum, in a matrix material 206, for example copper or silver.
  • the reinforcement material 204 may comprise an alloy of molybdenum with small amounts of titanium (Ti), zirconium (Zi) or Hafnium (Hf), for example up to about 1 % of one or more of Ti, Zi or Hf, to further strengthen the molybdenum. These elements are also immiscible in the copper or silver matrix and segregate to the molybdenum dispersoids in the solidification from the melt and become alloying additions in the molybdenum reinforcement fibers after drawing.
  • the matrix material 206 may provide the metal plate 200 with a desirable conductivity for use as an interconnect in an SOFC, while the reinforcement material 204 may provide reinforcing strength to the matrix 206.
  • the matrix material 206 and the reinforcement material may be selected to have desirable resistance to hydrogen embrittlement.
  • the reinforcement material 204 dispersed in the matrix 206 may be in the form of discontinuous, elongated, directional reinforcement wires.
  • the reinforcement wires may provide reinforcing strength to the metal plate 200 structure.
  • the plate 200 may be formed by binding two separate plates 200a, 200b together, for example hot isostatic pressing (HIP) or other suitable process.
  • the two separate plates 200a and 200b may be arranged so that a direction or axis of the reinforcement wires of one plate 200a are arranged along a different axis from the reinforcement wires of the other plate 200b, for example at about ninety degree angles with respect to one another.
  • the plate may comprise a 0/90 metallic composite or a biaxial metallic composite.
  • the reinforcement material 204 in layer 200a runs from left to right, the molybdenum or molybdenum alloy 204 runs perpendicular with the plane of the figure - the cross- sections of those wire reinforcement sections are shown as small circles.
  • the plate 200 may also include an oxide protection layer 210 of one of either rhenium or iridium. Where the channels are to be etched or machined in the plate, the rhenium or iridium may be vapor deposited onto the composite. Where the channels have been formed by rolling or shaping, the rhenium or iridium layer may co-rolled or hot isostatically pressed (HIP) onto the sheet of composite.
  • oxide protection layer 210 of one of either rhenium or iridium.
  • FIG. 3 illustrates a method 300 of fabricating a metallic composite having a reinforcement material dispersed within a matrix, for example reinforcing molybdenum or molybdenum alloy dispersed in a copper or silver matrix in accordance with an embodiment of the present invention.
  • the method may include forming 310 an ingot, forming 320 rods from the ingot, the rods being suitable for cold-drawing, forming 330 wires from the multiple rods, and forming 340 a sheet or plate from the wires.
  • Forming 310 the ingot may include melting 312 a charge.
  • the charge may be, for example copper or silver to form the matrix and molybdenum or a molybdenum alloy to be dispersed in the matrix.
  • the matrix material may be copper pellets and the molybdenum or molybdenum alloy may be provided in the form of molybdenum plugs.
  • the amount of molybdenum may be determined, at least in part, so that the sheet or plate of composite to be ultimately formed by the method 300 will have a coefficient of thermal expansion (CTE) that matches the coefficient of thermal expansion of the material used in the individual fuel cells, for example the PSV, Ni-PSV and/or LaCrO3.
  • the charge may include in a range of 20-38 volume percentage of molybdenum or molybdenum alloy in a copper or silver matrix.
  • the CTE of the resultant composite may have a CTE in a range from about 11 to about 14 microns per meter-degree Kelvin as discussed below with respect to FIG. 5A.
  • the charge may be melted 312 by arc-melting.
  • the copper may melt at about 1083 ° C.
  • the temperature may be further increased 314 until the molybdenum or molybdenum alloy dissolves into the copper melt, which may happen at about 2585 ° C.
  • the temperature may further be increased 314 to a temperature with about 100 ° C of superheat above the melting temperature of the molybdenum or molybdenum alloy, for example to about 2685 ° C.
  • the arc or other heat source may then be removed and the melted charge cooled 316.
  • the melt may be cooled rapidly, for example on a conductive, water cooled, copper hearth.
  • the cooling should take place at a rate of about a few hundred degrees per minute.
  • the cooling should take place at a rate such that the nucleation and growth process of molybdenum spheroids within the matrix occurs within about a minute. If the cooling rate is too slow, the molybdenum precipitates may become too big which may result in there being insufficient dispersion of molybdenum precipitates in the matrix.
  • the melt may precipitate a pure molybdenum or molybdenum alloy phase until the temperature reaches the melting point of the matrix material, about 1083.4 ° C in the case of copper.
  • the remaining matrix material may freeze at that point, forming a solidified ingot of molybdenum or molybdenum alloy dispersed within a matrix material.
  • the resultant microstructure may include a volume percentage of molybdenum or molybdenum alloy spheroid precipitates dispersed in the matrix.
  • the molybdenum or molybdenum alloy may be present with a volume percent in a range from 20 to 38 volume percentage of the composite, for example about 30 volume percentage of the composite.
  • a rough bar may then be formed from the solidified ingot by hammer-forging 322 and annealing 345.
  • the rough bar may then be swaged 326, for example cold-swaged, and annealed 328 to form 320 a plurality of rods suitable for cold drawing.
  • the rods may be, for example, about two feet long and roughly about a quarter inch in diameter.
  • the rods may be drawn 332, for example cold-drawn, with a 20-30 percent draw ratio.
  • the rods may be annealed 334, for example at about 800 ° C.
  • the annealing 334 may be performed at a temperature below the melting temperature of the matrix.
  • the annealing 334 may be performed under vacuum or Ar/4% H2.
  • the rods may be repeatedly drawn 332 with intermediate anneals 334 a number of times sufficient to form 330 wires having a desired radius with a microstructure of the matrix with long discontinuous molybdenum reinforcement fibers.
  • the rods may be drawn often enough to form 330 wires on the order of a few mils (for example 0.002" to 0.003") or as small as down to half a mil (0.0005").
  • the resultant wires may have discontinuous, elongated, directional wire reinforcements dispersed in the matrix formed from the molybdenum or molybdenum alloy spheroids which had been present in the original ingot prior to swaging, drawing and annealing.
  • the discontinuous wire reinforcements may increase the strength of the molybdenum/copper composite wires and increase the strength of the sheets or plates to be formed 340 from the wires over that of the matrix at room temperature and at elevated temperatures to 1000 C.
  • the wires may be canned 342, for example by bundling wires together in an appropriately shaped can, for example a flat sheet or plate shaped can.
  • the bundled/canned wires may be subjected to co-rolling 344 and/or hot isotropically pressing (HIP) 346, for example at the annealing temperature of 800 ° C, to sinter the copper wires together into a flat sheet or plate which may be, for example, from about 1 mil to about 1.5 mil thick.
  • HIP hot isotropically pressing
  • the sheets may then be removed 347 from the can by acid pickling in HNO3 or decanning.
  • the sheets may be finished by cold rolling 348 in the direction of the molybdenum wire fibers through a 10% reduction followed by annealing 349 at a lower temperature, for example 400 ° C.
  • the final annealing 349 operation may anneal the copper matrix while leaving the molybdenum wires with residual cold work for increased strength.
  • the sheet may be finished with a final 10% cold reduction to increase the strength of the wires.
  • the sheet or plate may then be cleaned, for example in dilute HNO3 acid, prior to use.
  • the resultant sheet or plate may be a composite having discontinuous, elongated, directional reinforcement wires dispersed in a conductive metal matrix.
  • the wires may be molybdenum or a molybdenum alloy and the matrix may be copper or silver.
  • the density of the resulting sheet or plate of composite at 20-38 volume percent reinforcement wires may be in a range from about 9.2 to about 9.5 g/cm3, or about 15% to 18% more dense than "316 Stainless Steel".
  • the composite may have a yield strength in excess of 200 ksi at room temperature and 100 Ksi at 800 ° C, which is significantly higher than the yield strength for stainless steel at those temperatures. Therefore, the interconnects made from the composite may be made thinner and lighter than the stainless steel interconnects, despite the higher density.
  • the metal composite may have a conductivity in a range from about 41 to about 51 x10 6 1/ohm-m at room temperature, significantly higher than stainless steel.
  • FIG. 4 illustrates a method of further processing sheets of plates of composite to fabricate 400 interconnects for use in an SOFC in accordance with an embodiment of the present invention.
  • two sheets or plates of composite may be bonded 410 together.
  • the sheets or plates may be bonded 410 to form a 0/90 lay-up metal-matrix composite or biaxial lay-up metal-matrix composite. Having the reinforcement wires of the two layers run at different angles may increase the strength of the interconnects in an SOFC in two directions to withstand pressure and thermal stresses.
  • the plates may be bonded, for example by HIP at about 900 degrees under pressure.
  • the surfaces of the two-layer plate may be etched, machined, rolled, pressed or otherwise processed to form 420 channels.
  • the channels may define fuel or air passages in an assembled SOFC. Etching or machining may result in channels with generally quadrilateral cross-sections as shown in FIG. 1.
  • the channels may be about 1 -2 mm deep and about 1 -2 across.
  • Rolling, pressing or otherwise processing may result in channels having a less-discontinuous profile, for example a wave or sinusoidal profile, as shown, for example, in FIG. 6 below for an embodiment.
  • the channels may be about 1-2 mm across from peak to peak and about 1-2 mm deep.
  • the channels on one side may run at approximately 90 degree angle with respect to the channels on the other side which may accommodate the flow of fuel and/or air in an assembled SOFC.
  • the channels may run in the direction of the reinforcement fibers on the side of the plate on which the channels are on. Having the channels run in the direction of the fibers on the side on which the channels are formed may facilitate the ease of forming of the channels.
  • an oxide protection layer for example rhenium or iridium, may be disposed 430 on at least one side of the sheet or plate.
  • the oxide protection layer may be a thin layer, for example less than about 0.001 ".
  • the manner and order of applying the oxide protection may depend, at least in part, on the form of the channels in the interconnect. For example, in the event that the channels are etched or machined, the oxide protection layer may be disposed 430 onto the sheet or plate of in-situ metallic composite by a vapor deposition process after the channels have been formed.
  • the oxide protection layer may be disposed 430 onto the sheet by co-rolling or hot isostatically pressing (HIP) the in-situ metallic composite sheet onto a thin film of rhenium or iridium, for example before rolling, pressing or otherwise processing the sheet to form the channels.
  • HIP hot isostatically pressing
  • the use of copper or silver as the matrix and molybdenum or molybdenum alloy in the composite may be desirable for their resistance to hydrogen embrittlement since neither copper nor molybdenum form hydrides by an exothermic reaction with hydrogen near room temperature.
  • the formation of hydrides might otherwise render a ductile alloy to be as brittle as glass, with no ductility or fracture toughness and may render an alloy to be unsuitable as a structural material in the presence of hydrogen.
  • Other refractory and noble platinum metals for example Ti, Zr, W, Mo, V, Ta, Hf, Pt, Pd, Rh, Re, Ru, Ir and Os may experience the formation of hydrides when exposed to hydrogen near room temperature.
  • Using molybdenum and copper may provide a desirably strong and non- brittle structural material for use in a solid oxide fuel cell.
  • a layer of one of rhenium or iridium may be desirable to the substrate, for example electrode, from oxidation.
  • Providing a layer of rhenium or iridium on at least one side of an interconnect, for example on the air or oxygen side, of the interconnect, may protect the matrix material from oxidation or internal oxidation of the molybdenum reinforcement fibers.
  • iridium may be preferred because it may also be immiscible in solid copper and may not dissolve and/or diffuse in the copper during high temperature exposure, which might otherwise weaken its ability to protect the copper from oxidation. In other embodiments, iridium may be used.
  • Iridium may form an adherent oxide to provide a slow oxidation rate, protecting the matrix material from high temperature oxidation and the reinforcement wires from internal oxidation. Pure iridium may also have excellent ductility and may resist thermal cracking that might otherwise create a short circuit oxidation path to the copper matrix to oxidize beneath the iridium coating in the area of a crack. Molybdenum without a protective layer of rhenium or iridium, while having excellent high temperature strength, might otherwise have problems with oxidation at high temperatures because its oxide will volatilize above 900 ° C, leaving it unprotected to rapid oxidation.
  • the molybdenum wires may be protected by the copper matrix and the rhenium or iridium coating.
  • a solid oxide fuel cell with copper-molybdenum composite interconnects or plates may be used in any application in which the use of a solid oxide fuel cell is considered desirable.
  • the increased strength for lighter weight plates may make the use in fuel cells for automobiles desirable as a means of increasing fuel economy and reducing emissions.
  • the lighter weight may make such a fuel cell desirable for use in an aircraft, for example in an unmanned aerial vehicle.
  • a lighter weight fuel cell may increase the range and endurance of an aircraft, for example high altitude, long endurance aircraft. For every one hundred pounds of weight loss, the endurance of an air vehicle may be increased by about 0.1 days.
  • molybdenum and copper may be immiscible, for example completely immiscible, in each other.
  • copper and molybdenum do not dissolve into each other or form a solid-solution or an intermetallic phase between them on their phase diagram. This means that a cast ingot of an alloy of these two elements creates two distinct phases; one that is pure copper and the other that is pure molybdenum with no potentially brittle inter-metallic phases or a solid solution transition.
  • the immiscibility of the molybdenum in the matrix may provide increased strength. Having closely-spaced reinforcement wires within the matrix may prevent dislocation motion within the matrix. Because the molybdenum or molybdenum alloy may be immiscible in the matrix material, the reinforcements may not coarsen at high temperatures, which may provide increased strength over other materials, such as stainless steel whose microstructures coarsen, at the operating temperatures of an SOFC, for example between 750 ° C and 900 ° C. Furthermore, since the reinforcement material is immiscible in the high-conductivity matrix material, the conductivity of the composite may also have a high conductivity.
  • Both copper and molydbdenum may be sufficiently ductile, for example very ductile, at slightly elevated temperatures.
  • the metals may be rolled, swaged, cross rolled or drawn with intermediate anneal heat treatments to form a in-situ metallic composite of 20 to 38 volume percent molybdenum reinforcement wires dispersed in a pure copper matrix.
  • These composites may have a room temperature resistivity of from about 2.0 to about 2.4 micro-ohm-cm, depending on the volume percent of molybdenum fiber reinforcement, and degree of recrystallization by annealing in the copper matrix.
  • the resistivity of the material may increase at higher temperatures, for example climbing to about 8 micro-ohm-cm at about 750 ° C.
  • the fine dispersion of aligned molybdenum or molybdenum alloy wires may give the metal composite a yield-strength in excess of about 200 Ksi at room temperature and in excess of 100 Ksi at operating temperatures of about 800 ° C.
  • Molybdenum is a refractory material and may have a sufficiently high temperature strength, for example excellent high temperature strength that does not begin to weaken until above 1100 ° C. Since Molybdenum is not miscible in the copper alloy matrix, the reinforcement may not coarsen and/or weaken when exposed to high operating temperatures, for example operating temperatures in a range from 800-900 ° C.
  • the high conductivity and high elevated temperature strength may permit the cell interconnects to be sized at about 0.015", which may result in a 50 percent weight reduction in the interconnects or plates which may correspond to about a 25% weight reduction in an SOFC, in comparison with a solid oxide fuel cell system using different metals, for example stainless steel.
  • the particular materials to use as the matrix and reinforcement wires and the volume percent of the materials may be selected, at least in part, to have desirable properties for a given application or embodiment.
  • the desirable properties may be a coefficient of thermal expansion (CTE) that matches the CTE of the materials used in the individual fuel cells.
  • the desirable properties may include good electrical conductivity or bulk thermal conductivity.
  • FIGS. 5A, 5B and 5C show the thermal expansion coefficient, bulk thermal conductivity and RT electrical conductivity versus percent volume of molybdenum in a copper matrix in example embodiments.
  • FIG. 5A shows a range of exemplary volume percent of molybdenum or molybdenum alloy in a copper matrix which may fall within the desired range of CTE.
  • the desired CTE may be in a range from about 11 to 14 millimeters per meter-degree Kelvin (mm/m-K).
  • the CTE may be about 12 mm/m-K which may correspond to a percent volume of molybdenum or molybdenum alloy of about 30 volume percent.
  • the CTE of the composite used as an interconnect in an SOFC may be selected, at least in part, to match the CTE of the material used in the individual fuel cells.
  • FIG. 5B shows a range of electrical conductivities at room temperature corresponding to the range of volume percentages of molybdenum or molybdenum alloys that have a desirable CTEs.
  • a composite with 20-30 percent volume molybdenum in a copper matrix may have electrical conductivity in a range from 41x10 6 1/ohm-m to 51x10 6 1/ohm-m.
  • the electrical conductivity may be about 44x10 6 1/ohm-m.
  • Using reinforcing materials which are immiscible in a high-conductivity matrix may provide for a metal-matrix or in situ composite with high conductivity.
  • FIG. 5C shows a range of bulk thermal conductivity corresponding to the range of volume percentages of molybdenum or molybdenum alloys that have a desirable CTEs.
  • a composite with 20-38 percent volume molybdenum in a copper matrix may have bulk thermal conductivity in a range from 28.4 to 36.5(W/m- K)/(g/cm 3 ).
  • the composite may have a bulk thermal conductivity of about 31.0 (W/m-K)/(g/cm 3 ).
  • Using a composite with high bulk thermal conductivity may reduce thermal stresses during operation, which may result in using even further weight reductions for interconnects, by reducing the stresses experienced during operation.
  • FIG. 6 shows a detail view of an interconnect 120 of a solid oxide fuel cell 100 adjacent an anode 106 and a cathode 108 in accordance with an embodiment of the present invention.
  • the interconnect has channels 125.
  • the channels have a continuous, wave or sinusoidal profile.
  • the interconnect may be a 0/90 lay-up metal-matrix composite or biaxial lay-up metal-matrix composite having crossed reinforcement fibers in two layers.
  • Each side of the interconnect has a plurality of channels which run at 90 degrees with respect to the direction of the channels on the opposite face.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Sustainable Energy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

A solid oxide fuel cell (SOFC) interconnect comprises a metal sheet with an air side and a fuel side in accordance with an embodiment of the present invention. The metal sheet comprises a metallic composite having a matrix. The matrix comprises a first metal. The metal sheet also comprises a plurality of discontinuous, elongated, directional reinforcement wires. The reinforcement wires comprise a second metal that is immiscible in the first metal. An oxidation protection layer is disposed on the air side of the metal sheet.

Description

SOLID OXIDE FUEL CELL ELECTRODE SYSTEMS AND METHODS
BRAD L. KIRKWOOD
TECHNICAL FIELD
The present disclosure relates generally to solid oxide fuel cells and, more particularly, to a metal-matrix or in situ composite for use as an interconnect in a solid oxide fuel cell.
BACKGROUND
Metallic plates used as interconnects between individual fuel cells of a solid oxide fuel cell can make the fuel cells quite heavy for aircraft flight applications. Interconnects may be made for example of stainless steel alloys. Solid oxide fuel cell systems fabricated from heavy gage, dense materials such as this are less attractive for long endurance aircraft propulsion applications because of their weight.
Stainless steel, while heavy, has other materials characteristics which make it suited for use in fuel cells. For example, stainless steel has resistance to hydrogen embrittlement (formation of hydrides), good resistance to oxidation,with fair creep strength and conductivity at temperatures above 800 °C.
As a result, there is a need for a material to be used as a an interconnect in a solid oxide cell that has adequate structural and thermal/ electrical conductivity characteristics at a lower weight than materials currently in use (such as stainless steel), while having adequate resistance to hydrogen embrittlement and oxidation.
SUMMARY
In accordance with an embodiment of the present invention, a solid oxide fuel cell (SOFC) interconnect comprises a metal sheet with an air side and a fuel side. The metal sheet comprises a metallic composite having a matrix. The matrix comprises a first metal. The metal sheet also comprises a plurality of discontinuous, elongated, directional reinforcement wires. The reinforcement wires comprise a second metal that is immiscible in the first metal. An oxidation protection layer is disposed on the air side of the metal sheet.
In accordance with another embodiment, a solid oxide fuel cell (SOFC) comprises a plurality of individual fuel cells. Each individual fuel cell comprises an anode layer, a cathode layer, and a catalyst layer between the anode layer and the cathode layer. The SOFC also comprises a plurality of interconnects separating adjacent individual fuel cells. Each one of the plurality of interconnects comprises a metal sheeta metallic composite. The metallic composite has a matrix comprising copper or silver and a plurality of discontinuous, elongated, directional reinforcement wires dispersed in the matrix. The reinforcement wires comprise molybdenum.
In accordance with another embodiment, a method of fabricating an interconnect for a solid oxide fuel cell (SOFC), comprises melting a charge comprising copper and from 20 to 38 volume percent molybdenum and then cooling to form an ingot comprising a metallic composite. The metallic composite has a copper matrix and spheroids dispersed within the matrix. The method also includes forging the ingot followed by a first anneal to form a rough bar of metallic composite, swaging the rough bar followed by a second anneal to form a plurality of rods suitable for drawing, drawing the plurality of rods followed by a third anneal to form a plurality of wires of the metallic composite, bundling and canning to form a sheet of the metallic composite. The sheet is suitable for use as an interconnect in an SOFC.
The scope of the disclosure is defined by the claims, which are incorporated into this section by reference. A more complete understanding of embodiments will be afforded to those skilled in the art, as well as a realization of additional advantages thereof, by a consideration of the following detailed description of one or more embodiments. Reference will be made to the appended sheets of drawings that will first be described briefly. BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows a block diagram illustrating a detail of a portion of a solid oxide fuel cell in accordance with an embodiment.
FIG. 2 shows a cross-section of an interconnect of a solid oxide fuel cell in accordance with an embodiment.
FIG. 3 shows a flow diagram illustrating a method of fabricating a metal plate in accordance with an embodiment.
FIG. 4 shows a flow diagram illustrating a method of fabricating an interconnect for use in a solid oxide fuel cell.
FIGS. 5A, 5B and 5C show the thermal expansion coefficient, bulk thermal conductivity and RT electrical conductivity versus percent volume of molybdenum in a copper matrix in example embodiments.
FIG. 6 shows an interconnect of a solid oxide fuel cell in accordance with an embodiment.
Embodiments and their advantages are best understood by referring to the detailed description that follows. It should be appreciated that like reference numerals are used to identify like elements illustrated in one or more of the figures.
DETAILED DESCRIPTION
Fig. 1 shows a detail view of a solid oxide fuel cell 100 in accordance with an embodiment of the present invention. The solid oxide fuel cell 100 may include a plurality of individual solid oxide fuel cells 105. Each individual fuel cell may include an anode 106, an electrolyte 107 and a cathode 108. The electrolyte 107 may comprise a partially stabilized zirconia (PSZ), for example an yttrium-stabilized zirconia (YSZ). The anode 106 may comprise a surmet (sur-metal), for example nickel-PSZ. The cathode 108 may comprise lanthanum chromite (LaCrO3). In other embodiments, the anode 106, catalyst 107 and cathode 108 may comprise any other suitable materials for use in a solid oxide fuel cell.
Each individual fuel cell may be separated from neighboring individual fuel cells by an interconnect 120. The interconnect may seal neighboring individual fuel cells from one another, at least along the entire interface 122a,b where the interconnect and adjacent individual fuel cells face one another.
The interconnects 120 may have passages or channels 125 extending along the interface between the anode or cathode and the adjacent interconnects. The passages or channels 125 may permit either fuel or air to pass through the opening, across the surface of one of either the anode or cathode, to permit operation of the solid oxide fuel cell. For example, the interconnect/anode interface 122a may have passages for fuel, for example H2. The cathode/interconnect interface 122b may have passages 125 for air. The interaction of the air, individual fuel cell components and the hydrogen fuel generate a electrical current flow from the anode to the cathode. The interconnects act as conductors to channel the generated power to the electrical load.
The channels 125 may be arranged to run at approximately 90 degree angles to each other, to facilitate the air inlet and outlet and the fuel inlet and outlet on various sides of the fuel cell. In some embodiments, the channels may be etched or machined. In other embodiments, the channels may be formed in a pressing or rolling process to have a smoother profile, for example an approximately sinusoidal or wave form, as shown in FIG. 6.
The interconnects 120 may comprise a composite, for example a metallic composite or in situ metallic composite. The composite may include a reinforcement material, for example molybdenum or molybdenum alloy, dispersed in a matrix material, for example copper or silver. A layer of rhenium or iridium disposed on the surface of the interconnect will provide protection against oxidation. Molybdenum is used because for several reasons, for example, it does not form hydrides, is not soluble in either copper or silver, has good ductility, has a high tensile strength after wire drawing and maintains this strength to temperatures above 1000 degrees C, and has a moderate density when compared to other refractory or noble metal materials. FIG. 2 shows a cross-section of a metal plate 200 for use as an interconnect 120 (see FIG. 1 ) in accordance with an embodiment of the present invention. The metal plate 200 may comprise a composite 202, for example a metallic composite or in situ metallic composite. The composite 202 may comprise a reinforcement material 204, for example molybdenum, in a matrix material 206, for example copper or silver. The reinforcement material 204 may comprise an alloy of molybdenum with small amounts of titanium (Ti), zirconium (Zi) or Hafnium (Hf), for example up to about 1 % of one or more of Ti, Zi or Hf, to further strengthen the molybdenum. These elements are also immiscible in the copper or silver matrix and segregate to the molybdenum dispersoids in the solidification from the melt and become alloying additions in the molybdenum reinforcement fibers after drawing.
In an example embodiment, the matrix material 206 may provide the metal plate 200 with a desirable conductivity for use as an interconnect in an SOFC, while the reinforcement material 204 may provide reinforcing strength to the matrix 206. In an example embodiment, the matrix material 206 and the reinforcement material may be selected to have desirable resistance to hydrogen embrittlement.
The reinforcement material 204 dispersed in the matrix 206 may be in the form of discontinuous, elongated, directional reinforcement wires. The reinforcement wires may provide reinforcing strength to the metal plate 200 structure. The plate 200 may be formed by binding two separate plates 200a, 200b together, for example hot isostatic pressing (HIP) or other suitable process. The two separate plates 200a and 200b may be arranged so that a direction or axis of the reinforcement wires of one plate 200a are arranged along a different axis from the reinforcement wires of the other plate 200b, for example at about ninety degree angles with respect to one another. In other words, the plate may comprise a 0/90 metallic composite or a biaxial metallic composite. In FIG. 2, the reinforcement material 204 in layer 200a runs from left to right, the molybdenum or molybdenum alloy 204 runs perpendicular with the plane of the figure - the cross- sections of those wire reinforcement sections are shown as small circles.
The plate 200 may also include an oxide protection layer 210 of one of either rhenium or iridium. Where the channels are to be etched or machined in the plate, the rhenium or iridium may be vapor deposited onto the composite. Where the channels have been formed by rolling or shaping, the rhenium or iridium layer may co-rolled or hot isostatically pressed (HIP) onto the sheet of composite.
FIG. 3 illustrates a method 300 of fabricating a metallic composite having a reinforcement material dispersed within a matrix, for example reinforcing molybdenum or molybdenum alloy dispersed in a copper or silver matrix in accordance with an embodiment of the present invention. The method may include forming 310 an ingot, forming 320 rods from the ingot, the rods being suitable for cold-drawing, forming 330 wires from the multiple rods, and forming 340 a sheet or plate from the wires.
Forming 310 the ingot may include melting 312 a charge. The charge may be, for example copper or silver to form the matrix and molybdenum or a molybdenum alloy to be dispersed in the matrix. The matrix material may be copper pellets and the molybdenum or molybdenum alloy may be provided in the form of molybdenum plugs.
In an example embodiment, the amount of molybdenum may be determined, at least in part, so that the sheet or plate of composite to be ultimately formed by the method 300 will have a coefficient of thermal expansion (CTE) that matches the coefficient of thermal expansion of the material used in the individual fuel cells, for example the PSV, Ni-PSV and/or LaCrO3. The charge may include in a range of 20-38 volume percentage of molybdenum or molybdenum alloy in a copper or silver matrix. In an example embodiment, the CTE of the resultant composite may have a CTE in a range from about 11 to about 14 microns per meter-degree Kelvin as discussed below with respect to FIG. 5A.
The charge may be melted 312 by arc-melting. The copper may melt at about 1083 °C. The temperature may be further increased 314 until the molybdenum or molybdenum alloy dissolves into the copper melt, which may happen at about 2585 °C. The temperature may further be increased 314 to a temperature with about 100 °C of superheat above the melting temperature of the molybdenum or molybdenum alloy, for example to about 2685 °C.
The arc or other heat source may then be removed and the melted charge cooled 316. The melt may be cooled rapidly, for example on a conductive, water cooled, copper hearth. The cooling should take place at a rate of about a few hundred degrees per minute. The cooling should take place at a rate such that the nucleation and growth process of molybdenum spheroids within the matrix occurs within about a minute. If the cooling rate is too slow, the molybdenum precipitates may become too big which may result in there being insufficient dispersion of molybdenum precipitates in the matrix.
During cooling, the melt may precipitate a pure molybdenum or molybdenum alloy phase until the temperature reaches the melting point of the matrix material, about 1083.4 °C in the case of copper. The remaining matrix material may freeze at that point, forming a solidified ingot of molybdenum or molybdenum alloy dispersed within a matrix material.
In an example embodiment, the resultant microstructure may include a volume percentage of molybdenum or molybdenum alloy spheroid precipitates dispersed in the matrix. The molybdenum or molybdenum alloy may be present with a volume percent in a range from 20 to 38 volume percentage of the composite, for example about 30 volume percentage of the composite.
A rough bar may then be formed from the solidified ingot by hammer-forging 322 and annealing 345. The rough bar may then be swaged 326, for example cold-swaged, and annealed 328 to form 320 a plurality of rods suitable for cold drawing. The rods may be, for example, about two feet long and roughly about a quarter inch in diameter.
The rods may be drawn 332, for example cold-drawn, with a 20-30 percent draw ratio. After drawing 332, the rods may be annealed 334, for example at about 800 °C. The annealing 334 may be performed at a temperature below the melting temperature of the matrix. The annealing 334 may be performed under vacuum or Ar/4% H2. The rods may be repeatedly drawn 332 with intermediate anneals 334 a number of times sufficient to form 330 wires having a desired radius with a microstructure of the matrix with long discontinuous molybdenum reinforcement fibers. For example, the rods may be drawn often enough to form 330 wires on the order of a few mils (for example 0.002" to 0.003") or as small as down to half a mil (0.0005").
The resultant wires may have discontinuous, elongated, directional wire reinforcements dispersed in the matrix formed from the molybdenum or molybdenum alloy spheroids which had been present in the original ingot prior to swaging, drawing and annealing. The discontinuous wire reinforcements may increase the strength of the molybdenum/copper composite wires and increase the strength of the sheets or plates to be formed 340 from the wires over that of the matrix at room temperature and at elevated temperatures to 1000 C.
To form 340 the sheets, the wires may be canned 342, for example by bundling wires together in an appropriately shaped can, for example a flat sheet or plate shaped can. The bundled/canned wires may be subjected to co-rolling 344 and/or hot isotropically pressing (HIP) 346, for example at the annealing temperature of 800 °C, to sinter the copper wires together into a flat sheet or plate which may be, for example, from about 1 mil to about 1.5 mil thick.
The sheets may then be removed 347 from the can by acid pickling in HNO3 or decanning. The sheets may be finished by cold rolling 348 in the direction of the molybdenum wire fibers through a 10% reduction followed by annealing 349 at a lower temperature, for example 400 °C. The final annealing 349 operation may anneal the copper matrix while leaving the molybdenum wires with residual cold work for increased strength. The sheet may be finished with a final 10% cold reduction to increase the strength of the wires. The sheet or plate may then be cleaned, for example in dilute HNO3 acid, prior to use. The resultant sheet or plate may be a composite having discontinuous, elongated, directional reinforcement wires dispersed in a conductive metal matrix. The wires may be molybdenum or a molybdenum alloy and the matrix may be copper or silver.
The density of the resulting sheet or plate of composite at 20-38 volume percent reinforcement wires may be in a range from about 9.2 to about 9.5 g/cm3, or about 15% to 18% more dense than "316 Stainless Steel". However, the composite may have a yield strength in excess of 200 ksi at room temperature and 100 Ksi at 800 °C, which is significantly higher than the yield strength for stainless steel at those temperatures. Therefore, the interconnects made from the composite may be made thinner and lighter than the stainless steel interconnects, despite the higher density. The metal composite may have a conductivity in a range from about 41 to about 51 x106 1/ohm-m at room temperature, significantly higher than stainless steel. FIG. 4 illustrates a method of further processing sheets of plates of composite to fabricate 400 interconnects for use in an SOFC in accordance with an embodiment of the present invention. In an example embodiment, two sheets or plates of composite may be bonded 410 together. The sheets or plates may be bonded 410 to form a 0/90 lay-up metal-matrix composite or biaxial lay-up metal-matrix composite. Having the reinforcement wires of the two layers run at different angles may increase the strength of the interconnects in an SOFC in two directions to withstand pressure and thermal stresses. The plates may be bonded, for example by HIP at about 900 degrees under pressure.
The surfaces of the two-layer plate may be etched, machined, rolled, pressed or otherwise processed to form 420 channels. The channels may define fuel or air passages in an assembled SOFC. Etching or machining may result in channels with generally quadrilateral cross-sections as shown in FIG. 1. The channels may be about 1 -2 mm deep and about 1 -2 across. Rolling, pressing or otherwise processing may result in channels having a less-discontinuous profile, for example a wave or sinusoidal profile, as shown, for example, in FIG. 6 below for an embodiment. The channels may be about 1-2 mm across from peak to peak and about 1-2 mm deep. The channels on one side may run at approximately 90 degree angle with respect to the channels on the other side which may accommodate the flow of fuel and/or air in an assembled SOFC. The channels may run in the direction of the reinforcement fibers on the side of the plate on which the channels are on. Having the channels run in the direction of the fibers on the side on which the channels are formed may facilitate the ease of forming of the channels.
In an example embodiment, an oxide protection layer, for example rhenium or iridium, may be disposed 430 on at least one side of the sheet or plate. The oxide protection layer may be a thin layer, for example less than about 0.001 ". The manner and order of applying the oxide protection may depend, at least in part, on the form of the channels in the interconnect. For example, in the event that the channels are etched or machined, the oxide protection layer may be disposed 430 onto the sheet or plate of in-situ metallic composite by a vapor deposition process after the channels have been formed. In the event that the channels are to have a more continuous profile, the oxide protection layer may be disposed 430 onto the sheet by co-rolling or hot isostatically pressing (HIP) the in-situ metallic composite sheet onto a thin film of rhenium or iridium, for example before rolling, pressing or otherwise processing the sheet to form the channels.
In an example embodiment, the use of copper or silver as the matrix and molybdenum or molybdenum alloy in the composite may be desirable for their resistance to hydrogen embrittlement since neither copper nor molybdenum form hydrides by an exothermic reaction with hydrogen near room temperature. The formation of hydrides might otherwise render a ductile alloy to be as brittle as glass, with no ductility or fracture toughness and may render an alloy to be unsuitable as a structural material in the presence of hydrogen. Other refractory and noble platinum metals, for example Ti, Zr, W, Mo, V, Ta, Hf, Pt, Pd, Rh, Re, Ru, Ir and Os may experience the formation of hydrides when exposed to hydrogen near room temperature. Using molybdenum and copper may provide a desirably strong and non- brittle structural material for use in a solid oxide fuel cell.
The use of a layer of one of rhenium or iridium may be desirable to the substrate, for example electrode, from oxidation. Providing a layer of rhenium or iridium on at least one side of an interconnect, for example on the air or oxygen side, of the interconnect, may protect the matrix material from oxidation or internal oxidation of the molybdenum reinforcement fibers. In one embodiment, iridium may be preferred because it may also be immiscible in solid copper and may not dissolve and/or diffuse in the copper during high temperature exposure, which might otherwise weaken its ability to protect the copper from oxidation. In other embodiments, iridium may be used. Iridium may form an adherent oxide to provide a slow oxidation rate, protecting the matrix material from high temperature oxidation and the reinforcement wires from internal oxidation. Pure iridium may also have excellent ductility and may resist thermal cracking that might otherwise create a short circuit oxidation path to the copper matrix to oxidize beneath the iridium coating in the area of a crack. Molybdenum without a protective layer of rhenium or iridium, while having excellent high temperature strength, might otherwise have problems with oxidation at high temperatures because its oxide will volatilize above 900 °C, leaving it unprotected to rapid oxidation. In embodiments of the system described herein, the molybdenum wires may be protected by the copper matrix and the rhenium or iridium coating. In an example embodiment, a solid oxide fuel cell with copper-molybdenum composite interconnects or plates may be used in any application in which the use of a solid oxide fuel cell is considered desirable. For example, the increased strength for lighter weight plates may make the use in fuel cells for automobiles desirable as a means of increasing fuel economy and reducing emissions. The lighter weight may make such a fuel cell desirable for use in an aircraft, for example in an unmanned aerial vehicle. A lighter weight fuel cell may increase the range and endurance of an aircraft, for example high altitude, long endurance aircraft. For every one hundred pounds of weight loss, the endurance of an air vehicle may be increased by about 0.1 days.
In an example embodiment, molybdenum and copper may be immiscible, for example completely immiscible, in each other. In other words, copper and molybdenum do not dissolve into each other or form a solid-solution or an intermetallic phase between them on their phase diagram. This means that a cast ingot of an alloy of these two elements creates two distinct phases; one that is pure copper and the other that is pure molybdenum with no potentially brittle inter-metallic phases or a solid solution transition.
In an exemplary embodiment, the immiscibility of the molybdenum in the matrix may provide increased strength. Having closely-spaced reinforcement wires within the matrix may prevent dislocation motion within the matrix. Because the molybdenum or molybdenum alloy may be immiscible in the matrix material, the reinforcements may not coarsen at high temperatures, which may provide increased strength over other materials, such as stainless steel whose microstructures coarsen, at the operating temperatures of an SOFC, for example between 750 °C and 900 °C. Furthermore, since the reinforcement material is immiscible in the high-conductivity matrix material, the conductivity of the composite may also have a high conductivity.
Both copper and molydbdenum may be sufficiently ductile, for example very ductile, at slightly elevated temperatures. As a result, the metals may be rolled, swaged, cross rolled or drawn with intermediate anneal heat treatments to form a in-situ metallic composite of 20 to 38 volume percent molybdenum reinforcement wires dispersed in a pure copper matrix. These composites may have a room temperature resistivity of from about 2.0 to about 2.4 micro-ohm-cm, depending on the volume percent of molybdenum fiber reinforcement, and degree of recrystallization by annealing in the copper matrix. The resistivity of the material may increase at higher temperatures, for example climbing to about 8 micro-ohm-cm at about 750 °C. The fine dispersion of aligned molybdenum or molybdenum alloy wires may give the metal composite a yield-strength in excess of about 200 Ksi at room temperature and in excess of 100 Ksi at operating temperatures of about 800 °C.
Molybdenum is a refractory material and may have a sufficiently high temperature strength, for example excellent high temperature strength that does not begin to weaken until above 1100 °C. Since Molybdenum is not miscible in the copper alloy matrix, the reinforcement may not coarsen and/or weaken when exposed to high operating temperatures, for example operating temperatures in a range from 800-900 °C. The high conductivity and high elevated temperature strength may permit the cell interconnects to be sized at about 0.015", which may result in a 50 percent weight reduction in the interconnects or plates which may correspond to about a 25% weight reduction in an SOFC, in comparison with a solid oxide fuel cell system using different metals, for example stainless steel.
In a given application or embodiment, the particular materials to use as the matrix and reinforcement wires and the volume percent of the materials may be selected, at least in part, to have desirable properties for a given application or embodiment. The desirable properties may be a coefficient of thermal expansion (CTE) that matches the CTE of the materials used in the individual fuel cells. The desirable properties may include good electrical conductivity or bulk thermal conductivity.
FIGS. 5A, 5B and 5C show the thermal expansion coefficient, bulk thermal conductivity and RT electrical conductivity versus percent volume of molybdenum in a copper matrix in example embodiments.
FIG. 5A shows a range of exemplary volume percent of molybdenum or molybdenum alloy in a copper matrix which may fall within the desired range of CTE. In an exemplary embodiment, the desired CTE may be in a range from about 11 to 14 millimeters per meter-degree Kelvin (mm/m-K). In a preferred embodiment, the CTE may be about 12 mm/m-K which may correspond to a percent volume of molybdenum or molybdenum alloy of about 30 volume percent. The CTE of the composite used as an interconnect in an SOFC may be selected, at least in part, to match the CTE of the material used in the individual fuel cells.
FIG. 5B shows a range of electrical conductivities at room temperature corresponding to the range of volume percentages of molybdenum or molybdenum alloys that have a desirable CTEs. In an example embodiment, a composite with 20-30 percent volume molybdenum in a copper matrix may have electrical conductivity in a range from 41x106 1/ohm-m to 51x106 1/ohm-m. In a preferred embodiment, the electrical conductivity may be about 44x106 1/ohm-m. Using reinforcing materials which are immiscible in a high-conductivity matrix may provide for a metal-matrix or in situ composite with high conductivity.
FIG. 5C shows a range of bulk thermal conductivity corresponding to the range of volume percentages of molybdenum or molybdenum alloys that have a desirable CTEs. In an example embodiment, a composite with 20-38 percent volume molybdenum in a copper matrix may have bulk thermal conductivity in a range from 28.4 to 36.5(W/m- K)/(g/cm3). In a preferred embodiment, the composite may have a bulk thermal conductivity of about 31.0 (W/m-K)/(g/cm3). Using a composite with high bulk thermal conductivity may reduce thermal stresses during operation, which may result in using even further weight reductions for interconnects, by reducing the stresses experienced during operation.
FIG. 6 shows a detail view of an interconnect 120 of a solid oxide fuel cell 100 adjacent an anode 106 and a cathode 108 in accordance with an embodiment of the present invention. The interconnect has channels 125. The channels have a continuous, wave or sinusoidal profile. In an example embodiment, the interconnect may be a 0/90 lay-up metal-matrix composite or biaxial lay-up metal-matrix composite having crossed reinforcement fibers in two layers. Each side of the interconnect has a plurality of channels which run at 90 degrees with respect to the direction of the channels on the opposite face.
Embodiments described above illustrate but do not limit the invention. It should also be understood that numerous modifications and variations are possible in accordance with the principles of the present invention. Accordingly, the scope of the invention is defined only by the following claims.

Claims

CLAIMSWe claim:
1. A solid oxide fuel cell (SOFC) interconnect comprising: a metal sheet comprising an air side and a fuel side, wherein the metal sheet comprises a metallic composite having a matrix comprising a first metal and a plurality of discontinuous, elongated, directional reinforcement wires, the reinforcement wires comprising a second metal, wherein the second metal is immiscible in the first metal; and an oxidation protection layer disposed on the air side of the metal sheet.
2. The SOFC interconnect of claim 1 , wherein the oxidation protection layer comprises one of rhenium or iridium.
3. The SOFC interconnect of claim 1 , wherein the first metal comprises one of copper and silver and the second metal comprises molybdenum.
4. The SOFC interconnect of claim 1 , wherein the first metal comprises copper, the second metal comprises molybdenum and the metal sheet comprises molybdenum in a range from 20 to 38 volume percent.
5. The SOFC interconnect of claim 1 , wherein the reinforcement wires comprise pure molybdenum.
6. The SOFC interconnect of claim 1 , wherein the reinforcement wires comprise a molybdenum alloy comprising at least a small amount of one of titanium, zirconium or hafnium.
7. The SOFC interconnect of claim 1 , wherein the metal sheet comprises a 0/90 lay-up composite.
8. The SOFC of claim 1 , further comprising a first plurality of channels on the air side and a second plurality of channels on the fuel side.
9. The SOFC interconnect of claim 1 , further comprising: a first plurality of channels on the air side and a second plurality of channels on the fuel side; and wherein the first metal comprises copper, the second metal comprises molybdenum, the metal sheet comprises molybdenum in a range from about 20 to about 38 volume percent of the metal sheet, and the oxidation layer comprises one of rhenium or iridium.
10. A solid oxide fuel cell (SOFC) comprising: a plurality of individual fuel cells, each individual fuel cell comprising an anode layer, a cathode layer and an catalyst layer between the anode layer and the cathode layer; a plurality of interconnects, wherein each interconnect separates adjacent individual fuel cells; and wherein each one of the plurality of interconnects comprises a metal sheet comprising a metallic composite having a matrix comprising one of copper or silver and a plurality of discontinuous, elongated, directional reinforcement wires dispersed in the matrix, the reinforcement wires comprising molybdenum.
11. The SOFC of claim 10, wherein the metallic composite comprises molybdenum in a range from 20 to 38 volume percent.
12. The SOFC of claim 10, further comprising an oxidation protection layer disposed on an air side of the interconnect, wherein the air side of the interconnect is adjacent a cathode side of an adjacent one of the plurality of individual fuel cells.
13. The SOFC of claim 12, wherein the oxidation protection layer comprises one of rhenium or iridium.
14. The SOFC of claim 10, wherein the anode comprises Ni-PSV, the catalyst comprises PSZ and the cathode comprises LaCrO3.
15. The SOFC of claim 10, wherein the reinforcement wires comprise a molybdenum alloy comprising small amounts of at least one of titanium (Ti), zirconium (Zr) or halfnium (Hf).
16. A method of fabricating an interconnect for a solid oxide fuel cell (SOFC), comprising: melting a charge comprising copper and from 20 to 38 volume percent molybdenum and then cooling the melted charge to form an ingot comprising a metallic composite having a copper matrix and spheroids comprising molybdenum dispersed within the matrix; forging the ingot followed by a first anneal to form a rough bar of metallic composite; swaging the rough bar followed by a second anneal to form a plurality of rods suitable for drawing; drawing the plurality of rods followed by a third anneal to form a plurality of wires of the metallic composite; and bundling and canning the plurality of wires to form a sheet of the metallic composite, wherein the sheet is suitable for use as an interconnect in an SOFC.
17. The method of claim 16, wherein the drawing and third anneal are repeated a plurality of times before bundling and canning.
18. The method of claim 16, further comprising one of hot isotropically pressing (HIP) or co-rolling the bundled and canned plurality of wires to sinter the plurality of wires together to form a sheet or plate of metallic composite.
19. The method of claim 16, wherein the plurality of rods are cold drawn and the third anneal is performed at a temperature of about 800 °C.
20. The method of claim 16, further comprising providing an oxidation protection layer to at least one side of the sheet by one of co-rolling the sheet with a thin foil of one of iridium or rhenium or by vapor depositing a layer of one of iridium or rhenium onto the at least one side of the sheet.
PCT/US2008/070605 2007-07-31 2008-07-21 Solid oxide fuel cell electrode systems and methods Ceased WO2009017998A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/831,776 US20090035632A1 (en) 2007-07-31 2007-07-31 Solid oxide fuel cell electrode systems and methods
US11/831,776 2007-07-31

Publications (1)

Publication Number Publication Date
WO2009017998A1 true WO2009017998A1 (en) 2009-02-05

Family

ID=39760823

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/070605 Ceased WO2009017998A1 (en) 2007-07-31 2008-07-21 Solid oxide fuel cell electrode systems and methods

Country Status (2)

Country Link
US (2) US20090035632A1 (en)
WO (1) WO2009017998A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019029769A1 (en) * 2017-08-11 2019-02-14 Schaeffler Technologies AG & Co. KG METHOD FOR PRODUCING COMPONENTS AND COMPONENTS PRODUCED THEREBY
WO2020193292A1 (en) 2019-03-22 2020-10-01 Norwegian University Of Science And Technology Implant for stoma

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102320128B1 (en) 2014-10-07 2021-11-02 프로토넥스 테크놀로지 코퍼레이션 Sofc-conduction
US10790523B2 (en) 2015-10-20 2020-09-29 Upstart Power, Inc. CPOX reactor control system and method
CN108370043B (en) 2015-10-20 2021-09-07 新兴电力公司 Improved CPOX fuel reformer and SOFC system
JP7267915B2 (en) 2016-08-11 2023-05-02 アップスタート パワー、インコーポレイテッド Planar solid oxide fuel unit cells and stacks
AU2020329309B2 (en) 2019-08-14 2026-05-07 Upstart Power, Inc. SOFC-conduction

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1046723A1 (en) * 1999-04-19 2000-10-25 Sumitomo Metal Industries, Ltd. Stainless steel product for producing polymer electrode fuel cell
EP1231633A1 (en) * 2000-04-14 2002-08-14 A.L.M.T. Corp. Material of heat-dissipating plate on which semiconductor is mounted, method for fabricating the same, and ceramic package produced by using the same
EP1806799A1 (en) * 2004-08-27 2007-07-11 Sumitomo Metal Industries, Ltd. Titanium based material for fuel cell separator and process for producing same

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3406025A (en) * 1966-12-19 1968-10-15 Union Carbide Corp Process for producing metal fibers, textiles and shapes
US3705021A (en) * 1964-08-24 1972-12-05 David R Johnson Reinforced metal fibril mats and methods of making same
US6494971B1 (en) * 1996-10-28 2002-12-17 National Research Institute For Metals Iridium-containing nickel-base superalloy
US6326096B1 (en) * 1998-02-04 2001-12-04 Gas Research Institute Solid oxide fuel cell interconnector
JP4707786B2 (en) * 1998-05-07 2011-06-22 トヨタ自動車株式会社 Manufacturing method of gas separator for fuel cell
US6416876B1 (en) * 1999-09-27 2002-07-09 3M Innovative Properties Company Copper matrix composites
US6383677B1 (en) * 1999-10-07 2002-05-07 Allen Engineering Company, Inc. Fuel cell current collector
CA2323827A1 (en) * 1999-10-20 2001-04-20 Atsushi Miyazawa Carbonaceous composite material, process for production thereof, fuel cell separator and polymer electrolyte fuel cell
US7083759B2 (en) * 2000-01-26 2006-08-01 A.L.M.T. Corp. Method of producing a heat dissipation substrate of molybdenum powder impregnated with copper with rolling in primary and secondary directions
US20050053819A1 (en) * 2003-07-18 2005-03-10 Paz Eduardo E. Solid oxide fuel cell interconnect with catalyst coating
US20050037253A1 (en) * 2003-08-13 2005-02-17 Amir Faghri Integrated bipolar plate heat pipe for fuel cell stacks
WO2006101136A1 (en) 2005-03-23 2006-09-28 Nippon Shokubai Co., Ltd. Fuel electrode material for solid oxide fuel cell, fuel electrode using same, fuel-cell cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1046723A1 (en) * 1999-04-19 2000-10-25 Sumitomo Metal Industries, Ltd. Stainless steel product for producing polymer electrode fuel cell
EP1231633A1 (en) * 2000-04-14 2002-08-14 A.L.M.T. Corp. Material of heat-dissipating plate on which semiconductor is mounted, method for fabricating the same, and ceramic package produced by using the same
EP1806799A1 (en) * 2004-08-27 2007-07-11 Sumitomo Metal Industries, Ltd. Titanium based material for fuel cell separator and process for producing same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019029769A1 (en) * 2017-08-11 2019-02-14 Schaeffler Technologies AG & Co. KG METHOD FOR PRODUCING COMPONENTS AND COMPONENTS PRODUCED THEREBY
WO2020193292A1 (en) 2019-03-22 2020-10-01 Norwegian University Of Science And Technology Implant for stoma

Also Published As

Publication number Publication date
US20130137012A1 (en) 2013-05-30
US20090035632A1 (en) 2009-02-05
US8530114B2 (en) 2013-09-10

Similar Documents

Publication Publication Date Title
US8530114B2 (en) Solid oxide fuel cell electrode systems and methods
TWI502086B (en) Copper alloy sheet and method for producing same
US20150122378A1 (en) Solar cell interconnector and manufacturing method thereof
CN102947043A (en) Aluminum copper clad material
JP2546551B2 (en) γ and β two-phase TiAl-based intermetallic alloy and method for producing the same
KR20200045432A (en) Complex copper alloy comprising high entropy alloy and method for manufacturing the same
WO2012144600A1 (en) Steel for solid oxide fuel cells having excellent oxidation resistance, and member for solid oxide fuel cells using same
Gao et al. High strength and thermal stability of multilayered Cu/Al composites fabricated through accumulative roll bonding and cryorolling
EP2104167B1 (en) Fuel cell separator and method for producing the same
Medvedev et al. Microstructure and properties of the Al-0.5 wt.% Fe alloy wire, copper-clad by electrochemical deposition
Guo et al. Effect of pulse current on interface microstructure and bonding properties of TA1/304 double-layer clad plates
CN111033840A (en) Method for producing a component and component produced according to the method
CN101797687B (en) A kind of preparation method of TiAl alloy with fine-grained full-layer lamellar structure
CN110343909A (en) A kind of multiple grain scale strengthens the preparation method of multi-layer sheet structure aluminium alloy
Chen et al. Development of Ductile Refractory Alloys With Excellent High‐Temperature Strength for Extreme Environments
CN111500957A (en) A kind of preparation method of 700 ℃ high temperature titanium matrix composite material sheet
KR102912952B1 (en) Narrow-width titanium-aluminum solid-liquid composite materials, their manufacturing methods and applications
Lin et al. Mechanisms for manufacturing NiAl thin-walled spherical shell by combining superplastic forming of Ni/Ni2Al3 heterogeneous bimodal-grained composite sheet with subsequent in-situ reaction
CN101020983A (en) Heat treatment process for large size as-cast high-Nb TiAl-base alloy to obtain complete lamellar structure
CN119748988A (en) A method for preparing a layered composite material and a layered composite material
CN113481414A (en) Preparation method of 1-series aluminum alloy foil for positive electrode of soft-package lithium battery tab
DE102018202915A1 (en) New materials for solar cell connectors
WO2008124436A1 (en) Composite substrates for high temperature superconductors having improved properties
Liu et al. Microstructure and Mechanical Properties of Layered Al/MgLiZnY/Al Composite Sheets Processed by Accumulative Roll Bonding (ARB)
Rice Metallurgy and properties of thoria-strengthened nickel

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08782130

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08782130

Country of ref document: EP

Kind code of ref document: A1