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WO2006001995A2 - Materiel cote cathode pour piles a combustible au carbonate - Google Patents

Materiel cote cathode pour piles a combustible au carbonate Download PDF

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Publication number
WO2006001995A2
WO2006001995A2 PCT/US2005/020153 US2005020153W WO2006001995A2 WO 2006001995 A2 WO2006001995 A2 WO 2006001995A2 US 2005020153 W US2005020153 W US 2005020153W WO 2006001995 A2 WO2006001995 A2 WO 2006001995A2
Authority
WO
WIPO (PCT)
Prior art keywords
fuel cell
accordance
carbonate fuel
coating
cathode
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/US2005/020153
Other languages
English (en)
Other versions
WO2006001995A3 (fr
Inventor
Gengfu Xu
Chao-Yi Yuh
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.)
Fuelcell Energy Inc
Original Assignee
Fuelcell Energy Inc
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 US10/867,975 external-priority patent/US7914946B2/en
Application filed by Fuelcell Energy Inc filed Critical Fuelcell Energy Inc
Priority to JP2007516554A priority Critical patent/JP2008503058A/ja
Priority to EP05757500A priority patent/EP1782490A4/fr
Priority to KR1020077000786A priority patent/KR101250692B1/ko
Publication of WO2006001995A2 publication Critical patent/WO2006001995A2/fr
Publication of WO2006001995A3 publication Critical patent/WO2006001995A3/fr
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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • H01M8/021—Alloys based on iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • H01M8/0254—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form corrugated or undulated
    • 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
    • H01M8/14—Fuel cells with fused electrolytes
    • 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
    • H01M8/14—Fuel cells with fused electrolytes
    • H01M8/141—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
    • H01M8/142—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers with matrix-supported or semi-solid matrix-reinforced electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • cathode side hardware is defined as the current collector and/or the bipolar plate on the cathode side of a fuel cell and, in particular, a molten carbonate fuel cell. Corrosion is a life-limiting factor for molten carbonate fuel cells. The prevailing corrosion is at the oxide-gas (or liquid) interface, i.e., at the cathode side hardware.
  • This hardware is typically formed from chromium containing stainless steel and corrosion of the hardware is governed by the outward cation diffusion via metal vacancies. It is estimated that twenty five percent (25%) of the internal resistance of a molten carbonate fuel cell could be attributed to the oxide corrosion layer that forms on the cathode side hardware. More particularly, the cathode current collector, generally made of 316L stainless steel, becomes corroded during fuel cell operation and multi-corrosion oxide layers having a relatively high electrical resistance are formed on the surface of the collector. Moreover, the formed corrosion layers usually thicken with time. Additionally, the corrosion layers on the cathode side hardware cause electrolyte loss through surface and corrosion creepage.
  • Electrolyte surface creepage is controlled by capillary forces dominated by the surface roughness, porosity and pore size in corrosion layers. Electrolyte corrosion creepage is controlled by scale thickness and phase composition of the formed scale. In cathode side hardware formed with stainless steel, a high roughness of the scale surface and the porous structure of the scale cause high electrolyte surface creepage. It has been estimated that electrolyte loss in a molten carbonate fuel cell is a significant life-limiting factor for achieving a lifetime of 40,000 hours. Analysis of cathode side hardware has indicated that sixty five percent (65%) of electrolyte loss is attributed to this hardware.
  • US Patent 5,643,690 discloses a coating of this type in the form of a non- stoichiometric composite oxide layer (Ni ferrite based oxide) formed by in cell oxidation of a layer of Fe, Ni and Cr clad on cathode current collector.
  • a non- stoichiometric composite oxide layer Ni ferrite based oxide
  • Japanese patent 5-324460 discloses a stainless steel collector plate covered with a NiO layer (formed by oxidation of a Ni layer plated or clad on a cathode current collector).
  • the coatings formed in these cases are porous and consume a significant amount of electrolyte. Also, the electrical conductivity of the layers may not be as high as desired.
  • US 2002/0164522 assigned to the same assignee hereof, discloses another coating layer which is formed as a conductive layer of ceramic material using a sol-gel process.
  • the materials used for the conductive layer in this case are, preferably, LiCoO 2 or Co doped LiFeO 2 , and the thickness of the layer is between 1 to 5 ⁇ m.
  • the aforesaid conductive ceramic layers of the 2002/0164522 publication have proven satisfactory in providing corrosion resistance of the cathode side hardware. However, the materials are costly and add to the overall expense of the fuel cell. Moreover, higher conductivities are still desired. Fuel cell designers have thus continued to search for other coating materials which offer the desired corrosion resistance, but are more cost effective and are higher in conductivity. It is therefore an object of the present invention to provide cathode side hardware which does not suffer from the above disadvantages; and It is a further object of the present invention to provide cathode side hardware having a high corrosion resistance and electrical conductivity and a lower cost.
  • the above and other objects are realized in cathode side hardware by forming the hardware to have a thin film of a dense conductive ceramic coating comprised of Perovskite AMeO 3 , wherein A is at least one of lanthanum and a combination of lanthanum and strontium and Me is one or more of transition metals, lithiated NiO (Li x NiO, where x is 0.1 to 1) and X-doped LiNiO 2 , wherein X is one of Mg, Ca and Co.
  • the coating is realized using a sol-gel process.
  • FIG. 1 schematically illustrates a fuel cell including cathode side hardware in accordance with the principles of the present invention
  • FIGS. 2A and 2B show SEM micrographs of different magnifications of a conductive lithiated NiO coating of cathode side hardware in accordance with the principles of the present invention
  • FIG. 3 shows an SEM micrograph of a conductive LSC coating of cathode side hardware in accordance with the principles of the present invention
  • FIG. 4 shows the phase evolution with heat treatment temperature of a lithiated NiO coating of the type shown in FIGS.
  • FIGS. 5A-5D illustrate the effect of immersion corrosion testing both on cathode side hardware coated with a lithiated NiO conductive coating in accordance with the invention and on uncoated cathode side hardware
  • FIGS. 6 A and 6B show the out-of-cell electrical resistivity and the out-of-cell metal-to-metal electrical resistivity, respectively, of uncoated cathode side hardware and cathode side hardware coated with a lithiated NiO coating and an LSC coating in accordance with the invention
  • FIG. 7 and 8 show the resistance lifegraphs of molten carbonate fuel cells having cathode side hardware with the lithiated NiO and LSC conductive ceramic coatings of the invention and fuel cells with uncoated cathode side hardware;
  • FIG. 9 shows the corrosion thickness after fuel cell testing of cathode side hardware using the conductive ceramic coating of the invention as compared to the corrosion thickness after fuel cell use of uncoated cathode side hardware;
  • FIG. 10 illustrates the electrolyte loss in a molten carbonate fuel cell using cathode side hardware having the conductive ceramic coating of the invention as compared to the electrolyte loss in a molten carbonate fuel cell using uncoated cathode side hardware;
  • FIG. 9 shows the corrosion thickness after fuel cell testing of cathode side hardware using the conductive ceramic coating of the invention as compared to the corrosion thickness after fuel cell use of uncoated cathode side hardware;
  • FIG. 10 illustrates the electrolyte loss in a molten carbonate fuel cell
  • FIG. 11 shows an SEM micrograph of a conductive LSCF coating of cathode side hardware in accordance with the principles of the present invention
  • FIG. 12 shows an SEM micrograph of a conductive Mg-doped LiNiO 2 coating of cathode side hardware in accordance with the principles of the present invention
  • FIG. 13 shows an SEM micrograph of a conductive Co-doped LiNiO 2 coating ' of cathode side hardware in accordance with the principles of the present invention.
  • FIG. 1 schematically shows a fuel having a cathode 2 and an anode 3. Between the cathode 2 and the anode 3 is a matrix 4 containing an alkali carbonate electrolyte. Adjacent the anode 3 is a corrugated current collector 3a and a bipolar plate 3b. Adjacent the cathode 2 is the cathode side hardware 5 comprising a corrugated current collector 5 a and a bipolar plate 5b. As shown, the bipolar plates 3b and 5b are the same. In accordance with the principles of the present, cathode side hardware 5 of the fuel cell 1 of FIG. 1 is coated with a conductive ceramic to obtain lower electrical resistivity for lower contact voltage loss.
  • Perovskite materials having a general formula AMeO 3 where A is at least one of lanthanum and a combination of lanthanum and strontium and Me is a transition metal
  • lithiated NiO Li x NiO, where x is 0.1 to 1
  • X-doped LiNiO 2 materials, where X is one of Mg, Co and Ca can be utilized as coating materials for the cathode side hardware.
  • Transition metals indicated as "Me" in AMeO 3 include, but are not limited to, Co, Fe, Cr, Mn, and mixtures thereof.
  • Perovskite materials include, but are not limited to, LSC (La x Sr 1-x CoO 3 and, specifically La C sSr 0 ⁇ CoO 3 ), LaMnO 3 , LaCoO 3 , LaCrO 3 and LSCF (Lao.gCr 0 .2Coo.8Feo. 2 0 3 ).
  • X-doped LiNiO 2 materials include Mg-doped LiNiO 2 , Ca-doped LiNiO 2 and Co-doped LiNiO 2 . These materials have a low solubility in alkali molten carbonate (e.
  • the sol is then coated on the hardware surface by a spray or dipping process, subsequently gelled, and dried, followed by densification and crystallization. Drying is generally performed between room temperature and 200°C.
  • the densification and recrystallization processes are usually carried out at temperatures above 35O 0 C.
  • the surface of the metal substrate may require degreasing and pickling to remove surface debris and oxide for better coating adhesion. Although 100% of coating coverage is not necessary for carbonate fuel cell application in terms of ohmic contact resistance, it is desirable to have >95% coverage of the surface by the ceramic coating to achieve the desired benefits of increased corrosion protection and reduced electrolyte loss.
  • the resultant cathode side hardware can thus be provided with the required structure and phase assemblage to provide the desired properties.
  • the precursors for the Perovskite materials, lithiated NiO (Li x NiO, where x is 0.1 to 1) and X-doped LiNiO 2 materials can be acetates or inorganic salts like nitrate or hydroxide.
  • the solutions can be aqueous based or solvent based.
  • the body or substrate member of the cathode side hardware can be stainless steel.
  • the dense oxide coating significantly delays mobile carbonate ion attack of the underlying body (e.g., stainless steel body) of the hardware.
  • the main effect of the formed oxide layer is to barrier gas, vapor and liquid contact with the hardware body.
  • the corrosion resistant oxide layer being highly conductive, the contact resistance between the hardware body and the cathode electrode is also reduced as compared with corrosion scale formed on hardware which is uncoated. In comparison to an uncoated hardware body formed of chromium steel, the electrical resistance is lowered 50% as exhibited in out of cell testing.
  • lithiated NiO and X-doped LiNiO 2 coatings of the cathode side hardware of the invention surface roughness and corrosion are both minimized. Accordingly, electrolyte surface and corrosion creepage are also minimized.
  • the coatings of the cathode side hardware have also been found to exhibit favorable adhesion, well matched thermal expansion coefficients, effective electronic conductivity, and protection against hot oxidation/corrosion. Accelerated thermal cyclic testing of the coatings have indicated that the coatings are thin and are very adhesive. Good adhesion is attributed to reaction-bonded structure between the coating and the body of the hardware and also its thin film character (tensile stress is proportional to coating thickness).
  • the coatings of the invention (Lio . iNiO, Perovskite materials and X-doped LiNiO 2 ) also exhibit a much higher conductivity (e.g. 33 S/cm for LiojNiO, 650 S/cm for LSC, and 26 S/cm for Mg-doped LiNiO 2 and 15 S/cm of Co- doped LiNiO 2 at 65O 0 C) and more importantly, are dense and smooth with a controlled coating thickness, as compared with the LiCoO 2 coating (conductivity of lS/cm) of the 2002/0164522 publication.
  • the following are examples of the invention. EXAMPLE I - Lithiated NiO Cathode Side Hardware
  • Lithiated NiO Sol-Gel A starting solution with a nominal Li:Ni composition of 0.1 : 1 (molar ratio) was prepared using reagent grade Li acetate and Ni acetate as cation source compounds. Appropriate quantities of these materials to be included in the starting solution were then calculated on the basis of obtaining 1 M NiO sol-gel. Measured amounts of the cation source compounds were then mixed with 200 ml distilled water, 300 ml ethylene glycol and 1.5 mol citric acid in a 600 ml beaker to form a precipitate-free starting solution. The starting solution was heated on a hot plate at about 80 0 C to concentrate until it turned to a viscous liquid. A green, transparent solution resulted.
  • the solution was allowed to stand at 25 0 C in a sealed glass beaker for at least half a year without precipitation.
  • the change in the viscosity of the solution due to polymerization was measured at room temperature by means of a Brookfield viscometer.
  • the viscosity of the precursor increases significantly with increased heating time due to the increase in average molecular weight as a result of polymerization.
  • precursors with viscosity below 125 cp at room temperature could not homogeneously wet a smooth substrate, such as stainless steel.
  • highly viscous precursors having a viscosity above about 1000 cP at room temperature resulted in inhomogeneous films and crack formation unless the substrate was heated at higher temperatures. Therefore, it is important to control the viscosity of the solution to obtain high quality films.
  • the viscosity of the precursor solutions used in this Example ranged between 200 and 275 cP at room temperature.
  • FIGS. 2A and 2B show SEM photographs of a fractured cross section of the film coated hardware at different magnifications. From these figures, it can be seen that a thin lithiated Ni oxide film of substantially uniform thickness ⁇ 1 micron, was realized.
  • I l comprising a polymer containing the metal cations. It is important that the cations remain in solution throughout the polymerization process. The change in the viscosity of the solution as it was converted into the polymeric precursor was measured at room temperature by means of a Brookfield viscometer.
  • (2) Deposition and Formation of Cathode Side Hardware With Smooth, Dense LSC Films To increase sol wetting and increase bond strength between the LSC film and the stainless steel (316L) cathode side hardware, the stainless steel was acid treated first, followed by acetone washed ultrasonically to remove any possible dust and carbon film formed during heat treatment in graphite furnace.
  • FIG. 3 shows a SEM photograph of the surface morphology of the LSC coated cathode side hardware. The effect of thermal cycling on the integrity of the lithiated NiO and LSC coated cathode side hardware sheets was also evaluated.
  • FIGS. 5A-5D The cross sectional SEM observations for a representative example of cathode side hardware coated with lithiated NiO in accord with the invention as compared with uncoated cathode side hardware is shown in FIGS. 5A-5D.
  • the lithiated NiO coating of the invention (FIGS. 5 A and 5B), had significantly reduced the thickness of the corrosion scale, as compared to the uncoated hardware (FIGS. 5C and 5D). More particularly, the corrosion scales show a similar dual-layered structure whether or not sol-gel coated.
  • FIG. 6 A shows the out-of-cell electrical resistivity of cathode side hardware in the form of a cathode current collector ("CCC") having the lithiated NiO and LSC coatings of the invention. It also shows the out-of-cell electrical resistivity of a non- coated stainless steel current collector. As can be seen, the coated CCCs of the invention have comparable resistivities to the non-coated CCC.
  • CCC cathode current collector
  • FIGS. 7 and 8 show the resistance lifegraphs of a fuel cells utilizing CCCs coated with the lithiated NiO and LSC coatings of the invention, respectively, as compared to fuel cells utilizing uncoated stainless steel CCCs. As can be appreciated from these graphs, an improved resistance life is realized for the fuel cells using the CCCs with the coatings of the invention.
  • FIG. 9 shows the corrosion thickness after fuel cell testing of CCCs coated with coatings of the invention as compared to the corrosion thickness after fuel cell testing of uncoated CCCs.
  • the coated CCCs of the invention are seen to exhibit measurably less corrosion than the uncoated CCCs.
  • FIG. 10 illustrates the electrolyte loss in a molten carbonate fuel cell using CCCs coated with the coatings of the invention as compared to the electrolyte loss in a molten carbonate fuel cell with uncoated CCCs. As can be seen, the electrolyte loss is considerably less in the fuel cell using the coatings of the invention.
  • Measured quantities of the cation source compounds were then mixed with distilled water (150 ml) and ethylene glycol (350 ml) in a 1,000 ml beaker to form a starting solution.
  • the starting solution was then heated on a hot plate to about 65 0 C and stirred at 65 0 C for about 48 hours to expel water and other volatile matter and to form a viscous polymer containing the metal cations. It is important that the solution is not overheated during the formation of the viscous polymer since this formation is an exothermic process. After the heating of the solution was turned off, the change in the viscosity of the solution as it was converted into the polymeric precursor was measured using a Brookfield viscometer.
  • FIG. 11 shows an SEM photograph of the surface morphology of the LSCF coated cathode side hardware. Similar to LSC coated cathode side hardware shown in FIG. 3, the SEM shown in FIG. 11 reveals that the LSCF coating is thermally compatible with the hardware body or substrate, and that no thermal stress induced cracks were detected.
  • Mg acetate, Li acetate and hydrated Ni acetate were then mixed with distilled water (400 ml) and citric acid (2 mol) in a 1,000 ml beaker while heating the solution to about 80°C and stirring it using a magnetic agitator to form a clear precipitate-free starting solution.
  • the starting solution was then heated on a hot plate at 80°C until a green transparent viscous solution was formed. After the solution reached a desired concentration, the heating was turned off and the viscosity of the solution was measured. The change in viscosity of the solution as it was converted into the viscous solution was measured at room temperature by means of a Brookfield viscometer.
  • Measured quantities of the cation source compounds were then mixed with distilled water (400 ml) and citric acid (2 mol) in a 1,000 ml beaker, while heating the solution to about 80°C and stirring it using a magnetic agitator to form a clear precipitate-free starting solution.
  • the starting solution was heated at about 80°C to expel the water and other volatile matter and to form a green, transparent viscous solution.
  • the change in viscosity of the solution as it was converted into the viscous solution was measured at room temperature by means of a Brookfield viscometer. As in the previous example, the viscosity of the solution increased significantly with increased heating time due to the increase in the average molecular weight as a result of polymerization.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)
  • Chemically Coating (AREA)

Abstract

L'invention concerne un matériel côté cathode de pile au carbonate présentant un revêtement mince d'une céramique conductrice formée à partir d'une pérovskite AMeO3, dans laquelle A représente un lanthane et/ou une combinaison de lanthane et de strontium et Me représente un ou plusieurs métaux de transition, de NiO lithié (LixNiO, dans lequel x est compris entre 0,1 et 1) et de LiMeO2 X-dopé, X représentant un élément sélectionné parmi Mg, Ca et Co.
PCT/US2005/020153 2004-06-15 2005-06-09 Materiel cote cathode pour piles a combustible au carbonate Ceased WO2006001995A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2007516554A JP2008503058A (ja) 2004-06-15 2005-06-09 炭酸塩燃料電池のカソード側のハードウェア
EP05757500A EP1782490A4 (fr) 2004-06-15 2005-06-09 Maretiel cote cathode pour piles à combustible au carbonate
KR1020077000786A KR101250692B1 (ko) 2004-06-15 2005-06-09 탄산염 연료전지의 음극측 하드웨어

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/867,975 US7914946B2 (en) 2004-06-15 2004-06-15 Cathode side hardware for carbonate fuel cells
US10/867,975 2004-06-15
US11/137,018 2005-05-25
US11/137,018 US7919214B2 (en) 2004-06-15 2005-05-25 Cathode side hardware for carbonate fuel cells

Publications (2)

Publication Number Publication Date
WO2006001995A2 true WO2006001995A2 (fr) 2006-01-05
WO2006001995A3 WO2006001995A3 (fr) 2006-05-11

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JP (1) JP2008503058A (fr)
KR (1) KR101250692B1 (fr)
WO (1) WO2006001995A2 (fr)

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KR101693557B1 (ko) * 2014-12-24 2017-01-06 재단법인 포항산업과학연구원 용융탄산염 연료전지용 코팅강판 및 그의 제조방법

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2604437B2 (ja) * 1987-10-15 1997-04-30 東燃株式会社 高温型燃料電池用電極間接合体及び高温型燃料電池用カソード集電体
US4950562A (en) * 1988-04-21 1990-08-21 Toa Nenryo Kogyo Kabushiki Kaisha Solid electrolyte type fuel cells
JPH07183038A (ja) * 1993-12-22 1995-07-21 Toshiba Corp 溶融炭酸塩型燃料電池用集電板
KR100196008B1 (ko) * 1995-10-31 1999-06-15 김징완 용융탄산염 연료전지용 분리판
JPH11233121A (ja) * 1998-02-18 1999-08-27 Yoyu Tansanengata Nenryo Denchi Hatsuden System Gijutsu Kenkyu Kumiai 溶融炭酸塩型燃料電池の空気極材料及びその製造方法
US6296972B1 (en) * 1998-04-24 2001-10-02 Korea Institute Of Science And Technology Method for preparing LICOO2-coated NiO cathodes for molten carbon fuel cell
US6054231A (en) * 1998-07-24 2000-04-25 Gas Research Institute Solid oxide fuel cell interconnector
US6645657B2 (en) * 2001-05-03 2003-11-11 Fuelcell Energy, Inc. Sol-gel coated cathode side hardware for carbonate fuel cells
KR100519938B1 (ko) * 2001-11-01 2005-10-11 한국과학기술연구원 다공성 세라믹 막이 코팅된 용융탄산염 연료전지용 연료극
CA2487265A1 (fr) * 2002-05-07 2003-11-20 The Regents Of The University Of California Ensemble de piles de cellules electrochimiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of EP1782490A4 *

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Publication number Publication date
KR20070026800A (ko) 2007-03-08
EP1782490A2 (fr) 2007-05-09
EP1782490A4 (fr) 2010-05-05
WO2006001995A3 (fr) 2006-05-11
JP2008503058A (ja) 2008-01-31
KR101250692B1 (ko) 2013-04-03

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