WO2009033498A1 - Pile à combustible à oxyde solide - Google Patents

Pile à combustible à oxyde solide Download PDF

Info

Publication number
WO2009033498A1
WO2009033498A1 PCT/EP2007/007941 EP2007007941W WO2009033498A1 WO 2009033498 A1 WO2009033498 A1 WO 2009033498A1 EP 2007007941 W EP2007007941 W EP 2007007941W WO 2009033498 A1 WO2009033498 A1 WO 2009033498A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel cell
solid oxide
oxide fuel
metal
weight
Prior art date
Application number
PCT/EP2007/007941
Other languages
English (en)
Inventor
Xicola Agustin Sin
Marina Cancellier
Antonino Salvatore Arico'
Daniela La Rosa
Original Assignee
Pirelli & C. S.P.A.
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 Pirelli & C. S.P.A. filed Critical Pirelli & C. S.P.A.
Priority to PCT/EP2007/007941 priority Critical patent/WO2009033498A1/fr
Priority to EP07818123A priority patent/EP2205538A1/fr
Publication of WO2009033498A1 publication Critical patent/WO2009033498A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/241—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
    • 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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting 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
    • H01M8/10—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid oxide fuel cell, to a cermet material, and to a method for producing energy using such cell.
  • Solid-oxide fuel cells convert chemical energy into electrical energy with high efficiency and low emission of pollutants.
  • Ni nickel
  • cermets ceramic and metallic composite materials prepared by high-temperature calcination of NiO and ceramic powders, usually yttria-stabi- lized zirconia (YSZ) powders.
  • YSZ yttria-stabi- lized zirconia
  • Ni-YSZ anode fuel cell A. M ⁇ ller et al., Proc. of the 3rd European Solid Fuel Cell Forum, France, June 1998, 353-362, relate to a Ni-YSZ anode fuel cell. It is envisaged a degradation of the anode related to microstructural changes occurring during operation.
  • the nickel particles have a mean diameter of about 0.5 ⁇ m, and are homogeneously distributed in the anode. After long term operation at high current density and fuel utilization (H 2 +H 2 O), the agglomeration of the nickel particles leads to a decrease of the amount of three-phase boundary (TPB), resulting in an increase in the anode losses.
  • TPB three-phase boundary
  • A.C. M ⁇ ller et al., HTMC IUPAC J ⁇ lich 2000 suggest that the degradation described by the previous document could be prevented by a multilayer anode whose divers layers differ in their microstructure to fulfill the locally dif- ferent requirements for SOFC anodes.
  • the content of Ni and the Ni particle size should increase from first layer (that in contact with the elec- trolyte) to last layer, thus increasing electronic conductivity, TEC (Thermal Expansion Coefficient) and porosity.
  • the YSZ content should simultaneously decrease.
  • the cermet samples were prepared by mixing 65-85 mol% NiO powder with YSZ powder and sintering them in air at 1300 0 C for 5 hours.
  • the particle size of the metallic portion was 0.5-8 ⁇ m.
  • nickel as the metallic component of a cermet anode is advantageous, but its performance drops in short time, especially when a dry hydrocarbon is the fuel, due to graphite formation.
  • the Applicant has faced the problem of providing a solid oxide fuel cell which is able to show high efficiency and to maintain its performace over time, particularly in terms of electrochemical properties in a wide range of temperatures. Moreover, the fuel cell should be able to show the above characteristics when fed with different fuels. Endurance of performance is particularly important when a dry hydrocarbon is used as fuel, since it tends to form graphite fibers on the metallic portion of the cermet anode, which eventually annihilate the fuel cell activity.
  • the Applicant has now found that by using a nickel alloy with one or more metals as metallic portion of a cermet anode, and by adding a certain amount of an alkaline or an alkaline earth metal to said nickel alloy, the resulting SOFC shows enduring efficiency when fuelled with different fuels, including hydrocarbons and alcohols, in a wide range of operating temperatures, and particularly at temperatures ranging from 500 0 C to 900 0 C. Particularly, when a dry hydrocarbon or alcohol is used as fuel, deposition of graphite residuals is remarkably reduced.
  • the present invention thus relates to a solid oxide fuel cell including
  • a ceramic material and an alloy comprising nickel at least a second metal selected from aluminium, titanium, molybdenum, cobalt, iron, chromium, copper, silicon, tungsten, niobium, and at least 0.05% by weight of a third metal selected from alkaline and alkaline earth metals.
  • said third metal is selected from the group of sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium.
  • said third metal is selected from the group of rubidium, cesium, strontium and barium.
  • said third metal is selected from the group of cesium and barium.
  • said third metal is barium.
  • said alloy comprises from 0.1 to 20% by weight of barium, and more preferably from 1 to 10% by weight of barium.
  • the anode of the invention comprises an alloy wherein said alloy has an average particle size not higher than 20 nm. More preferably said - A -
  • average particle size is not lower than 1 nm.
  • the alloy of the anode of the invention can show a mean surface area higher than 20 m 2 /g, preferably higher than 30 m 2 /g, and more preferably higher than 40 m 2 /g.
  • the alloy has a second metal content of from about 1 % by weight to about 99% by weight, more preferably, and even more preferably from about 40% by weight to about 60% by weight.
  • the alloy has a nickel content of from about 1 % by weight to about 99% by weight, more preferably from about 30% by weight to about 70% by weight, and even more preferably of about 50% by weight.
  • said second metal is copper.
  • Said alloy can comprise an additional metal, for example, an element belonging to one of the classes from 3 to 13 of the periodic table of elements according to Chemical and Engineering News, 63(5), 27, 1985, lanthanides series included.
  • the ceramic material of the anode of the invention can be selected from yttria-stabilized zirconia (YSZ), cerium gadolinium oxide (CGO), samarium-doped ceria (SDC), mixed lanthanum and gallium oxides.
  • YSZ yttria-stabilized zirconia
  • CGO cerium gadolinium oxide
  • SDC samarium-doped ceria
  • mixed lanthanum and gallium oxides Preferably the ceramic material is cerium gadolinium oxide (CGO).
  • the ceramic material of the anode of the present invention can show a particle size not higher than 50 nm, preferably from about 1 to about 25 nm.
  • said ceramic material is doped with at least one cation selected from calcium, magnesium, strontium, lanthanum, yttrium, ytterbium, neodymium and dysprosium.
  • the alloy of the invention comprises cerium oxide (Ce ⁇ 2 ), optionally added with additives like cobalt.
  • the solid oxide fuel cell according to the present invention can be operated in a wide range of temperatures, usually ranging from 450 0 C to 900 0 C, and preferably from 500°C to 800 0 C
  • the present invention relates to a cermet comprising an alloy comprising nickel, at least a second metal selected from aluminium, titanium, molybdenum, cobalt, iron, chromium, copper, silicon, tungsten, niobium, and at least 0.05% by weight of a third metal selected from alkaline and alkaline earth metals.
  • said third metal is selected from the group of sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium.
  • said third metal is selected from the group of rubidium, cesium, strontium and barium. Most preferably, said third metal is selected from the group of cesium and barium.
  • said third metal is barium.
  • said alloy comprises from 0.1 to 20% by weight of barium, and more preferably from 1 to 10% by weight of barium.
  • Both the metallic and the ceramic portion of the cermet anode of the present invention can be prepared from the corresponding metal salts, which may be compounded in a solid solution of the oxides thereof as described, for example, in WO2004/038844.
  • the oxides of the present invention are prepared starting from hydrosoluble salts of the desired metals which are dissolved in water and added with a chelating agent, for example, EDTA, oxalic, citric, acetic acid and the organic salts thereof, while maintaining the reaction mixture at a suitable pH, for example, higher than about 5. Oxidation is then carried out, e.g. by addition of a peroxide, such as hydrogen peroxide, and co-precipitate of amorphous metal oxides is obtained.
  • a peroxide such as hydrogen peroxide
  • This co-precipitate comprises very fine amorphous particles substantially free from any crystallographic ordering as revealed by XRD (X-ray diffraction) and TEM (transmission electron microscopy) analyses.
  • XRD X-ray diffraction
  • TEM transmission electron microscopy
  • the particle size can range from about 3 to about 20 nm, preferably from about 4 to about 7 nm, more preferably of about 5 nm.
  • the ceramic portion of the cermet anode according to the invention is prepared through the above mentioned process, crystallization of the amorphous oxide precursor, for example at a temperature ranging between about 200 0 C and about 700 0 C, more preferably between about 300°C and about 500 0 C, can yield a ceramic with small particle size, for example ranging between about 6 and about 2nm.
  • the preparation of the cermet anode i.e. the material system comprising a metallic and a ceramic phase, can be carried out as follows.
  • Amorphous mixed oxide precursor, obtained as said above, and a ceramic powder, preferably CGO or SDC, are admixed, and a slurry is prepared by dispersing the reactants in an organic solvent, for example ethanol or isopropanol, and further treated with ultrasounds.
  • the resulting slurry is added with a solution of a barium salt, such as, for example, barium nitrate in an organic solvent, for example ethanol or isopropanol.
  • the mixture is heated for solvent evaporation, and a reduction, for example in H 2 atmosphere, is carried out while heating, for example at a temperature ranging between about 400 0 C and about 1000°C, more preferably between about 500°C and about 800°C.
  • a solid oxide fuel cell of the invention can be prepared by applying said slurry of composite on an electrolyte membrane comprising a ceramic material, for example, CGO, SDC or YSZ.
  • a cathode for the solid oxide fuel cell of the invention can comprise a perovskite such as wherein ⁇ can range from 0 to 0.5.
  • a specific example of cathode for the solid oxide fuel cell of the invention can be a Lao.6Sro. 4 Feo. 8 C ⁇ o.2 ⁇ 3- ⁇ /CGO.
  • the solid oxide fuel cell according to the invention displays great flexibility in the choose of the fuel to be fed with. It can performs by feeding the anode with a fuel selected from hydrogen; an alcohol such as methanol, ethanol, propanol; a hydrocarbon in gaseous form such as methane, ethane, butene; carbon dioxide, carbon monoxide, natural gas, reformed natural gas, biogas, syngas and mixture thereof, either in the presence of water or substantially dry; or an hydrocarbon in liquid form, e.g. diesel, toluene, kerosene, jet fuels (JP-4, JP-5, JP-8, etc) or a biofuel.
  • Preferred by the present invention is substantially dry methane.
  • the direct oxidation of a dry fuel such as a dry hydrocarbon yields coking phenomena (deposition of graphite fibers) at the metallic portion of the cermet thus exhausting the catalytic activity.
  • the solid oxide fuel cell of the invention can perform by direct oxidation of a dry fuel.
  • the present invention relates to a method for producing energy comprising the steps of:
  • an anode including a ceramic material and an alloy comprising nickel, at least a second metal selected from aluminium, titanium, molybdenum, cobalt, iron, chromium, copper, silicon, tungsten, niobium, and at least 0.05% by weight of a third metal selected from alkaline and alkaline earth metals; and
  • the operating temperature of the solid oxide fuel cell of the invention can range from 450 0 C to 900 0 C, preferably from 500 0 C and 800 0 C.
  • An advantage provided by low operating temperatures, such those preferred by the present invention, is the reduction of NO x formation at the cathode. The formation of such undesired by-products is due to the reaction of the nitrogen present in the air fed at the cathode side, such reaction being related to temperature increase.
  • the fuel In case of operating with reformed fuel, the fuel is internally reformed at the anode side.
  • FIG. 2 shows electrochemical polarisation curves for Ni 0 5 Cu 0 5 -CGO cermet anode/CGO electrolyte interface, with and without the addition of Ba 1 in dry CH 4 at the temperature of 750° - 800 0 C;
  • FIG. 3 shows impedance spectroscopy curves for Ni O sCu 0 5 -CGO cermet anode/CGO electrolyte interface, with and without the addition of Ba, in dry CH 4 at the temperature of 750° - 800 0 C;
  • - Figure 4 shows electrochemical polarisation curves for Ni 0 5 Cu 0 5 -CGO cermet anode/CGO electrolyte interface, with and without the addition of Ba, in dry CH 3 OH at the temperature of 750° - 800 0 C;
  • - Figure 5 shows impedance spectroscopy curves for Ni 0 5 Cu 0 5 -CGO cermet anode/CGO electrolyte interface, with and without the addition of Ba, in dry CH 3 OH at the temperature of 750° - 800 0 C;
  • FIG. 6 shows chronoamperometry curves for Ni 05 Cu 0 5 -CGO cermet anode/CGO electrolyte interface with the addition of Ba, in dry CH 3 OH and CH 4 at 0.3 V and 800 0 C.
  • FIGS 1a and 1 b schematically illustrate a solid oxide fuel cell power systems.
  • the solid oxide fuel cell (1 ) comprises an anode (2), a cathode (4) and an electrolyte membrane (3) disposed between them.
  • a fuel generally a hydrocarbon
  • Hydrogen is fed to the anode side of the solid oxide fuel cell (1 ).
  • Cathode (4) is fed with air.
  • the fuel cell (1 ) produces energy in form of heat and electric power.
  • the heat can be used in a bottoming cycle or conveyed to fuel reformer (5).
  • the electric power is produced as direct current (DC) and may be exploited as such or converted into alternate current (AC) via a power conditioner (6).
  • Figure 1 b shows a preferred embodiment of the invention.
  • a substantially dry fuel is fed to the anode (2) where direct oxidation is effected.
  • the heat can be used in a bottoming cycle.
  • the direct current produced is ex- ploited as such, for example in telecommunication systems.
  • an effluent flows which can be composed by unreacted fuel and/or reaction product/s, for example water and/or carbon dioxide in the case of Figure 1 b.
  • Ce I-X Gd x O 1 95 was prepared from reagent graded Ce(NO 3 ) 3 6H 2 O and Gd(NO 3 ) 3 6H 2 O (Aldrich 99.99).
  • Ni n sCuo sO/CGO 0.79 g of Ceo. 9 Gdo .1 O 1.95 (CGO) as prepared in example 2 and 1.00 g of Nio .5 Cuo .5 O as obtained in Example 1 were intimately mixed in an agate mortar. The mixture was put for 5 hour in a ball milling with 20 ml of ethanol, which was further ultrasonicated in order to reduce the formation of ag- glomerates. The composite was then heated to about 150 0 C for solvent evaporation, followed by reduction at about 500 0 C for 5 h under hydrogen flux. The formation of the NiCu alloy on CGO was confirmed by X-ray diffraction.
  • Example 2 0.79 g of Ceo .9 Gdo .1 O 1.95 (CGO) as prepared in example 2 and 1.00 g of Nio .5 Cuo .5 O as obtained in Example 1 were intimately mixed in an agate mortar. The mixture was put for 5 hour in a ball milling with 20 ml of ethanol, which was further ultrasonicated in order to reduce the formation of ag- glomerates. 1g of Nio .5 Cuo .5 O/CGO was impregnated with 38 mg of Ba(NO 3 ) 2 dissolved in 15 ml of EtOH. The composite was then heated to about 100 0 C for solvent evaporation, followed by thermal treatment at 500 0 C for 5 h in air.
  • CGO Ceo .9 Gdo .1 O 1.95
  • a first cell C1 was fabricated having a CGO electrolyte, a LSCFO/CGO layer as a cathode and a NiCu-CGO layer of Example 3 as an anode.
  • the CGO electrolyte ( ⁇ 300 ⁇ m, >90% theoretical density) was pre- pared by uniaxial pressing at 300 MPa of a Ceo. 80 Gdo. 20 O1.
  • a 30 ⁇ m LSCFO was deposited by a spray process on one side of the pellet and fired at 950°C for 1 hour in air to assure good adhesion to the electrolyte.
  • the slurry used was composed of 1 g LSCFO (Lao .6 Sro .4 Fei -y C ⁇ y ⁇ 3 , Praxair) dispersed in 20 ml of isopropanol.
  • a 30 ⁇ m anodic cermet layer of a slurry of Nio .5 Cuo .5 O/CGO prepared according to Example 3 was deposited by spraying in one step on the CGO dense layer of the CGO-LSCFO/CGO substrate.
  • the slurry was prepared by dispersing 1 g of Nio .5 Cuo. 5 O/CGO powders in 20 ml of ethanol (Carlo Erba) that are sprayed on the electrolyte membrane.
  • the total amount of deposited metal phase was 15 mg/cm 2 . This was sintered at 1000 0 C for 2h in air.
  • the cells (0.25 cm 2 active area) were mounted on an alumina tube and sealed with quartz adhesive. Finally the system was heated at 800 0 C for 1 h in air to allow formation of a crystalline Nii -x Cu x O 2 oxide. Inert gas (Ar) was passed through the anode before hydrogen supply. A hydrogen stream flow rate (25 cc min "1 ) was fed to the anode at 800 0 C to assure the alloy formation.
  • a cell C2 was fabricated having a CGO electrolyte, a LSCFO/CGO layer as a cathode and a NiCu+Ba-CGO layer of Example 4 as an anode.
  • Example 4 was deposited by spraying in one step on the CGO dense layer of the CGO-LSCFO/CGO layer.
  • the slurry was prepared by dispersing 1 g of
  • the cells were conditioned for at least 1 h in methane at 800 0 C before recording the polarization curves and ac-impedance spectra.
  • Electrochemical experiments were carried out both under galvanostatic and potentiostatic controls by using an AUTOLAB Ecochemie potentiostat/ galvanostat and impedance analyser.
  • the polarization data were collected under steady state conditions.
  • Ac-impedance spectra were collected in the range 1 MHz-1 mHz with a 20 mV rms sinusoidal signal under open circuit conditions.
  • a four-electrode configuration was used in all cases.
  • one potential probe was connected to a non-polarized reference electrode and the overpotential of the working electrode was measured against this reference.
  • Fig.1 shows a clear increase of performance with the Ba addition after
  • the polarisation resistance (Rp) and the total resistance (Rt) of the cell shows a clear improvement with the Ba addition. It is observed from the Nyquist diagrams that the polarization resistance (Rp) has the major impact in the cell performance. This means that the electrocatalysis is highly influenced by the anode composition showing the benefits of the Ba addition. Also, is observed the presence of C in the anode without the Ba, but it disappears with the presence of Ba.
  • Methanol flow rate was 50 cc min '1 , and static air was used as oxidant. No humidification was used for the anode stream.
  • the cells were conditioned for at least 1 h in methanol at 800 0 C before recording the polarization curves and ac-impedance spectra.
  • the electrochemical performance measured at 800°C showed after 3 days of working conditions slightly better results for the sample with Ba with respect the sample without Ba. This effect is also observed by the impedance spectroscopy showed in Fig.4.
  • the polarisation resistance (Rp) and the total resistance (Rt) of the cell shows a clear improvement with the Ba addition. It is observed from the Nyquist diagrams that the polarization resistance (Rp) has the major impact in the cell performance.
  • the electrocatalysis is highly influenced by the anode composition showing the benefits of the Ba addition.
  • a big difference remains in the the amount of C deposition. It is very high in the sample without Ba and the sample with Ba showed C-free analysed by XRD and SEM (scansion electron microscopy).
  • Chronoamperometry evaluation of the performance of solid oxide fuel cell C2 fed with dry methane and methanol was carried out. Chronoamperometry is an electrochemical technique in which the potential of the working electrode is stepped, and the resulting current from faradaic processes occurring at the electrode (caused by the potential step) is monitored as a function of time. The test was made using AUTOLAB Ecochemie potentiostat/galvanostat and impedance analyser at 0.3 V and 800 0 C. The sample was working for 5 days in pure methanol and pure dry methane keeping almost constant the performance after 6Oh, as showed in Fig. 6. Both samples showed absence of carbon deposition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Composite Materials (AREA)
  • Sustainable Development (AREA)
  • Nanotechnology (AREA)
  • Structural Engineering (AREA)
  • Sustainable Energy (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Inert Electrodes (AREA)

Abstract

L'invention concerne une pile à combustible à oxyde solide qui comprend une cathode, au moins une membrane électrolytique et une anode constituée d'un matériau céramique et d'un alliage comprenant du nickel, au moins un deuxième métal choisi parmi l'aluminium, le titane, le molybdène, le cobalt, le fer, le chrome, le cuivre, le silicium, le tungstène, le niobium, et au moins 0,05 % en poids d'un troisième métal choisi parmi les métaux alcalins et alcalino-terreux.
PCT/EP2007/007941 2007-09-12 2007-09-12 Pile à combustible à oxyde solide WO2009033498A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/EP2007/007941 WO2009033498A1 (fr) 2007-09-12 2007-09-12 Pile à combustible à oxyde solide
EP07818123A EP2205538A1 (fr) 2007-09-12 2007-09-12 Pile à combustible à oxyde solide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2007/007941 WO2009033498A1 (fr) 2007-09-12 2007-09-12 Pile à combustible à oxyde solide

Publications (1)

Publication Number Publication Date
WO2009033498A1 true WO2009033498A1 (fr) 2009-03-19

Family

ID=39102998

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/007941 WO2009033498A1 (fr) 2007-09-12 2007-09-12 Pile à combustible à oxyde solide

Country Status (2)

Country Link
EP (1) EP2205538A1 (fr)
WO (1) WO2009033498A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014117263A1 (fr) * 2013-02-01 2014-08-07 Uti Limited Partnership Compositions chimiques adaptées pour une utilisation comme anodes de pile à combustible à oxyde solide et procédés de fabrication associés
CN113178586A (zh) * 2021-04-29 2021-07-27 黑龙江大学 一种固体氧化物燃料电池复合阴极催化剂及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0388558A2 (fr) * 1989-03-22 1990-09-26 Westinghouse Electric Corporation Electrode poreuse, extérieure à combustible en cermet à grande activité
WO2004038844A1 (fr) * 2002-10-25 2004-05-06 Pirelli & C. S.P.A. Pile a combustible a oxyde solide et a anode a base de ceramique
US20040166394A1 (en) * 2001-07-06 2004-08-26 Joseph Sfeir Lanthanide chromite-based sofc anodes
US20050048356A1 (en) * 2002-01-09 2005-03-03 Raphael Ihringer Sofc pen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0388558A2 (fr) * 1989-03-22 1990-09-26 Westinghouse Electric Corporation Electrode poreuse, extérieure à combustible en cermet à grande activité
US20040166394A1 (en) * 2001-07-06 2004-08-26 Joseph Sfeir Lanthanide chromite-based sofc anodes
US20050048356A1 (en) * 2002-01-09 2005-03-03 Raphael Ihringer Sofc pen
WO2004038844A1 (fr) * 2002-10-25 2004-05-06 Pirelli & C. S.P.A. Pile a combustible a oxyde solide et a anode a base de ceramique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MAT ET AL: "Development of cathodes for methanol and ethanol fuelled low temperature (300-600<o>C) solid oxide fuel cells", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, ELSEVIER SCIENCE PUBLISHERS B.V., BARKING, GB, vol. 32, no. 7, 5 May 2007 (2007-05-05), pages 796 - 801, XP022060111, ISSN: 0360-3199 *
MONDAL P ET AL: "Enhanced specific grain boundary conductivity in nanocrystalline Y2O3-stabilized zirconia", SOLID STATE IONICS, NORTH HOLLAND PUB. COMPANY. AMSTERDAM, NL, vol. 118, no. 3-4, 2 March 1999 (1999-03-02), pages 331 - 339, XP004159091, ISSN: 0167-2738 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014117263A1 (fr) * 2013-02-01 2014-08-07 Uti Limited Partnership Compositions chimiques adaptées pour une utilisation comme anodes de pile à combustible à oxyde solide et procédés de fabrication associés
CN113178586A (zh) * 2021-04-29 2021-07-27 黑龙江大学 一种固体氧化物燃料电池复合阴极催化剂及其制备方法和应用

Also Published As

Publication number Publication date
EP2205538A1 (fr) 2010-07-14

Similar Documents

Publication Publication Date Title
US7855003B2 (en) Ceramic and alloy anode solid oxide fuel cell
Song et al. Self-assembled triple-conducting nanocomposite as a superior protonic ceramic fuel cell cathode
Dwivedi Solid oxide fuel cell: Materials for anode, cathode and electrolyte
Fabbri et al. Electrode materials: a challenge for the exploitation of protonic solid oxide fuel cells
CN101847725B (zh) 一种a缺位型钙钛矿结构固体氧化物燃料电池阴极材料
US8247113B2 (en) Titanates of perovskite or derived structure and applications thereof
Zhang et al. Bismuth doped La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3− δ perovskite as a novel redox-stable efficient anode for solid oxide fuel cells
Duan et al. Exploring Ni (Mn 1/3 Cr 2/3) 2 O 4 spinel-based electrodes for solid oxide cells
US9666891B2 (en) Gas phase modification of solid oxide fuel cells
US8337939B2 (en) Method of processing a ceramic layer and related articles
Du et al. A SmBaCo 2 O 5+ δ double perovskite with epitaxially grown Sm 0.2 Ce 0.8 O 2− δ nanoparticles as a promising cathode for solid oxide fuel cells
US9660273B2 (en) Liquid phase modification of solid oxide fuel cells
Panuh et al. Effect of yttrium-stabilized bismuth bilayer electrolyte thickness on the electrochemical performance of anode-supported solid oxide fuel cells
Guo et al. Performance of SrSc0. 2Co0. 8O3− δ+ Sm0. 5Sr0. 5CoO3− δ mixed-conducting composite electrodes for oxygen reduction at intermediate temperatures
JP5389378B2 (ja) 複合セラミック電解質構造、その製造方法及び関連物品
Teng et al. Designing one-step co-assembled Pr1. 95Ce0. 05CuO4-Ce0. 8Pr0. 2O1. 9 composite cathode with extraordinary oxygen reduction activity for solid oxide fuel cells
Deli̇baş et al. Reduction of operation temperature in SOFCs utilizing perovskites
WO2009033498A1 (fr) Pile à combustible à oxyde solide
CA2893153A1 (fr) Materiau d&#39;electrode d&#39;oxydes metalliques mixtes pour les applications de pile a l&#39;oxyde solide reversible et a l&#39;oxyde solide
US8617762B2 (en) Method of processing a ceramic electrolyte, and related articles
KR102137988B1 (ko) 페로브스카이트 구조를 가지는 대칭형 고체 산화물 연료전지, 그 제조 방법 및 대칭형 고체 산화물 수전해 셀
Chen Engineering solid oxide fuel cell materials
Aruna et al. Solution Combustion Approach for the Synthesis of Solid Oxide Fuel Cell Materials and Coatings
Irshad et al. Evaluation of BaCo0. 4Fe0. 4Zr0. 2Àx Nix O3Àd perovskite cathode using nickel as a sintering aid for IT-SOFC
KR20240073589A (ko) 루들스덴 포퍼 구조의 화합물을 포함하는 고체산화물 공전해 셀용 공기극, 이를 포함하는 고체산화물 공전해 셀 및 고체산화물 공전해 셀의 제조방법

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: 07818123

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2007818123

Country of ref document: EP