WO2005112153A1 - Anode pour pile a combustible haute temperature, et procede de realisation - Google Patents

Anode pour pile a combustible haute temperature, et procede de realisation Download PDF

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Publication number
WO2005112153A1
WO2005112153A1 PCT/DE2005/000662 DE2005000662W WO2005112153A1 WO 2005112153 A1 WO2005112153 A1 WO 2005112153A1 DE 2005000662 W DE2005000662 W DE 2005000662W WO 2005112153 A1 WO2005112153 A1 WO 2005112153A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
anode
base body
temperature fuel
sol
Prior art date
Application number
PCT/DE2005/000662
Other languages
German (de)
English (en)
Inventor
Norbert Menzler
Ralf Hansch
Hans Peter Buchkremer
Detlev STÖVER
Original Assignee
Forschungszentrum Jülich GmbH
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 Forschungszentrum Jülich GmbH filed Critical Forschungszentrum Jülich GmbH
Publication of WO2005112153A1 publication Critical patent/WO2005112153A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to an anode for a high-temperature fuel cell and a suitable method for producing the same.
  • SOFC Solid Oxide Fuel Cell
  • the spatial separation of the reactants required for energy conversion takes place by means of a solid electrolyte that conducts oxygen ions and is in contact with porous electrodes on both sides.
  • the anode side of the fuel cell is continuously gaseous fuel, for. B. hydrogen, which is oxidized with the aid of the oxygen ions transported by the ceramic electrolyte. Air flows through the cathode side.
  • the required electron exchange between the reactants takes place via an external circuit and supplies the electrical energy.
  • yttrium-stabilized zirconium dioxide Y 2 O 3 -stabilized ZrO 2
  • scandium-stabilized zirconium dioxide Sc 2 O 3 -stabilized ZrO 2
  • the cathode usually consists of strontium or calcium-doped lanthanum manganite, in short
  • Ni / YSZ cermets are mostly used as anode material.
  • the anode serves not only as an electrochemical function but also as a mechanically supporting element of the cell.
  • Starting materials are usually used NiO and doped ZrO 2 .
  • This anode substrate is usually first coated with a thin, microstructured, so-called anode functional layer, the actual anode (composition likewise NiO and ZrO 2 ).
  • the anode After firing, the anode usually initially consists of a porous nickel oxide / YSZ mixture. At the start of operation of the SOFC, the nickel oxide is reduced to metallic nickel.
  • the so-called cermet (ceramic + metal) thus formed has excellent electrical conductivity due to its nickel content.
  • the continuous pore structure allows a high flow rate for the fuel gas.
  • the electrocatalytic effect is based on the metallic nickel, which not only binds the surface hydrogen, but also absorbs the electrons that result from the oxidation of the hydrogen.
  • the required oxygen ions are provided by the electrolyte and via the branched YSZ network, while the fuel gas and its products are transported via the gas phase. This means that all anode components have important functions and only the specific coordination of the Ni, YSZ and pore structure leads to optimal electrochemical conversions.
  • a disadvantage of the above-mentioned anodes is that in the event of an unwanted re-oxidation of the nickel to nickel oxide, for example by an air break-in or a small leak in the electrolyte, there is an increase in volume within the anode substrate, which leads to voltages and
  • the object of the invention is to provide an anode for a high-temperature fuel cell, which can be used even when there is an unwanted supply of acid. Erstoff or air and a resulting re-oxidation of the nickel in the anode cermet, the formation of cracks or defects, which can lead to a partial or complete destruction of the composite material and thus the entire cell, reduced or even prevented. Furthermore, it is the object of the invention to provide a suitable method for producing such an anode for a high-temperature fuel cell.
  • an anode for a high-temperature fuel cell with all the features according to the main claim, and by a manufacturing method for such an anode according to the secondary claim.
  • Advantageous embodiments of the anode and of the method can be found in the claims which refer back to them.
  • the object of the invention relates to a novel anode for a high-temperature fuel cell.
  • the anode has an open-pored, but mechanically stable base body. This can in particular have partially or fully stabilized zirconium dioxide.
  • Nickel is arranged on the surface of the base body, in particular on the inner surface in the pores. Depending on the environmental conditions, the nickel can be either reduced nickel or nickel oxide.
  • a method suitable for producing a suitable anode provides for a porous base body to be formed first, in particular from partially or fully stabilized zirconium dioxide.
  • the porous structure can be obtained by incorporating, for example, polymeric binders as space fillers, burning-out particles such as graphite, ammonium hydrogen carbonate or sodium hydrogen carbonate, or other placeholder materials.
  • the base body can then be infiltrated with a nanostructured suspension or a sol from a nickel-containing precursor, for example a polymer or colloid sol, or a nickel nitrate or acetate.
  • a nickel-containing precursor for example a polymer or colloid sol, or a nickel nitrate or acetate.
  • the inner surface of the base body is occupied and the pores are filled. Evaporation, evaporation and / or pyrolysis of the volatile components of the infiltrate results in the surface being coated with nickel oxide as a kind of precursor.
  • this nickel precursor is usually reduced to metallic nickel.
  • Yttrium fully stabilized zirconium dioxide graphite as a burnout
  • solvent various additives
  • a hot-pressed substrate made of 8 YSZ and binder can be produced using the coat mix process. Usually a NiO to 8YSZ ratio of approx. 3: 2 is used.
  • solvents such as toluene, isopropanol, methyl ethyl ketone, ethanol or water or mixtures thereof;
  • organic additives such as binders, dispersers, plasticizers and others are added to this mixture if necessary.
  • the coat mix process for example, in addition to the oxidic raw materials
  • Formaldehyde resin added as a binder.
  • the substrate is debindered, pre-sintered and then infiltrated with a nickel acetate solution by immersion.
  • the subsequent layer thickness of the nickel oxide layer in the submicrometer to ⁇ m range can be set in a targeted manner by repeated infiltration processes with any intermediate drying steps.
  • the organic constituents are then burned out at temperatures in the range of 600.degree.

Abstract

La présente invention concerne une anode destinée à être utilisée dans une pile à combustible haute température, comprenant un corps de base poreux en dioxyde de zirconium entièrement ou partiellement stabilisé, à la surface duquel se trouve du nickel métallique et/ou un composé de nickel. La présence de nickel ou d'un composé de nickel exclusivement sur la surface du corps de base poreux, a pour conséquence favorable, qu'au cours d'une réoxydation possible du nickel en oxyde de nickel et d'une variation de volume liée à cette réoxydation, a lieu une croissance non nocive de cette couche uniquement à l'intérieur d'un espace de pores, et non à l'intérieur du corps de base. Cela permet d'éviter complètement ou de réduire fortement l'apparition régulière de tensions et de fissures. La fonctionnalité d'une pile à combustible haute température ou d'un empilement de piles à combustible, est ainsi garantie, même dans le cas d'une pénétration inopinée d'oxygène dans l'anode.
PCT/DE2005/000662 2004-05-15 2005-04-13 Anode pour pile a combustible haute temperature, et procede de realisation WO2005112153A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004024297.6 2004-05-15
DE102004024297 2004-05-15

Publications (1)

Publication Number Publication Date
WO2005112153A1 true WO2005112153A1 (fr) 2005-11-24

Family

ID=34969222

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2005/000662 WO2005112153A1 (fr) 2004-05-15 2005-04-13 Anode pour pile a combustible haute temperature, et procede de realisation

Country Status (1)

Country Link
WO (1) WO2005112153A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1146483A (en) * 1965-06-24 1969-03-26 Raffinage Cie Francaise Improvements in or relating to electrolyte-electrode assemblies for cells
US5035962A (en) * 1990-03-21 1991-07-30 Westinghouse Electric Corp. Layered method of electrode for solid oxide electrochemical cells
US5629103A (en) * 1993-04-30 1997-05-13 Siemens Aktiengesellschaft High-temperature fuel cell with improved solid-electrolyte/electrode interface and method of producing the interface
EP1081778A1 (fr) * 1998-04-21 2001-03-07 Toto Ltd. Pile a electrolyte solide et son procede de production
US20020102450A1 (en) * 2000-05-18 2002-08-01 Badding Michael E. High performance solid electrolyte fuel cells

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1146483A (en) * 1965-06-24 1969-03-26 Raffinage Cie Francaise Improvements in or relating to electrolyte-electrode assemblies for cells
US5035962A (en) * 1990-03-21 1991-07-30 Westinghouse Electric Corp. Layered method of electrode for solid oxide electrochemical cells
US5629103A (en) * 1993-04-30 1997-05-13 Siemens Aktiengesellschaft High-temperature fuel cell with improved solid-electrolyte/electrode interface and method of producing the interface
EP1081778A1 (fr) * 1998-04-21 2001-03-07 Toto Ltd. Pile a electrolyte solide et son procede de production
US20020102450A1 (en) * 2000-05-18 2002-08-01 Badding Michael E. High performance solid electrolyte fuel cells

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