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WO1993011574A1 - Pile a combustible - Google Patents

Pile a combustible Download PDF

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Publication number
WO1993011574A1
WO1993011574A1 PCT/GB1992/002172 GB9202172W WO9311574A1 WO 1993011574 A1 WO1993011574 A1 WO 1993011574A1 GB 9202172 W GB9202172 W GB 9202172W WO 9311574 A1 WO9311574 A1 WO 9311574A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
cathode
anode
cell
solid oxide
Prior art date
Application number
PCT/GB1992/002172
Other languages
English (en)
Inventor
Brian Charles Hilton Steele
Original Assignee
Imperial College Of Science, Technology & Medicine
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 Imperial College Of Science, Technology & Medicine filed Critical Imperial College Of Science, Technology & Medicine
Publication of WO1993011574A1 publication Critical patent/WO1993011574A1/fr

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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid electrolytes
    • H01M8/2428—Grouping by arranging unit cells on a surface of any form, e.g. planar or tubular
    • 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
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/242—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes comprising framed electrodes or intermediary frame-like gaskets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H01M8/2425—High-temperature cells with solid 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

Definitions

  • a number of successful cells have also been constructed with a tubular configuration, basically comprising a similar series of layers arranged concentrically, an internal air flow, and an external fuel flow.
  • a tubular configuration basically comprising a similar series of layers arranged concentrically, an internal air flow, and an external fuel flow.
  • difficulties involved in scaling these up to large sizes and there are also complications involved in the fabrication of the assembly with its various layers.
  • the level of performance and ease of construction of a solid oxide fuel cell do, of course, depend very much on the properties of the materials used, and it is, in fact, rather difficult to find materials for both the electrodes and the electrolyte which have the required characteristics at the necessary operating temperatures.
  • the current zirconia solid oxide electrolyte (Zr 0>g Y 0#1 0 1>95 ) requires operating temperatures in excess of 900°C to achieve conductivities comparable to liquid electrolytes for electrodes of 200-300 microns thick, i.e. with adequate structural properties. It would be most desirable to reduce the operating temperature, so as to be able to use stainless steel (for example) in the construction of the cell.
  • the present invention provides an electrolyte structure for a fuel cell, comprising a structural support material carrying a thin layer of ceramic electrolyte as an ionic conductor, in which the structural material is impermeable and in which conduction occurs by self diffusion rather than molecular diffusion through pores.
  • the support material is arranged to form the cathode or anode of the fuel cell, thus avoiding the necessity for separate support means for each of the electrolyte and corresponding electrode structures.
  • This construction is particularly suitable for solid oxide fuel cells but the same principle of a strong impermeable electrode supported thin film electrolyte structures can be extended to different systems, for example, composite Bi 2 0 3 - Tb 2 0 3 mixed cathode with Ce Q 9 G ⁇ o.l°1.95 thick film electrolytes can be used at 400°- 500°C in methanol fuel cells in transport applications for heavy lorries, buses, fleet vehicles, etc.
  • the support material is one having a lattice structure that allows oxygen ions to diffuse through, such as lanthanum cobalt manganese oxide which has good gas diffusion properties at a temperature of 800°C.
  • Figure 2 shows some examples of the conductivities of materials of this kind, at 800°C.
  • suitable materials include solid solutions of Uo 2 -Y 2 0 3 (U 0 . 7 Y 0 . 3 O 2 -x) or Ce0 2 -Tb 2 0 3 (Ce 0#7 b 0>3 O 2 -_ ⁇ ) and composite materials which comprise ionic/mixed conductors e.g. (Ce0 2 -Gd 2 0 3 ) + ZnO(Fe).
  • impermeable mixed conductivity cathode materials such as -L Q>6 Se 0#4 Co 0> gFe 0 2 0 3 _ ⁇ can be incorporated into the heat exchange stage of a fuel cell to separate oxygen from air. Pure oxygen is then fed to the fuel cell and the excess oxygen can be burnt with unused fuel to provide thermal energy for heat exchanger, steam turbines, process heat etc.
  • the advantage of combusting excess fuel with pure oxygen is that the pollutant N0 ⁇ will not be produced.
  • the invention also extends to a solid oxide fuel cell construction
  • a solid oxide fuel cell construction comprising: a housing; a metal bipolar separator plate: an open structured resilient support means supported on said bipolar plate; a porous anode plate supported on said resilient support means; a compound cathode/electrolyte structure comprising a cathode of a mixed conductor material allowing both ionic and electronic conduction and a coating of ceramic solid oxide forming the electrolyte, on the side of the cathode facing the anode; a further separator plate above the cathode; means for introducing air on the cathode side, and means for introducing fuel on the anode side, whereby oxygen in the air passes through the cathode material and is ionically conducted through the electrolyte to react with the fuel at the anode.
  • the construction in respect of the anode and cathode may be reversed, i.e. with a separate porous cathode plate, and an
  • the invention also extends to a planar multi-cell solid oxide fuel cell comprising a rigid frame structure formed with a plurality of side-by-side apertures each of which is adapted to receive a cell assembly; each assembly comprising a compound first electrode/electrolyte plate structure, in which the first electrode is of a mixed conductor material and the electrolyte is a coating of ceramic solid oxide, and a second electrode plate facing the electrolyte, the frame also providing means for insulating the edges of adjacent cells from one another, means for electrically connecting the anode of one cell to the cathode of the next, and means for passing air over the cathode side of the frame and fuel over the anode side so as to pass over each cell in turn.
  • Figure 3 is a vertical cross-section of a first type of fuel cell in accordance with the invention
  • Figure 4 is a cross-section on line A-A of Figure
  • Figure 5 shows the relationship between various types of fluorite and fluorite related oxygen ion conductors
  • Figure 7 shows a cross-section through a planar multi-cell structure
  • the electrolyte layer 34 comprises a zirconia solid oxide such as •Z-r 0#9 Y 0# ⁇ O 1 ⁇ g5 coated onto the cathode (e.g. by sputtering) or chemical vapour deposition and which can thus be made very thin e.g. 20-25 microns.
  • a zirconia solid oxide such as •Z-r 0#9 Y 0# ⁇ O 1 ⁇ g5 coated onto the cathode (e.g. by sputtering) or chemical vapour deposition and which can thus be made very thin e.g. 20-25 microns.
  • Thick electrolyte films (l-50 ⁇ m) can also be fabricated by a variety of techniques including pulsed laser depositions MOCVD, CVD, calendering tape-casting, electrophoresis etc. For some processing routes it will be necessary for dense electrode substances to be co-fired with the solid electrolyte which requires high temperature chemical compatibility.
  • a chamber 36 above the cathode carries air which is introduced at an inlet 38, positioned transversely relative to the fuel inlet 40, Figure 4 , which supplies the chamber 22 as mentioned above.
  • the oxygen in the air thus enters the cathode and oxygen ions are transported through it by self-diffusion to the electrolyte, where they react with the hydrocarbon fuel in a known fashion.
  • impermeable cathode member 32 Whilst the impermeable cathode member 32 provides oxygen ion transport to the solid cathode/electrolyte interface it also has to act as an electro-catalyst, for example, for the Faradaic reduction of oxygen,
  • a metal interconnecting frame 50 shown separately in Figure 8, comprises a separator plate 52 which is arranged to separate adjacent cell locations, and a pair of perforated support plates 54, 56 which extend at right angles from its opposite sides.
  • One support plate 54 is arranged near the lower end of the separator plate 52 so as to extend underneath the cell which is to the right of the separator plate, whilst the other support plate 56 is arranged near the upper end of the separator plate so as to extend above the left-hand cell.
  • Flanges 58 also extend outwardly from the top and bottom edges of plate 52 so as to locate the adjacent edges of the cells and co-operate with the adjacent frame 50, and thus it will be appreciated that a multi-cell structure of a large number of cells can be built up in this way.
  • the electrical components of a cell of this kind will typically comprise: (60) Mixed conducting cathode as a dense impermeable structural support component ( « 200 ⁇ m thick)
  • Porous anode structure e.g. Zr0 2 -Ni ( « 20 ⁇ m thick)
  • a large insulator 66 for example of MgO or Mg A1 2 0 4
  • a small insulator 68 of the same material is positioned at the top right hand side of the plate, so that the adjacent anode 64 to the right is also insulated from the plate.
  • the frame structure 50 which is preferably of a high-Cr alloy, then acts to connect all the cells in series.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

Structure électrolytique conçue pour une pile à combustible, particulièrement une pile à combustible à ''oxydes solides''. On constitue une structure de support à partir d'un conducteur mixte imperméable, tel qu'un oxyde de manganèse-cobalt de lanthane, dans lequel la conduction s'effectue par autodiffusion plutôt que par diffusion moléculaire à travers des pores, ce qui constitue une électrode de la pile et porte l'électrolyte à oxydes solides en tant que revêtement d'un matériau, tel que Zr0,9Y0,1O¿1,95. Ceci permet de réaliser une couche électrolytique très mince, ce qui est nécessaire pour un fonctionnement en température relativement basse, tout en optimisant la solidité structurale. On peut constituer des structures à piles multiples, disposées sous forme d'empilages ou situées sur le même plan.
PCT/GB1992/002172 1991-11-25 1992-11-25 Pile a combustible WO1993011574A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919125012A GB9125012D0 (en) 1991-11-25 1991-11-25 Solid oxide fuel cell
GB9125012.6 1991-11-25

Publications (1)

Publication Number Publication Date
WO1993011574A1 true WO1993011574A1 (fr) 1993-06-10

Family

ID=10705189

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1992/002172 WO1993011574A1 (fr) 1991-11-25 1992-11-25 Pile a combustible

Country Status (3)

Country Link
AU (1) AU2951192A (fr)
GB (1) GB9125012D0 (fr)
WO (1) WO1993011574A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996019015A3 (fr) * 1994-12-17 1996-08-15 Univ Loughborough Agencements de piles voltaique et de piles combustibles
EP1288658A3 (fr) * 2001-09-03 2004-02-11 NGK Spark Plug Company Limited Capteur de gaz avec une couche à conduction protonique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130693A (en) * 1976-05-28 1978-12-19 Den Berghe Paul Van Electrolyte-cathode assembly for a fuel cell
DE1771829B2 (de) * 1967-07-19 1980-04-03 Compagnie Francaise De Raffinage S.A., Paris Mehrschichtige Elektrode für Hochtemperatur-Brennstoffelemente
US4490444A (en) * 1980-12-22 1984-12-25 Westinghouse Electric Corp. High temperature solid electrolyte fuel cell configurations and interconnections
DE3436597A1 (de) * 1984-10-05 1986-04-10 Max Planck Gesellschaft Oxidischer koerper mit ionischer und elektronischer leitfaehigkeit
US4702971A (en) * 1986-05-28 1987-10-27 Westinghouse Electric Corp. Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1771829B2 (de) * 1967-07-19 1980-04-03 Compagnie Francaise De Raffinage S.A., Paris Mehrschichtige Elektrode für Hochtemperatur-Brennstoffelemente
US4130693A (en) * 1976-05-28 1978-12-19 Den Berghe Paul Van Electrolyte-cathode assembly for a fuel cell
US4490444A (en) * 1980-12-22 1984-12-25 Westinghouse Electric Corp. High temperature solid electrolyte fuel cell configurations and interconnections
DE3436597A1 (de) * 1984-10-05 1986-04-10 Max Planck Gesellschaft Oxidischer koerper mit ionischer und elektronischer leitfaehigkeit
US4702971A (en) * 1986-05-28 1987-10-27 Westinghouse Electric Corp. Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. Electrochem Soc., Volume 138, No. 7, July 1991, Junichiro Mizusaki et al, "Reaction Kinetics and Microstructure of the Solid Oxide Fuel Cells Air Electrode La0.6Ca0.4MnO03/YSZ" *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996019015A3 (fr) * 1994-12-17 1996-08-15 Univ Loughborough Agencements de piles voltaique et de piles combustibles
US6040075A (en) * 1994-12-17 2000-03-21 Loughborough University Of Technology Electrolytic and fuel cell arrangements
EP1288658A3 (fr) * 2001-09-03 2004-02-11 NGK Spark Plug Company Limited Capteur de gaz avec une couche à conduction protonique

Also Published As

Publication number Publication date
AU2951192A (en) 1993-06-28
GB9125012D0 (en) 1992-01-22

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