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WO1999057777A1 - Scellement destine a une electrode a plaque matrice - Google Patents

Scellement destine a une electrode a plaque matrice Download PDF

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Publication number
WO1999057777A1
WO1999057777A1 PCT/NL1999/000271 NL9900271W WO9957777A1 WO 1999057777 A1 WO1999057777 A1 WO 1999057777A1 NL 9900271 W NL9900271 W NL 9900271W WO 9957777 A1 WO9957777 A1 WO 9957777A1
Authority
WO
WIPO (PCT)
Prior art keywords
matrix
electrochemical cell
cell according
foil
electrode
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/NL1999/000271
Other languages
English (en)
Inventor
Gijsbertus Rietveld
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.)
Energy Research Centre of the Netherlands
Original Assignee
Energy Research Centre of the Netherlands
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 Energy Research Centre of the Netherlands filed Critical Energy Research Centre of the Netherlands
Priority to AU37368/99A priority Critical patent/AU3736899A/en
Publication of WO1999057777A1 publication Critical patent/WO1999057777A1/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
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • 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
    • H01M8/244—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes with matrix-supported molten electrolyte
    • 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
    • H01M2008/147—Fuel cells with molten carbonates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0048—Molten electrolytes used at high temperature
    • H01M2300/0051—Carbonates
    • 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 present invention relates to an electrochemical cell according to the preamble of Claim 1.
  • a cell of this type is disclosed in US Patent 5 298 342.
  • the matrix plate consists of a ceramic material that has been filled with a carbonate material solidified at room temperature. On heating to approximately 650 °C the carbonate becomes fluid and provides, on the one hand, the electrolyte and, on the other hand, a seal between the electrodes.
  • a matrix plate of this type is provided with openings for transporting gases in a direction perpendicular to the plate. Close to said openings there is a special construction on either side of the matrix plates, which special construction provides for communication between such an opening and the gas distribution element of the electrode concerned.
  • a special construction of this type must be constructed such that a seal is provided with respect to the other electrode, that is to say the electrode that is located on the other side of the matrix.
  • support plates are used which meet the separator plate and are joined to one another, so as to provide a seal, at the location of the opening.
  • a stainless steel support plate is used.
  • the support plates can be provided with elevations or ribs which are of a highly local nature and in combination with the matrix plate prevent cracking of the latter.
  • Such cracks can arise during operation and especially during warming up.
  • Such cracks form openings extending through the matrix and, certainly in the region between support plate and electrode, which region will hereinafter be referred to as transition, can have particularly disastrous effects because in an extreme case the reactants can come into direct contact with one another.
  • the aim of the present application is to restrict the consequences of such cracking as far as possible.
  • such compression is achieved if at least 50 % of the thickness of the foil component is taken up in the surrounding matrix material by compression of the latter.
  • the compression that takes place is such that the matrix at the location of the transition, that is to say including the foil component located therein, is no more than 30 % thicker than the rest of the matrix.
  • a local foil layer of this type can be applied in various ways. For instance, it is possible for the foil layer to have been applied such that it extends parallel to the boundary surface of the matrix plate, the layer having been placed against one side of the matrix plate and contact pressure being thus exerted thereon by the support plate and the electrode concerned. It is also possible to make a recess in the matrix plate or to make said plate of stepped construction. On the other hand, such a recess will automatically be formed during heating of the electrochemical cell. It is also possible to allow such a foil layer to extend from the heart of the matrix to the edge limit. This can be of importance when a metallic foil layer is used where direct electrical contact between support plate and electrode and foil is not desired or, on the contrary, is desired. Of course, numerous other embodiments of the foil layer are possible, sealing always being provided in the event of cracking of the matrix plate.
  • the foil material consists 3 of a stainless steel support on which an aluminium layer has been applied.
  • an aluminium layer is formed which consists of a mixture of intermetallic compounds of, on the one hand, iron, nickel and chromium and, on the other hand, aluminium.
  • This aluminising layer has a melting point that is significantly higher than the operating temperature of the cell.
  • the aluminium in the aluminising layer reacts with the carbonate material to form a sealing layer (in general this will be lithium aluminate) which counteracts further attack.
  • the thickness of the foil material is preferably between 0.05 and 0.6 mm and more particularly is approximately 0.2 mm.
  • the aluminium layer is present in a thickness of between 10 and 60 ⁇ m and preferably 20 ⁇ m.
  • the aluminium is applied, for example, by PVD.
  • the foil material can comprise a metallic material. This will be the case in particular if operating at elevated temperatures, as in an MCFC cell. However, it is certainly conceivable to use foil layers in electrochemical cells which operate at relatively low temperatures. In this case plastic materials can be used. If metallic material is used it is, of course, important that the material is not (too rapidly) attacked by chemical reactions and/or does not prevent the electrochemical reaction. To this end the foil material is preferably a (semi-)noble material such as copper, nickel, silver and/or gold or a material having a high corrosion resistance, such as aluminium-alloyed nickel or steel, or an aluminised metal.
  • a (semi-)noble material such as copper, nickel, silver and/or gold
  • a material having a high corrosion resistance such as aluminium-alloyed nickel or steel, or an aluminised metal.
  • anode-support plate end delimition and the cathode-support plate end delimitaton are in line with one another with respect to a perpendicular to the plane of the matrix. It has been found that as a result local 4 high stress concentrations can arise in the matrix, which is one of the reasons for cracking, the effect of which can be eliminated by means of the measures described above.
  • Such cracking can be appreciably restricted or prevented by no longer arranging the anode-support plate/cathode-support plate end delimitations in one line with respect to a perpendicular to the separator plate. That is to say the end delimitions are offset with respect to one another.
  • the adaptability of the construction can be increased by making one or both gas distribution elements again offset with respect to the electrode current collector assembly.
  • Fig. 1 shows part of a fuel cell stack close to a discharge opening for gases
  • Fig. 3 shows a second embodiment of the detail shown in Fig. 1, and
  • Fig. 4 shows, in detail, a modified foil component according to the invention.
  • Fig. 1 the fuel cell stack according to the invention is indicated in its entirety by 1.
  • This fuel cell stack consists of a number of fuel cells 13.
  • Each fuel cell 13 consists of a cathode 2 and an anode 3.
  • MCFC molten carbonate fuel cell
  • a cathode current collector which is indicated by 4
  • a cathode current collector is joined to the cathode 2 and the same applies in respect of the anode 3, which is joined to an anode current collector 5.
  • Gas distribution elements abut the current collectors.
  • the gas distribution elements are indicated by 21 for the cathode and by 20 for the anode.
  • the gas distribution element for the anode consists, for example, of a wire mesh.
  • a separator plate is indicated by 6, whilst the matrix plate containing carbonate material is indicated by 7.
  • Such a plate can be produced by any method known from the prior art, such as by tape casting. Only the discharge of gas via element 9 is shown in the drawing.
  • Two support plates join onto the separator plate 6. Said support plates are indicated in
  • Fig. 2 by 10 and 11. These plates are stainless steel components which have been welded to the separator plate 6 close to opening 9 so as to provide a seal. Openings, which are not indicated in more detail, will be present in one of the support plates in order to provide gas communication with either the cathode gas distribution element or the anode gas distribution element.
  • the support plates 10, 11 extend over a relatively short length and then merge into the anode 3 and, respectively, the cathode 2.
  • the transition between anode 3 and support plate 10 is indicated by 15. It can be seen from the drawing that these 5 have been arranged offset with respect to one another.
  • a foil 8 of metallic material has been arranged in the heart of the matrix 7.
  • the foil extends essentially parallel to the plane of the matrix plate 7.
  • the gas distribution element 20 extends less far than the corrugation 5.
  • the length of the foil component 8 is indicated by 1 in Fig. 2. According to the invention this length is between 5 and 21 mm and is preferably approximately 9 mm. In the latter case aways 3 mm of the foil extends in a different area of the electrochemical cell, that is to say 3 mm extends beyond component 11, 3 mm extends in the area where only component 11 and not component 10 as well is located and 3 mm extends in an area where both component 11 and component 10 are present.
  • the foil material can be any material that is able to withstand the environment in the matrix and in the case of an MCFC cell this will be carbonate material that is appreciably aggressive at 650 °C, so that preference is given to a (semi-)noble metal foil.
  • a foil of this type for example made of gold material, can have a thickness of 50 ⁇ m.
  • (semi-)noble metals other materials able to withstand the environment concerned can also be used.
  • a nickel foil containing 5 - 50 % by weight aluminium may be mentioned by way of example.
  • Another possibility is a stainless steel alloy containing an appreciable proportion of 6 aluminium.
  • Gas distribution element 20 has the same length, whilst element 21 has been offset somewhat.
  • the foil layer is indicated here by 18 and it can be seen that said layer is in contact with anode 3. So as to avoid contact with support plate 10, said foil layer extends into the interior of the matrix close to said support plate 10.
  • a further foil component is indicated diagrammatically by 28. This can be used either as a curved foil component or as a straight foil component.
  • This consists of a core of stainless material of the 300 series, which core is indicated by 29, provided with a layer of aluminium applied thereon on all sides, which layer of aluminium is indicated by 30.
  • the thickness of the layer of stainless steel is 0.2 mm, whilst the aluminium layer applied by PVD has a thickness of 20 ⁇ m.
  • Such a strip of material is arranged in the electrochemical cell and on starting up the electrochemical cell, under the influence of high temperature and the environment prevailing in the cell, an aluminate is formed by aluminium material that forms a compound with the lithium or potassium present in the matrix. Moreover, an intermetallic aluminium-nickel-chromium-iron compound is formed. It will be understood that numerous variants for the positioning of the foil layer are possible. The only essential aspect is that, by local compression of the matrix, the foil prevents cracking in said matrix and, in the unlikely event of fracture still occurring, that passage of gases and the coming together of reactants is effectively prevented. It will be understood that such variants lie within the scope of the appended claims.

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  • 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)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une cellule électrochimique se composant d'une plaque matrice de scellement sur chaque côté de laquelle viennent buter des ensembles électrodes (2, 3). Cette plaque matrice est dotée d'ouvertures servant à l'alimentation/évacuation de gaz participant à la réaction électrochimique. A proximité de ces ouvertures sont situées des plaques de support (10, 11), lesquelles soutiennent les électrodes. De manière à empêcher une fuite locale, on a proposé de disposer un matériau métallique en feuille dans la plaque matrice (7) ou de l'adjoindre à celle-ci, lequel matériau s'étend au-dessus dudit espacement. En outre, il est possible d'agencer de manière décalée les extrémités délimitant la cathode (2) et l'anode (3) l'une par rapport à l'autre, par rapport à une perpendiculaire à la plaque matrice.
PCT/NL1999/000271 1998-05-04 1999-05-04 Scellement destine a une electrode a plaque matrice Ceased WO1999057777A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37368/99A AU3736899A (en) 1998-05-04 1999-05-04 Seal for matrix plate electrode

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1009062A NL1009062C2 (nl) 1998-05-04 1998-05-04 Afdichting voor matrixplaat/elektrode.
NL1009062 1998-05-04

Publications (1)

Publication Number Publication Date
WO1999057777A1 true WO1999057777A1 (fr) 1999-11-11

Family

ID=19767072

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1999/000271 Ceased WO1999057777A1 (fr) 1998-05-04 1999-05-04 Scellement destine a une electrode a plaque matrice

Country Status (3)

Country Link
AU (1) AU3736899A (fr)
NL (1) NL1009062C2 (fr)
WO (1) WO1999057777A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004004040A3 (fr) * 2002-06-28 2005-03-24 Honda Motor Co Ltd Pile a combustible
WO2004020559A3 (fr) * 2002-08-28 2005-03-24 Honda Motor Co Ltd Pile a combustible
FR2887687A1 (fr) * 2005-06-28 2006-12-29 Peugeot Citroen Automobiles Sa Plaque bipolaire de pile a combustible a fonction etancheite integree et cellule de pile a combustible comportant de telles plaques

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61109261A (ja) * 1984-11-01 1986-05-27 Fuji Electric Co Ltd 溶融炭酸塩型燃料電池の電解質板
JPS63307670A (ja) * 1987-06-08 1988-12-15 Ishikawajima Harima Heavy Ind Co Ltd 積層燃料電池
JPH01276565A (ja) * 1988-04-27 1989-11-07 Mitsubishi Electric Corp 溶融炭酸塩型燃料電池
JPH0374058A (ja) * 1989-08-15 1991-03-28 Mitsubishi Electric Corp 溶融塩型燃料電池
JPH0434860A (ja) * 1990-05-29 1992-02-05 Matsushita Electric Ind Co Ltd 溶融炭酸塩型燃料電池
US5298342A (en) * 1992-10-20 1994-03-29 M-C Power Corporation Fuel cell crossover arrestor and pressure seal
JPH06290797A (ja) * 1993-03-31 1994-10-18 Toshiba Corp 積層型燃料電池
JPH07153473A (ja) * 1993-11-30 1995-06-16 Toshiba Corp 積層型燃料電池
JPH0963599A (ja) * 1995-08-25 1997-03-07 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池用セパレータ
US5616431A (en) * 1994-01-27 1997-04-01 Mitsubishi Denki Kabushiki Kaisha Fuel cell and its bipolar plate
JPH10112327A (ja) * 1996-10-04 1998-04-28 Yoyu Tansanengata Nenryo Denchi Hatsuden Syst Gijutsu Kenkyu Kumiai 溶融炭酸塩型燃料電池

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61109261A (ja) * 1984-11-01 1986-05-27 Fuji Electric Co Ltd 溶融炭酸塩型燃料電池の電解質板
JPS63307670A (ja) * 1987-06-08 1988-12-15 Ishikawajima Harima Heavy Ind Co Ltd 積層燃料電池
JPH01276565A (ja) * 1988-04-27 1989-11-07 Mitsubishi Electric Corp 溶融炭酸塩型燃料電池
JPH0374058A (ja) * 1989-08-15 1991-03-28 Mitsubishi Electric Corp 溶融塩型燃料電池
JPH0434860A (ja) * 1990-05-29 1992-02-05 Matsushita Electric Ind Co Ltd 溶融炭酸塩型燃料電池
US5298342A (en) * 1992-10-20 1994-03-29 M-C Power Corporation Fuel cell crossover arrestor and pressure seal
JPH06290797A (ja) * 1993-03-31 1994-10-18 Toshiba Corp 積層型燃料電池
JPH07153473A (ja) * 1993-11-30 1995-06-16 Toshiba Corp 積層型燃料電池
US5616431A (en) * 1994-01-27 1997-04-01 Mitsubishi Denki Kabushiki Kaisha Fuel cell and its bipolar plate
JPH0963599A (ja) * 1995-08-25 1997-03-07 Ishikawajima Harima Heavy Ind Co Ltd 燃料電池用セパレータ
JPH10112327A (ja) * 1996-10-04 1998-04-28 Yoyu Tansanengata Nenryo Denchi Hatsuden Syst Gijutsu Kenkyu Kumiai 溶融炭酸塩型燃料電池

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* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 010, no. 289 (E - 442) 2 October 1986 (1986-10-02) *
PATENT ABSTRACTS OF JAPAN vol. 013, no. 147 (E - 741) 11 April 1989 (1989-04-11) *
PATENT ABSTRACTS OF JAPAN vol. 014, no. 045 (E - 0880) 26 January 1990 (1990-01-26) *
PATENT ABSTRACTS OF JAPAN vol. 015, no. 240 (E - 1079) 20 June 1991 (1991-06-20) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 210 (E - 1203) 19 May 1992 (1992-05-19) *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 001 28 February 1995 (1995-02-28) *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 009 31 October 1995 (1995-10-31) *
PATENT ABSTRACTS OF JAPAN vol. 097, no. 007 31 July 1997 (1997-07-31) *
PATENT ABSTRACTS OF JAPAN vol. 098, no. 009 31 July 1998 (1998-07-31) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004004040A3 (fr) * 2002-06-28 2005-03-24 Honda Motor Co Ltd Pile a combustible
US7258944B2 (en) 2002-06-28 2007-08-21 Honda Giken Kogyo Kabushiki Kaisha Fuel cell with improved separators and circular disk-shaped electrolyte electrode assemblies
WO2004020559A3 (fr) * 2002-08-28 2005-03-24 Honda Motor Co Ltd Pile a combustible
US7122267B2 (en) 2002-08-28 2006-10-17 Honda Giken Kogyo Kabushiki Kaisha Fuel cell configured with discharge passages that preheat fuel gas and prevent cross leakage
FR2887687A1 (fr) * 2005-06-28 2006-12-29 Peugeot Citroen Automobiles Sa Plaque bipolaire de pile a combustible a fonction etancheite integree et cellule de pile a combustible comportant de telles plaques
WO2007003751A1 (fr) * 2005-06-28 2007-01-11 Peugeot Citroen Automobiles S.A. Plaque bipolaire de pile à combustible à fonction étanchéité intégrée et cellule de pile à combustible comportant de telles plaques

Also Published As

Publication number Publication date
AU3736899A (en) 1999-11-23
NL1009062C2 (nl) 1999-11-05

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