WO2000008702A1 - Procede de fabrication d'une cellule electrochimique a base de carbonate fondu - Google Patents

Procede de fabrication d'une cellule electrochimique a base de carbonate fondu Download PDF

Info

Publication number
WO2000008702A1
WO2000008702A1 PCT/NL1999/000501 NL9900501W WO0008702A1 WO 2000008702 A1 WO2000008702 A1 WO 2000008702A1 NL 9900501 W NL9900501 W NL 9900501W WO 0008702 A1 WO0008702 A1 WO 0008702A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
cathode
green
tape
semi
Prior art date
Application number
PCT/NL1999/000501
Other languages
English (en)
Inventor
Robert Christiaan Makkus
Eric Franciscus Sitters
Original Assignee
Stichting Energieonderzoek Centrum Nederland
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 Stichting Energieonderzoek Centrum Nederland filed Critical Stichting Energieonderzoek Centrum Nederland
Priority to AU53095/99A priority Critical patent/AU5309599A/en
Publication of WO2000008702A1 publication Critical patent/WO2000008702A1/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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/14—Fuel cells with fused electrolytes
    • H01M8/141—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
    • H01M8/142—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers with matrix-supported or semi-solid matrix-reinforced electrolyte
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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
    • 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 method according to the precharacterising clause of Claim 1.
  • a method of this type is disclosed in EP 0 509 424 A-2.
  • a cathode consisting of two layers is described in PCT application PCT NL 95/00306 in the name of the Applicant (European Application no. 95930058,3).
  • a cathode of this type is produced by placing said two layers on top of one another in the green state, for example by tape casting, and then combining the green cathode together with the other green components of the cell and heating. With this arrangements a matrix plate is present between the anode and cathode and the electrolyte material is introduced into the matrix plate in the cell in some way or other during start-up.
  • the aim of the present invention is to prevent the disadvantages described above.
  • the electrolyte is introduced into the green, i.e. unsintered. cathode material in a separate step.
  • Such introduction can take place at elevated temperature, but this temperature is lower than the temperature at which sintering takes place.
  • a value of 500°C for melting-in and a value of 950-1050°C tor sintering may be mentioned by way of example.
  • a sintered structure containing pores is not produced during the first-mentioned treatment. Combination with other (green) components of the cell takes place only thereafter, preferably only after cooling of the cathode provided with electrolyte to room temperature.
  • the method described above imparts adequate strength to the cathode to enable the latter to be placed against the matrix with adequate contact force during start-up.
  • the reduction in thickness that is detected during start-up is appreciably restricted, as will be illustrated in more detail below with the aid of the examples.
  • the green cathode described above can be any cathode known in the prior art.
  • the cathode comprises a tape in which the carbonate (electrolyte) material has been incorporated.
  • This tape is preferably produced by using a mixture of lithium cobaltite and carbonate particles as the starting material. This is in contrast to what is described in PCT application 94/18713, in which the starting material is cobalt particles which oxidise in the cell. Structural modifications, which have consequences for the pore size distribution, are found to take place as a result of this oxidation. This is avoided by using lithium cobaltite powder as the starting material.
  • the cathode consists of a structure of at least two layers. These layers are placed on top of one another in the green state, after which melting-in of electrolyte takes place.
  • These layers can be a layer based on lithium cobaltite and a layer containing (semi-)noble metal particles.
  • An example thereof is a layer containing nickel particles and the last-mentioned layer will be directed towards the separator plate or current collector during use and is primarily of importance because of the conductance, whilst the layer based on lithium cobaltite is designed more in order to allow the cathodic reaction to proceed in an optimum manner.
  • the method is carried out under oxidising conditions. If a tape in which the nickel layer is already present is used as the starting material, the method is carried out under a reducing atmosphere and during this procedure the electrolyte can optionally be applied as a tape.
  • an electrolyte tape is applied to the cathode.
  • the electrolyte tape consists of electrolyte and the electrolyte and binder are melted into the green cathode under elevated temperature. This process can take place under reducing conditions. In this case also the product thus obtained is not sintered. Sintering takes place later, either in a separate step or after combining the assembly in the electrochemical cell with anode and other components.
  • a green lithium cobaltite tape is produced by mixing together LiCoO 2 powder, ethanol and Tween (surface-active agent). Methylcellulose (with binder), demineralised water and TBP (solvent) are then added with continuous stirring. A tape is then cast in the manner described in PCT application PCT/NL95/00306. The tape is then dried.
  • An electrolyte tape consisting of a mixture of Li 2 CoO3, Na 2 CO 3 and K 2 CO 3 is then placed by the tape casting technique on top of said green LiCoO 2 tape.
  • the whole is heated in an oxidising gas atmosphere to 500 °C just above the melting point of the electrolyte and remains at this temperature for approximately 30 minutes.
  • the liquid electrolyte transfers from the electrolyte tape into the green LiCoO 2 tape. Cooling to room temperature then takes place. It has been found that the solidified electrolyte now present in the cathode tape increases the strength of the latter and protects the lithium cobaltite during start-up in an MCFC fuel cell.
  • a green nickel layer with a thickness of approximately 50 ⁇ m is applied to that side which subsequently comes into contact with the current collector. Good electrical contact between current collector and cathode is ensured by this means.
  • a 3 cm specimen was then subjected to a start-up operation, this start-up taking place under both dry and wet nitrogen gas.
  • Fig.. 1 the reduction in thickness of a cathode in the start-up phase is plotted as a function of the temperature, both for cathodes produced according to the prior art in combination with a separate supply of electrolyte and for cathodes according to the invention.
  • cathodes according to the prior art are indicated by a and b and a indicates start-up under dry conditions in nitrogen and b start-up under wet conditions.
  • the starting material used in this example is a green double tape, that is to say a tape consisting of two layers, in this case a layer of lithium cobaltite and a layer of nickel particles.
  • the UC0O2 tape is obtained in the manner described above.
  • a nickel suspension is then cast on top of this using the tape casting technique.
  • the nickel suspension is obtained by mixing nickel powder, methylcellulose, Tween, TBP and ethanol. After some time demineralised water is added and the mixture is stirred for half an hour.
  • an electrolyte tape consisting of a mixture of U2C0O 3 , Na 2 CO 3 and K2CO3 is applied thereto.
  • the electrolyte tape is placed on the lithium cobaltite part of the double tape. Melting-in of the electrolyte then takes place, that is to say electrolyte moves from the electrolyte tape to the LiCoO 2 layer as a result of heating under a reducing gas atmosphere to just above the melting point of the electrolyte
  • the electrolyte solidified in the cathode imparts strength to the cathode and protects the LiCoO 2 against reduction during start-up in the fuel cell. Because the green LiCoO 2 /Ni tape is placed with the nickel side against a current collector when applying the electrolyte tape, said current collector can give the package that is thus obtained strength during subsequent transport and contact between the nickel layer and the current collector is optimised. It has been found that an MCFC cell obtained with the aid of this method has the same good characteristics as the MCFC cell described on the basis of Example 1.

Landscapes

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

Abstract

L'invention concerne un procédé de fabrication d'une cellule électrochimique constituée d'une anode et d'une cathode séparées par une matrice contenant un électrolyte. Selon ce procédé, l'électrolyte est fondu dans la cathode crue à une température élevée afin d'améliorer sa stabilité; la cellule est ensuite combinée à la cathode crue puis chauffée. Selon ce procédé, la cathode peut être constituée de deux couches ou plus ; on peut également la fabriquer à partir d'un mélange, en coulant une bande constituée d'un mélange de cobaltite de lithium et de carbonate. Pour fondre la matière électrolytique, on la chauffe dans un four.
PCT/NL1999/000501 1998-08-06 1999-08-06 Procede de fabrication d'une cellule electrochimique a base de carbonate fondu WO2000008702A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53095/99A AU5309599A (en) 1998-08-06 1999-08-06 Method for the production of an mcfc electrochemical cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1009815 1998-08-06
NL1009815A NL1009815C2 (nl) 1998-08-06 1998-08-06 Werkwijze voor het vervaardigen van een MCFC elektrochemische cel.

Publications (1)

Publication Number Publication Date
WO2000008702A1 true WO2000008702A1 (fr) 2000-02-17

Family

ID=19767616

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1999/000501 WO2000008702A1 (fr) 1998-08-06 1999-08-06 Procede de fabrication d'une cellule electrochimique a base de carbonate fondu

Country Status (3)

Country Link
AU (1) AU5309599A (fr)
NL (1) NL1009815C2 (fr)
WO (1) WO2000008702A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003073544A2 (fr) * 2002-02-27 2003-09-04 Gencell Corporation Boue d'electrolyte a base aqueuse pour piles a combustible au carbonates fondus et mode d'utilisation

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6366858A (ja) * 1986-09-08 1988-03-25 Matsushita Electric Ind Co Ltd 溶融炭酸塩燃料電池用電極の製造法
US4891280A (en) * 1986-04-25 1990-01-02 The United States Of America As Represented By The United States Department Of Energy Cathode for molten carbonate fuel cell
EP0509424A2 (fr) * 1991-04-16 1992-10-21 Institute of Gas Technology Composite d'une matrice et d'électrolyte activé et bandes laminées à composants différents pour piles à combustible à carbonates fondus
JPH04351854A (ja) * 1991-05-28 1992-12-07 Mitsubishi Electric Corp 溶融炭酸塩型燃料電池の製造方法
US5240786A (en) * 1992-03-13 1993-08-31 Institute Of Gas Technology Laminated fuel cell components
WO1994018713A1 (fr) * 1993-02-04 1994-08-18 Mtu Motoren- Und Turbinen-Union Friedrichshafen Gmbh Procede de production de la couche cathodique de cellules electrochimiques en carbonate fondu
EP0678926A1 (fr) * 1994-04-19 1995-10-25 FINMECCANICA S.p.A. AZIENDA ANSALDO Méthode de fabrication de cathodes pour piles à combustible
US5468573A (en) * 1994-06-23 1995-11-21 International Fuel Cells Corporation Electrolyte paste for molten carbonate fuel cells
WO1996008050A1 (fr) * 1994-09-09 1996-03-14 Stichting Energieonderzoek Centrum Nederland Bande double adaptee a l'utilisation dans les piles a carbonates fondus
JPH1074529A (ja) * 1996-08-30 1998-03-17 Toshiba Corp 溶融炭酸塩型燃料電池及び製造法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4891280A (en) * 1986-04-25 1990-01-02 The United States Of America As Represented By The United States Department Of Energy Cathode for molten carbonate fuel cell
JPS6366858A (ja) * 1986-09-08 1988-03-25 Matsushita Electric Ind Co Ltd 溶融炭酸塩燃料電池用電極の製造法
EP0509424A2 (fr) * 1991-04-16 1992-10-21 Institute of Gas Technology Composite d'une matrice et d'électrolyte activé et bandes laminées à composants différents pour piles à combustible à carbonates fondus
JPH04351854A (ja) * 1991-05-28 1992-12-07 Mitsubishi Electric Corp 溶融炭酸塩型燃料電池の製造方法
US5240786A (en) * 1992-03-13 1993-08-31 Institute Of Gas Technology Laminated fuel cell components
WO1994018713A1 (fr) * 1993-02-04 1994-08-18 Mtu Motoren- Und Turbinen-Union Friedrichshafen Gmbh Procede de production de la couche cathodique de cellules electrochimiques en carbonate fondu
EP0678926A1 (fr) * 1994-04-19 1995-10-25 FINMECCANICA S.p.A. AZIENDA ANSALDO Méthode de fabrication de cathodes pour piles à combustible
US5468573A (en) * 1994-06-23 1995-11-21 International Fuel Cells Corporation Electrolyte paste for molten carbonate fuel cells
WO1996008050A1 (fr) * 1994-09-09 1996-03-14 Stichting Energieonderzoek Centrum Nederland Bande double adaptee a l'utilisation dans les piles a carbonates fondus
JPH1074529A (ja) * 1996-08-30 1998-03-17 Toshiba Corp 溶融炭酸塩型燃料電池及び製造法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 109, no. 2, 11 July 1988, Columbus, Ohio, US; abstract no. 9417, NIIKURA JUNJI ET AL: "Electrodes for molten-carbonate fuel cells" XP002125957 *
NIIKURA J ET AL: "FABRICATION AND PROPERTIES OF COMBINED ELECTRODE/ELECTROLYTE TAPE FOR MOLTEN CARBONATE FUEL CELLS", JOURNAL OF APPLIED ELECTROCHEMISTRY, vol. 20, no. 4, 1 July 1990 (1990-07-01), pages 606 - 610, XP000453540 *
PATENT ABSTRACTS OF JAPAN vol. 017, no. 214 (E - 1357) 27 April 1993 (1993-04-27) *
PATENT ABSTRACTS OF JAPAN vol. 098, no. 008 30 June 1998 (1998-06-30) *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 291 (E - 644) 9 August 1988 (1988-08-09) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003073544A2 (fr) * 2002-02-27 2003-09-04 Gencell Corporation Boue d'electrolyte a base aqueuse pour piles a combustible au carbonates fondus et mode d'utilisation
WO2003073544A3 (fr) * 2002-02-27 2004-10-21 Gencell Corp Boue d'electrolyte a base aqueuse pour piles a combustible au carbonates fondus et mode d'utilisation
US6844102B2 (en) 2002-02-27 2005-01-18 Gencell Corporation Aqueous based electrolyte slurry for MCFC and method of use

Also Published As

Publication number Publication date
AU5309599A (en) 2000-02-28
NL1009815C2 (nl) 2000-02-15

Similar Documents

Publication Publication Date Title
JP7089494B2 (ja) 金属支持固体酸化物燃料電池
US5582624A (en) Process for producing molten-carbonate fuel cells
CN105518921A (zh) 金属支撑型固体氧化物燃料电池的制备方法
JP2016533017A5 (fr)
TWI342635B (en) Fuel cell and passive support
EP0714146B1 (fr) Anode pour pile à combustible et pile à combustible
US4654195A (en) Method for fabricating molten carbonate ribbed anodes
US6063141A (en) Cathode for a molten carbonate fuel cell and method for manufacturing same
JPH0746610B2 (ja) 溶融炭酸塩燃料電池正極及びその製造方法
US5415833A (en) Method for forming molten carbonate fuel cell anodes
WO2000008702A1 (fr) Procede de fabrication d'une cellule electrochimique a base de carbonate fondu
KR100681771B1 (ko) 니켈-알루미늄 합금의 인-시츄 소결에 의한 용융탄산염연료전지용 니켈-알루미늄 합금 연료극 및 그 제조방법
CN115700938A (zh) 一种金属锂电池负极的制备方法
KR102082691B1 (ko) 전해질이 함침된 매트릭스를 포함하는 용융탄산염 연료전지 및 이의 제조 방법
EP0473882B1 (fr) Méthode pour fabriquer des cathodes pour éléments galvaniques à carbonates fondus
JP2514748B2 (ja) 溶融炭酸塩燃料電池の始動法
CN114634177A (zh) 一种石墨膜的制备方法
JPH0520872B2 (fr)
KR101047717B1 (ko) 용융탄산염 연료전지용 전해질 함침형 다공성 금속 전극의 동시 건식 제조 방법
KR101311782B1 (ko) Ｍｃｆｃ용 대형 전해질 함침 전극의 제조법
US6238619B1 (en) Process for the production of an electrode for a fused carbonate fuel cell
JP2517750B2 (ja) 溶融塩型燃料電池の製造方法
JPS62213066A (ja) ガス拡散電極の製造方法
JPH06176764A (ja) 燃料電池用リブ付き電極およびその製造方法
JPH09283160A (ja) 固体電解質型燃料電池の固体電解質の製造方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase