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WO1997034331A1 - Procede pour revetir d'une couche vitreuse, un composant d'une pile a combustible a haute temperature et empilage de piles a combustible a haute temperature - Google Patents

Procede pour revetir d'une couche vitreuse, un composant d'une pile a combustible a haute temperature et empilage de piles a combustible a haute temperature Download PDF

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Publication number
WO1997034331A1
WO1997034331A1 PCT/DE1997/000382 DE9700382W WO9734331A1 WO 1997034331 A1 WO1997034331 A1 WO 1997034331A1 DE 9700382 W DE9700382 W DE 9700382W WO 9734331 A1 WO9734331 A1 WO 9734331A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
fuel cell
temperature fuel
layer
component
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/DE1997/000382
Other languages
German (de)
English (en)
Inventor
Thomas Jansing
Ludger Blum
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Priority to JP9532170A priority Critical patent/JP2000506309A/ja
Priority to AU25031/97A priority patent/AU713015B2/en
Priority to EP97916319A priority patent/EP0886886A1/fr
Publication of WO1997034331A1 publication Critical patent/WO1997034331A1/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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D5/00—Coating with enamels or vitreous layers
    • C23D5/02—Coating with enamels or vitreous layers by wet methods
    • 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
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • 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 invention relates to a method for coating a component of a high-temperature fuel cell with a glass-like layer, to a use of the method for the production of a high-temperature fuel cell stack and to a high-temperature fuel cell stack.
  • planar components for example the planar components of a high-temperature fuel cell stack
  • the planar components are usually connected to one another with glass solders or with composite glass solders.
  • a suitable composite glass solder consists, for example, of a glass base made of B 2 0 3 -Si0 2 -CaO or B 2 0 3 -Si0 2 -BaO and corresponding ceramic composite parts made of, for example, Zr0 2 , Al 2 0 3 or MgO.
  • One advantage of glass solders is that they can be soldered in both atmosphere and vacuum.
  • a practiced technique for joining the various planar components is with so-called green foils.
  • the composite glass solder is mixed together with an organic binder and, for example, by means of
  • the total density of the green film is relatively low due to the volume fraction of the binder.
  • the green film shrinks, which can be up to 80%. Since gas-carrying channels and spaces are formed between the individual planar components, which must be gas-tightly separated from one another, gas-tight separation of the various channels and spaces can be achieved only with difficulty and with great uncertainty due to the shrinkage when using green foils.
  • the binder must be removed from the green film without leaving any residue. This can lead to additional problems between the various planar components, since the substances released, such as binders, disperse yaws, solvents and plasticizers, can only reach the outside very poorly via the seal created when the planar components are joined together. A residue-free burnout of these released substances is therefore not guaranteed inside the high-temperature fuel cell stack.
  • the invention is based on the object of specifying a method for coating a component of a high-temperature fuel cell, in which the above-mentioned technical disadvantages are largely avoided.
  • the invention is based on the object of specifying a use of the method for producing a high-temperature fuel cell stack, in which the power density is not reduced when the components forming the high-temperature fuel cell stack are joined together.
  • a high-temperature fuel cell stack for performing the method is to be specified.
  • the first-mentioned object is achieved according to the invention by a method for coating a component of a high-temperature fuel cell with at least one glass-like layer, the glass-like layer being produced by enamelling.
  • the second-mentioned object is achieved according to the invention by using the method for producing a high-temperature fuel cell stack.
  • the third object is achieved according to the invention by a high-temperature fuel cell stack with a plurality of components, in which the components have at least one a glass-like layer are connected to one another, the glass-like layer being produced by enamelling.
  • the product of the enamel is a glass-like, chemically quite resistant layer.
  • the enamel can be defined as melt mixtures of silicates, borates and fluorides of the glass-forming elements which solidify at a relatively low temperature, in particular Na, K, Pb and Al, which solidify through the separation of solid or gaseous substances, such as gas bubbles.
  • the enamelling can be done either with wet enamel or with powder enamel as an enamel base.
  • the basic material with which the enamelling is carried out is called the enamel basic material.
  • This method for producing a glass-like layer in which the enamel base material is preferably applied to the component by wet powder spraying, is moreover at least 15 to 20 times cheaper than the thermal spraying methods known from the prior art.
  • FIG. 1 shows a coated component of a high-temperature fuel cell in a detail and in a schematic representation
  • FIG. 2 shows a section of a high-temperature fuel cell stack in a schematic representation.
  • a plurality of layers 6, 8, 10, 8, 10, 12 are applied to a planar component 4 of a high-temperature fuel cell 2.
  • the planar component 4 is, for example, a composite printed circuit board. It preferably consists of the metal CrFe 5 Y 2 0 3 l, Haynes Alloy 230, Inconel 600 or a common industrial steel.
  • An electrode (not shown in more detail) is supplied with an operating medium via this planar component 4 and, moreover, the Electricity is discharged from the high-temperature fuel cell 2 for use.
  • the ceramic layer 6 is first arranged on the planar component 4 of the high-temperature fuel cell 2.
  • the ceramic layer 6 consists for example of Al 2 0 3 , spinel or Zr0 2 . In practice, however, several ceramic layers 6 of different compositions are arranged one above the other, which is not shown in this embodiment.
  • the ceramic layer 6, whose thermal expansion coefficient is adapted to the thermal expansion coefficient of the component 4 of the high-temperature fuel cell 2, ensures good adhesion of the subsequently arranged glass-like layers 8, 10, 12 to the component 4. Electrical insulation is also achieved through the ceramic layer 6.
  • the glass-like layer 8 is produced by enamelling, for example from one
  • glass solder is a lightly melting soldering glass which is characterized by low viscosity and small surface tensions and whose melting temperature lies in the temperature range between 600 and 1000 ° C.
  • Glass ceramics is the name for a polycrystalline solid, which is controlled devitrification of a glass is produced. These glassy substances can be in the powdery state, i.e. in other words as an enamel base material, apply very tightly and firmly to the component.
  • the enamel base material for the enamelling is applied to the component 4 by wet powder spraying or by a screen printing process before the actual enamelling process.
  • the enamel base material contains a binder, the proportion of the binder being between 5 and 20% by weight of the enamel base material.
  • the costs saved by these cold processes compared to the thermal spraying processes are a factor of at least 15 to 20. The total cost saving in the present process is thus already achieved when the enamel base material is applied.
  • the enamel base material After applying the enamel base material, it is dried out in a defined manner. This happens for example at a temperature T between 50 and 100 ° C in a period of 2 hours to 3 days.
  • the enamel base material adheres poorly to the planar component 4 due to its powdery structure.
  • the enamelling achieves a material connection between the glass-like layer 8, consisting of the enamel base material processed by enamelling, and the planar component 4.
  • the enamelling in other words the production of the glass-like, solid, binder-free and low-pore layer 8, takes place at a predetermined temperature T E of, for example, approximately 800 ° C. This is above the softening temperature for the components of the enamel base material and below the soldering temperature for joining the components 4 of the high-temperature fuel cell 2.
  • the heating rate is dependent on the components of the enamel base material and is, for example, 5K / min.
  • a further glass-like layer 10 is arranged on the glass-like layer 8.
  • the glass-like layer 10 can have the same or a different composition as the glass-like layer 8.
  • a succession of different glass-like layers 8, 10 has the advantage that different requirements, such as electrical insulation, thermal linear expansion, tion coefficient and gas-tightness, can be fulfilled separately by different glass-like layers 8, 10.
  • the thickness of the individual glass-like layers 8, 10 is limited by the occurrence of mechanical stresses. Depending on the desired total layer thickness, the sequence of glass-like layers 8, 10 is repeated periodically. Total layer thicknesses of, for example, 500 ⁇ m can be achieved without the resulting residual stress of the arrangement of several layers 8, 10 increasing. This leads to a substantial mechanical stabilization of the entire high-temperature fuel cell.
  • a further glass-like layer 12 is applied to the glass-like layer 10 last produced by the enamelling process that no enamelling is carried out.
  • This embodiment of the glass-like layer 12 is optional.
  • the section of a high-temperature fuel cell stack 20 comprises two components 22 and 24, which are connected to one another in a gas-tight manner by a glass-like layer 26 and are electrically insulated from one another, the glass-like layer 26 being produced by enamelling.
  • Composite glass solders are particularly suitable as glass-like substances, for example 75% by weight from a glass solder, for example B 2 0 3 -Si0 2 -CaO and / or BaO, and 25% by weight. consist of a ceramic, such as Zr0 2 , MgO or Al 2 0 3 , as a mixture.
  • the glass-like layer 26 can be replaced by an arrangement consisting of the sequence of layers 6, 8, 10, 8, 10, 12, which is shown in the exemplary embodiment in FIG.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

Procédé pour revêtir d'au moins une couche vitreuse (8, 10), un composant (4) d'une pile à combustible à haute température (2), par émaillage. On réduit ainsi les coûts de production de la couche vitreuse (8, 10) d'au moins 15 à 20 fois par rapport aux procédés de fabrication conventionnels.
PCT/DE1997/000382 1996-03-14 1997-03-03 Procede pour revetir d'une couche vitreuse, un composant d'une pile a combustible a haute temperature et empilage de piles a combustible a haute temperature Ceased WO1997034331A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP9532170A JP2000506309A (ja) 1996-03-14 1997-03-03 高温燃料電池の構造要素にガラス状の層を被層する方法、この方法を高温燃料電池スタックの製造に適用する方法及び高温燃料電池スタック
AU25031/97A AU713015B2 (en) 1996-03-14 1997-03-03 Process for coating a component of a high temperature fuel cell with a vitreous layer, use of the process for the production of a high temperature fuel cell stack, and high temperature fuel cell stack
EP97916319A EP0886886A1 (fr) 1996-03-14 1997-03-03 Procede pour revetir d'une couche vitreuse, un composant d'une pile a combustible a haute temperature et empilage de piles a combustible a haute temperature

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19610136 1996-03-14
DE19610136.0 1996-03-14

Publications (1)

Publication Number Publication Date
WO1997034331A1 true WO1997034331A1 (fr) 1997-09-18

Family

ID=7788336

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1997/000382 Ceased WO1997034331A1 (fr) 1996-03-14 1997-03-03 Procede pour revetir d'une couche vitreuse, un composant d'une pile a combustible a haute temperature et empilage de piles a combustible a haute temperature

Country Status (5)

Country Link
EP (1) EP0886886A1 (fr)
JP (1) JP2000506309A (fr)
AU (1) AU713015B2 (fr)
CA (1) CA2248916A1 (fr)
WO (1) WO1997034331A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0907215A1 (fr) * 1997-10-02 1999-04-07 Siemens Aktiengesellschaft Rendre étanche une pile à combustible fonctionnant à haute température ou un empilement de piles à combustible fonctionnant à haute température

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130004881A1 (en) * 2010-03-15 2013-01-03 Nima Shaigan Composite coatings for oxidation protection

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0036558A1 (fr) * 1980-03-22 1981-09-30 Bayer Ag Objet métallique enduit et procédé pour sa fabrication
JPH03285268A (ja) * 1990-03-31 1991-12-16 Tonen Corp 高温型燃料電池およびその製造方法
JPH0745295A (ja) * 1993-07-30 1995-02-14 Sanyo Electric Co Ltd 固体電解質燃料電池用ガスシール材
EP0714147A1 (fr) * 1994-11-23 1996-05-29 Sulzer Innotec Ag Pile à combustible fonctionnant à haute température avec des éléments de connexion contenant du chrome entre des plaques électrochimiquement actives
WO1996017394A1 (fr) * 1994-12-01 1996-06-06 Siemens Aktiengesellschaft Cellule electrochimique a joues bipolaires a revetement ceramique et leur production

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0036558A1 (fr) * 1980-03-22 1981-09-30 Bayer Ag Objet métallique enduit et procédé pour sa fabrication
JPH03285268A (ja) * 1990-03-31 1991-12-16 Tonen Corp 高温型燃料電池およびその製造方法
JPH0745295A (ja) * 1993-07-30 1995-02-14 Sanyo Electric Co Ltd 固体電解質燃料電池用ガスシール材
EP0714147A1 (fr) * 1994-11-23 1996-05-29 Sulzer Innotec Ag Pile à combustible fonctionnant à haute température avec des éléments de connexion contenant du chrome entre des plaques électrochimiquement actives
WO1996017394A1 (fr) * 1994-12-01 1996-06-06 Siemens Aktiengesellschaft Cellule electrochimique a joues bipolaires a revetement ceramique et leur production

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 116, no. 18, 4 May 1992, Columbus, Ohio, US; abstract no. 177737k, YOSHIDA ET AL: "High-temperature fuel cells and their manufacture" XP000286217 *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 112 (E - 1180) 19 March 1992 (1992-03-19) *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 005 30 June 1995 (1995-06-30) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0907215A1 (fr) * 1997-10-02 1999-04-07 Siemens Aktiengesellschaft Rendre étanche une pile à combustible fonctionnant à haute température ou un empilement de piles à combustible fonctionnant à haute température

Also Published As

Publication number Publication date
JP2000506309A (ja) 2000-05-23
AU713015B2 (en) 1999-11-18
CA2248916A1 (fr) 1997-09-18
EP0886886A1 (fr) 1998-12-30
AU2503197A (en) 1997-10-01

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