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EP2342166A2 - Liaison pour réacteurs chimiques ou thermiques - Google Patents

Liaison pour réacteurs chimiques ou thermiques

Info

Publication number
EP2342166A2
EP2342166A2 EP08756836A EP08756836A EP2342166A2 EP 2342166 A2 EP2342166 A2 EP 2342166A2 EP 08756836 A EP08756836 A EP 08756836A EP 08756836 A EP08756836 A EP 08756836A EP 2342166 A2 EP2342166 A2 EP 2342166A2
Authority
EP
European Patent Office
Prior art keywords
reactors
compound according
connection
thermal
chemical
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.)
Withdrawn
Application number
EP08756836A
Other languages
German (de)
English (en)
Inventor
Dirk Peter Claassen
Klaus Sascha KÜHN
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.)
Alpps Fuel Cell Systems GmbH
Original Assignee
Alpps Fuel Cell Systems 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 Alpps Fuel Cell Systems GmbH filed Critical Alpps Fuel Cell Systems GmbH
Publication of EP2342166A2 publication Critical patent/EP2342166A2/fr
Withdrawn legal-status Critical Current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
    • H01M8/24—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
    • H01M8/243—Grouping of unit cells of tubular or cylindrical configuration
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C03C8/12—Frit compositions, i.e. in a powdered or comminuted form containing lead containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • 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
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • 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
    • 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 the provision of a connection between components of one or more chemical or thermal reactors, in particular tubular fuel cells made of cermet or metal or ceramic or a mixture of cermet, metal or ceramic and their attachment points in a metallic or ceramic plate.
  • a gas-tight connection for high-temperature fuel cells with the aid of a solder is provided which is such that it hardens on the one hand at room temperature and on the other hand in the operating range of the fuel cell (the chemical or thermal reactor), preferably in a range of 400 0 C to 1000 0 C is viscous and plastic to compensate for when the cell is raised to operating temperature or shutting down the cell from the operating to the ambient temperature and the alternating voltages resulting thermal stresses as well as in operation by external mechanical stress resulting voltages or counteracts and remains gas-tight and mounted between at least two components which must be able to move relative to each other and to components of the chemical or thermal reactors incorporating such a seal.
  • oxidizing and reducing agents supplied to the separate subchambers ionize via electron exchange with the corresponding charged electrodes of the chambers are physically sealed from diffusion (reaction gases and ions). Also, no leaks may occur in such reactors, through which one of the two reactants can escape from the reactors and come into contact with the environment or the other reactants, so that no unwanted and uncontrolled reactions can occur.
  • BAS glass barium aluminum silicate glass
  • EP1010675 describes further different possible variants of solder glasses, for the connection of components in high temperature fuel cells, such as alkali oxide silicate glasses, mica glass ceramic, alkaline earth metal oxide borosilicate / silica borate glasses or alkaline earth aluminum oxide silicates. Briefly, their respective advantages as well as disadvantages for certain applications are listed, and even a laminated glass solder based on Al 2 O 3 and SiO 2 with one or more components from the group of metal oxides, which is interspersed with a filler claimed , These and other patents known glass solders are almost exclusively oxide powder, which are usually mixed with an organic binder to be applied as a brazing material targeted to the parts to be joined.
  • the reactors In order to be able to avoid these effects, which are extremely undesirable for the lifetime of the reactors, the reactors must be mounted so as to be freely movable at least at one of the two anchoring points despite perfect gas-tightness and stability of the connection.
  • the aim of the invention is now to provide a novel method and a novel bonding material, such as a connection between a holder and / or a shell of metal or ceramic and a chemical or thermal reactor of coated cermet, metal or ceramic, or one or more reactors coated cermet, metal or ceramic with each other, in particular of high-temperature fuel cells, which remains stable and gas-tight in the application of the reactors underlying temperature range in thermal alternating load operation, while still the due to the slightly different expansion coefficients of the materials to be joined and their thermal load conditions arising voltages in and between the components as well as voltages and relative movements by external mechanical influences on and between the components degraded or compensated.
  • crown glass as joining material.
  • This possesses the properties important to the integrity of the reactors that it adheres to the materials to be bonded and is gas-tight in the temperature range of interest between 800 K and 1300 K, and has the essential property of a corresponding viscosity to the thermal Strains between the components of chemical or thermal reactors and the brackets or sheaths as well as under the reactors themselves to compensate.
  • Fig. 1 Static temperature distribution for a cermet tube made of NiO / YSZ.
  • Fig. 2 enlarged Stark deformation shown an NiO / YSZ cermet tube with a temperature gradient of 27 ° and an operating temperature of 1100 0 K.
  • Fig. 3 Comparison of the expansion coefficients of typical materials for high-temperature fuel cells with the claimed glass solder.
  • Fig. 4 Schematic representation of the connection without support ring.
  • Fig. 5 Schematic representation of the connection with overhead support ring.
  • Fig. 6 Schematic representation of the connection with the bottom support ring.
  • Fig. 7 Schematic representation of the connection with double-sided support ring.
  • Fig. 8 Schematic representation of the connection with cambered bracket and overhead cambered support ring.
  • Fig. 9 Schematic representation of the connection for an upwardly tapered tubular reactor without support ring.
  • Fig. 10 Schematic representation of the connection for an upwardly reinforced tubular reactor without support ring.
  • Fig. 11 Schematic representation of the compound in a reactor assembly with alternately arranged support ring.
  • Fig. 12 Schematic representation of the compound in a reactor assembly with cambered holder and alternately arranged cambered support rings.
  • Fig. 13 Schematic representation of the compound in a reactor assembly with cambered support and tubular reactors installed alternately in depressions and elevations. Detailed description of the drawing
  • Figure 3 now shows the range of coefficients of expansion of materials typically used in the range of SOFCs. These move in the temperature ranges of interest between 10 -5 K -1 and 1.2 ⁇ 10 -5 K -1 .
  • the coefficient of expansion of the claimed solder lies in a favorable position relative to the other materials
  • the thermal expansion of the solder after the transformation point T 9 changes greatly, can no longer be determined unambiguously and expands, and this property is fundamentally desirable because it allows a larger working area to be covered by the solder.
  • connection area consists of a perforated holder (2), which is referred to below as a cover plate or perforated plate and preferably consists of Crofer 22 APU.
  • These supports serve to "fix" the chemical or thermal reactors (1), which in a preferred embodiment consist of cermet, in particular of a NiO / YSZ cermet coated with a thin layer of YSZ A tubular expansion joint remains between the tubular unit and the holder, which is necessary in order to be able to compensate for different thermal stresses resulting from slightly different expansion coefficients in the individual materials as well as relative mechanical movements.
  • this expansion joint must be used a connecting element (3), in particular by a glass solder, gas-tight.
  • the connecting element can be applied, for example annularly or as a paste and a gas-tight bond can be produced by a defined heating cycle with the parts to be joined, wherein the connecting element covers the expansion joint to be closed or penetrates into this and the parts to be joined (the holder and The compound thus obtained is gas-impermeable, as well as heat, oxidation and reduction resistant.
  • connection is to be additionally reinforced, an additional component (4) for reducing the gap dimension can be applied.
  • This additional component is hereinafter referred to as a support ring for ease of description of the figures, but may also be designed differently.
  • This device is in a preferred embodiment of Crofer 22 APU.
  • Fig. 5 in the appendix shows the function of the support ring.
  • This optionally used support ring itself has two essential functions for the connection.
  • the support ring (the additional component) is used by the surface tension of the connecting element in operation on the holder and thereby reduces the gap to be closed.
  • the support ring also completely covers the expansion joint which is enlarged on one side during a lateral movement of the chemical or thermal reactor.
  • the connecting element remains more stable in the expansion joint because it is additionally prevented by the support ring from flowing out.
  • the reactor remains flexible in the desired area in the expansion joint and at the same time the connection is tight. For this reason, damage, and ultimately even breakage of the reactor, can be avoided. Considering the compound thus obtained, one can speak in this context of a high temperature storage of the reactor.
  • the additional support ring (4) can also be arranged below the holder (2), on both sides or in a reactor assembly alternately above and below the holder.
  • Figures 12 and 13 are due to the different arrangement of the tubular reactors.
  • the tubular units are always placed in the same position of the bracket, either in the depressions or elevations, in Figure 13, the tubular units are inserted alternately into the depressions and elevations.
  • the connection itself can, as before, again be carried out with only one connecting element, but also all other variants with one or two support rings as they have already been made earlier are possible.
  • the solder as stated in claim 6, consists of the basic components SiO 2 , Na 2 O, K 2 O, CaO, ZnO and BaO with additions of TiO 2 as nucleations and Sb 2 O 3 as flux. Additions of Al 2 O 3 , ZrO 2 , B 2 O 3 , BO 2 , MgO and / or LiO 2 in order to improve the long-term stability of the solder are also conceivable or desirable.
  • composition of this solder is above all suitable as a connecting element for chemical or thermal reactors, in particular of high-temperature fuel cells, because it is a so-called "long" glass. This means the lower relaxation limit, the upper cooling point, the softening point and the processing point of the glass are on the temperature scale "far" apart.
  • the transformation point T 9 which separates the brittle energy-elastic range from the soft entropy-elastic range, is below 550 ° C. in a very favorable range for the connection. Thermal stresses and deformations due to unilateral thermal loading, as normally occur during operation or when the fuel cells are shut down during operation, can thus be cushioned much more easily and already at a lower temperature range than is the case with currently common glass solders ,
  • compositions can be heated to around 1300 K without essentially vaporizing components thereof, contaminating the reactors (cells) and thereby reducing power, as well as making the connection unstable as a result of the evaporation of components can.
  • a Glaslotmischung is considered, which is based on a commercially available colorless highly transparent crown glass (modified soda-lime glass).
  • Advantageous methods of applying the glass solder to the parts to be joined are making rings in appropriate sizes, or grinding the glass into a fine powder and mixing the powder with a liquid or suitable binder to make a paste therefrom.
  • This paste can be applied directly to the parts to be joined, and the compound made gas-tight by heating the liquid or binder.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Glass Compositions (AREA)

Abstract

L'invention concerne une liaison pour un ou plusieurs réacteurs thermiques et/ou chimiques (1), en particulier des cellules à combustible, avec un composant (2) voisin ou situé entre deux réacteurs ou entre deux composants, les réacteurs présentant une plage préférée de température de fonctionnement comprise en particulier entre 400 et 1100°C, caractérisée en ce que cette liaison est établie par l'intermédiaire d'un élément de liaison (3) qui durcit à température ambiante (état normal, conditions normales) et est plastique à la température de fonctionnement.
EP08756836A 2007-05-04 2008-06-23 Liaison pour réacteurs chimiques ou thermiques Withdrawn EP2342166A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0069407A AT505141B1 (de) 2007-05-04 2007-05-04 Verbindung von chemischen oder thermischen reaktoren
PCT/AT2008/000226 WO2008134789A2 (fr) 2007-05-04 2008-06-23 Liaison pour réacteurs chimiques ou thermiques

Publications (1)

Publication Number Publication Date
EP2342166A2 true EP2342166A2 (fr) 2011-07-13

Family

ID=39938156

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08756836A Withdrawn EP2342166A2 (fr) 2007-05-04 2008-06-23 Liaison pour réacteurs chimiques ou thermiques

Country Status (3)

Country Link
EP (1) EP2342166A2 (fr)
AT (1) AT505141B1 (fr)
WO (1) WO2008134789A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011083784A1 (de) * 2011-09-29 2013-04-04 Robert Bosch Gmbh Brennstoffzellenfixierung
ITMI20132127A1 (it) * 2013-12-19 2015-06-20 Fiamm Energy Storage Solutions S P A Composizione vetrosa per saldatura a vetro `glass welding¿ di parti ceramiche per celle elettrochimiche

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3743544A (en) * 1970-12-16 1973-07-03 United Aircraft Corp Fuel cell
DE4334438C2 (de) * 1993-10-08 1996-12-19 Siemens Ag Composit-Glaslot sowie Verwendung des Composit-Glaslotes
DE19608727C1 (de) * 1996-03-06 1997-06-19 Siemens Ag Elektrisch isolierende Schicht zum Verbinden von elektrisch leitenden Bauelementen einer Hochtemperatur-Brennstoffzelle
DE19827568C1 (de) * 1998-06-20 2000-01-05 Schott Glas Bleifreie optische Bariumflintgläser, Bariumleichtflintgläser und Bariumkrongläser
DE69940420D1 (de) * 1998-12-15 2009-04-02 Topsoe Fuel Cell As Hitzebeständiger Abdichtungswerkstoff
DE10122327A1 (de) * 2001-05-08 2002-11-28 Forschungszentrum Juelich Gmbh Glaslot als Fügematerial für den Hochtemperatureinsatz sowie Herstellung und Verwendung
WO2004031088A1 (fr) * 2002-10-07 2004-04-15 Nippon Sheet Glass Co., Ltd. Fritte de verre pour etancheification
US7189470B2 (en) * 2005-01-18 2007-03-13 Corning Incorporated Sealing materials and devices utilizing such materials
DE102005002435A1 (de) * 2005-01-19 2006-07-27 Forschungszentrum Jülich GmbH Herstellung einer Glaskeramik sowie dessen Verwendung als Fügematerial für den Hochtemperatureinsatz

Also Published As

Publication number Publication date
AT505141A1 (de) 2008-11-15
WO2008134789A3 (fr) 2009-01-15
WO2008134789A4 (fr) 2009-03-12
AT505141B1 (de) 2009-02-15
WO2008134789A2 (fr) 2008-11-13

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