EP2115804A1 - Empilement de piles à combustible et joint pour un empilement de piles à combustible et leur procédé de fabrication - Google Patents

Empilement de piles à combustible et joint pour un empilement de piles à combustible et leur procédé de fabrication

Info

Publication number
EP2115804A1
EP2115804A1 EP07817774A EP07817774A EP2115804A1 EP 2115804 A1 EP2115804 A1 EP 2115804A1 EP 07817774 A EP07817774 A EP 07817774A EP 07817774 A EP07817774 A EP 07817774A EP 2115804 A1 EP2115804 A1 EP 2115804A1
Authority
EP
European Patent Office
Prior art keywords
component
solder
fuel cell
cell stack
spacer
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Withdrawn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
EP07817774A
Other languages
German (de)
English (en)
Inventor
Christian Wunderlich
Andreas Reinert
Karl-Hermann Bucher
Ralf Otterstedt
Hans-Peter Baldus
Michael Stelter
Axel Rost
Mihails Kusnezoff
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.)
HC Starck GmbH
Original Assignee
Staxera 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 Staxera GmbH filed Critical Staxera GmbH
Publication of EP2115804A1 publication Critical patent/EP2115804A1/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Withdrawn legal-status Critical Current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
    • H01M8/242—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
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • 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
    • 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
    • H01M8/0276—Sealing means characterised by their form
    • 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
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • 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
    • 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
    • H01M8/2404—Processes or apparatus for grouping fuel cells
    • 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
    • H01M8/2432—Grouping of unit cells of planar configuration
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • the invention relates to a gasket for gas-tight connection of two elements of a fuel cell stack, with an electrically non-conductive spacer component and at least one solid at the operating temperature of the Brennstoffzellen- stapeis over its entire extent or viscous solder component, the gas-tight distance component with at least one of the elements to be connected of the fuel cell stack coupled.
  • the invention further relates to a fuel cell stack having a plurality of repeating units stacked in the axial direction, and having at least one gasket for gas-tightly connecting two elements of the fuel cell stack, the gasket having an electrically non-conductive spacer component and at least one solder component comprising at least one spacer component the elements to be connected of the fuel cell stack coupled.
  • the invention further relates to a method for producing a gasket which is suitable for the gas-tight connection of two elements of a fuel cell stack, the gasket having an electrically nonconductive spacer component and at least one solder component which is solid or viscous over its entire extent at the operating temperature of the fuel cell stack, which gas-tightly couples the distance component with at least one of the elements of the fuel cell stack to be connected
  • the invention also relates to a method for producing a fuel cell stack having a plurality of repeating units stacked in the axial direction, and having at least one gasket for gas-tightly connecting two elements of the fuel cell stack, wherein the gasket has an electrically non-conductive spacer component and at least one Operating temperature of the fuel cell stack ü over its entire extent solid or viscous Lotkompo- component has that gas-tightly couples the distance component with at least one of the elements to be connected to the fuel cell stack.
  • the invention also relates to methods for producing a fuel cell stack having a plurality of repeating units stacked in the axial direction, and having at least one gasket for gas-tightly connecting two elements of the fuel cell stack, the gasket having an electrically non-conductive spacer component and at least one solder component the distance component couples with at least one of the elements of the fuel cell stack to be connected.
  • Planar high temperature fuel cells are known for converting chemically bound energy into electrical energy.
  • oxygen ions pass through a solid electrolyte permeable only to them and react with hydrogen ions on the other side of the solid electrolyte to form water. Since electrons can not overcome the solid electrolyte, an electrical potential difference arises, which can be used to perform electrical work when electrodes are attached to the solid electrolyte and these are connected to an electrical load.
  • the composite of the two electrodes and The electrolyte is referred to as MEA ("Membrane Electrolyte Assembly").
  • MEA Membrane Electrolyte Assembly
  • the breakthroughs in the bipolar plates must be sealed so that the fluids within the stack do not mix.
  • the functioning of high-temperature fuel cells results in numerous requirements for the seals.
  • the seals must be at pressures up to around 0.5 bar gas-tight, in the range from - 30 0 C to be usable to 1000 0 C, be thermally zyklisierbar and its long-term stability for a service life of about 40,000 hours. Since the seals separate the fuel gas space from the air space, they must be made of a material that is stable on the one hand and stable on the other side oxidation stable. If the seals are inserted between two repeating units, they must also be electrically insulated from each other, since leakage currents in the stack reduce its performance.
  • the seals are also in the direct mechanical load path of the fuel cell stack, which is loaded with a compressive clamping force, and thus have to conduct the applied clamping force from one repeat unit to the next.
  • This bracing force which can be realized, for example, via an external bracing of the fuel cell stack or weights above the stack, is of crucial importance for a good internal, electrical contacting of the individual components and thus for the performance of the overall system.
  • the seals between the repeating units and the electrolytes do not have to be made electrically insulating, since both components are at the same electrical potential. However, these gaskets must achieve a gastight connection between two different materials, often between the two different classes of metal and ceramic materials.
  • the repeating units or bipolar plates are often made of high-temperature ferritic steels, oxide dispersion-strengthened alloys (ODS alloys), chromium-base alloys or other high-temperature-resistant materials, and in some embodiments can be provided with protective layers.
  • the electrolyte usually consists of yttrium-stabilized zirconium oxide (YSZ), but may also consist of other materials such as scandium, ytterbium, or cerstabilized zirconium oxide.
  • mica seals as they are known for example from WO 2005/024280 Al.
  • mica has the advantage of enabling compressible seals in which the joining partners are not rigidly connected to one another.
  • the coefficient of expansion does not have to be adapted exactly, the mica seals permitting low relative rotational movements of the parts to be joined to one another.
  • pure mica gaskets have high to very high levels - -
  • the crystallization of components of the molten glass can counteract this process only partially and therefore only insufficiently, so that glass solders always have the problem that they become too soft for use in SOFCs under high mechanical loads and / or high temperatures.
  • the partially crystallized glass has a thermal expansion coefficient of about 9-10 "6 K -1 , which is significantly lower than that of the metal of the bipolar plate (about 12.5 l (r 6 K -1 )
  • Connecting the electrolyte of the cell to the metal of the bipolar plate advantageously results in the electrolyte remaining under compressive stress has a detrimental effect on the strength of the connection between two bipolar plates and the limitation to about 300 mm in height, because the weight force to be applied during joining forces the viscous glass flat, and a sealing member whose insulation resistance is larger than that of the joining glass used hitherto is desirable.
  • the settling can be counteracted with the introduction of spacer elements, as proposed for example in DE 101 16 046 Al.
  • the glass solder is added to a preferably ceramic powder whose powder grains are as large as the gap to be sealed and thus can absorb the load.
  • the powder grains must be distributed very evenly in the glass solder to absorb the load evenly. With pulverulent spacer elements of this size, another problem occurs, namely the particle size distribution.
  • a powder with the nominal particle diameter of, for example, 100 microns will always have particles that are greater than 100 microns and those whose diameter is 100 microns, so that not the total introduced powder, but only a small part of the load to Available. This reduces the effectively used part of the powder preferably added to the glass solder with a proportion of 10%.
  • the round particles proposed in DE 101 16 046 A1 conduct the load pointwise.
  • solder feasible.
  • the joining takes place at high temperatures, above the melting temperature of the metal solder, by wetting the joint surface with the liquid metal solder, the filling of the joint gap by capillary forces and the erosion. stare of the metal plumb bob.
  • a big advantage over glass solders is the shorter joining times, which can be realized with metal solders.
  • the heating and soldering time as well as the total residence time of the components in the furnace can be reduced by more than 60%. By using modern joining methods such as resistance soldering or induction soldering, even shorter joining times are possible.
  • This shortening of the joining time can be achieved by a number of favorable parameters. For one thing, one can
  • Increasing the heating rate can be used, which can be up to 10 K / min in furnace soldering and with inductive heating up to 300 K / min.
  • solder foils additionally shortens the joining process. Films of the metallic solders contain no binder, because they are either alloys or laminated individual foils. Therefore, the holding time for the debindering can be dispensed with in comparison to glass solder foils.
  • metal solders are used for mechanically rigid and electrically conductive connections, as proposed, for example, in DE 198 41 919 A1 for the contacting and fastening of connection elements with an anode. If two bipolar plates are to be joined with metal solder, electrical insulation of the components can only be achieved by using insulating intermediate layers.
  • Such an electrically nonconductive intermediate layer of ceramic material is known from DE 101 25 776 A1 in connection with metal alloys. which are liquid at the operating temperature of the fuel cell stack.
  • a sealing arrangement which has a ceramic carrier coated with ceramic insulating.
  • the thus-available component having a ceramic surface is coupled to the elements to be connected by soldering or welding methods.
  • the brazing of ceramic materials differs from the brazing of metallic materials.
  • Conventional solders are not able to wet ceramic materials.
  • One approach is to metallize ceramic components and join them using a conventional soldering process.
  • the metallization is carried out for example by the molybdenum-manganese process.
  • a paste of eg molybdenum oxide and manganese is applied to the ceramic surface and sintered at high temperatures (> 1000 0 C) in forming gas on the ceramic surface.
  • the metallized ceramic is additionally provided with a nickel or copper coating. The thus metallized ceramic can now be soldered in a subsequent step with conventional metal solders.
  • the invention has for its object to provide a seal and a fuel cell stack available, so that improvements and simplifications are to be recorded in terms of tightness, stability and the use of manufacturing processes.
  • the invention builds on the generic seal in that the spacer component is made of ceramic. If, for example, two bipolar plates of a fuel cell arrangement are to be connected to one another in a gastight manner with the gasket according to the invention, the result is a dense, electrically well insulating, stable, thermally stable and at the same time simple structure. Compared to a construction in which the spacer component is made of ceramic coated metal, fewer process steps are required in the manufacture of the gasket. Furthermore, the thermal behavior of the spacer component is determined solely by the thermal properties of the ceramic. For example, it can be provided that the at least one solder component has a glass solder.
  • the at least one solder component has a metal solder.
  • the at least one solder component has an active solder.
  • the spacer component has at least one recess which is filled by the solder component.
  • the recesses are adapted to receive solder before the coupling of the seal is made to the elements to be connected.
  • the seal is therefore easy to handle as a spacer component with solder introduced in recesses. Since the solder can be located in the region of the recesses in this way, other areas of the surfaces facing the elements to be connected in the fuel cell stack may be free of solder. Consequently, the distance between the elements to be connected is determined by the distance component, since the solder-free surfaces of the distance component contact the elements to be connected directly, that is to say without solder interlayer.
  • the solder component has a larger volume than the recess.
  • the solder can protrude beyond the surface in the direction of the elements to be connected.
  • the solder is thus under load during the joining phase, so that the isotropic sintering shrinkage of the solder is converted into a pure vertical shrinkage.
  • the solder flows viscous until the bipolar plates rest on the spacer element. Consequently, the spacer carries the main part of the load.
  • the recess extends along an edge of the spacer component.
  • the solder has the possibility of flowing away from the contact surface of the spacer component.
  • the recess is arranged in a surface facing a member to be connected and is limited perpendicular to the extension of the solder component of the surface.
  • Such a structure may be advantageous in view of the fact that the solder components are fixed on both sides by the spacer component.
  • the coupling of the spacer component with at least one of the elements to be connected takes place by means of a plurality of solder seams, wherein each of these solder seams provides a gastight connection when intact.
  • cracks may occur at temperature changes below the transition temperature, that is, in the state in which the glass is almost completely solid. Cracks that occur in this temperature range, immediately migrate through the entire cross section. If the fuel cell is then connected to the hydrogen and oxygen-containing gases applied, it comes at these locations to a fire. As a result of the resulting local overheating even adjacent areas are damaged, so that the entire fuel cell system can fail.
  • the glass solder Due to the use of glass solder with several solder seams, usually only one of the solder seams fails under mechanical stress.
  • the crack can penetrate into a second solder seam only if there is a weak point of the second solder seam in the vicinity of the crack of the first solder seam. This is very unlikely, so that overall a dense connection persists.
  • the glass may anneal the crack by viscous flow when the fuel cell is brought to operating temperature, especially when the operating temperature is above the transition temperature of the glass.
  • the arrangement of two or more solder seams which is particularly advantageous in the case of glass solder, can also be advantageous when using metal solder.
  • solder component extends over the entire surface facing a member to be connected. After coupling of the solder component with the elements to be joined then results in a Lot, slaughter plant, or the solder component is urged by the Verspannkraft to the outside, so that even in this case with a solder component over the entire surface ultimately at the edges extending solder seams result. Remains a Lot aside harsh, so there is a very secure connection in terms of tightness, which is comparable to a solution using multiple juxtaposed solder seams.
  • the spacer component on a surface facing a member to be connected to a MetallIotkomponente and on the opposite surface carries a Glaslotkomponente.
  • the joining of the distance component with the elements to be connected takes place in two steps due to the two different soldering systems.
  • the previously metallized spacer is soldered to a metal solder or directly by an active soldering process on one of the elements to be connected.
  • the spacer element is already positioned on the one hand.
  • the tightness of the already existing connection can be checked. If the seal is soldered to a bipolar plate and the membrane electrode assembly is already attached to the bipolar plate, it is possible to check the entire repeat unit for leaks in this state. This makes it possible to ensure that only intact components are joined together to form a fuel cell stack. Only after the leakproofness has been successfully checked does the repeating units be joined via the glass solder joints.
  • the spacer component is sintered gas-tight.
  • the spacer component has an axial thickness between 0.1 and 0.2 mm.
  • the spacer component has an axial thickness between 0.3 and 0.8 mm.
  • the solder component has an axial thickness between 0.02 and 0.2 mm.
  • the solder component bearing surface of the spacer component is roughened.
  • the distance component has a coefficient of thermal expansion in the range from 10.5 to 13.5 ⁇ T 6 K -1 , which ensures that the coefficient of thermal expansion better matches the thermal expansion coefficient of ferritic steel than conventionally used joining glasses
  • Ferritic steel has a thermal expansion coefficient of 12 to 13 -10 "6 K " 1.
  • a typical joining glass solder has a thermal expansion coefficient of 9,6-lCr 6 K "1 .
  • the spacer component has at least one of the following materials: barium disilicate, calcium disilicate, barium calcium orthosilicate. These ceramics all have a coefficient of thermal expansion in the range of 12-10 " 5K " 1 and are thus particularly suitable for use in the context of the present invention.
  • the spacer component prefferably has partially stabilized zirconium oxide.
  • Partially stabilized zirconium oxide is zirconium oxide containing 2.8 to 5 mol% of rare earth metal oxide, namely Y 2 O 3 , Sc 2 O 3 , MgO or CaO.
  • rare earth metal oxide namely Y 2 O 3 , Sc 2 O 3 , MgO or CaO.
  • Such systems have a thermal expansion coefficient of about 10, 8 -ICT 6 K '1 .
  • alumina is added to the partially stabilized zirconia.
  • the Solder component of at least one of the following materials: gold, silver, copper.
  • the invention further relates to a fuel cell stack with a seal according to the invention.
  • the invention is based on a generic fuel cell stack in that a force flow compressing the fuel cell stack in the axial direction transitions from the distance component directly to at least one of the elements to be connected. In this way, the distance between the adjacent elements to be connected can be accurately adjusted by the spacer element.
  • the rigid spacer receives the load during operation of the fuel cell without the interposition of solder components. The load path thus no longer leads through the soldering components applying the sealing effect, but through the rigid element. This prevents the elements to be connected from coming into contact by squeezing the solder, which would lead to a short-circuit in the case of bipolar plates to be connected.
  • the spacer component is made of ceramic. Even if, in connection with the direct contacting of the elements to be connected with the spacer element, any non-conductive spacer elements can be used, it is particularly advantageous to produce the spacer component from ceramic. This leads to the peculiarities and advantages which have already been mentioned in connection with the gasket according to the invention. This also applies to the following particularly advantageous embodiments of the fuel cell stack according to the invention. This may for example be designed so that the at least one solder component has a glass solder.
  • the at least one solder component has a metal solder.
  • the at least one solder component has an active solder.
  • the spacer component has at least one recess which is filled by the solder component.
  • solder component has a larger volume than the recess.
  • the recess extends along an edge of the spacer component.
  • the recess may be arranged in a surface facing an element to be connected and to be bounded perpendicular to the extension of the solder component from the surface.
  • the coupling of the spacer component is carried out with at least one of the elements to be connected by means of multiple solder seams, each of these solder seams in the intact state provides a gas-tight connection.
  • a reliable seal can also be provided by the fact that the solder component extends over the entire surface facing a member to be connected.
  • the distance component on a surface facing an element to be connected a MetallIotkomponente and on the opposite surface carries a glass solder component.
  • the spacer component may be gas-tight sintered.
  • the spacer component has an axial thickness between 0.1 and 0.2 mm.
  • the spacer component has an axial thickness between 0.3 and 0.8 mm.
  • the solder component has an axial thickness between 0.02 and 0.2 mm.
  • the fuel cell stack can be provided with a stable and dense structure in such a way that the surface of the spacer component carrying the solder component is roughened.
  • the distance component has a coefficient of thermal expansion in the range of 10.5 to 13. 5 ICT 6 K -1 .
  • the spacer component comprising at least one of the following materials: barium disilicate, calcium disilicate, barium calcium orthosilicate.
  • the spacer component has partially stabilized zirconium oxide.
  • solder component comprises at least one of the following materials: gold, silver, copper.
  • the invention furthermore relates to a seal for a fuel cell stack according to the invention, that is to say a seal with a total of non-conductive spacer element and solder components arranged thereon.
  • the invention is based on the generic method for producing a seal in that the spacer component is made of ceramic material. This results in the advantages and special features that have already been mentioned in connection with the gasket according to the invention.
  • the spacer component may be prepared by dry pressing of ceramic powder.
  • the spacer component is produced by film casting, lamination and stamping. On the basis of such a distance component it can be provided that a glass solder in the form of a stamped film is applied to the spacer component.
  • an adhesive layer may be applied to the spacer component before the metal solder is applied.
  • the distance component is roughened before the application of a solder.
  • the invention is based on the generic method for the manufacturer of the fuel cell stack in that a spacer component made of ceramic material is used.
  • Fuel cell stack and gaskets are stacked with solder components of glass solder and the elements to be connected are then connected to each other simultaneously via the seals. So it's a manufacturing process possible, in which there is a parallel joining of all coupling areas associated with the sealing components.
  • seals are used whose distance components on a surface facing a member to be joined a metal solder component and wear on the opposite surface a Glaslotkomponente that the distance components first on the metal solder components with elements of the
  • Fuel cell stack are connected to the repeating units are completed, the repeating units are stacked and that the repeating units are connected to each other via the glass solder components.
  • Such fabrication based on a seal having different solder systems is particularly useful in that the repeat units are inspected for leaks after joining the spacer components to the metal solder components with elements of the fuel cell stack.
  • the invention is based on arranging the solder components on the spacer components in such a way that a force flow compressing the fuel cell stack in the axial direction transitions directly from the distance component to at least one of the elements to be connected.
  • this manufacturing process can basically different distance components are used, as long as they are electrically insulating.
  • the use of ceramic is of particular advantage, it is not necessarily intended.
  • elements of the fuel cell stack and seals are brazed with solder components made of glass solder and the elements to be connected are then connected to one another simultaneously via the seals.
  • seals whose spacer components carry a metal solder component on a surface facing a member to be bonded and a glass solder component on the opposite surface, that first connect the spacer components to elements of the fuel cell stack via the metal solder components that the repeating units are finished, that the repeating units are stacked and that the repeating units are connected to each other via the glass lot components.
  • FIG. 1 shows an axial section through part of a fuel cell stack according to the invention
  • FIG. 2 different plan views of seals
  • FIG. 3 shows different axial sections for the description of a seal according to the invention and of a manufacturing method according to the invention for manufacturing a seal and a fuel cell stack;
  • Figure 4 shows various axial sections for describing a further embodiment of a seal according to the invention and for explaining manufacturing process for the production of inventive
  • Figure 5 shows various axial sections for describing a further embodiment of an inventive
  • Figure 6 shows various axial sections for describing a further embodiment of a seal according to the invention and for explaining manufacturing method for the production of inventive Seals and fuel cell stacks according to the invention
  • Figure 7 shows various axial sections for describing a further embodiment of an inventive
  • Figure 8 shows various axial sections for describing a further embodiment of a gasket according to the invention and for explaining manufacturing processes for the production of gaskets and fuel cell stacks according to the invention.
  • FIG. 1 shows an axial section through part of a fuel cell stack according to the invention.
  • Two repeat units 28 of a fuel cell stack are shown.
  • Each of these repeating units 28 comprises a bipolar plate 12.
  • This defines a main plane 30 and a side plane 32 axially offset therefrom.
  • the plate sections lying in the main plane 30 and in the secondary plane 32 extend in the radial direction and are connected to one another via axial sections 34 , In this way results in a cassette-like structure, which is a total e- lektrisch compromisingd.
  • At the lying in the main plane 30 part of the bipolar plate 12 includes a first gas guide region 36 at. This gas routing area is for it provided to guide the gases reacting in the fuel cell stack.
  • first electrode 38 of a membrane-electrode assembly 38, 40, 42 available.
  • first electrode 38 Above the first electrode 38 is a solid electrolyte 40.
  • second electrode 42 On this solid electrolyte 40 is in turn a second electrode 42.
  • the second electrode 42 is followed by another gas guide region 44.
  • the first electrode 38 is a cathode
  • the lower gas guide region 36 serves to guide air
  • the upper gas guide region 44 conducts hydrogen, which is supplied to the adjacent anode 42.
  • axial air channels 46 are provided.
  • seals 10, 10 'prevent the air from flowing into the region of the upper gas-guiding regions 44 and thus the anodes 42.
  • the seals 10 prevent leakage of air from the fuel cell stack. Another picture results from another cut through the fuel cell stack. In such an axial channels would be recognizable, which supply hydrogen to then supply the upper gas guide portions 44 and thus the anodes 42, while the lower gas guide portions 36 and the cathodes are protected by seals from the hydrogen.
  • the seals 10, which connect the bipolar plates 12 together, must be made of electrically non-conductive material, since the mutually facing sides of two adjacent bipolar plates 12 are at opposite potential.
  • the seal 10 described in the context of the present invention is intended primarily for this connection of the bipolar plates 12. However, other gaskets that are needed in the fuel cell stack can be constructed in the same way, for example example, the seals 10 'between the solid electrolyte 40 and the bipolar plates 12th
  • Figure 2 shows various plan views of seals.
  • the viewing direction is perpendicular to the viewing direction in FIG. 1.
  • Various forms of seals which, for example, are arranged circumferentially around the entire fuel cell stack, are shown. So you can see a rectangular ( Figure 2a), a round ( Figure 2b), an ellipti- see ( Figure 2c) and a partially concave (Figure 2d) seal shape.
  • the seals may also have openings, for example, on both sides to seal an axial passage provided for fluid guidance, that is to say in particular against the atmosphere and against the gas guidance area which is not to be reached by the gases guided in the fluid guidance.
  • FIG. 3 shows various axial sections for the description of a seal according to the invention and of a manufacturing method according to the invention for manufacturing a seal and a fuel cell stack.
  • FIG. 3 a shows a spacer component 16 of a seal 10 according to the invention. At its edges 24, the spacer component 16 has recesses 20 which are suitable for receiving a solder component 18.
  • FIG. 3b shows the seal 10 in the sealing state between two bipolar plates 12.
  • the solder component for example glass solder
  • the solder component 18 projects beyond the spacer element 16.
  • the solder component 18 is thereby under load. So the isotropic sintering shrinkage are converted into a pure Honenschwindung.
  • the glass flows viscously until the bipolar plates 12 rest on the spacer element 16.
  • a tensioning force applied to the fuel cell stack is then transmitted substantially via the spacer component 16. Since each bipolar plate 12 faces a plurality of solder seams 18, in the illustrated case by way of example two solder seams, the defect of one of the solder seams 18 does not yet lead to the leakiness of the system.
  • FIG. 4 shows various axial sections for describing a further embodiment of a seal according to the invention and for explaining manufacturing methods for producing seals according to the invention and fuel cell stacks according to the invention.
  • the spacer element 16 according to FIG. 4 a has recesses 22 which lie in the surface 26 of the spacer component 16, which is coupled to the bipolar plate 12.
  • the coupled state is shown in FIG. 4 d, the solder component 18 also being additionally introduced into the recesses 22 here.
  • the solder component 18 that is, in particular the glass solder, completely surrounded by the spacer element, so that it is fixed in the joining and sealing area.
  • FIG. 5 shows various axial sections for describing a further embodiment of a seal according to the invention and for explaining manufacturing methods for producing seals according to the invention and fuel cell stacks according to the invention.
  • the solder component 18 is applied over the entire surface of the spacer component 16.
  • the distance component 16 is shaped in such a way that, during the transition from the state shown in FIG. 5 a to the state according to FIG. men in which the solder component 18 can be displaced.
  • the solder component 18 is applied over the entire surface of the spacer component 16.
  • the distance component 16 is shaped in such a way that, during the transition from the state shown in FIG. 5 a to the state according to FIG. men in which the solder component 18 can be displaced.
  • FIG. 6 shows various axial sections for describing a further embodiment of a seal according to the invention and for explaining production methods for producing seals according to the invention and fuel cell stacks according to the invention.
  • solder component 18 glass solder is provided.
  • the embodiment is comparable to the embodiment according to FIG. 5, but here the spacer component 16 is given no special shape with regard to the reception of the solder component 18.
  • the solder component 18 lies completely on the spacer component 16.
  • part of the solder component 18 remains between the spacer component 16 and the bipolar plates 12. The remainder is displaced into the edge regions.
  • the amount of solder forming the intermediate layer may be so small that the force flow between the bipolar plate 12 and the spacer component 16 is practically less direct than in the case when the spacer component 16 directly contacts the bipolar plate 12.
  • FIG. 7 shows various axial sections for describing a further embodiment of a seal according to the invention and for explaining manufacturing methods for producing seals according to the invention and fuel cell stacks according to the invention.
  • solder component 18 metal solder is provided.
  • the embodiment according to FIG. 7 is identical to the embodiment according to FIG. 6.
  • the soldering process can either be a two-stage process take place, wherein first a metallization of the spacer element 16 is made, whereupon then soldered with conventional metal solder. It is also possible to carry out a one-stage active soldering process.
  • FIG. 8 shows various axial sections for describing a further embodiment of a seal according to the invention and for explaining manufacturing methods for producing seals according to the invention and fuel cell stacks according to the invention.
  • a hybrid pilot system is shown.
  • FIG. 8 a Before the state shown in FIG. 8 a, there is a spacer component 16 with recesses 20 provided on one side at the edges of the spacer component 16. This is then provided with a metal solder component 18 'on the side opposite the recesses 20. The partial seal thus present can then be soldered onto a bipolar plate 12. In this state, the tightness test of the connection between the spacer component 16 and the bipolar plate 12 can already take place via the metal component 18 '.
  • the bipolar plates thus equipped with the partial seals are prefabricated for the entire fuel cell stack, in order then to introduce into the recesses 20 of the spacer component 16 a glass solder component 18.
  • the fuel cell stack may then be assembled, and the connections of the spacer components 16 via the glass solder components 18 to the bipolar plates 12 may then be coupled in parallel for the entire stack.

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

Abstract

L'invention concerne un joint (10) servant à connecter de façon étanche aux gaz deux éléments (12) d'un empilement de piles à combustible avec un composant de distance (16) non conducteur d'électricité et au moins un composant de soudure (18) solide ou visqueux sur l'ensemble de son extension à la température de fonctionnement de l'empilement de piles à combustible, qui couple de façon étanche au gaz les composants de distance (16) à au moins l'un des éléments à connecter de l'empilement de piles à combustible. L'invention prévoit que le composant de distance (16) soit constitué de céramique. L'invention concerne en outre un empilement de piles à combustible dans lequel un flux de force du composant de distance (16) comprimant l'empilement de piles à combustible dans la direction axiale passe directement au-dessus d'au moins l'un des éléments à connecter (12). L'invention concerne de plus des procédés de fabrication de joints (10) et d'empilements de piles à combustible.
EP07817774A 2006-12-11 2007-11-05 Empilement de piles à combustible et joint pour un empilement de piles à combustible et leur procédé de fabrication Withdrawn EP2115804A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006058335A DE102006058335A1 (de) 2006-12-11 2006-12-11 Brennstoffzellenstapel und Dichtung für einen Brennstoffzellenstapel sowie deren Herstellungsverfahren
PCT/DE2007/001983 WO2008071137A1 (fr) 2006-12-11 2007-11-05 Empilement de piles à combustible et joint pour un empilement de piles à combustible et leur procédé de fabrication

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Publication Number Publication Date
EP2115804A1 true EP2115804A1 (fr) 2009-11-11

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EP07817774A Withdrawn EP2115804A1 (fr) 2006-12-11 2007-11-05 Empilement de piles à combustible et joint pour un empilement de piles à combustible et leur procédé de fabrication

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US (1) US20100068602A1 (fr)
EP (1) EP2115804A1 (fr)
JP (1) JP5154570B2 (fr)
KR (1) KR101098956B1 (fr)
CN (1) CN101573818A (fr)
AU (1) AU2007331948B2 (fr)
BR (1) BRPI0720099A2 (fr)
CA (1) CA2671905A1 (fr)
DE (1) DE102006058335A1 (fr)
IL (1) IL199213A0 (fr)
NO (1) NO20092152L (fr)
WO (1) WO2008071137A1 (fr)

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JP5371041B2 (ja) * 2009-04-15 2013-12-18 国立大学法人埼玉大学 固体酸化物型燃料電池
US20130177830A1 (en) * 2010-10-29 2013-07-11 Jason B. Parsons Fuel cell assembly sealing arrangement
JP5554740B2 (ja) * 2011-03-30 2014-07-23 株式会社日本触媒 固体酸化物形燃料電池用電解質シート
FR2974401B1 (fr) * 2011-04-22 2013-06-14 Commissariat Energie Atomique Joint d'etancheite metallique a ame ceramique
JP5701697B2 (ja) * 2011-06-15 2015-04-15 日本特殊陶業株式会社 燃料電池及びその製造方法
US9196909B2 (en) * 2011-11-18 2015-11-24 Bloom Energy Corporation Fuel cell interconnect heat treatment method
FR2988916B1 (fr) * 2012-03-27 2019-11-08 Commissariat A L'energie Atomique Et Aux Energies Alternatives Joint d'etancheite preservant l'integrite de cellules electrochimiques, et ses procedes de fabrication et d'utilisation
DE102012006864A1 (de) * 2012-04-04 2013-10-10 Forschungszentrum Jülich GmbH Hochtemperaturdichtung umfassend Glaslot sowie Verfahren zur Herstellung derselben
DE102013204308A1 (de) * 2013-03-13 2014-09-18 Volkswagen Ag Bipolarplatte für eine Brennstoffzelle, Brennstoffzelle und Verfahren zur Herstellung der Bipolarplatte
DE102013108413B4 (de) * 2013-08-05 2021-05-20 Gerhard Hautmann Verfahren zum Herstellen eines Brennstoffzellenstapels sowie Brennstoffzellenstapel und Brennstoffzelle/Elektrolyseur
FR3014246B1 (fr) 2013-12-04 2016-01-01 Commissariat Energie Atomique Joint d'etancheite pour dispositif electrochimique, procede de fabrication et d'assemblage du joint et ce dispositif.
CN107230797B (zh) * 2016-03-25 2024-03-12 安徽巨大电池技术有限公司 电池组及其组装方法
KR102089828B1 (ko) * 2016-08-25 2020-04-23 주식회사 엘지화학 고체 산화물 연료전지용 지그 모듈
US10790521B2 (en) * 2018-03-08 2020-09-29 Fuelcell Energy, Inc. Wet seal caulk with enhanced chemical resistance
CN112467166A (zh) * 2019-09-06 2021-03-09 杭州中科氢能科技有限公司 一种钒电池电堆结构
DE102024104248A1 (de) 2023-03-03 2024-09-05 Schaeffler Technologies AG & Co. KG Elektrochemischer Zellenstapel
WO2024183850A1 (fr) 2023-03-03 2024-09-12 Schaeffler Technologies AG & Co. KG Empilement de cellules électrochimiques

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Also Published As

Publication number Publication date
IL199213A0 (en) 2010-03-28
KR101098956B1 (ko) 2011-12-28
NO20092152L (no) 2009-09-04
JP5154570B2 (ja) 2013-02-27
KR20090091763A (ko) 2009-08-28
WO2008071137A1 (fr) 2008-06-19
CN101573818A (zh) 2009-11-04
AU2007331948A1 (en) 2008-06-19
AU2007331948B2 (en) 2011-06-23
CA2671905A1 (fr) 2008-06-19
JP2010512626A (ja) 2010-04-22
US20100068602A1 (en) 2010-03-18
BRPI0720099A2 (pt) 2013-12-24
DE102006058335A1 (de) 2008-06-12

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