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WO2018191765A1 - Unité électrode-électrolyte - Google Patents

Unité électrode-électrolyte Download PDF

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Publication number
WO2018191765A1
WO2018191765A1 PCT/AT2018/000017 AT2018000017W WO2018191765A1 WO 2018191765 A1 WO2018191765 A1 WO 2018191765A1 AT 2018000017 W AT2018000017 W AT 2018000017W WO 2018191765 A1 WO2018191765 A1 WO 2018191765A1
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WIPO (PCT)
Prior art keywords
electrode
layer
gas
carrier substrate
electrolyte
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PCT/AT2018/000017
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German (de)
English (en)
Inventor
Markus HAYDN
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Plansee SE
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Plansee SE
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Filing date
Publication date
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Publication of WO2018191765A1 publication Critical patent/WO2018191765A1/fr
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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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • 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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • 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
    • H01M4/861—Porous electrodes with a gradient in the porosity
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0236—Glass; Ceramics; Cermets
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0245—Composites in the form of layered or coated products
    • 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
    • H01M8/10—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 present invention relates to an electrode-electrolyte unit for a metal-based electrochemical module according to claim 1 and an electrochemical module according to claim 21.
  • the electrode-electrolyte unit according to the invention is used in an electrochemical module which is used inter alia as a high-temperature fuel cell or solid oxide fuel cell (SOFC), as a solid oxide electrolyzer cell (SOEC) and as a reversible catalyst Solid oxide fuel cell (R-SOFC) can be used.
  • SOFC high-temperature fuel cell or solid oxide fuel cell
  • SOEC solid oxide electrolyzer cell
  • R-SOFC Solid oxide fuel cell
  • Basic configuration includes an electrochemically active cell of the
  • electrochemical module a gas-tight solid electrolyte, which is arranged between a gas-permeable anode and gas-permeable cathode.
  • the electrochemically active components such as anode, electrolyte and cathode are often formed as comparatively thin layers.
  • a mechanical support function required thereby can be achieved by one of the electrochemically active layers, e.g. through the electrolyte, the anode or the cathode, which are then each made correspondingly thick (in these cases we speak of an electrolyte, anode or cathode-supported cell), or by an electrolyte these functional layers separately formed component, such as an electrically conductive ceramic or metallic carrier substrate.
  • metallic carrier substrate one speaks of a metal-supported cell (MSC). Since with an MSC the electrolyte, its electrical resistance with decreasing thickness and with increasing
  • Temperature decreases can be made relatively thin (e.g., with a thickness in the range of 2 to 10 m), MSCs at a
  • MSCs are particularly suitable for mobile applications, such as For example, suitable for the electrical supply of passenger cars or commercial vehicles (APU - auxiliary power unit).
  • the electrochemically active cell units are formed as flat individual elements, which in conjunction with corresponding
  • MSC Metal housing parts (such., Interconnector, frame plate, gas lines, etc.) are stacked on a stack and electrically contacted in series. MSC have a great advantage in this regard, as the connection and sealing of individual modules to a stack
  • fuel for example, hydrogen or conventional hydrocarbons, such as methane, natural gas, biogas, etc.
  • Gas separation function is taken over by the gas-tight electrolyte in the region of the electrochemically active layers, whereby a major challenge in the sealing in the transition region from the porous carrier substrate to a subsequent gas-tight surface.
  • WO2014187534 of the applicant is a powder metallurgically produced metallic
  • carrier substrate in which a porous central region, over which the electrochemically active layers are arranged, is surrounded by a pressed edge region, the surface of which is additionally melted for the purpose of gas-tightness by a laser treatment and thereby sealed gas-tight.
  • the electrolyte layer becomes over the porous area with the anode layer
  • this transition region from the porous central region to the gas-tight Edge area is a weak point and there may be problems with the gas tightness. For example, occur in the transition region repeatedly flaking of the layers, which inter alia on a conditional on the melting by the laser beam irregular, partially meandering, surface structure of the edge region
  • the present invention is based on the object, an electrode-electrolyte unit for a metal-based electrochemical module,
  • the electrode-electrolyte unit according to the invention is in a metal-based electrochemical module, in particular in a high-temperature fuel cell or solid oxide fuel cell (SOFC), a solid oxide electrolyzer cell (SOEC) or in a reversible solid oxide fuel cell (R-SOFC), can be used. It instructs
  • metallic, in particular plate-shaped carrier substrate having a porous, gas-permeable central region and a materially connected to the central region along an edge portion thereof, at least superficially gas-tight on the cell-facing side
  • the gas-permeable surface of the carrier substrate is separated from the at least superficially gas-tight surface of the edge region by a boundary line.
  • On the porous central area of the carrier substrate is separated from the at least superficially gas-tight surface of the edge region by a boundary line.
  • Carrier substrate is at least one porous gas-permeable first electrode, and arranged at least one gas-tight ceramic electrolyte layer which extends beyond the first electrode in the direction of the edge region and gas-tight with the gas-tight edge region of the carrier substrate.
  • At least one porous, ceramic bonding layer is formed, which extends at least over a bordering to the boundary portion of the edge region.
  • the central region of the carrier substrate and the edge region may be two originally separate components which are interconnected by a material connection such as a welded or soldered connection.
  • a material connection such as a welded or soldered connection.
  • the central region and the edge region are made in one piece (monolithic), the carrier substrate then consists of two imaginary components, which are in material contact.
  • the edge region is rendered gas-tight at least superficially, for example by pressing the porous carrier substrate on the edge side and / or by superficial superficial melting in the edge region on the side of the carrier substrate facing the electrochemically active layers (as described, for example, in WO2014187534).
  • a gas-permeable surface is present, while at least the surface of the edge region is gas-tight.
  • a boundary line is defined, wherein surfaces with gas-tight welds or solder joints are assigned to the gas-tight surface.
  • the metallic carrier substrate is preferably produced by powder metallurgy.
  • Suitable materials for the carrier substrate are in particular iron (Fe) based (ie at least 50 wt.%, In particular at least 70 wt.% Fe-containing), a high chromium content (chromium: Cr) containing alloys (eg at least 16 wt.% Cr ), to which further additives, such as, for example, yttrium oxide (Y 2 O 3) (for increasing the oxidation resistance), titanium (Ti) and molybdenum (Mo) may be added, the proportion of these additives overall being preferably less than 3% by weight (cf.
  • the electrochemically active layers such as first and second electrode (anode, cathode) and
  • Electrolyte layer arranged.
  • the electrodes are gas-permeable and can be constructed both as a single layer and as a layer composite of several layers.
  • the anode is usually the electrochemically active layer next to the carrier substrate (first
  • Electrode while the cathode (second electrode) is formed on the side facing away from the carrier substrate of the electrolyte.
  • the cathode second electrode
  • the first electrode is formed by the cathode.
  • Electrochemically active layers are preferably carried out in a known manner by means of PVD (PVD, physical vapor deposition), e.g. Sputtering, and / or thermal coating processes, e.g. Flame spraying or
  • Plasma spraying and / or wet chemical processes e.g. Screen printing
  • Layer structure of an electrochemical cell unit and several of these methods can be used in combination.
  • the anode is usually made of a composite, a so-called cermet, preferably consisting of nickel and yttria fully stabilized zirconia or nickel and gadolinia-doped ceria, while the cathode is usually made of mixed conducting perovskites such
  • the first electrode may be multi-layered and have a graded structure in which the mean sintered grain size decreases with increasing distance from the carrier substrate from layer to layer.
  • a gas-tight solid electrolyte of a solid, ceramic material of a metal oxide is formed which is conductive for oxygen ions or in a younger generation of SOFC for protons, but not for electrons.
  • oxygen ion-conducting electrolyte layer material are doped zirconium oxide, wherein the doping of at least one oxide of
  • a proton conductive electrolyte material are barium-zirconium oxide, barium-cerium oxide, lanthanum-tungsten oxide or lanthanum-niobium oxide.
  • the electrolyte layer typically has a layer thickness in the range of 3 to 5 pm and will
  • the electrolyte layer can be in direct contact with the gas-tight surface of the edge region of the carrier substrate or leak on one or more optional gas-tight intermediate layers, which are applied directly to the carrier substrate.
  • gas-tight intermediate layer can, for example, by a
  • Diffusion barrier layer differently doped lanthanum strontium manganite (LSM), lanthanum stronitum chromite (LSCr) with different lanthanum and strontium or gadolinium oxide doped ceria (CGO); the
  • Diffusion barrier layer is usually mitteis PVD directly on the
  • the layer thickness is usually up to 2 pm and therefore comparatively thin (in comparison, the average
  • Carrier substrate separates, so it remains unchanged with the coating.
  • the core idea of the invention is to provide at least one additional porous, ceramic bonding layer in the edge region of the carrier substrate between the electrolyte layer and the carrier substrate (or any gas-tight intermediate layer disposed thereon). This intermediate layer in the
  • Edge area serves to compensate for irregularities in the surface of the edge region and can therefore over its course a varying
  • Have layer thickness Preferably, it becomes thinner and thinner towards its edges. Irregularities caused, for example, by the above-mentioned laser guidance in the superficial melting process, or sharp-edged gradations or discontinuities at the transitional area between the first electrode and the surface of the edge area can be compensated or smoothed by the bonding layer.
  • the leveling is for the application of the relatively thin
  • Electrolyte layer provided a more uniform surface, whereby the risk of mechanical weaknesses and cracking of the gas-tight, as thin as possible running electrolyte layer is significantly reduced.
  • the porous bonding layer also helps to reduce stress due to
  • the carrier substrate, the electrode and the electrolyte layer lead to stresses within the layer structure, in particular during production during the sintering process or later during operation, which can lead to cracking or flaking and subsequently to failure of the electrochemical module.
  • a further advantage of the bonding layer is an improved adhesion of the layer structure in the critical transition region.
  • the bonding layer is preferably a sintered ceramic layer which is connected via sintered necks with the carrier substrate (or an optional gas-tight intermediate layer). It is preferred via a wet-chemical process (eg wet powder coating, brushing, screen printing, etc.)
  • the mean pore size of the sintered bonding layer is smaller than the middle one
  • Pore size of the first electrode in a multi-layered first electrode with different porosity, the pore size of the lowest, the
  • a preferred average pore size for the attachment layer is in the range of from 0.20 ⁇ m to 2.00 ⁇ m inclusive, more preferably in the range of 0.31 ⁇ m to 1 ⁇ m inclusive, more preferably in the range of 0.32 ⁇ m to 2 ⁇ m
  • a cross-section running perpendicular to the layer to be examined is made through the electrode-electrolyte unit and a suitably prepared micrograph in the scanning electron microscope (SEM) is examined on the basis of a BSE image (BSE: back-scattered electrons) ,
  • SEM scanning electron microscope
  • BSE back-scattered electrons
  • the analysis is carried out by threshold value of the different gray levels from the respective REM-BSE image, wherein the brightness and the contrast of the REM-BSE image is adjusted such that the pores and particles in the image are easily recognizable and distinguishable from each other.
  • a suitable grayscale value is selected as the threshold value.
  • the porosity is determined by determining the area fraction within a selected
  • the bonding layer extending from the boundary line in the direction of the edge region over a maximum length of up to and including 3 cm, in particular up to and including 2 cm, particularly advantageously including 1 cm.
  • the bonding layer extends in the opposite direction, ie in the direction of the central region of the carrier substrate, starting from the boundary line over a maximum length of up to and including 1 cm, in particular up to and including 0.5 cm, particularly advantageously up to and including 0, 3 cm.
  • the bonding layer at least in a subsection of the edge region in the immediate,
  • the bonding layer preferably consists of the same base material as the electrolyte layer.
  • the bonding layer contains at least one oxide of the doping elements from the group of the rare earth elements such as Gd, Sm and / or from the group Y, Sc, Al, Sr, Ca (in particular CGO).
  • suitable materials for the bonding layer are barium zirconium oxide, barium cerium oxide, lanthanum tungsten oxide or lanthanum niobium oxide.
  • Diffusion barrier layer is coated, it is also advisable, the material of the bonding layer to the material of the gas-tight intermediate layer
  • the various layers (optional diffusion barrier layer, first electrode, and the various layers (optional diffusion barrier layer, first electrode, and the various layers (optional diffusion barrier layer, first electrode, and the various layers (optional diffusion barrier layer, first electrode, and the various layers (optional diffusion barrier layer, first electrode, and the various layers (optional diffusion barrier layer, first electrode, and the various layers (optional diffusion barrier layer, first electrode, and the various layers (optional diffusion barrier layer, first electrode, and first electrode, first electrode, and
  • Bonding layer electrolyte layer successively applied to the carrier substrate.
  • layers to be sintered such as the porous bonding layer
  • a layer containing the respective ceramic particles and a corresponding organic binder is applied by a wet-chemical method, subsequently sintered and only then
  • the individual layers are distinguishable from each other, even if they have the same composition.
  • the layer structure can be seen, for example, when perpendicular to the
  • Layer profile made a cross section through the electrode-electrolyte unit and a correspondingly prepared micrograph in the scanning electron microscope (SEM) on the basis of a REM-BSE image (BSE: back-scattered electrons;
  • connection layer can thereby T T2018 / 000017
  • first electrode 11 or after application of the first electrode which - as explained in more detail below - may also be implemented as a multilayer composite layer, in a preferred variant, more, in particular two Anbind ungs harshen are provided, a first
  • Bonding layer which is applied before the application of the first electrode
  • a second bonding layer which is applied after the application of the first electrode
  • Layer (s) of the first electrode is applied, the bonding layer in direct materially bonded contact with the carrier substrate or a gas-tight ceramic intermediate layer with which the carrier substrate has been directly coated.
  • the attachment layer dilutes toward its ends and may infiltrate into the material of the carrier substrate in the transition region to the porous central region of the carrier substrate.
  • Layer thickness can thus vary, in particular in the embodiment of the carrier substrate, which originally two separate from each other
  • Components is constructed by a welded or soldered connection
  • the bonding layer in the region of the cohesive connection (weld) is usually thicker.
  • the layer of the first electrode runs on or on the bonding layer;
  • the lowermost layer of the layer composite lying closest to the carrier substrate may leak out at the attachment layer, while the subsequent layer (s) extend beyond the layer immediately beneath it and extend on top of the underlying layer
  • Bonding layer is applied in front of the first electrode, in particular has advantages in electrode-electrolyte units in which a gas-tight
  • the ceramic intermediate layer (diffusion barrier layer) is provided and the first electrode is made of a cermet.
  • optionally finer porosity bonding layer usually adheres better on the ceramic basis than a layer of cermet.
  • the bonding layer is applied after the first electrode, the bonding layer is in direct material contact with the subsequent electrolyte layer.
  • (Lowermost) layer of the first electrode except for a region with a maximum distance of 2 mm from the boundary line away from the central gas-permeable region of the support substrate, and extends - except from an area with a maximum distance of 5 mm from the boundary line removed - not on the gas-tight surface of the
  • the (lowest) layer of the first electrode is in direct contact with the carrier substrate or with any intermediate layer (diffusion barrier layer) applied to the carrier substrate.
  • the extent of the attachment layer does not only have to be limited to the transition region, but the attachment layer can be extended over the entire first electrode.
  • a first bonding layer is directly on the carrier substrate or with a gas-tight
  • the first electrode is deposited, which terminates at and / or on the first bonding layer.
  • a second bonding layer preferably of the same material as the first bonding layer. This is connected at least partially cohesively with the first connection layer.
  • the central region of the carrier substrate it extends at least over a part of the first electrode, it can also
  • the second bonding layer can also be pulled out completely beyond the first bonding layer so that it runs out on the carrier substrate (or the gastight ceramic intermediate layer arranged directly on the carrier substrate).
  • the first electrode can be designed as a layer composite, that is to say in multiple layers, in particular in two layers.
  • the material composition preferably does not change, but the individual layers of the layer composite of the first electrode differ only with regard to the mean sintered grain size or, associated therewith, the porosity.
  • the layer composite can have a gradation of the sintering size, with the mean sintered grain size decreasing from layer to layer as the distance from the carrier substrate increases.
  • the layer composite of the first electrode extends
  • next layer which is usually finer-grained than the immediately underlying layer, beyond the immediately underlying layer, whereby a step-shaped transition with improved adhesion properties is formed in the transition region.
  • the stepped transition is compensated by the underlying and / or subsequent bonding layer.
  • the layer composite of the first electrode is constructed in two layers.
  • care is taken that the lowermost, comparatively coarse-grained layer of the first electrode extends substantially to but not significantly beyond the boundary line, while the subsequent, finer-grained layer the first electrode extends beyond the lowermost layer in the direction of the gas-tight surface of the carrier substrate.
  • Fig. 1 a schematic cross-sectional view of an inventive
  • Electrode-electrolyte unit according to a first embodiment of the invention
  • FIG. 2 a schematic cross-sectional view of an inventive
  • Electrode-electrolyte unit according to a second embodiment of the invention
  • FIG. 3 a schematic cross-sectional view of an inventive
  • Electrode-electrolyte unit according to a third embodiment of the invention.
  • FIG. 4 shows a schematic cross-sectional view of a device according to the invention
  • Electrode-electrolyte unit according to a fourth embodiment of the invention.
  • FIG. 1 Unit according to FIG. 1 in an exploded view.
  • Fig. 1 is a schematic cross-sectional view of a first
  • FIG. 5 shows an exploded view of an electrochemical module (20) in the form of an SOFC, in which the electrode-electrolyte unit of Fig. 1 is used.
  • the section plane of the section of the electrode-electrolyte unit shown in FIG. 1 takes place in the carrier substrate in FIG. 5 along the line I-II (it should be noted that in the electrochemical module a second terminating electrode is also applied, which is shown in FIG. 1 not
  • the support substrate (11) for the electrode-electrolyte unit is according to
  • the carrier substrate (1 1) is in the edge region (12), which surrounds a porous and gas-permeable central region (13), compressed. On the porous central region (3), the chemically active layers shown in the cross-sectional view in FIG. 1 are arranged.
  • the compaction of the edge area is advantageous, but not mandatory.
  • the carrier substrate (11) was melted on the cell-facing side in the edge region over a large area by means of a laser beam. Due to the solidified melt is a gas-tight
  • the gas permeable surface of the central region (13) of the carrier substrate is defined by the gas impermeable surface of the
  • the peripheral edge region (12) of the carrier substrate is connected to two
  • a diffusion barrier layer (15) of CGO or LSM with a thickness of up to about 2 m is applied directly to the surface of the metallic carrier substrate in the central area (13) and an adjacent part of the edge area (12) by means of PVD, which interdiffuses metal between the carrier substrate (1 1) and the first electrode (16,16 ') (in the case of an SOFC, the anode) blocked (in the porous central region (13) while the pores are not closed by the diffusion barrier layer (15), so that further gas permeability is given).
  • the first electrode which consists of two layers (16, 16 ') with different average sintered grain size and porosity. The mean sintered grain size or
  • the first electrode is produced in layers by printing a suitable paste for each layer by means of screen printing and then sintering the arrangement in a reducing hydrogen atmosphere at temperatures above 1000 ° C.
  • the graduated Aoifbau can of course be refined by using more than the illustrated two layers.
  • the material used for the electrode layers is a cermet of nickel and yttria fully stabilized zirconia (Ni / 8YSZ).
  • the lowermost layer (16) of the first electrode covers the entire porous central region (13) of the carrier substrate (11) as far as the boundary line (19) (apart from a small gap which possibly occurs due to the production), but does not extend significantly beyond that. Only the subsequent, finer-grained layer (16 '), due to their
  • a porous ceramic bonding layer (17) of 8YSZ or CGO wet-chemically by brushing a corresponding powder suspension, for example, with addition of dispersant, solvent (eg BCA [2- (2-butoxyethoxy) ethyl] in the transition region of the gas-tight edge region (12) ] acetate, available from Merck KGaA Darmstadt) and binder, and then sintered at about 1000 ° C to 1300 ° C under a hydrogen atmosphere.
  • solvent eg BCA [2- (2-butoxyethoxy) ethyl] in the transition region of the gas-tight edge region (12) ] acetate, available from Merck KGaA Darmstadt
  • the fine-grained bonding layer (17) helps meandering irregularities on the otherwise locally smooth carrier substrate surface, caused by the laser guide during
  • the bonding layer (7) extends beyond the first electrode and runs out in the direction of the edge of the carrier substrate (11). Due to the porosity of the first electrode, it can infiltrate it more or less strongly in the region of the electrode and fill up the pores of the uppermost electrode layer somewhat. This penetration into the pores can additionally facilitate the adhesion and sealing by the electrolyte (18) in the relevant area.
  • the bonding layer (17) has direct contact with the subsequent electrolyte layer (18) on one side, on the other hand, immediately contact with the ceramic
  • DifTusionbarrieretik (15) and in the present example, in which the diffusion barrier layer is applied using coating masks and does not extend over the entire carrier substrate, also in contact with the surface of the metallic carrier substrate.
  • ElectroJyt layer (18) is applied by PVD, has a thickness of less than 5 ⁇ im and consists of 8YSZ. It accomplishes a gas-tight separation of the first electrode from the second electrode.
  • the second electrode in the case of an SOFC the cathode
  • a ceramic porous bonding layer (17 ') of 8YSZ or CGO is arranged directly on the diffusion barrier-coated carrier substrate (1), the layers of the first electrode (16, 16') follow and run on or on the
  • the bonding layer (17 ') protrudes slightly beyond the edge region (12) into the central region (13) of the carrier substrate (11). Since the carrier substrate (11) has relatively large pores in this non-compressed central region (13), the porous attachment layer (17 ') infiltrates into the pores of the carrier substrate (11).
  • Fig. 3 shows a third embodiment with two bonding layers (17, 17 '), a first (17'), analogous to the variant in Fig. 2 directly on the with the
  • Diffusion barrier (15) coated carrier substrate (1) is arranged, and a second bonding layer (17), which is applied analogously to the variant in Fig. 1 after the first electrode (16, 16 ').
  • the second bonding layer (17) can be expanded in the direction of the central region and extend over the entire first electrode (16, 16 ').
  • the second bonding layer (17) causes both a smoothing in the transition region and a reduction of the surface roughness of the first electrode, whereby the thickness of the
  • Electrolyte layer (18) can be reduced.
  • Fig. 4 shows an embodiment of an electrode-electrolyte unit (10 "'), wherein the carrier substrate (1 1) of two originally separate components 0017
  • a metallic powder-metallurgically produced porous substrate part (13), which is welded to a circumferential gas-tight frame plate (12).
  • the challenge with the seal lies in this example, especially in the relatively deep and sharp-edged weld.
  • the porous substrate part is analogous to the preceding one
  • connection layers (7, 17 ') are used. Variants with a connection layer as in FIG. 1 or FIG. 2 are also conceivable. If the first electrode (16, 16 ') is applied in front of a bonding layer, care should be taken that at least the lowermost, comparatively coarse-grained layer of the first electrode does not exist

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  • Inert Electrodes (AREA)

Abstract

La présente invention concerne une unité électrode-électrolyte (10, 10', 10'', 10''') destinée à un module électrochimique à base de métal (20), en particulier à une pile à combustible à oxyde solide (SOFC). Cette unité comporte un substrat de support métallique (11) comprenant une région centrale poreuse (13) perméable aux gaz et une région de bord (12) qui est étanche aux gaz au moins superficiellement (du côté dirigé vers la pile) et qui est reliée par liaison de matière à la région centrale le long d'une partie de bord de celle-ci. La surface perméable aux gaz de la région centrale poreuse est séparée de la surface étanche aux gaz de la région de bord par une ligne de délimitation (19). L'unité comporte également au moins une première électrode poreuse (16, 16'), perméable aux gaz, qui est formée sur la région centrale poreuse du substrat de support, et au moins une couche d'électrolyte céramique (18) étanche aux gaz qui est formée sur la première électrode et qui s'étend au-delà de la première électrode en direction de la région de bord et se termine de manière étanche aux gaz (par la zone de bord étanche aux gaz). Au moins une couche de liaison céramique poreuse (17, 17'), qui s'étend au moins sur une partie de la région de bord adjacente à la ligne de délimitation, est formée entre le substrat de support (11) et la couche d'électrolyte (18) au moins le long d'une partie de la longueur de liaison totale de la ligne de délimitation.
PCT/AT2018/000017 2017-04-19 2018-04-10 Unité électrode-électrolyte Ceased WO2018191765A1 (fr)

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US20100098996A1 (en) * 2008-10-16 2010-04-22 Institute Of Nuclear Energy Research Atomic Energy Council, Executive Yuan Solid oxide fuel cell and manufacturing method thereof
US20120186976A1 (en) * 2009-08-03 2012-07-26 Commissariat à l'énergie atomique et aux énergies alternatives Metal-supported electrochemical cell and method for fabricating same
JP2017033799A (ja) * 2015-08-03 2017-02-09 株式会社日本触媒 メタルサポートセル

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102023206638A1 (de) 2023-07-12 2025-01-16 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung einer elektrochemischen Zelle, elektrochemische Zelle, Elektrolysezellenvorrichtung und Brennstoffzellenvorrichtung

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