EP4620046A1 - Solid electrochemical cell stack - Google Patents
Solid electrochemical cell stackInfo
- Publication number
- EP4620046A1 EP4620046A1 EP23808926.2A EP23808926A EP4620046A1 EP 4620046 A1 EP4620046 A1 EP 4620046A1 EP 23808926 A EP23808926 A EP 23808926A EP 4620046 A1 EP4620046 A1 EP 4620046A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrochemical
- cell
- stack
- electrochemical cell
- adjacent
- 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.)
- Pending
Links
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
- C25B1/042—Hydrogen or oxygen by electrolysis of water by electrolysis of steam
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
- C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
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- 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
- H01M8/002—Shape, form of a fuel cell
- H01M8/006—Flat
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- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- 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
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- 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
- H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
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- 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
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- 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
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- 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
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- 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
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- 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
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/248—Means for compression of the fuel cell stacks
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- 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
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
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- 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
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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 disclosure relates to an electrochemical stack and an electrochemical device comprising solid electrochemical cells, a kit of parts for assembly with a solid electrochemical cell to form the electrochemical stack, a method of manufacturing parts, and to uses of the electrochemical stack.
- a solid oxide cell is an electrochemical conversion device that, as a solid oxide fuel cell (SOFC), can directly produce electricity from oxidizing a fuel; or, as a solid oxide electrolyzer cell (SOEC), can produce fuel such as hydrogen (H2), carbon-monoxide (CO), and/or syngas (mixture of H2 and CO) from water (H2O) and carbon-dioxide (CO2), e.g. using electricity and/or heat.
- SOFC solid oxide fuel cell
- SOEC solid oxide electrolyzer cell
- SOCs can be characterized by their ceramic-based electrolyte material able to operate at high temperature, e.g. between 500 and 850 °C.
- a single SOC may comprise a fuel electrode layer formed in porous ceramic to allow the fuel to flow towards the electrolyte; an air electrode, formed as a thin porous layer where oxygen reduction takes place; an electrolyte, which is a dense layer of ceramic that conducts oxygen ions positioned in between the fuel and air electrodes.
- a current collecting layer may be positioned adjacent to the fuel electrode.
- a SOC stack may consist of multiple (typically hundreds) of cells, where different SOCs can be connected to each other in a stack configuration.
- the repeating unit of the stack configuration in conventional configurations can comprise two separator plates; a SOC cell positioned between the separator plates; a gas manifold for fuel and gas to enter/exit the cell; and a combination of multiple seals and a manifolding frame for sealing the SOC cell and separator plates together.
- the multiple components constituting a SOC stack can make assembly complex and/or costinefficient.
- operation of SOC stacks under pressure is difficult, e.g. requiring the use of a pressure vessel.
- W02022043087A1 describes of a stack of so-called metal-supported cells. The metal supported cells form part of a manifold in combination with an external skirt.
- EP3846265A1 describes a fuel cell interconnect assembly.
- the stack configuration as disclosed comprises an interconnect plate that is connected through joints with both a cathode and anode interface, and requires on each side a seal.
- the present invention aims to eliminate or at least mitigate the limitations associated to known stack assemblies. Alternatively, or in addition, the present invention aims to provide an assembly having a reduced number of parts per repeat unit and/or having an internal manifolding and/or an assembly being operable without a need for an external pressure vessel.
- the stack is comprised of a cell unit that is disposed between first and second adjacent cell units.
- the stack can be used to particular advantage in an electrochemical device.
- the stacked units are generally held in compression, e.g. by applying opposing forces onto terminal end plates of the stack.
- the stack comprises electrode-supported cells. Electrode-supported cells rely on the electrode material for structural support. Typically, the electrolyte is relatively thin and deposited on the electrodes. The electrodes may be porous and provide mechanical support for the cell structure, and the electrolyte layer may help in the ionic conduction between the two electrodes.
- the separator plate comprises a central portion and a border portion that extends around the central portion.
- the central portion includes i) a comparatively recessed bottom face and ii) an outward face, opposite the recessed bottom face.
- the recessed bottom face defines a contact face that supports the solid electrochemical cell (e.g. solid oxide cell).
- the outward face contacts the solid electrochemical cell (solid oxide cell) of the first adjacent cell unit.
- the border portion provides an upstanding sidewall extending circumferentially from the recessed bottom face and that ends at a comparatively raised top face.
- the seal element extends between the electrically conductive separator plate and the electrically conductive separator plate of the second adjacent cell unit.
- the seal is dimensioned to extend between the raised top face of the border portion and an opposing bottom face of the border portion of a separator plate of the second adjacent cell unit.
- a separation distance between the recessed bottom face of the separator plate and the outward face of the second adjacent separator plate as defined by a combined height of the seal element and the upstanding side wall matches a thickness of the solid electrochemical cell (solid oxide cell).
- the disclosure thus provides a stack and corresponding device wherein each cell is confined by a cavity that is that is bound longitudinally by contact faces of adjacent separator plates and laterally by the upstanding sidewall of the comparatively raised border in combination with the seal element.
- the seal element extends inwardly from the raised top face of the border portion, past the upstanding sidewall to form an overlap with a free top face of the solid electrolyte layer. Overlapping the seal with the solid electrolyte layer advantageously mitigates leakage of feedstock (e.g. fuel of air) via a gap between the sidewall and the solid oxide cell, i.e. from a “fuel: side or compartment to an “air” side or compartment or vice versa. This improves overall efficiency and/or safety during use.
- feedstock e.g. fuel of air
- the seal preferably forms a circumferential overlap with the electro solid electrolyte layer.
- the overlap advantageously reduces a manufacturing accuracy of matching the shapes of the recess and cell and/or the need for a supplemental lateral seal between sidewall and cell.
- at least one of the fuel and air electrode layers is configured to leave a circumferential edge portion of the electrolyte layer uncovered for direct contact with the seal.
- the overlap with a free top face of the solid electrolyte can be realized in a number of ways. For example, by providing the seal element with a correspondingly dimensioned protruding or recessed portion.
- the overlay is realized by aligning the free top face of the solid electrolyte layer with the top face of the border portion.
- the thickness of the seal element can cover the remaining distance to the adjacent separator plate. Matching the height of the upstanding sidewall (the depth of the recess) to a thickness of the cell up to and including the solid electrolyte layer simplifies manufacturing of the parts.
- each separator plate are parts of a monolithic metal plate.
- each cell unit comprises no more than single ones of the separator plate and the seal element. Forming the plated from a single monolithic object and/or using only a single seal element further mitigates potential leakage of process feeds by limiting the number of contact interfaces between parts and simplifies assembly of the stack.
- the seal element is preferably provided as a compressive seal, preferably a ceramic compressive seal able to withstand operating temperatures in a range of at least 500-700°C, preferably up to 850°C or 900°C.
- the compressive seal providing the thickness under working compression so seal of the space between adjacent plates and a larger transient thickness.
- Materials suitable for a compressive seal are generally known in the art.
- the seal is a ceramic compression seal, preferably vermiculite-based seal.
- the seal is embodied as a multilayer seal having a rigid core, preferably a metal core, sandwiched between electrically insulating compressive seal layers.
- the metal core advantageously provides the sealing element with increased rigidity/structural rigidity, e.g. during its manufacturing, storage, and/or during assembly of the stack.
- the electrochemical stack further comprising a porous current collector layer disposed along an outer face of one or more of the electrode layer and the counter electrode layer.
- the current collector e.g. a metal mesh
- the porous current collector layer can even be the carrier substrate for the stack of functional layers of the cell.
- the porous current collector layer can be a metal grid/mesh structure, e.g. Ni-based, or otherwise electrically conductive material (e.g. Carbon-based).
- an oxidant side (e.g. air) side the structure is preferably formed of a composition resistant/inert to oxidation by oxygen at process conditions (e.g. Au, Pt or a protective layer coated structure, e.g. a coated ferritic steel mesh).
- the present disclosure further relates to an electrochemical device.
- the device comprising: the stack according to any of the preceding claims, and an endplate disposed along opposing terminal ends of the stack. During use a compressing force can be applied to the endplates.
- a pressure vessel surrounding the stack is not required but can be provided. Feedstock can be provided directly to the internal gas headers comprised of aligned apertures, e.g. from respective connectors provided at the endplates.
- one or more, preferably all of the cell units comprises at least two of the solid oxide cells, e.g. 2, 3, 4 or more.
- the cells can be arranged in an array (e.g. a 2 x 2 array). It will be appreciated that the separator plate will be adjusted accordingly. For example, to include a corresponding plurality of the recessed areas to accommodate the cells.
- the plurality e.g. the array, can advantageously covers a larger surface area than a single cell. Use of a plurality of cells as opposed to a single larger cell with the same area offers relaxed manufacturing of the cell.
- the use of a plurality of cells can further limit a total height of a stack assembly for a given application (at the expense of a comparatively limited increase in lateral dimensions).
- the use of a plurality of cells can further improve a conversion (of fuel and/or oxidant) within the layer of the stack.
- the present disclosure further relates a method of manufacturing the electrochemical stack as disclosed herein.
- the method comprising providing: a) a solid oxide cell comprising an electrode layer and a counter electrode layer that are separated by a solid electrolyte layer; b) an electrically conductive separator plate as disclosed herein for extending between the solid oxide cell and a solid oxide cell of a first adjacent cell unit, the separator plate comprising: a central portion providing i) a comparatively recessed bottom face for contacting the solid oxide cell and ii) an outward face, opposite the inward face, for contacting the solid oxide cell of the first adjacent cell unit; and a border portion providing a compactivity raised top face and an upstanding sidewall circumferentially extending from the recessed bottom face; and c) a seal element as disclosed herein configured for extending between the top face of the border portion and a bottom face of the border portion of the electrically conductive separator plate of the second adjacent cell unit, wherein a combined height of the seal element and the sidewall matches
- the method conveniently employs comparatively simple pick and place steps to assemble the stack from premade parts.
- the respective parts may be provided with alignment means, e.g. holed, pins, and the like. Because the parts are held in compression no separate welding or gluing steps are required. Accordingly, the stack can be disassembled with comparative ease, e.g. for maintenance purposed.
- the present disclosure further relates to parts for assembly of the stack/device comprising the stack.
- a kit of parts for assembly of the electrochemical stack as disclosed herein.
- the kit comprises: the electrically conductive separator plate and the seal element as disclosed herein.
- the separator plate comprises at least a central portion providing: i) a comparatively recessed bottom face comprising a first cell support area configured for receiving the solid oxide cell, and ii) an outward face, opposite the recessed bottom face, comprising a second cell support area configured for contacting the solid oxide cell of the first adjacent cell unit, and a border central portion providing a comparatively raised top face and an upstanding sidewall circumferentially extending from the recessed bottom face.
- the seal element correspondingly configured for at least extending between the raised top face of the border portion and a recessed bottom face of the border portion of the electrically conductive separator plate of the second adjacent cell unit, and whereby the seal element and the upstanding sidewall are configured provide a separation distance between the first cell support area of the separator plate and the second cell support of the second adjacent separator plate that matches a thickness of the solid oxide cell.
- the kit further comprises an inlay plate as disclosed herein.
- the seal element may be the multilayer seal as disclosed herein.
- kit can comprise a plurality of these parts, e.g. 10, 100, or more.
- kit can further comprise one or more of the half endplates as disclosed herein and/or a manual with instructions as to the assembly/disassembly of the stack.
- the kit may further include a corresponding number of solid electrochemical cells, e.g. solid oxides cells as disclosed herein.
- the present disclosure further relates to a method of manufacturing the separator plate as defined herein.
- the method comprises machining, e.g. milling, a central portion of an essentially planar metal base plate to form the recessed bottom face configured to receive a solid oxide cell, and leaving a comparatively raised border portion around the central portion.
- the method can further comprises machining, preferably with the same tool, a first structure of grooves in the recessed bottom face forming a first channel structure extending between a first pair of apertures provided in the border portion, and providing (e.g.
- the method may comprised a step providing the inlay plate as disclosed herein.
- the present disclosure further relates to a use of the electrochemical stack according or device as disclosed herein for the generation electrical power or for the manufacture of hydrogen and/or syngas and carbon monoxide.
- FIG 1A and IB provide schematic overviews of operating a solid oxide cell
- FIG 2 provides a cross-section side view of a stack repeating unit, comprising a solid oxide cell, separator plate and seal;
- FIG 3 illustrates aspects of a solid oxide cell
- FIG 4A provides an exploded perspective top -view of an electrochemical stack
- FIG 4B provides an exploded perspective bottom -view of an electrochemical stack
- FIG 5A provides a perspective view of an electrochemical stack
- FIG 5B provides a top down view of an electrochemical stack
- FIG 8A illustrates aspects of a seal element
- FIG 8B illustrates aspects of an electrochemical device
- FIG 80 provides a top view an electrochemical device
- FIGs 9A and 9B provide photographs of parts of the electrochemical device
- FIG 90 provide photographs of an assembled electrochemical device during use
- FIGs 10 and 11 illustrate aspects of the assembly of an electrochemical device
- FIGs 12A and 12B provide perspective views of a plate configured to receive a plurality of solid oxide cells and of that plate partially provided with corresponding cells.
- a SOC operating in fuel cell mode is also referred to as solid oxide fuel cell (SOFC).
- a SOC operating in electrolyzer mode is also referred to as a solid oxide electrolyzer cell (SOEC).
- the cathode is the electrode of an electrochemical cell at which reduction occurs. The cathode can be negative like when the cell is electrolytic (where electrical energy provided to the cell is being used for decomposing chemical compounds); or positive as when the cell is galvanic (where chemical reactions are used for generating electrical energy).
- a solid oxide cell is an electrochemical conversion device that either produces in fuel cell mode electricity directly from oxidizing a fuel or produces in electrolyzer mode hydrogen, syngas, CO from resp. H2O and CO2.
- Solid oxide cells are characterized by their ceramic-based electrolyte material able to operate at high temperature (600-850°C).
- an oxidant flow (02) is supplied to an air side of the cell.
- a reagent flow is provided to the fuel side of the cell.
- oxygen ions are formed at the air electrode are transported across the electrolyte to react with fuel.
- SOEC mode a reagent is reduced at the fuel electrode.
- Formed oxide ions are transported to the air electrode to be released as oxygen.
- the fuel X can be hydrogen (H2) or carbon monoxide (CO), which are respectively oxidized (XO) to water (H2O(g)), carbon dioxide (CO2), etc.
- Oxidized fuel (XO) is supplied such as steam, carbon dioxide, which are reduced to hydrogen, CO, etc.
- the process is typically performed at high temperatures (500-900°C).
- the pressure can be atmospheric or above.
- Fig 2 provides a cross-section side view of an electrochemical stack 100 comprising a cell unit 10, a first adjacent cell unit 10-1, and a second adjacent cell unit 10-2. Note that during use the cell unit 10 is in direct contact with, sandwiched between, the adjacent cell units.
- Each cell unit comprises a solid oxide cell 20,20-1,20-2, a separator plate 30,30-1,30-2 and a seal 40,40-1,40-2.
- the separator plate is 30 electrically conductive, e.g. metallic, preferably a ferritic stainless steel, e.g. CROFER® 22H and/or CROFER® APU.
- the seal or sealing element 40 is electrically insulating, and may thus form a respective electrical insulation between adjacent electrically conductive separator plates.
- the solid oxide cell 20 is held in a cavity or recess.
- Each cell comprises at least an electrode layer 21, a counter electrode layer 22, and a solid electrolyte layer 23.
- a porous current collector layer 25, e.g. a Ni-mesh is provided which extends along an anode side or cathode side of the cell.
- the cathode side in SOEC-mode and the anode side in SOFC-mode.
- the separator plate 30 comprises a central portion 31 forming a cavity or recess for accommodating the electrochemical cell 20, and a protruding border portion 36 circumferentially surrounding the electrochemical cell 20 accommodated by the recess.
- the cavity or recess is preferably provided on one side of the separator plate, e.g. on the top side.
- the recess at the central portion 31 of the separator plate 30 is configured to accommodate the electrochemical cell 20 such that the seal 40 may cover both the top face 37 of the protruding border portion 36 of the separator plate 30, and partly overlap the solid electrolyte layer 23 of the electrochemical cell 20.
- the raised top face 37 of the protruding border portion 36 is preferably flush with the solid electrolyte layer 23.
- a height of the upstanding sidewall 38 i.e. difference in height of the raised top face 37 of the protruding border portion 36 with respect to (the ridges of) the bottom contacting face 32 of the central portion 31, is the same as the total thickness of the electrochemical cell 20 minus the top layer electrode 21, i.e. the combined thickness of the bottom electrode layer 22, optional porous current collector layer 25, and the solid electrolyte layer 23.
- the thickness of the (compressed) seal element 40 is preferably the same as the thickness of the electrode layer 21, which may be sticking out above the solid electrolyte layer 23 and the top face 37 of the protruding border portion 36. In this way, the electrochemical cell 20 may fit exactly between adjacent separator plates 30, 30-2, and form electrical connections on the top and bottom.
- a cavity or recess is defined by a recessed bottom face 32 provided in a central portion 31 of the plate.
- the central portion 31 may be lower than the surrounding border portion 36.
- surrounding the recess is a border portion 36 with upstanding sidewall 38 that extend upward in a direction along the stack.
- the separator plates 30 as shown could also be flipped upside down, such that the cavity or recess may be defined by the central portion 31 being raised with respect to the surrounding border portion 36.
- the seal element 40 extends between respective top and bottom faces 37,39 of the protruding border portion 36 of the separator plate 30 and opposing faces of respective border portions of the respective adjacent cell units 10-1,10-2.
- the seal element 40 comprises an aperture 49 (best seen in FIG 4A) at a location of the electrode layer 21 and extends between the raised top face 37 of the border portion 36 of the seal element 40 and a bottom face 39 of an adjacent separator plate 30-2.
- the central portion 31 has a bottom contacting face 32 electrically contacting a bottom side of the electrochemical cell 20, and a top contacting face 34, opposite the bottom contacting face 32, electrically contacting a top side of an adjacent electrochemical cell 20-1 of the respective bottom-side adjacent cell unit 10- 1.
- the bottom contacting face 32 forms a structure of bottom ridges and bottom grooves.
- the bottom ridges can provide electrical contact with the bottom side of the electrochemical cell 20, and the bottom grooves can provide fluid access to the bottom side of the electrochemical cell 20.
- the top contacting face 34 comprises a structure of top ridges and top grooves.
- the top ridges can provide electrical contact with the top side of the adjacent electrochemical cell 20-1, and the top grooves can provide fluid access to the top side of the adjacent electrochemical cell 20.
- a periodic structure of multiple grooves and ridges is formed on the bottom contacting face 32 and/or top contacting face 34.
- the grooves comprise an array of parallel channels covering the respective electrode layer 21 and/or 22. For example, at least five, at least ten, or more (separate) parallel channels may be formed with ridges there between. In this way, the fluid may be evenly distributed I flowed over the respective electrode layers via the many channels/grooves, while sufficient electrical contact may be provided by the many ridges..
- a combined height of the thickness of the seal element 40 (minus the depth of an optional seal accommodating recess as shown in FIG 7B) and the height of the cavity or recess formed in the central portion 31 matches the thickness of the electrochemical cell 20 (including the optional porous current collector layer 25).
- the electrochemical cell 20 may be electrically contacted from both sides by the respective separator plates.
- a separation distance between the recessed bottom face 32 and an opposing outward face 34 as defined by the combined height of the seal and the sidewall matches a thickness of the solid oxide cell 20.
- the SOC stack configuration is embodied as a so-called electrode-supported cell, where one of the electrodes provides the mechanical integrity on top of which a thin (e.g. ⁇ 10 micron) electrolyte layer is positioned.
- the electrolyte layer permits passage of oxygen ions but not electrons. It is typically embodied as a dense ceramic layer.
- the solid electrolyte layer 23 is an Yttria-stabilized zirconia layer (e.g. 8YSZ).
- the cell further comprises an electrolyte layer a counter electrode layer 22, also referred to a functional fuel electrode layer.
- the fuel electrode layer is embodied as NiO-8YSZ layer (8 mol% Y2O3 fully stabilized ZrO2).
- a support layer shown as TZ3Y-NiO layer, supports the electrolyte and functional electrode layers.
- a contact layer can be provided to improve current collection.
- the contact layer is a NiO-based layer.
- the TEM image in an illustration of the porosity of the stack. Note that the electrode layer 21 does not extend over the full area of the solid electrolyte layer 23, a boundary portion of the solid electrolyte layer 23 is left free. In some embodiment this free top surface 23t is in direct contact with the seal element 40 (see e.g. Figs 2 and 7B).
- the thickness of the solid oxide cell 20 is generally in the order of hundreds of microns (e.g. 0.1-2 mm), typically in a range of 0.3-0.6 mm, e.g. about 400 or 500 microns, whereas the surface area is generally in a range of hundreds of square centimeters (e.g. 50-1000 cm 2 ) or more.
- the side lengths are generally in a range of 10-40 cm, e.g. in a range or 15 ⁇ 5cm, or more. Larger cells can be preferred but may become increasingly hard to manufacture. Of course other shapes and thicknesses are also envisioned.
- the cavity as provided by the seal and opposing plates is dimensioned accordingly.
- the separator plate can be comparatively thick, preferably > 1mm, e.g. about 2-4 mm, to provide mechanical stability even when machined and acts as support for the SOC
- the seal overlaps (L) with a free top face of the solid electrolyte layer 23.
- fluid transfer e.g. air or fuel
- the overlap length L along the free top surface 23t of the electrolyte layer is typically > 1 mm, preferably more e.g. 0.5-1 cm or even up to 2 cm.
- the seal extends across the vertical wall by a distance of up to 1-2 cm. This range was found to offer relaxed manufacturing conditions as a tolerance of small gap between the sidewalls of the recess and the SOC, with a comparatively minimal loss of active electrode area.
- the recessed bottom face comprises a support area for supporting the SOC and is provided with a first channel structure 51.
- the first channel structure 51 extends between a first pair of the apertures.
- a second channel structure 52 is provided along an outward face of the plate, opposite the recessed face.
- the second channel structure running along a second support is for supporting an adjacent SOC.
- the second channel structure 52 extends between a second pair of apertures 54-1,54-2.
- the seal element 40 is dimensioned to extend along between the raised top face 37 of the plate and an adjacent plate.
- the seal is provided with an aperture providing access the solid oxide cell 20, whereby the seal is dimension to extends inwardly along the free top surface 23t of the solid electrolyte layer 23.
- the seal is also provided with apertures at positions corresponding the apertures in the border portion of the plate. Together with adjacent units these aperture form heads providing fluid access to/from each unit.
- a fuel side of each SOC is exposed by a first fluid flow Fl (e.g. fuel) running from aperture 54-1 to 54-2 via second channel structure 52.
- the corresponding air electrode side of each SOC can, during use, be exposed by a second fluid flow F2 (e.g. air) running from aperture 53-1- to 53-2 via first channel structure 51.
- first fluid flow Fl e.g. fuel
- F2 e.g. air
- Inlay plates 57-1 and 57-2 are provided.
- Inlay plate 57-1 covers groove structure 51 along a portion of its trajectory between the apertures and the cell support area.
- Inlay plate 57-2 covers groove structure 52 along a portion of its trajectory between the apertures and the cell support area.
- Inlay plate 57-1 has a thickness so that the plate matches a height level of the raised top face 37 of the plate.
- Inlay plate 57-2 has a thickness so that the plate matches a height level of the bottom face 39 of the plate (see FIG 2).
- Figs 5A and 5B further illustrate aspects of the stack 1 in assembled state, whereby FIG 5A provides perspective view of an electrochemical stack and FIG 5B provides a plan view of the electrochemical stack.
- the border portions with the aligned apertures can be understood as forming zones Al and A2 with gas headers that provide fluid access to each of the cell.
- the groove structure distributes the respective flows F1,F2 over the active cell areas.
- FIGs 6A, 6B, and 60 provide cross-section side detail views of an electrochemical stack at header area A2, whereby FIG 6A is a cross section side view along line A-A in Fig 5B, and FIGs 6B and 60 are detail views of portions marked in FIG 6A. As shown most clearly in FIGs 6B and 60 inlays 57-1 and 57-2 ensure that seal 40 perceives a level contact surface at a location between the corresponding apertures and the active cell areas. This spreads out contact forces and mitigates buildup of local stress between adjacent plates.
- FIGs 7 A, and 7B provide cross-section side views of an electrochemical stack at an active area, whereby FIG 7 A is a cross section side view along line B-B in Fig 5B, and FIG 7B is a detail view of the portion marked in FIG 7 A.
- seal 40 overlaps a free top face 23t of the SOO 20 over a distance L.
- a border portion of the bottom face 39 of the plate 30-2, opposite the recess, can be recessed.
- the bottom face 39 of the adjacent separator plate 30-2 may have a seal accommodating recess which may at least partially accommodate the seal element 40 at a region of the partially uncovered edges 23t of the solid electrolyte layer 23 and/or at the border portion 36 of the adjacent separator plate 30-2.
- a thickness 40t of the compressed seal element 40 may match a sum of a thickness 2 It of the top electrode layer 21 of the electrochemical cell 20 plus a depth 30-2t of the seal accommodating recess.
- the electrode layer may electrically contact bottom ridges 52r of the adjacent separator plate 30-2. This seal accommodating recess may also facilitate positioning of the seal element 40.
- FIG 8A provides a cross-section side view of an embodiment that differs from the embodiment shown in FIG 7 in that the seal element 40 is embodied as a multilayer stack.
- the seal comprises three layers: two sealing layers 42, 43, preferably compression seals, most preferably vermiculitebased, with a metal foil 41 (preferably ferritic steel) in between.
- the seal was found to further guarantee the sealing tightness between fuel and aircompartments.
- FIG 8B is a schematic side view illustrating aspects of an electrochemical device 100 comprising the stack as disclosed herein.
- FIG 8C provides a top view of the device.
- the device comprises endplates 60,61 that are disposed along opposing terminal ends of the stack.
- the stacked is held in compression, e.g. by applying opposing forces onto terminal end plates of the stack.
- the devices can be provided with one or more means to measure and preferably regulate one or more of: a temperature one or more of the plates and the endplates; a temperature of the flows; and/or a pressure applied between the opposing ends of the stack.
- the device is preferably configured to measure/regulate an electrical potential V or an electrical current I between opposing terminal ends of the electrochemical stack 1 and/or between individual ones of the separator plates comprised in the stack.
- the endplates are provided with sensors 62-1 and 62-2 form measuring the temperature of the endplate.
- the device is configured with sensors 62-3,62-4,62-5,62-6 for measuring the temperature of possess flow in the corresponding apertures.
- the device is provided with plurality of terminals Tl,T2,Tn for measuring/applying electrical potentials and/or currents during device operation.
- the stack can also include so-called half-plates 30a and 30b between the stack and the endplates. These half plates differ from the separator plates in that these plates are unpatterned, flat, at a side contacting the endplates.
- each repeating unit in the stack can comprise at least two of the solid oxide cells.
- FIG 12A illustrates a separator plate 30 which differs from described plates in that it is configured to receive four solid oxide electrochemical cells in a 2 x 2 array. Of course other configurations with different number of cells on or alternate relative positioning are also envisioned.
- the plate comprises four comparatively recessed bottom faces 32-1,32-2,32-3,32-4.
- the plate is configured for positioning the solid oxide electrochemical cells in two rows (R1,R2), whereby in each row adjacent cells are connected in series. Note that the raised side wall extends circumferentially around the array and the headers. Advantageously adjacent rows can share a common header.
- the plate preferably also comprises a raised separator wall 36a between adjacent rows.
- the plate preferably also includes a separator wall between adjacent cells within a row.
- the plate preferably comprises a groove structure and the inlay plates 57 as described herein above in relation to FIGs 4-6.
- FIG 12B illustrates the same plate carrying three of the four solid electrochemical cells 20.
- a seal element (not shown) would be provided after positioning the fourth cell. It will be understood that the seal comprises apertures that correspond to the positions of the solid electrochemical cells and the gas headers.
- the disclosure further relates to a method of manufacturing the electrochemical stack.
- method comprises at least: providing a) the solid oxide cell com as disclosed herein; b) the electrically conductive separator plate as disclosed herein and a solid oxide cell of a first adjacent cell unit, and c) the seal element as disclosed herein.
- the method further comprises an assembly process including, placing, the solid oxide cell onto the recessed bottom face of the separator plate, and placing the seal element onto the raised top face of the border portion.
- the parts as provided can preferably include one or more or even all of the aspects as discussed herein above in relation for FIGs 1-8.
- the parts may be provided as a kit of parts for assembly with a solid oxide cell to form the electrochemical stack as disclosed herein.
- the kit comprising at least: an electrically conductive separator plate 30 for assembly between adjacent solid oxide cells, and a seal element 40 for assembly between the adjacent electrically conductive separator plate, wherein the separator plate comprises a central portion 31 providing: i a comparatively recessed bottom face 32 comprising a first cell support area 33 configured for receiving the solid oxide cell 20, and ii) an outward face 34, opposite the recessed bottom face 32, comprising a second cell support area 35 configured for contacting the solid oxide cell of the first adjacent cell unit 10-1, and a border central portion 31 providing a comparatively raised top face 37 and an upstanding sidewall 38 circumferentially extending from the recessed bottom face 32.
- the kit may include a solid oxide cell 20 as disclosed herein and/or one or more of the other parts as discussed herein, e.g. the inlay plates.
- FIGs 9A and 9B provide photographs of parts of the electrochemical device during assembly.
- FIG 9C provides a photograph of an assembled electrochemical device 100.
- FIG 9A depicts a partial stack as assembled on a bottom endplate 61. Visible are the border portion 36 of the top most separator plate a solid oxide cell 20.
- FIG 9B depicts two separator plates having a border portion 36 with apertures and recessed bottom face 32 with a patterned groove structure.
- the assembled electrochemical device 100 depicted in FIG 9C includes a complete stack. Also indicated are top and bottom pressure cylinders applying a contact pressure P onto the stack 100.
- a controller 101 measures and regulates temperature at the separator plate level.
- FIGs 10 and 11 illustrate aspects of the assembly of an electrochemical device. Stage A illustrates a bottom endplate 61.
- first half separator plate 30a is disposed onto end seal element 40a.
- the half separator plate 30a is in electrical contact with endplate 61.
- a porous Nickle mesh current collector layer 25 is disposed over the recessed bottom face of the first half separator plate 30a.
- a solid oxide cell 20 as discussed in relation to FIG 3 is placed onto the porous current collector layer 25.
- a first seal element 40 is positioned onto the border portion of the half separator plate. The seal partially overlaps a free top face of the solid electrolyte layer of the solid oxide cell 20.
- first full separator plate 30 with inlays as disclosed herein is placed onto of the partial stack formed under F.
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Abstract
Description
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP22207293.6A EP4369443A1 (en) | 2022-11-14 | 2022-11-14 | Solid electrochemical cell stack |
| PCT/NL2023/050601 WO2024107049A1 (en) | 2022-11-14 | 2023-11-14 | Solid electrochemical cell stack |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4620046A1 true EP4620046A1 (en) | 2025-09-24 |
Family
ID=84331563
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22207293.6A Withdrawn EP4369443A1 (en) | 2022-11-14 | 2022-11-14 | Solid electrochemical cell stack |
| EP23808926.2A Pending EP4620046A1 (en) | 2022-11-14 | 2023-11-14 | Solid electrochemical cell stack |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22207293.6A Withdrawn EP4369443A1 (en) | 2022-11-14 | 2022-11-14 | Solid electrochemical cell stack |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP4369443A1 (en) |
| JP (1) | JP2025537021A (en) |
| KR (1) | KR20250115387A (en) |
| CN (1) | CN120226171A (en) |
| AU (1) | AU2023381536A1 (en) |
| WO (1) | WO2024107049A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292599A (en) * | 1991-09-27 | 1994-03-08 | Ngk Insulators, Ltd. | Cell units for solid oxide fuel cells and power generators using such cell units |
| JP3857960B2 (en) * | 2002-02-22 | 2006-12-13 | 日本特殊陶業株式会社 | Solid oxide fuel cell |
| JP5667100B2 (en) * | 2012-02-14 | 2015-02-12 | 日本電信電話株式会社 | Method for producing solid oxide fuel cell |
| WO2018154656A1 (en) * | 2017-02-22 | 2018-08-30 | 株式会社 東芝 | Flat plate type electrochemical cell stack |
| US10790519B2 (en) * | 2018-06-05 | 2020-09-29 | Saudi Arabian Oil Company | Solid oxide fuel cell stack with reduced-leakage unit cells |
| US20210143447A1 (en) * | 2019-11-12 | 2021-05-13 | Bryan M. Blackburn | Stack configurations for solid oxide electrochemical cells |
| US11430998B2 (en) | 2020-01-06 | 2022-08-30 | The Boeing Company | Fuel cell interconnect assembly |
| US20230352700A1 (en) | 2020-08-26 | 2023-11-02 | Ceres Intellectual Property Company Limited | Electrochemical cell stack |
-
2022
- 2022-11-14 EP EP22207293.6A patent/EP4369443A1/en not_active Withdrawn
-
2023
- 2023-11-14 JP JP2025527792A patent/JP2025537021A/en active Pending
- 2023-11-14 EP EP23808926.2A patent/EP4620046A1/en active Pending
- 2023-11-14 CN CN202380079177.2A patent/CN120226171A/en active Pending
- 2023-11-14 KR KR1020257017775A patent/KR20250115387A/en active Pending
- 2023-11-14 AU AU2023381536A patent/AU2023381536A1/en active Pending
- 2023-11-14 WO PCT/NL2023/050601 patent/WO2024107049A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CN120226171A (en) | 2025-06-27 |
| WO2024107049A1 (en) | 2024-05-23 |
| EP4369443A1 (en) | 2024-05-15 |
| AU2023381536A1 (en) | 2025-05-22 |
| KR20250115387A (en) | 2025-07-30 |
| JP2025537021A (en) | 2025-11-12 |
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