Electrolysis or co-electrolysis reactor (SOEC) or fuel cell (SOFC) with a stack of electrochemical cells integrating mechanical reinforcement elements with variable rigidity with temperature.

Abstract

Electrolysis or co-electrolysis reactor (SOEC) or fuel cell (SOFC) with a stack of electrochemical cells incorporating mechanical reinforcement elements with variable rigidity with temperature. The invention relates to an electrochemical device formed by assembly by alternating conventional stacking of electrochemical cells and electrical and fluidic interconnectors in which at least one mechanical reinforcement element is placed at each stage which will absorb the bending forces which are likely to appear in the stack during the initial thermomechanical treatment step. Figure for the abstract: fig.6

Description

Title of the invention: Electrolysis or co-electrolysis reactor (SOEC) or fuel cell (SOFC) with stack of electrochemical cells integrating mechanical reinforcement elements with variable rigidity with temperature. Technical field

[0001] The present invention relates to the field of solid oxide fuel cells (SOFC, English acronym for "Solid Oxide Fuel Cell"), that of high temperature water electrolysis (EHT, or EVHT for high temperature water vapor electrolysis, or HTE English acronym for High Temperature Electrolysis, or HTSE English acronym for High Temperature Steam Electrolysis) also with solid oxides (SOEC, English acronym for "Solid Oxide Electrolyser Cell"), and that of high temperature co-electrolysis of water and another gas chosen from carbon dioxide CO2. nitrogen dioxide NO2.

[0002] The invention relates more particularly to the production of an electrochemical device constituting a high-temperature water electrolysis or co-electrolysis (HTE) reactor of the SOEC type, or a fuel cell of the SOFC type, with a stack of elementary electrochemical cells.

[0003] The present invention aims firstly to improve the assembly of such a device and also its operation.

[0004] Although described with reference mainly to the application of high temperature water electrolysis, the invention applies equally well to co-electrolysis of water and another gas chosen from carbon dioxide CO2, as to a SOFC fuel cell.

[0005] The invention applies to a SOFC fuel cell using as fuel either hydrogen or a hydrocarbon, for example methane CH4, or any other fuel such as NH3. Prior art

[0006] A SOFC fuel cell or an EHT electrolyser is an electrochemical device consisting of a stack of elementary patterns each comprising a solid oxide electrochemical cell, consisting of three layers superimposed on each other anode / electrolyte / cathode, and interconnection plates made of metal alloys also called bipolar plates, or interconnectors. The function of the interconnectors is to ensure both the passage of the electric current and the circulation of gases in the vicinity of each cell (injected water vapour, hydrogen and oxygen produced in an EHT electrolyser; air and hydrogen injected and water produced in an SOFC stack) and to separate the anode and cathode compartments which are the gas circulation compartments on the anode and cathode sides of the cells respectively.

[0007] To carry out the electrolysis of water vapor at high temperature EHT, typically between 600 and 950°C, water vapor H2O is injected into the cathode compartment. Under the effect of the current applied to the cell, the dissociation of water molecules in vapor form is carried out at the interface between the hydrogen electrode (cathode) and the electrolyte: this dissociation produces dihydrogen gas H2 and oxygen ions. The dihydrogen is collected and evacuated at the outlet of the hydrogen compartment. The oxygen ions O2- migrate through the electrolyte and recombine into dioxygen at the interface between the electrolyte and the oxygen electrode (anode).

[0008] To ensure the operation of a SOFC fuel cell, air (oxygen) is injected into the cathode compartment and hydrogen into the anode compartment. The hydrogen H2 will transform into H+ ions and release electrons which are captured by the anode. The H+ ions arrive at the cathode where they combine with O2- ions formed from the oxygen in the air, to form water. The transfer of H+ ions and electrons to the cathode will produce a direct electric current from the hydrogen.

[0009] To increase the flow rates of hydrogen and oxygen produced in the case of EHT electrolysis or to increase the electrical power supplied in the case of a SOFC fuel cell, it is known to stack several elementary electrochemical cells on top of each other by separating them by the interconnectors. The assembly is positioned between two end connection plates which support the electrical power supplies and the gas supplies / collection of an electrolyzer (electrolysis reactor) or of a SOFC fuel cell.

[0010] Furthermore, to improve the quality of the electrical contacts established between the interconnectors and the electrodes, and therefore the performance of the aforementioned electrochemical devices, electrical contact elements are individually intercalated and arranged on the electrodes. In an electrochemical device, a nickel grid is conventionally used for contact with the hydrogen electrode (cathode in an EHT reactor, anode in an SOFC cell), because it gives satisfactory results at low cost.

[0011] During the entire preparation of an electrochemical device, it is necessary that each layer of the stack and each stage be positioned very precisely and that this position be maintained.

[0012] Before the operation of a aforementioned electrochemical device, it is necessary to subject its stack to at least one heat treatment step called reduction, in order to put the electrochemical cells in their reduced form, and not not oxidized as they are initially.

[0013] This reduction step can be a thermomechanical cycle under gas, a reducing gas for the hydrogen electrode and air or neutral gas for the oxygen electrode.

[0014] A particular heat treatment step has been described in patent EP2870650B1.

[0015] The stacks implemented to date generally use, at each of their stages, joints which must guarantee the seal between two distinct adjacent gas circulation compartments, i.e. an anode compartment and a cathode compartment. Advantageous joints have been described in patent EP3078071B1. These joints have the particularity of requiring thermal conditioning during which they are crushed.

[0016] Contact elements, such as the layers described in patent application EP2900846A1 or nickel grids, also collapse during thermal conditioning and during operation of the electrochemical device, which ensures their proper placement. Elements that serve as contact elements in the hydrogen chamber also collapse. In other words, during the thermal conditioning step, a stack of an aforementioned electrochemical device collapses, typically by several centimeters. To date, the collapse is proceeding correctly.

[0017] However, in certain SOEC / SOFC stacks, the inventors have been able to observe harmful deformations during the heat treatment step prior to operation. These deformations reduce the contact areas between electrochemical cells and electrical contact elements.

[0018] This undesirable situation is shown in figures 1 and 2, with an electrochemical device 1 with a stack of electrochemical cells 2 based on solid oxides of the SOEC / SOFC type and electrical and fluidic interconnectors 3 made of electronically conductive and gas-tight material for bringing or collecting the electric current to the cells and for bringing, collecting and circulating gases on each electrode of each electrochemical cell. Each electrochemical cell consists of a first electrode forming a cathode, a second electrode forming an anode and an electrolyte intercalated between the two electrodes.

[0019] For the sake of clarity, in these figures 1 and 2, a single electrochemical cell 2 is shown as arranged between two interconnectors 3.

[0020] A first electrical contact element 4 is arranged in contact with an electrode of the cell 2 opposite an interconnector 3. This element may be in the form of a nickel grid, preferably perforated as described in patent application FR2213927 and which may incorporate glass in the form of cord(s) to guide the gases, as described in patent EP3156721B1.

[0021] A second electrical contact element 5 is arranged in contact with another in interconnector 3 opposite the other electrode of the cell 2. This element may be a conductive ceramic layer, in particular grooved. It may be a strip of strontium-doped Lanthanum manganite (LSM), which has been previously cut, and which is glued or heat-pressed directly onto the interconnector 3. The bonding may be carried out without residue as described in patent application WO2022 / 234214. The LSM strip may also be secured by heat-pressing to one face of the interconnector 3, as described in EP2900846B1.

[0022] As shown at the end of the stack, an electrical contact element 5, in particular identical to that in contact with an interconnector, can be fixed to the inner face of a so-called terminal plate 6 of the stack 1.

[0023] Sealing gaskets 7, preferably made of glass-ceramic, are interposed around the cell 2 and the gas passages, being in contact with the cell 2 or one and the other of the electrical contact elements 4, 5. The gaskets 7 between two adjacent interconnectors 3 within the stack may be supported by a sealed frame 8 made of electrically insulating material, preferably mica.

[0024] In this configuration, initially the metal elements (end plates 6, interconnectors 3) rest on the sealing gaskets 7, as shown in [Fig.l].

[0025] The tightening of the stack 1 is carried out cold between a support point P and an axial load C, carried out vertically. During the first temperature rise, the mechanical resistance of the metal elements 6, 3 decreases while that of the sealing joints 7 does not change before, typically at 650°C or even 700°C, when the latter are made of glass-ceramic.

[0026] However, it may happen that the bending load applied to the metal elements 3, 6 leads to their irreversible deformations ([Fig.2]), which is detrimental to subsequent electrical contacts. Indeed, as shown schematically, the flat faces of the metal elements, which should ideally be in direct contact on all their surfaces, are no longer so.

[0027] There is therefore a need to further improve electrochemical devices with a stack of electrochemical cells, forming an SOEC type electrolysis reactor or a SOFC type fuel cell, in particular in order to avoid the consequences of irreversible, unwanted deformations of electrical contact elements within the stack, which may appear in the transient phase of the first temperature rise during thermal conditioning before the first operating cycle. Statement of the invention

[0028] To do this, the invention firstly relates to an electrochemical device, constituting an electrolysis or co-electrolysis SOEC reactor or a fuel cell. SOFC fuel, intended to operate at high temperature, comprising:

[0029] - a stack of electrochemical cells based on solid oxides of the SOEC type / SOFC and electrical and fluidic interconnectors arranged individually on either side of each of the electrochemical cells, each interconnector comprising at least one component made of electronically conductive and gas-tight material for bringing or collecting the electrical current to the cells and for bringing, collecting and circulating gases on each electrode of each electrochemical cell;

[0030] - two plates, called end plates, arranged at the ends of the stack;

[0031] - a plurality of electrical contact elements, each arranged with contact with one face of one of the terminal plates or with an electrode of the electrochemical cells or with one face of an interconnector;

[0032] - a plurality of seals, each arranged around each of the or through-holes to ensure sealing around each gas inlet / outlet within the stack;

[0033] - a plurality of mechanical reinforcement elements, each arranged with contact with one face of one of the terminal plates or with an electrode of the electrochemical cells or with one face of an interconnector, the mechanical reinforcement elements being made of an electrically insulating material and having a rigidity which varies depending on the temperature and is substantially equal to that of the sealing joints so that during a first rise in temperature of the device, before its operation, the reinforcement elements soften then melt simultaneously with the sealing joints, limiting the bending of the terminal plates and the interconnectors.

[0034] Preferably, the mechanical reinforcement elements are made of the same constituent material as that of the sealing joints, preferably a glass-ceramic.

[0035] Advantageously, the mechanical reinforcement elements are in the form of cords, preferably closed on themselves, and / or solid pellets.

[0036] Advantageously again, at least a portion of the mechanical reinforcement elements being arranged in the center of the faces of the terminal plates or the electrodes of the electrochemical cells or the faces of the interconnectors. When it is in the center of the constituents of the stack, the position of the force absorption by the reinforcement elements makes it possible to reduce the bending moment by a factor of 4 since this depends on the square of the length. A mechanical reinforcement element according to the invention may be a point support in the center of the part or any other geometric shape reducing the bending moment.

[0037] The material used for the shim ensuring the force absorption is advantageously in the same material as the sealing joint so that the change in rigidity occurs concomitantly when the softening / melting temperature is reached.

[0038] Preferably, the surface area of ​​a mechanical reinforcement element is between 0.1 and 10 cm2, more preferably 0.5 cm2.

[0039] According to a first advantageous variant embodiment, the electrical contact elements comprise at least one electrically conductive grid, preferably made of gold.

[0040] A gold grid can have a surface area between 0.5 and 5cm2, preferably of the order of 2cm2 with a number of meshes of 100 to 3600 meshes / cm2. A nickel grid can also be considered. In this case, care should be taken to create a seal around the grid to prevent it from oxidizing. A copper grid can also be considered. A conductive ceramic grid can also be considered. Ferritic steel grids, preferably ferritic steel with about 20% chromium, preferably CROFER® or K41 (441 steel) can work if they are in the form of a grid. Indeed, these steels with a high Cr content are highly resistant to corrosion and are good electrical conductors.

[0041] Precious metal grids, such as platinum, may also be considered.

[0042] The number of grids supported per face of the interlayer plate may be between 1 and 10, preferably equal to 5. With a single grid, the quantity of material is limited but the mechanical balance within a stack may not be optimal. With a number of 10 grids, the mechanical balance is ensured but the quantity of material used may be significant.

[0043] Preferably, the surface area of ​​a grid is between 0.5 and 5cm2, preferably of the order of 2cm, for a sheet metal surface area of ​​the order of 500 cm2.

[0044] More preferably, the grid(s) is(are) welded directly to one face of an interconnector and / or a terminal plate. The welding may be by spots.

[0045] According to an advantageous variant embodiment, a mechanical reinforcement element is in the form of a solid pellet arranged in an opening made in the center of the grid.

[0046] According to an advantageous embodiment, a number of five grids are provided in contact with a cell electrode, distributed in a square or rectangle with one of them in the center of the square or rectangle.

[0047] According to this mode and an advantageous configuration, a mechanical reinforcement element is in the form of a cord closed on itself surrounding the grid in the center of the square or rectangle.

[0048] According to a second advantageous embodiment variant, the electrical contact elements comprise at least one layer of a conductive ceramic material.

[0049] According to this second variant, the conductive ceramic material is advantageously chosen from the group consisting of:

[0050] - Lao,6Sro,4Coo,8Feo,203 (LSCF) ; - Lao,sSro,2Cuo,9Feo,16)2,5 (LSCuF) ; - Laoj7Sr0j3Co03 (LSC) ; - Sm0j5Sr0j5CoO3 (SSC) ; - SmBaoj5Sr0j5Co205 (SBSC) ; - GdSrCo2O5 (GSC); - La0j65Sr0j3MnO3 (LSM) ; - LaBaCo2O5 (LBC) ; - YBaCo2O5 (YBC) ; - Ndlj8Ce0j2CuO4 (NCC) ; ■ Lao>8Sro,2Coo,3 Mn03 Fe0>6O3 (LSCMF) ; ■ Lao^Nio^Feo^O;; (LNF) ; - Lalj2Sr0j8NiO4 (LSN) ; - La0j7Sr0j3FeO3 (LSF) ; - La2Nio,6Cu0,404 (LNC).

[0051] Avantageusement encore, the ceramic material conductrice is chosen in the group constituted by the LSM, the LSC, the LNF, and the LSCF.

[0052] Preferably, the layer of conductive ceramic material is hollowed out over at least part of its thickness. The hollowing may consist of grooves, holes or any other shape. Hollowing out, in particular grooving the contact layer, allows for the same crushing force to increase the stress and therefore to crush the layer more and thereby better correct the surface defects. In other words, by grooving a contact layer, its crushing capacity is improved. Conversely, a solid contact layer promotes electrical contact due to a larger current flow surface.

[0053] Advantageously, the layer of conductive ceramic material is bonded, preferably by heat pressing or by means of an adhesive or by heat pressing by the sheet heated beforehand by Joule effect by passage of current or inductively. Reference may be made to the advantageous heat pressing methods described in patent EP2900846B1 or residue-free bonding described in patent application WO2022 / 234214. Inductive heat pressing consists of heating the interconnector or terminal plate sheet(s) by Joule effect and then applying the layer of ceramic material directly to the desired location.

[0054] Advantageously, the thickness of the layer of conductive ceramic material on each face of the sheet is between 100 μm and 5 mm.

[0055] Care is also taken to ensure that the surface area of ​​a layer of ceramic material is minimized so as to increase the local clamping stresses applied to the stack. Indeed, the clamping force applied is constant. Also, by reducing the surface area of ​​the contact layer the stress (F / S) will be increased. For example, with the same force and a layer of ceramic material whose surface area is two times smaller, the constraint is twice as high.

[0056] Thus, the invention essentially consists of an electrochemical device formed by assembly by alternating conventional stacking of electrochemical cells and electrical and fluidic interconnectors in which at least one mechanical reinforcement element is placed at each stage which will take up the bending forces which are likely to appear in the stack during the initial thermomechanical treatment step.

[0057] This treatment serves to finalize at least the installation of the electrical contact elements and the sealing joints within the stack.

[0058] And, in stacks according to the state of the art, during the first temperature rise phase due to the softening of the sealing joints, the flexions appear.

[0059] Implanting mechanical reinforcements made with materials with variable rigidity depending on the temperature allows said reinforcements to act by taking up the forces during the first rise in temperature.

[0060] These reinforcements, advantageously in the same material as the joints, more particularly in glass-ceramic, will remain rigid until their softening / melting temperature identical to the joints.

[0061] Once this temperature is reached, all mechanical forces are transmitted uniformly to the electrical contact elements.

[0062] Ultimately, the invention has numerous advantages, among which we can cite: - the elimination of deformations in the SOEC / SOFC stacks, likely to reduce the contact areas between electrochemical cells and electrical contact elements; - as a corollary, obtaining greater control over the level of electric current passing through the SOEC / SOFC stacks; - simplicity and speed of implementation of the mechanical reinforcement elements which are installed during the step of removing the sealing joints; - a low additional cost because it can consist of a simple addition of cords and / or solid pads in the same material as the sealing gaskets.

[0063] Other advantages and characteristics will become more apparent upon reading the detailed description, given for illustrative and non-limiting purposes, with reference to the following figures. Brief description of the drawings

[0064] [Fig.l] [Fig.l] is a schematic view in longitudinal section of a part of an electrochemical device with a stack of solid oxide cells according to the state of the art, once the step of stacking the different constituents has been carried out.

[0065] [Fig.2] [Fig.2] takes up [Fig.l] and illustrates the bending deformations which can occur during the first temperature rise during the initial thermomechanical treatment step applied to the device.

[0066] [Fig.3] [Fig.3] is a schematic view in longitudinal section at the level of an end plate forming a cover of an electrochemical device with a stack of solid oxide cells according to the state of the art.

[0067] [Fig.4A], [Fig.4B] Figures 4A and 4B are schematic views in longitudinal section tudinal at the level of an end plate forming a cover of an electrochemical device with a stack of solid oxide cells according to the invention, respectively before and after the concomitant installation of the sealing joints and the mechanical reinforcement elements in accordance with the invention.

[0068] [Fig.5] [Fig.5] is a photographic reproduction showing a mica sheet supporting seals and a mechanical reinforcement element, placed on an end plate of an electrochemical device according to the invention.

[0069] [Fig.6] [Fig.6] is a photographic reproduction of an interlayer according to the invention supporting electrical contact elements and a mechanical reinforcement element.

[0070] [Fig.7] [Fig.7] is a schematic view in longitudinal section of a part of another example of an electrochemical device with a stack of solid oxide cells according to the invention, once the step of stacking the different constituents has been carried out. Detailed description

[0071] For the sake of clarity, the same elements of an electrochemical device according to the state of the art and of an electrochemical device according to the invention are designated by the same numerical references.

[0072] Throughout the present application, the terms “lower”, “upper”, “above”, “below”, “inner”, “outer”, “internal” “external” are to be understood with reference to an electrochemical device according to the invention in operating configuration, i.e. the modules being stacked vertically.

[0073] It is also specified that the electrolysers or fuel cells described are of the solid oxide type (SOEC, English acronym for “Solid Oxide Electrolyte Cell” or SOFC, English acronym for “Solid Oxide Fuel Cell”) operating at high temperature.

[0074] Thus, all the constituents (anode / electrolyte / cathode) of an electrolysis cell or battery are ceramics.

[0075] The high operating temperature of an electrolyser (electrolysis reactor) or a battery is typically between 600°C and 1000°C.

[0076] Typically, the characteristics of a SOEC electrolysis cell suitable for the invention, of the cathode support type (CSC), may be those indicated as follows: in Table 1 below.

[0077] [Tables 1] Electrolysis cell Unit Value Cathode Constituent material Ni-YSZ Thickness pm 400 Thermal conductivity W m1K 1 13.1 Electrical conductivity Q 1 m1 105 Porosity 0.37 Permeability m2 1013 Tortuosity 4 Current density A.m2 5300 Anode Constituent material LSM , LSC Thickness pm between 10 and 50 Thermal conductivity W m1K 1 9.6 Electrical conductivity Q 1 m1 1 104 Porosity 0.37 Permeability m2 1013 Tortuosity 4 Current density A.m2 2000 Electrolyte Constituent material YSZ Thickness pm <10 Resistivity Q m 0.42

[0078] Figures 1 and 2 relating to an electrochemical device 1 according to the state of the art have been described in the preamble. They are therefore not commented on below.

[0079] Having observed deformations harmful to the electrical contacts in a stack of an electrochemical device according to the state of the art, the inventors thought of implanting in this type of stack mechanical reinforcement elements whose role is to take up the mechanical forces to reduce to a minimum the bending moments during the first rise in temperature of the stack necessary to achieve the installation of sealing gaskets.

[0080] In order to best follow the deformation of these joints, the inventors thought of making these reinforcement elements in the same constituent material, typically in a sealing glass-ceramic.

[0081] The vitroceramic of the reinforcement elements will thus remain rigid until its softening / melting temperature, then all the mechanical clamping forces will be transmitted to the electrical contact elements.

[0082] Thus, the reinforcing elements, made of the same material as the seals, act as force-absorbing shims. The force absorption therefore occurs as long as the bending moment is present and is less as soon as the bending moment reduces.

[0083] A first example of embodiment of the mechanical reinforcement elements is shown in relation to a plate 9 forming the cover of an electrochemical device with a stack of cells 2.

[0084] As shown in [Fig. 3], a cover 9 of a device 1 according to the state of the art, that is to say without the installation of a reinforcing element for the absorption of force, rests on vitroceramic seals 7 arranged at the periphery which can also be supported by a support 8 generally in the form of a mica sheet.

[0085] Subjected to a clamping load C, such a cover 9 is therefore subjected to bending stresses which can lead to its plastic deformation. Indeed, the sealing gaskets 7 remain rigid up to high temperatures, typically around 650 to 700°C, before softening and then melting and being put into place. The temperatures and cycles necessary for the installation of the gaskets, typically made of glass or glass-ceramic, can vary depending on the nature of the composition. Typically, the temperatures can be between 750 and 900°C for a duration of 1 to 48 hours according to one or more cycles. The temperature rise can be done for a device 1 at up to 10°C / min.

[0086] With a mechanical reinforcement element 10, for example in the form of a glass-ceramic washer in the center of the cover 6, preferably in an opening 80 made in the mica support 8, as illustrated in [Fig.4A], then the bending stresses are drastically reduced before the glass-ceramic melts.

[0087] As shown in [Fig.4B], due to the melting of the glass-ceramic for both the seals 7 and the washer 10 forming a force-recovery shim, there is no longer any bending stress.

[0088] [Fig.5] shows a concrete example of the production of a plate 9 forming a cover with a mica sheet 8 supporting both the sealing joints 7 at the periphery around the openings 90 which face the gas passages, and the force-recovery washer 10 in a central opening 80 of the sheet 8.

[0089] [Fig.6] shows another example of integration of a reinforcing element 10 for absorbing force on one face of an interconnector 3.

[0090] The face of the interconnector 3 supports, as electrical contact elements 4, a number of five gold grids, distributed in a square with one in the center of the square. These grids 4 are preferably directly welded to the face of the outer sheet of the interconnector 3. Sealing gaskets 7 have been deposited in the form of beads around each through opening 30 dedicated to the passage of gases in a device 1.

[0091] A glass-ceramic bead 10, closed on itself forming a circular ring around the central grid 4, forms a mechanical reinforcement element which will reduce the bending moments which the interconnector 3 could undergo during the first temperature rise.

[0092] [Fig.7] shows yet another example of implementation of the mechanical reinforcement elements 10, in vitroceramic.

[0093] As illustrated, a solid glass-ceramic pellet 10 can be arranged in the center of each of the electrical contact layers 5, in particular in LSM in an opening 50 made for this purpose.

[0094] Solid glass-ceramic pellets 10 can also be placed in an opening 40 of an electrical contact grid 4, in particular made of nickel.

[0095] This minimizes the bending force at any point of an electrochemical device 1 with a stack of solid oxide cells.

[0096] Whatever its location within a device 1, care is taken to ensure that the surface area of ​​a mechanical reinforcement element 10 is not too large to avoid reducing the active electrochemical surfaces of the cells 2 too much. Advantageously, the surface area of ​​a reinforcement element 10 is between 0.1 and 10 cm2, more preferably 0.5 cm2.

[0097] The invention is not limited to the examples which have just been described; it is possible in particular to combine characteristics of the examples illustrated within non-illustrated variants.

[0098] Other variants and improvements may be envisaged without departing from the scope of the invention.

[0099] A mechanical reinforcement element 10 made of glass-ceramic material according to the invention may preferably be arranged in the center between two constituents of the stack forming an electrochemical device.

[0100] The plate 9 forming the cover may be an end plate, arranged at the end of the top of a stack and whose primary function is to stiffen, to be able to bring the current onto a thick plate, to be able to take up the forces during the return to cold. In this case the end plate is not open because it does not have not the function of passing gases into the stack.

[0101] In a stack where the upper end plate must be open, as in patent application EP3955353A1, then the cover is formed by an additional, non-opening plate.

Claims

Claims

1. Electrochemical device (1) constituting an SOEC electrolysis or co-electrolysis reactor or an SOFC fuel cell, intended to operate at high temperature, comprising: - a stack of electrochemical cells (2) based on solid oxides of the SOEC / SOFC type and electrical and fluidic interconnectors (3) arranged individually on either side of each of the electrochemical cells, each interconnector comprising at least one component made of electronically conductive and gas-tight material for supplying or collecting the electric current to the cells and for supplying, collecting and circulating gases on each electrode of each electrochemical cell; - two plates (6), called terminal plates, arranged at the ends of the stack;- a plurality of electrical contact elements (4, 5), each arranged with contact with a face of one of the terminal plates or with an electrode of the electrochemical cells or with a face of an interconnector; - a plurality of sealing gaskets (7), each arranged around each of the through openings to ensure sealing around each gas inlet / outlet within the stack;- a plurality of mechanical reinforcement elements (10), each arranged with contact with a face of one of the terminal plates or with an electrode of the electrochemical cells or with a face of an interconnector, the mechanical reinforcement elements being made of an electrically insulating material and having a rigidity which varies as a function of the temperature and is substantially equal to that of the seals so that during a first rise in temperature of the device, before its operation, the reinforcement elements soften then melt simultaneously with the seals, limiting the bending of the terminal plates and the interconnectors.;

2. Electrochemical device according to claim 1, the mechanical reinforcement elements being made of the same constituent material as that of the sealing gaskets, preferably a glass-ceramic.

3. An electrochemical device according to claim 1 or 2, at least a portion of the mechanical reinforcing elements being arranged in the center of the faces of the terminal plates or electrodes of the electro-cells. chemicals or faces of interconnectors.

4. Electrochemical device according to one of the preceding claims, the surface area of ​​a mechanical reinforcement element being between 0.1 and 10 cm2, more preferably 0.5 cm2.

5. Electrochemical device according to one of the preceding claims, the mechanical reinforcement elements being in the form of cords, preferably closed on themselves, and / or solid pellets.

6. Electrochemical device according to one of the preceding claims, the electrical contact elements comprising at least one electrically conductive grid, preferably made of gold.

7. Electrochemical device according to claim 6, the number of grids in contact with a cell electrode being between 1 and 10, preferably equal to 5.

8. Electrochemical device according to claim 6 or 7, the surface area of ​​a grid being between 0.5 and 5cm2, preferably of the order of 2cm2.

9. Electrochemical device according to one of claims 6 to 8, the grid(s) being soldered directly to one face of an interconnector and / or a terminal plate.

10. Electrochemical device according to one of claims 6 to 9 in combination with claim 5, a mechanical reinforcement element being in the form of a solid pellet arranged in an opening made in the center of the grid.

11. Electrochemical device according to one of claims 6 to 10, comprising a number of five grids in contact with a cell electrode, distributed in a square or rectangle with one of them in the center of the square or rectangle.

12. An electrochemical device according to claim 11 in combination with claim 5, a mechanical reinforcing element being in the form of a cord closed on itself surrounding the grid at the center of the square or rectangle.

13. Electrochemical device according to one of claims 1 to 5, the electrical contact elements comprising at least one layer of a conductive ceramic material.

14. Electrochemical device according to claim 13, the conductive ceramic material being selected from the group consisting of: - Lao,6Sro,4Coo,8Feo,203 (LSCF); - Lao,8Sro,2Cuo,9Feo,101,5 (LSCuF); - Laoj7Sr0j3Co03 (LSC); - Sm0j5Sr0j5CoO3 (SSC); - SmBaoj5Sr0j5Co205 (SBSC); - GdSrCo2O5 (GSC); - La0j65Sr0j3MnO3 (LSM); - LaBaCo2O5 (LBC); - YBaCo2O5 (YBC); - Ndlj8Ce0j2CuO4 (NCC); ■ Lao>8Sro,2Coo,3 Mn03 Fe0j6O3 (LSCMF); ■ Lao^Nio^Feo^O;; (LNF); - La1>2Sr0j8NiO4 (LSN); - La0j7Sr0j3FeO3 (LSF); - La2Nio.6Cu0.404 (LNC).

15. Electrochemical device according to one of claims 13 or 14, the layer of conductive ceramic material being hollowed out over at least part of its thickness.

16. Electrochemical device according to one of claims 13 to 15, the layer of conductive ceramic material being bonded, preferably by heat pressing or by means of an adhesive or by heat pressing by the interconnector sheet(s) previously heated by Joule effect by passage of current or inductively.

17. Electrochemical device according to one of claims 13 to 16, the thickness of the layer of conductive ceramic material being between 100 pm and 5 mm.

18. Electrochemical device according to one of claims 13 to 17 in combination with claim 5, a mechanical reinforcement element being in the form of a solid pellet arranged in an opening made in the center of the ceramic layer.

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