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    • 专利摘要:
    The invention relates to a new module for EHT reactor or SOFC fuel cell, the module comprising a gas circulation circuit, additional to the reactive gases required for the electrolysis reaction or the reverse reaction in an SOFC cell, the circuit being adapted so that, during operation in pressure, this additional gas balances on one side of the glass-based seals and / or glass-ceramic the pressure of the reactive gases generated on the other side.
    公开号:FR3030893A1
    申请号:FR1462699
    申请日:2014-12-18
    公开日:2016-06-24
    发明作者:Michel Planque；Magali Reytier；Guilhem Roux
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] BACKGROUND OF THE INVENTION The present invention relates to the field of solid oxide fuel cells (SOFC). for "Solid Oxide Fuel Cell"), that of electrolysis of high temperature water (EHT, or EVHT for electrolysis of water vapor at high temperature, or HTE acronym for High Temperature Electrolysis, or HTSE acronym for High Temperature Steam Electrolysis) also with solid oxides (SOEC), and that of the high-temperature co-electrolysis of water and another gas chosen from The invention relates more particularly to the production of a new module integrating electrical and fluidic interconnectors for the distribution of electric current and gases in a SOEC-type high temperature water electrolysis or co-electrolysis reactor (EHT) to produce H2 hydrogen from H20 water vapor, or a stack SOFC fuel type, and an elementary electrochemical cell. The module according to the invention allows operation under pressure.
    [0002] Although described with reference mainly to the application of electrolysis of water at high temperature, the invention is equally applicable to a co-electrolysis of water and another gas chosen from carbon dioxide. CO2 or nitrogen dioxide NO2, than at a SOFC fuel cell. The invention applies to a SOFC fuel cell using as fuel either hydrogen or hydrocarbon, for example methane CH4. PRIOR ART The electrolysis of water is an electrolytic reaction which decomposes the water into dioxygen and gaseous dihydrogen with the aid of an electric current according to the reaction: H 2 O 2 + 1/202.
    [0003] To carry out the electrolysis of the water, it is advantageous to carry it out at high temperature, typically between 600 and 950 ° C., since part of the energy required for the reaction can be provided by the heat which is less expensive than the electricity and the activation of the reaction is more efficient at high temperature and does not require a catalyst. To implement high temperature electrolysis, it is known to use a SOEC electrolyser (acronym for "Solid Oxide Electrolyser Cell"), consisting of a stack of elementary patterns each comprising an electrolysis cell. solid oxide, consisting of three layers of anode / electrolyte / cathode superimposed on each other, and interconnect plates of metal alloys also called bipolar plates, or interconnectors. The function of the interconnectors is to ensure both the passage of electric current and the circulation of gases in the vicinity of each cell (injected water vapor, hydrogen and oxygen extracted in an EHT electrolyser, injected air and hydrogen and water extracted in a SOFC stack) and to separate the anode and cathode compartments which are the gas circulation compartments on the anode side and the cathode side of the cells respectively. To carry out the electrolysis of water vapor at high temperature EHT, water vapor H20 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 hydrogen gas H2 and oxygen ions. The hydrogen is collected and discharged at the outlet of the hydrogen compartment. O2-Oxygen ions migrate through the electrolyte and recombine in oxygen at the interface between the electrolyte and the oxygen electrode (anode).
    [0004] As shown schematically in FIG. 1, each elementary electrolysis cell 1 is formed of a cathode 2 and an anode 4 placed on either side of a solid electrolyte 3 generally in the form of a membrane. The two electrodes (cathode and anode) 2,4 are electrical conductors made of porous material, and the electrolyte 3 is gastight, electronic insulator and ionic conductor. The electrolyte may in particular be an anionic conductor, more specifically an anionic conductor of O 2 - ions and the electrolyzer is then called anionic electrolyzer. The electrochemical reactions are at the interface between each of the electronic conductors and the ionic conductor. At the cathode 2, the half-reaction is the following: 2 H 2 O + 4 e -> 2 H 2 + 2 O 2 -. At the anode 4, the half-reaction is the following: 202-> 02 + 4 e-.
    [0005] The electrolyte 3 interposed between the two electrodes 2, 4 is the place of migration of the O 2 - ions, under the effect of the electric field created by the potential difference imposed between the anode 4 and the cathode 2. As illustrated in parentheses in FIG. 1, the water vapor at the cathode inlet may be accompanied by hydrogen H 2 and the hydrogen produced and recovered at the outlet may be accompanied by steam. Similarly, as shown in dashed lines, a draining gas, such as air can also be injected at the inlet to evacuate the oxygen produced. The injection of a draining gas has the additional function of acting as a thermal regulator.
    [0006] An elementary electrolysis reactor consists of an elementary cell as described above, with a cathode 2, an electrolyte 3, and anode 4 and two mono-polar connectors which perform the functions of electrical, hydraulic and electrical distribution. thermal. To increase the flow rates of hydrogen and oxygen produced, it is known to stack several elementary electrolysis cells on each other by separating them by interconnection devices, usually called interconnectors or bipolar interconnection plates. The assembly is positioned between two end interconnection plates that support the power supplies and gas supplies to the electrolyser (electrolysis reactor).
    [0007] A high temperature water electrolyser (EHT) thus comprises at least one, generally a plurality of electrolysis cells stacked on top of one another, each elementary cell being formed of an electrolyte, a cathode and a cathode. an anode, the electrolyte being interposed between the anode and the cathode. The fluidic and electrical interconnection devices which are in electrical contact with one or more electrodes generally provide the power supply and collection functions and define one or more gas circulation compartments. Thus, a so-called cathodic compartment has the function of distributing electric current and water vapor as well as recovering hydrogen from the cathode in contact. A so-called anode compartment has the function of distributing the electric current as well as recovering the oxygen produced at the anode in contact, possibly with the aid of a draining gas. FIG. 2 represents an exploded view of elementary patterns of a high temperature steam electrolyser according to the state of the art. This electrolyser EHT comprises a plurality of elementary electrolysis cells C1, C2, .. of solid oxide type (SOEC) stacked alternately with interconnectors 5. Each cell C1, C2 ... consists of a cathode 2.1, 2.2 , ... and an anode 4.1, 4.2, between which is disposed an electrolyte 3.1, 3.2 .... The set of electrolysis cells is fed in series by the electric current and in parallel by the gases. The interconnector 5 is a metal alloy component which provides the separation between the cathode compartment 50 and the anodic compartment 51, defined by the volumes between the interconnector 5 and the adjacent cathode 2.1 and between the interconnector 5 and the adjacent anode 4.2. respectively. It also ensures the distribution of gases to the cells. The injection of water vapor into each elementary pattern is done in the cathode compartment 50. The collection of the hydrogen produced and the residual water vapor at the cathode 2.1, 2.2 ... is carried out in the cathode compartment 50 downstream of the cell C1, C2 ... after dissociation of the water vapor therefrom. The collection of the oxygen produced at the anode 4.2 is carried out in the anode compartment 51 downstream of the cell C1, C2 ... after dissociation of the water vapor with oxygen ions therefrom. The interconnector 5 ensures the passage of the current between the cells C1 and C2 by direct contact with the adjacent electrodes, that is to say between the anode 4.2 and the cathode 2.1. In a SOFC solid oxide fuel cell according to the state of the art, the cells Ci, C2 ... and interconnectors 5 used are the same components, but the operation is the opposite of that of an electrolyser EHT such that comes to be explained with a direction of the reversed current, with air that feeds the cathode compartments and hydrogen as a fuel that feeds the anode compartments. Satisfactory operation of an electrolyser EHT requires, among other things, the following essential functions: A / good electrical insulation between two adjacent interconnectors in the stack, otherwise the elementary electrolysis cell interposed between the two interconnectors will be short-circuited; B / a good seal between the two separate compartments, i.e. anodic and cathodic, under penalty of recombination of the gases produced causing a drop in efficiency and especially the appearance of hot spots damaging the electrolyser; this corresponds to looking for a complete initial voltage (acronym "OCV" for Open Cell Voltage); C / a good distribution of gases both in input and recovery of the gases produced, on pain of loss of efficiency, inhomogeneity of pressure and temperature within the various elementary cells or even crippling cell degradations; this corresponds to looking for the lowest polarization resistance; D / a good electrical contact and a sufficient contact surface between each cell and interconnector, in order to obtain the lowest ohmic resistance between cells and interconnectors. High temperatures greatly complicate the performance of the three essential functions A / to Cl mentioned above. In addition, the fragility of solid oxide cells imposes some constraining design rules to ensure their mechanical integrity. Different conceptions already exist to simultaneously perform the four essential functions A / to D /, but there are still various difficulties to overcome. In particular, with regard to the performance of the B / function, given the operating temperature ranges of EHT electrolysers and high SOFC fuel cells, typically 600 ° C to 1000 ° C, the seals are conventionally made from glass or glass ceramic. A glass joint is in the pasty state at the operating temperature. During the design, it is necessary to be careful not to drive the glass under the effect of a pressure difference applied to the seal. A glass-ceramic joint undergoes a thermal cycle in situ in order to crystallize it and thus make it solid at the operating temperature. As with the glass seal, care must be taken not to drive the ceramic hob before it is solid. The simplest configuration consists in placing the glass between two dense planes, as opposed to the different porous materials present in a SOEC reactor or an SOFC fuel cell: the surface tension makes it possible to avoid its flow up to a certain differential pressure on both sides of the joint.
    [0008] To promote this strength, it is necessary to reduce the height of the seal, to increase the area of the areas in contact with the glass and to reduce the pressure differential undergone by the seal. The realization of this type of glass-based sealing in SOEC reactors or SOFC cells faces several problems. Firstly, the electrodes on either side of the cell are porous and therefore can not simply support a glass-based seal. In addition, electrical insulation between adjacent interconnectors must be ensured, which a film of too thin glass can not provide without risk. Finally, these glasses must be crushed to reduce their height, but also to ensure the electrical contact between cell and interconnectors. This tightening must be done by avoiding any overhang of the cell to preserve its mechanical integrity. In the configuration shown diagrammatically in FIG. 3 and disclosed in the patent application FR3000108, part of these constraints is taken into account by the density of the non-porous surfaces on either side of a joint: the cell C1 is kept flat. on its support 2.1 (EHT cathode or SOFC anode) and sandwiched between two adjacent interconnectors 5, a first 61 and second 62 glass or vitroceramic type joints, separated from an electrical insulator 7 to avoid any circuit, are arranged between interconnectors to make it possible to seal the hydrogen produced (fuel supplied in SOFC) and finally, a third seal 63 of the same type is arranged on the side of the anode 4.1 (SOFC cathode) between the electrolyte 3.1 and the interconnector 5 to achieve the tightness of the product oxygen (or air brought in SOFC). Thus, each seal 61, 62, 63 rests on an inherently tight and therefore non-porous support. In addition, a high surface tension between the seals and their support makes it possible to prevent the flow of the glass to a certain differential pressure on either side of a seal. To promote the achievement of good mechanical strength of the seal, it is necessary as much as possible to reduce the joint height and increase the area of the areas in contact with the glass. The reduction in height of the glass or glass-ceramic joints as explained above is achieved by clamping. Clamping is also required to reduce the impact of the contact resistances in the stack, that is to say to ensure the D / function above, a good electrical contact between the cell and interconnectors. However, as shown in FIG. 3, an electrolysis cell C1, C2 ... is mounted cantilevered by virtue of its seal 63. Thus, the clamping required to reduce the height of the joints and to ensure the function D / good electrical contact between cell and interconnectors must also be achieved without prohibitive bending of the cell that could lead to its break. Thus, configurations with a glass-based or glass-ceramic joint, such as that illustrated in FIG. 3, have undeniable advantages of electrical insulation and accommodation of the deformations between pieces of an EHT or SOFC stack. However, as already mentioned, glass-based or glass-ceramic seals inherently have the major disadvantage of only withstanding small pressure differences of the order of a few hundred millibars. The internal operation of a SOFC cell or a pressure EHT reactor, typically from a few bars to a few tens of bars, typically 30 bars, then requires a solution to prevent the loss of seals by the joints. It is already known a solution that consists of placing the stacked reactor EHT or SOFC stack in a sealed chamber itself pressurized. There may be mentioned here the patent applications or patents FR 2957361A1, US2002 / 0081471 and US 6689499 B2 which disclose this type of solution. This known solution offers the advantage of being able to impose the same pressure between the inside and the outside of the stack. This therefore allows operation at a high pressure, from a few bars to a few tens of bars, without mechanical stress on the glass or glass-ceramic joints. But, this requires to guarantee the mechanical strength of a pressurized chamber at these pressures, typically 30 bars, and which contains a stack under a high temperature, typically at 800 ° C with circulation within it H2 hydrogen and oxygen 02. The safety management of this pressure vessel may not be trivial.
    [0009] In addition, the presence of the enclosure complicates the maintenance of clamping of the stack which ensures good electrical contact between interconnectors and cells. In particular, the offset of the clamping members in a relatively cold area is not easy. Finally, the pressurized chamber must be made with passages both through and sealed to achieve the supply / recovery of gas and electricity from outside the enclosure. Thus, these passages must be electrically insulating for some of them and be temperature controlled for those containing water vapor so as to avoid any flushing of water vapor. Indeed, if one does not control the temperature in the inlet and outlet pipes, the water vapor circulating continuously inside can meet a cold zone, and then condense in an uncontrolled way. This causes puffs that generate variations in gas supply and pressure. All these precautionary measures lead to a complete installation integrating the pressurized sealed enclosure and the EHT reactor or the SOFC stack, which is complicated and expensive. There is therefore a need to overcome existing configurations of SOEC type electrolyser (EHT) or SOFC type fuel cells that require the implementation of a pressurized sealed enclosure housing the EHT electrolyser or the SOFC stack to prevent loss of seals by glass-based or glass-ceramic seals. An object of the invention is to respond at least in part to this need.
    [0010] DESCRIPTION OF THE INVENTION To this end, the invention relates, under an alternative, to a module intended to form an elementary pattern of an electrolysis or co-electrolysis reactor of the SOEC type, comprising: an elementary electrochemical cell formed of a cathode, an anode, and an electrolyte interposed between the cathode and the anode, - a first and a second device each forming an electrical and fluidic interconnector, each constituted by a component made of an electronically conductive material and gas tight; the first and second interconnectors being arranged on either side of the elementary cell; the first interconnector being pierced with a conduit for supplying water vapor, opening onto the cell on the cathode side, and a conduit for recovering hydrogen produced, opening at the periphery of the cell of the the cathode side so as to achieve a homogeneous distribution respectively of the water vapor supplied and the hydrogen produced, from the supply duct to the recovery duct; the second interconnector being pierced with a product oxygen recovery duct, opening at the periphery of the cell on the side of the anode so as to achieve a homogeneous distribution of the produced oxygen to the recovery duct; a first seal arranged at the periphery of the elementary cell and bearing against both the first interconnector and the second interconnector; a second seal arranged at the periphery of the anode of the elementary cell and bearing both against the second interconnector and against the electrolyte; the first and second seals being based on glass and / or glass ceramic; an insulation and sealing device consisting of an electrically insulating washer sandwiched by a third and a fourth non-contacting seal with the other, the third and fourth seals being metallic, the device being arranged at the periphery of the first seal with the third and fourth seals bearing respectively against the first and against the second interconnector; module in which the first and / or second interconnectors is (are) pierced (s) of at least one supply duct and at least one gas recovery duct, said balancing gas, opening on the space defined between the first seal and the isolation and sealing device so as to achieve a homogeneous distribution of the equilibration gas from its supply duct to its recovery duct in order to balance the pressures of both sides of the first seal during operation in pressure of the reactor. According to a variant, the second interconnector is pierced with a duct for supplying draining gas, such as air, opening onto the cell on the anode side so as to achieve a homogeneous distribution respectively of the supplied draining gas and the oxygen produced, from the supply duct to the recovery duct.
    [0011] The invention also relates, according to another alternative, to a module intended to form an elementary pattern of a SOFC type fuel cell, comprising: an elementary electrochemical cell formed of a cathode, an anode, and an electrolyte interposed between the cathode and the anode, a first and a second device each forming an electrical and fluidic interconnector, each consisting of a component; the first and second interconnector being arranged on either side of the elementary cell; the first interconnector being pierced with a fuel supply conduit, opening on the cell on the side of the anode and, a conduit for recovering the produced water, opening at the periphery of the cell on the side of the anode so as to achieve a homogeneous distribution respectively of the supplied fuel and the produced water, from the supply conduit to the recovery conduit; the second interconnector being pierced with an air or oxygen supply duct leading to the cell on the cathode side, and a surplus air or oxygen recovery duct leading to the periphery of the cell on the cathode side so as to achieve a homogeneous distribution of air or oxygen, from the supply duct to the recovery duct; a first seal arranged at the periphery of the elementary cell and bearing against both the first interconnector and the second interconnector; a second seal arranged at the periphery of the cathode of the elementary cell and bearing both against the second interconnector and against the electrolyte; the first and second seals being based on glass and / or glass ceramic; an insulation and sealing device consisting of an electrically insulating washer sandwiched by a third and a fourth non-contacting seal with the other, the third and fourth seals being metallic, the device being arranged at the periphery of the first seal with the third and fourth seals bearing respectively against the first and against the second interconnector; module in which the first and / or second interconnectors is (are) pierced (s) of at least one supply duct and at least one gas recovery duct, said balancing gas, opening on the space defined between the first seal and the isolation and sealing device so as to achieve a homogeneous distribution of the equilibration gas from its supply duct to its recovery duct, in order to balance the pressures on both sides of the first seal when operating in pressure of the battery.
    [0012] In other words, the invention consists essentially of a module comprising a circulation circuit of a gas, additional to the reactive gases necessary for the electrolysis reaction or the reverse reaction in an SOFC cell, the circuit being adapted so that, when In operation under pressure, this additional gas balances the pressure of the reactive gases generated on the other side on one side of the glass-based and / or glass-ceramic seals. Thus, it eliminates the implementation solution of a pressurized sealed enclosure as in the state of the art, within which the EHT reactor or the SOEFC stack is housed (e). The only watertightness that must withstand the pressure differential between the inside, typically between 10 and 30 bars, and the outside, typically equal to 1 bar, of the module, while being electrically insulating is that outside the circulation of the balancing gas, the stresses undergone by this sealing being greater than those between anode and cathode compartments in which the reactive gases circulate. According to an advantageous embodiment, the elementary electrochemical cell, the first and second interconnectors, the first and second seals as well as the isolation and sealing device are of axisymmetric shape around a central axis (X). , the reactive gas supply ducts (water vapor or fuel), (draining gas, such as air, or air or oxygen) open along the central axis (X). According to an advantageous variant, the sealing device consists of an insulating washer with a square or rectangular cross-section and third and fourth seals comprising, on each of their faces, one or more projections, preferably of triangular cross section, the vertex projections of each of the third and fourth seals being adapted to deform by bearing respectively on the insulating washer and on the first or the second interconnector, in order to establish the seal on both the insulating washer and each interconnector.
    [0013] The third and fourth joints each having two projections facing one another, in contact with the washer and the first or second interconnector respectively, the projections being adapted to ensure a concentration of the force at the contact between seal and seal range, ie the part to be sealed. Thus, the projections make it possible to achieve the desired seal under a relatively low compression load on either side of the joints.
    [0014] Advantageously, the sealing device consists of an insulating washer based on zirconium oxide (zirconia) and third and fourth joints being based on iron-chromium-aluminum alloy Fecralloye type. According to an advantageous variant embodiment, the first and / or second interconnector comprises (nent) a first annular groove formed between the first seal and the cell, the supply conduit of the first interconnector being in communication with the first annular groove, so that performing the radial distribution of the supplied water vapor and the hydrogen produced or the fuel supplied and the produced water to the recovery conduit of the first interconnector.
    [0015] According to another advantageous embodiment, the second interconnector comprises a second annular groove formed inside an area delimited by the second seal, the supply duct of the second interconnector being in communication with the second annular groove so as to performing the radial distribution of the produced oxygen or the supply air to the recovery conduit of the second interconnector. Each of these first and second annular grooves makes it possible to ensure a good homogeneity of radial distribution of the gas on the electrode concerned, whatever the pressure level. According to an advantageous embodiment, the first and / or second interconnector comprises (ent) a third annular groove formed at the periphery of the interconnectors and in which are arranged the third or fourth seals and the insulating washer, the arrangement being such that the insulating washer protrudes from the third annular groove. This third annular groove facilitates the mounting and mechanical strength of the three components of the sealing device. In addition, the projecting arrangement of the insulating washer makes it possible to guarantee the absence of a short circuit between the interconnectors. According to an advantageous variant, the first seal consists of a mica washer having slots inside which is deposited a glass or glass-ceramic cord filling the slots of the mica after clamping the module. According to another advantageous variant, the first seal consists of a slotted mica washer, the mica washer being sandwiched between two glass-ceramic washers each bearing respectively with the first and second interconnectors and filling the slits. mica after tightening the module.
    [0016] When clamped, the glass or glass ceramic fills the slots of the mica and ensures a good seal between the interconnectors. Advantageously, the module comprises electrical contact elements, preferably metal grids, between each of the electrodes and one or the other of the interconnectors. Preferably, it may be a nickel grid for contact with the H2 / H2O electrode and gold or platinum for contact with the electrode O2. An LSM ceramic layer may also be envisaged for contact with the electrode 02. Preferably, the metal component of the first and / or second interconnector is (are) ferritic steel having about 20% chromium, preferably CROFER® 22APU or F18TNb, or Nickel base type Inconel® 600 or Haynes 230®. The subject of the invention is also an electrolysis or coelectrolysis reactor of the SOEC type or SOFC type fuel cell comprising a stack of modules which have just been described. Advantageously, the EHT reactor or the SOFC cell comprises mechanical means for assembling the interconnectors between them adapted to prevent the opening of the modules but not to compress one interconnector on the other. In other words, these mechanical assembly means prohibit the inadvertent opening of the modules, which ensures operational safety but not compression clamping of the cell between the adjacent interconnects. Clamping, guarantor of sealing and electrical contact is also achieved by applying a compressive force well adapted from one interconnector to the other. The rib chains of all the components of the module are determined to guarantee a crushing of the seals of the device at the periphery, as well as that possible of the electrical contact layers. Typically, the crushing performed by clamping is a few tens of microns. Of course, it is ensured that the compression clamping force is adjusted during the rise in pressure inside the module according to the invention. The mechanical assembly means may comprise one or more mounted bolts passing through housings in the interconnectors, the head of each through bolt resting in a housing of one of the end interconnectors of the stack and a nut screwed on. the through bolt protruding from the other of the end interconnectors of the stack, the head and / or the nut bearing directly or indirectly on an electrical insulating sleeve mounted in at least one of the housing. The bolts are easy to implement and reliable to ensure the desired security, i.e. preventing the opening of the modules in operation in case of overpressure.
    [0017] The invention also relates, in another of its aspects, to a method of operating an above-mentioned electrolysis or co-electrolysis reactor, according to which: the supply ducts of the first interconnector are supplied with steam; water or a mixture of water vapor and another gas selected from carbon dioxide and nitrogen dioxide and simultaneously the supply lines with pressure-balancing gas, the pressure of the water vapor or mixture being substantially equal to that of the equilibration gas; the hydrogen or hydrogen and the carbon monoxide or nitrogen product (s) are recovered by electrolysis or co-electrolysis of the water vapor, and simultaneously the equilibration gas, in their respective recovery ducts; According to an advantageous variant, the supply ducts of the second interconnector are supplied with draining gas, such as air, the pressure of the supplied draining gas being substantially equal to that of the equilibration gas, and the oxygen produced is recovered. The invention also relates, in another of its aspects, to a method of operating a SOFC fuel cell above, according to which: the supply ducts of the first interconnector are fed with fuel, such as hydrogen or hydrogen; methane, and simultaneously the feed ducts in pressure balancing gas; the supply ducts of the second interconnector are supplied with air or oxygen, the pressure of the supplied fuel and air or oxygen being substantially equal to that of the equilibration gas; the surplus fuel, the balancing gas, the water produced on the one hand and the surplus air or oxygen on the other hand, are recovered in their respective recovery ducts. temperature of the equilibrium gas so that the latter regulates the operating temperature of the EHT electrolysis or electrolysis reactor or the SOFC fuel cell.
    [0018] Advantageously, the balancing gas is air, a neutral gas, hydrogen and / or water vapor. The air is preferably chosen in the nominal operating mode of an EHT reactor or an SOFC cell.
    [0019] According to an advantageous variant, any leakage of fuel or products feeding or leaving the electrolysis / co-electrolysis reactor or of the SOFC fuel cell is detected by analysis of the flow of the balancing gas mixture at the outlet of the its recovery duct, then we adjust the air flow as a balancing gas input of its supply duct to burn leaks detected.
    [0020] Indeed, the air makes it possible to reduce the pressure differential at lower cost and also has the following advantages: - in the event of slight leakage of the sealing device at the periphery of the module, compensation for these leaks can be made by a strong flow of air injected into the interconnectors; - In the event of slight leaks from the glass-ceramic and / or glass-based seal which seals the compartment in which the hydrogen circulates, the air injected into the interconnectors makes it possible to burn the leakage hydrogen and thus provide security to the outside atmosphere. By burning the leaks, any accumulation of explosive mixture in the electrolysis / co-electrolysis reactor or in the SOFC fuel cell is avoided. In the nominal operating mode of an EHT reactor or an SOFC cell, in particular due to a loss of the tightness of the first seal, the balancing gas chosen is preferably hydrogen H 2 and / or water vapor H20 when the seal against the outside of the module is maintained, and a neutral gas when there is a concomitant loss of the seal vis-à-vis the outside . Thus, the balancing gas according to the invention not only has the function of managing the differential pressure between the inside or the outside of an EHT reactor or of a SOFC fuel cell, and thus allow reliable operation. under pressure, but it can also help burn gas leaks.
    [0021] In addition, the balancing gas may advantageously have a thermal regulation role of an EHT reactor or an SOFC fuel cell.
    [0022] Preferably, the electrochemical elementary cells are of the support cathode type. By "support cathode cell" is meant here and in the context of the invention the definition already given in the field of the electrolysis of water at high temperature EHT and designated by the acronym CSC for "Cathode- supported Cell ", i.e. a cell in which the electrolyte and the oxygen electrode (anode) are disposed on the thicker hydrogen electrode (cathode) which therefore serves as a support. DETAILED DESCRIPTION Other advantages and characteristics of the invention will emerge more clearly from a reading of the detailed description of exemplary embodiments of the invention, given by way of illustration and without limitation with reference to the following figures among which: FIG. 1 is a schematic view showing the principle of operation of a high temperature water electrolyser; FIG. 2 is a schematic exploded view of a portion of a high temperature water vapor electrolyser (EHT); SOEC type comprising interconnectors according to the state of the art, - Figure 3 is a schematic partial sectional view of an EHT electrolyser or a SOFC type fuel cell according to the state of the art showing the configuration of the seals and electrical contacts within the stack, - Figure 4 is a schematic sectional view of a module for EHT electrolyser or SOFC type fuel cell according to a first mo of the invention showing the configuration of the seals, the electrical contacts and the gas distribution within the stack, - Figure 5 is a schematic sectional detail view of Figure 4, showing the advantageous configuration of the device. of insulation and sealing between the inside and outside of a module according to the invention, - Figure 6 is a photographic reproduction of a sealing device adapted to achieve the seal between the interior and the outside of a module according to the invention, - Figure 7A is a photographic reproduction showing the underside of an upper interconnector of a module according to the invention, before its assembly with the lower interconnector shown in Figures 7B and 7C, - FIGS. 7B and 7C are photographic reproductions showing the top of a lower interconnector of a module according to the invention, respectively before and after placement of the seals, FIGS. s 8A and 8B are numerical simulation views of an interconnector according to the invention respectively devoid and provided with a radial distribution groove of a reactive gas between its axial feed duct and its recovery duct at the periphery; FIG. 9 is an exploded view of an embodiment of a module according to the invention for an EHT reactor; FIG. 10 is a sectional view of an assembled module according to FIG. 9, the section being respectively shown in the flow plane of the equalizing gas, - Figure 11 is a detail view of Figure 10, showing the passage of the balancing gas in the housing grooves of the insulation device and sealing between the inside and outside of a module according to the invention, - Figures 12 and 13 are sectional views of an assembled module according to Figure 9, the section being formed respectively in the steam flow plane water supply and hydrogen produced, in the circulating plane of the supply air and the oxygen produced, FIG. 14 is an exploded view of an embodiment of an EHT electrolysis reactor with a stack of two modules according to the invention, FIGS. 15, 16 and 17 are sectional views of an assembled module according to FIG. 14, the section being taken respectively in the plane of circulation of the air supplied and the oxygen produced, in the plane of circulation of the water vapor supplied and the hydrogen produced, and finally in the equilibrium gas circulation plane; FIG. 18 is a view from below of an electrolysis reactor according to FIGS. 14 to 17. Figures 1 to 3 relating to the state of the art have already been commented on in the preamble. They are therefore not detailed below. For the sake of clarity, the same elements of an EHT electrolysis reactor according to the state of the art and of an EHT electrolysis reactor according to the invention are designated by the same reference numerals.
    [0023] It is specified here throughout the present application, the terms "lower", "upper", "above", "below", "inside", "outside", "" internal "" external "are to be understood by reference to an interconnector according to the invention for cross-section along the axis of symmetry X.
    [0024] It is also specified that the electrolyser or fuel cell modules described are of the solid oxide type (SOEC), which is the acronym for "Solid Oxide Electrolyte Cell" (SOFC), which operates at high temperature. . Thus, all the constituents (anode / electrolyte / cathode) of an electrolysis cell or cell are ceramics. The high operating temperature of an electrolyser (electrolysis reactor) or a battery is typically between 600 ° C and 1000 ° C. Typically, the characteristics of a SOEC elemental electrolysis cell suitable for the invention, of the cathode support (CSC) type, may be those indicated as follows in Table 2 below. TABLE 2 Electrolysis cell Unit Value Cathode 2 Constituent material Ni-YSZ Thickness iam 315 Thermal conductivity w in-1 K-1 13.1 Electrical conductivity 1-2-1 m-1 105 Porosity 0.37 Permeability m2 10-13 Tortuosity 4 Current Density AM-2 5300 Anode 4 Constituent Material LSM Thickness iam 20 Thermal Conductivity w in-1 K-1 9.6 Electrical Conductivity 1-2-1 m-1 1 104 Porosity 0.37 Permeability m2 10-13 Tortuosity 4 Current density A. M-2 2000 Electrolyte 3 Constituent material YSZ Thickness i.tm Resistivity S2 m 0.42 Figure 4 shows a diagrammatic sectional view of a module M1 intended to form the basic pattern of a steam electrolyser EHT water according to the invention. The module M1 comprises an elementary electrochemical cell (C1) of axisymmetric shape around a central axis X, the cell being formed of a cathode, an anode, and an electrolyte interposed between the cathode and the anode, two electrical and fluidic interconnectors 5.1, 5.2 on either side of the cell. The two interconnectors 5.1, 5.2 are each made of a single piece of metal, preferably ferritic steel with about 20% chromium, preferably CROFER® 22APU or F 18TNb, or nickel-based Inconel® 600 or Haynes ®. The upper interconnector 5.1 is pierced with a conduit 50 for supplying water vapor, opening along the central axis on the cell on the cathode side. As explained below, there is provided a radial distribution of the supplied water vapor and the produced hydrogen to a conduit 59 for recovering the produced hydrogen, opening out parallel to the central axis at the periphery. of the cell on the side of the cathode. The lower interconnector 5.2 is pierced with a duct 51 for supplying draining gas, such as air, opening along the central axis on the cell on the side of the anode. As explained below, there is provided a radial distribution of the supplied air and produced oxygen to a conduit 54 for recovering oxygen produced, emerging parallel to the central axis at the periphery of the cell on the side of the anode. A first seal 61 of axisymmetric shape around the central axis X is arranged at the periphery of the elementary cell C1 and bears against both of the two interconnectors. This seal is intended to seal around the cathode compartment. A second axially symmetrical seal 63 around the central axis is arranged at the periphery of the anode of the elementary cell and bears against both the lower interconnector and the electrolyte. This seal is intended to seal around the anode compartment. Seals 61 and 63 are based on glass and / or glass ceramic, as detailed below. According to the invention, an electrical isolation and sealing device 8 of axisymmetric shape around the central axis X is arranged at the periphery of the first seal around the cathode compartment. The device 8 consists of an electrically insulating washer 80 forming a shim, enclosed by third and fourth metal seals 81, 82 without contact with each other. Each of these third and fourth seals 81, 82 is metallic and respectively bearing against the upper and lower interconnector. The lower interconnector 5.2 is pierced with at least one supply duct 58 of a gas, said equilibrium gas, and at least one recovery duct 58 of this equilibrium gas opening onto the annular space E delimited between the seal 61 and the device 8 so as to perform an annular distribution of the equilibration gas to balance the pressures on either side of the first seal 61 during operation. The device 8 is adapted to withstand a large pressure differential between the pressure of the equilibration gas, which is brought to the value as close as possible to the operating pressure of the EHT reactor, typically from 10 to 30 bar and the external pressure of the module, typically 1 bar. The insulating washer 80 makes it possible to avoid any short circuit between the lower interconnector 5.2 and the upper interconnector 5.1. Finally, the metal seals are adapted to have expansions compatible with the materials of the interconnectors, in particular ferritic stainless steel-based interconnectors. According to a variant illustrated in FIGS. 5 and 6, the insulating washer or shim 80 is of zirconia and the two metal seals 81, 82 are based on an alloy comprising chromium and iron, for example FecralloyEl. The upper metal seal 81 has on each of its faces a projection 83, 84 of triangular cross section. The lower metal seal 82 is identical to the upper one 81 and has on each of its faces a projection 85, 86 of triangular cross section.
    [0025] Thus, the shape of the cross section of each seal 81, 82 which carries the bearing respectively with the washer 80 and one of the interconnectors 5.1, 5.2 is a general diamond shape. The top of these triangular projections 83 to 86 is adapted to deform by bearing respectively on the insulating washer 80 and on the first 5.1 or on the second 5.2 interconnector, in order to establish the seal on both the insulating washer and on each interconnector. Thus, during compressive tightening of an EHT reactor comprising the module M1, the triangular projections 83 to 86 made of ductile material make it possible to concentrate the compressive deformations, which avoids having an excessive compression of the entire device. 8. This variant allows the establishment of the desired seal under differential pressure significant with a relatively low compression load. Typically, the compressive load is equal to a value of 5 to 10 N / mm of joint increased by a compensation value of the background effect due to the pressure. This compression load corresponds to the tightening of the seal to obtain the seal without pressure and the maintenance of this clamping for all pressure levels. Indeed, the operating pressure will generate a loosening force of a value F equal to the pressure multiplied by the surface of the disk on which the pressure is applied. Thus, this loosening force must be compensated for by the compensation value, otherwise the two interconnects separate from one another. FIGS. 7A to 7C and 9 to 13 show an embodiment of a module according to the invention. It is specified here that the plugs (B) shown in these figures serve to seal the penetrations made in the interconnector components to delimit the gas supply and recovery ducts. But, once the interconnectors are finished, they have no function in the operation of an EHT reactor according to the invention. In addition to what has already been described, the upper interconnector 5.1 is pierced by a lateral supply duct 52 opening into the central supply duct 50, as can be seen in FIGS. 7A and 12. The upper interconnector also comprises an annular groove 53 for receiving the upper metal seal 81 and the insulating shim 80 (Figures 7A, 10 and 11).
    [0026] The lower interconnector 5.2 comprises a range on which is positioned both the second seal 63 and the elementary cell. From the immediate periphery of the cell to the outside, the lower interconnector 5.2 comprises an annular groove 54 for the radial flow of the H 2 O / H 2 mixture, a flat surface and another annular groove 55 concentric with that around the cell for receiving the sealing device 8. The flat surface is pierced with a lateral supply duct intended to be in communication with the central supply duct 51 of the upper interconnector 5.1, as can be seen in FIGS. 7B and 13. visible in FIG. 7C, the flat surface of the lower interconnector serves to support the seal 61 and around the lateral supply duct 56. In this FIG. 7C, it can be seen that the seal 61 preferably comprises a washer or crown made of mica 610 having slits 611 in which a glass or glass-ceramic bead 612 is made. During tightening, this glass or glass-ceramic cord 612 will flow into the slots 611 and thus create a good bond between the two interconnectors 5.1 and 5.2 which is further wedged laterally by the mica crown 610. As visible in FIG. 14 instead of a bead 612 penetrating into the slots 611, it is conceivable to enclose the mica crown 610 between two washers 613, 614 glass-ceramic respectively each bearing respectively with the first 5.1 and second 5.2 interconnectors.
    [0027] Finally, in this FIG. 7C, it can also be seen that the insulating washer 80 protrudes from the lower interconnector 5.2, when housed in the annular groove 55 of the latter. As can be seen in FIGS. 10 and 11, the lower interconnector is pierced with an annular groove 55 opening into the supply ducts 58 and the recovery ducts 58 of the balancing gas. Each of these supply ducts 58 and recovery 58 of the balancing gas opens into the groove 55 of the sealing device 8 (Figures 10 and 11). According to the invention, there is provided a lateral mounting clearance of the sealing device 8 in the grooves 53, 55 respectively of the upper interconnector 5.1 and lower 5.2, which is sufficient to allow the passage of the balancing gas in the the annular space (E) thus defined between the device 8 and the inside of the grooves 53, 55. As can be seen in detail in FIG. 11, it is the passage formed at the bottom of the bore of the supply duct 58 inside the sealing device 8 which allows the arrival of the balancing gas in the annular space (E) and thus to ensure the annular distribution of the latter. In a way, this annular distribution of the balancing gas forms a peripheral gas curtain around the reactive gas compartments, which allows to balance the pressures. Thanks to the presence of the reactive gas distribution grooves 54, 57 on the lower interconnector 5.2, the module according to the invention with the two interconnectors and the cell in axisymmetric geometry around the X axis allows a homogeneous and radial supply of the cell in reactive gases whatever the level of pressure.
    [0028] To demonstrate the operating advantages of a module M1 according to the invention with these grooves compared to a module without these grooves, the inventors have proceeded with the aid of a commercial software, for example the software called "Fluent", simulations to calculate the homogeneity of gas distribution on the cathode of an electrolysis cell.
    [0029] FIGS. 8A and 8B illustrate these simulations by the flow velocity respectively without and with the annular groove 54. It is specified that the inlet conditions simulated a flow velocity in the feed duct 50 for a 90% mixture of H 2 O and 10% H 2 at a flow rate of 3.7 Nml / min at a pressure of 15 bar and 800 ° C. It emerges from these figures that it is necessary to introduce sufficient pressure losses upstream of the recovery duct 59 in order to guarantee homogeneous and radial flow. Indeed, in FIG. 7A, it is clearly seen that without a throat, the H 2 O / H 2 feeds only the cell zone between the central supply duct 50 and the lateral outlet duct 59. On the other hand, with a groove 54 at the periphery, the axisymmetry of the distribution on the cell is well preserved. As illustrated in FIG. 9, the module M1 according to the invention may advantageously comprise electrical contact grids 9, 10 which may in particular have the effect of compensating flatness defects in order to obtain a better electrical contact between, on the one hand, the upper interconnector and the cathode and secondly between the lower interconnector and the anode. Advantageously, as can be seen in FIG. 9, the module M1 may comprise, at the periphery of the isolation and sealing device 8, an electrically insulating ring 13 of the mica type, the ring 13 bearing on all the zones where the two peripheral surfaces of the interconnectors 5.1 and 5.2 are facing each other. FIGS. 14 to 18 show an electrolysis reactor EHT comprising two modules M1, M2 each made as described above, stacked one on top of the other. In this reactor, the lower interconnector 5.2 of the upper module M1 and the upper interconnector 5.2 of the lower module M2 are made in the same metal alloy component. As can be seen in FIGS. 15 and 16, the various vertical and horizontal bores through the superimposed interconnectors 5.1 to 5.3 make it possible to produce at the periphery and then along the central axis X the supply or air ducts respectively. (FIG. 15) and water vapor 56, 50 (FIG. 16), and at the periphery for the recovery ducts respectively 54 of the produced oxygen and 59 of the hydrogen, for each electrolysis cell C1, C2 .
    [0030] As can be seen in FIG. 17, the various vertical bores through the superimposed interconnectors 5.1 to 5.3 make it possible to carry out at the periphery the supply and recovery conduits 58 for the balancing gas around each electrolysis cell. Cl, C2. According to an advantageous embodiment, the module or the reactor according to the invention integrates a bolt 11 mounted through in housings formed in the interconnectors. As can be seen in FIGS. 10 and 17, the head 110 of the through bolt 11 rests in a housing of an end interconnector 5.2 or 5.3 and a nut 111 screwed onto the through bolt protrudes from the other end interconnector 5.1. the nut 111 being supported indirectly by means of a washer 112 on an electrical insulating sleeve 12 mounted in the housing of the upper interconnector 5.2 or 5.1. The bolt 11 prohibits the inadvertent opening of each module during operation under pressure, which ensures operational safety but not compression tightening of each cell between the interconnectors. Clamping, guarantor of sealing and electrical contact is also achieved by applying a compressive force well adapted from one interconnector to the other. The rib chains of all the components of the modules are determined to guarantee a crushing of the seals 81, 82 at the periphery, as well as that possible of the electrical contact grids 9, 10. Typically, the crushing performed by clamping is a few tens of microns. Of course, it is ensured that the compression clamping force is adjusted during the rise in pressure inside the module according to the invention. Finally, several pipes are connected to the different gas supply and recovery ducts made in the interconnectors in the following way: a lateral supply pipe 14 for the balancing gas is connected to the lateral supply duct 58 of the lower interconnector 5.2 or 5.3, while a balancing gas recovery pipe 15 is connected to the lateral recovery pipe 58 of the lower interconnector (FIGS. 10, 17 and 18); a central air supply pipe 16 is connected to the central supply duct of the lower interconnector 5.2 or 5.3 (FIGS. 12, 13, 15 and 18), whereas a recovery pipe 19 of the oxygen produced is connected to the annular groove 57 of the lower interconnector 5.2 or 5.3 (FIGS. 12, 13, 15 and 18); a central supply pipe for the water vapor 17 is connected to the lateral supply duct of the lower interconnector 5.2 or 5.3 itself opening onto that of the upper interconnector 5.1 (FIGS. 13, 16 and 18). ), while a hydrogen product recovery pipe 18 is connected to the lateral recovery pipe 59 of the lower interconnector (FIGS. 13, 16 and 18). The operation of an electrolysis reactor EHT comprising several modules according to the invention which have just been described is described next, the modules being stacked on top of one another, like that represented in FIGS. 14 to 18. The pipe is fed to the pipe 17 in water vapor and thus the steam supply ducts 56, 52 and 50 and simultaneously the equilibrium gas pipe 14 and thus the supply duct 58 and the annular space E, the pressure supplied water vapor being substantially equal to that of the equilibration gas. Simultaneously also, the pipe 16 is supplied with air, as a draining gas, and thus the supply duct 51, the pressure of the supplied air being substantially equal to that of the equilibrium gas. The water vapor distributed radially from the supply duct 50 and the hydrogen produced by the electrolysis of the water vapor circulates in the annular groove 54 and is then recovered radially in the recovery duct 59 and thus by the recovery pipe 18 (Figures 12 and 16).
    [0031] The balancing gas circulates in the annular space E and is recovered in the recovery duct 58 and thus through the recovery pipe 15 (FIGS. 10 and 17). The air radially distributed from the supply duct 51 and the oxygen produced by the electrolysis of the water vapor circulates radially in the annular groove 57 and is then recovered by the recovery pipe 19 (FIGS. 13 and 15). In the module M1 or the module stack reactor Ml, M2 according to the invention, no feed stream passes through all the pipes 14 to 19. Other variants and advantages of the invention can be realized without as far out of the scope of the invention.
    [0032] For example, it is possible to drill one or the other of the two interconnectors of a module to pass instrumentation means, such as a thermocouple (T) as shown in Figure 12. Although described for high temperature water electrolysis, the module M1 according to the invention or the module stack reactor Ml, M2 can equally well be used for co-electrolysis of mixed water vapor or with carbon dioxide either nitrogen dioxide. Although described for electrolysis of water at high temperature, the module M1 according to the invention or the module stack reactor Ml, M2 can equally well be used as a SOFC fuel cell. In this case, the feed pipes 17 are fed with fuel, for example hydrogen or methane, the pipes 14 are always supplied with balancing gas and the pipes 16 are supplied with air or oxygen. The invention is not limited to the examples which have just been described; it is possible in particular to combine with one another characteristics of the illustrated examples within non-illustrated variants. 25
    权利要求:
    Claims (6)
    [0001]
    REVENDICATIONS1. Module, intended to form an elementary pattern of a SOEC-type electrolysis or co-electrolysis reactor, comprising: - an elementary electrochemical (C1) cell formed of a cathode (2.1), an anode (4.1) , and an electrolyte (3.1) interposed between the cathode and the anode, - a first (5.1) and a second (5.2) device each forming an electrical and fluidic interconnector, each consisting of a component of electronic conductive material and gastight; the first and second interconnectors being arranged on either side of the elementary cell; the first interconnector (5.1) being pierced with a steam supply duct (50), opening on the cell on the cathode side (2.1) and a hydrogen recovery duct produced (59), opening at the periphery of the cell on the cathode side so as to achieve homogeneous distribution respectively of the water vapor supplied and the hydrogen produced, from the supply duct to the recovery duct ; the second interconnector (5.2) being pierced with a product oxygen recovery duct (57), opening at the periphery of the cell on the side of the anode (4.1) so as to achieve a homogeneous distribution of the oxygen produced up to the recovery duct; a first seal (61) arranged at the periphery of the elementary cell and bearing against both the first interconnector and the second interconnector; a second seal (63) arranged at the periphery of the anode of the elementary cell and bearing against both the second interconnector and against the electrolyte; the first and second seals being based on glass and / or glass ceramic; An insulating and sealing device (8) consisting of an electrically insulating washer (80) sandwiched by a third (81) and a fourth (82) non-contacting seals with each other; the third and fourth seals being metallic, the device being arranged at the periphery of the first seal with the third and fourth seals respectively bearing against the first and against the second interconnector; a module in which the first and / or the second interconnector is (are) pierced with at least one supply duct (58) and at least one gas recovery duct, referred to as a balancing gas, each opening on the annular space (E) delimited between the first seal (61) and the insulating and sealing device (8) so as to achieve a homogeneous distribution of the balancing gas from its supply duct up to to its recovery duct, in order to balance the pressures on either side of the first seal during reactor pressure operation.
    [0002]
    2. Module according to claim 1, the second interconnector (5.2) being pierced with a draining gas supply conduit (51), such as air, on the cell on the side of the anode so as to achieve a homogeneous distribution respectively of the supplied draining gas and the product oxygen, from the supply duct (51) to the recovery duct (57).
    [0003]
    Module for forming an elementary pattern of a SOFC fuel cell, comprising: - an elementary electrochemical cell (C1) formed of a cathode (2), an anode (4), and an electrolyte (3) interposed between the cathode and the anode, - a first (5.1) and a second (5.2) device each forming an electrical and fluidic interconnector, each consisting of a component made of an electronically conductive and gas-tight material ; the first and second interconnector being arranged on either side of the elementary cell; the first interconnector being pierced with a fuel supply duct (50), opening onto the cell on the side of the anode (4.1) and, from a duct for recovering the produced water, at the periphery of the the cell on the side of the anode so as to achieve a homogeneous distribution respectively of the supplied fuel and the produced water, from the supply duct to the recovery duct; the second interconnector being pierced with an air or oxygen supply duct, opening onto the cell on the side of the cathode (2.1) and a superheat or oxygen recovery duct; , opening at the periphery of the cell on the cathode side so as to achieve a homogeneous distribution of air or oxygen, from the supply duct to the recovery duct; a first seal (61) arranged at the periphery of the elementary cell and bearing against both the first interconnector and the second interconnector; a second seal (63) arranged at the periphery of the cathode of the elementary cell and bearing both against the second interconnector and against the electrolyte; the first and second seals being based on glass and / or glass ceramic; an insulation and sealing device (8) consisting of an electrically insulating washer (80) sandwiched by a third (81) and a fourth (82) non-contacting seal with each other, the third and fourth seals being metallic, the device being arranged at the periphery of the first seal with the third and fourth seals respectively bearing against the first and against the second interconnector; a module in which the first and the first or the second interconnector is (are) pierced with at least one supply duct (58) and at least one gas recovery duct (58), said balancing gas, opening on the annular space (E) delimited between the first seal (61) and the isolation and sealing device (8) so as to achieve a homogeneous distribution of the equilibrium gas from its feed duct to its recovery duct, in order to balance the pressures on either side of the first seal during operation in pressure of the battery.
    [0004]
    4. Module according to one of the preceding claims, the first and / or the second interconnector comprising a first groove (54) formed between the first seal (61) and the cell (C1), the supply duct (50) of the first interconnector being in communication with the first groove (54) so as to achieve the homogeneous distribution of the supplied water vapor and the hydrogen produced or the fuel supplied and the produced water, to the recovery pipe of the first interconnector.
    [0005]
    5. Module according to one of the preceding claims, the second interconnector (5.2) comprising a second groove (57) formed within an area defined by the second seal (63), the supply duct (51). the second interconnector being in communication with the second groove (57) so as to achieve homogeneous distribution of produced oxygen or supplied air to the recovery conduit (57) of the second interconnector.
    [0006]
    6. Module according to one of the preceding claims, the first and / or second interconnector comprising a third groove (53, 55) formed at the periphery of the interconnectors and in which are arranged the third (81) or the fourth (82) joints and the insulating washer (80), the arrangement being such that the insulating washer projects from the third groove (53, 55). The module according to one of the preceding claims, the elementary electrochemical cell (Cl), the first (5.1) and second (5.2) interconnectors, the first (61) and second (63) seals as well as the insulation and sealing device (8) being of axisymmetric shape around a central axis (X ), the reactant gas supply ducts (50) (water vapor or fuel) and (51) (draining gas (51), such as air, or air or oxygen) emerging according to the central axis (X). 8. Module according to one of the preceding claims, the sealing device consisting of an insulating washer (80) of square or rectangular cross-section and third (81) and fourth seals (82) having, on each of their one or more projections, preferably of triangular cross section, the top of the projections being adapted to deform by bearing respectively on the insulating washer and on the first or on the second interconnector, in order to establish the seal on both the insulating washer and on each interconnector. 9. Module according to one of claims 1 to 8, the sealing device consisting of an insulating washer (80) based on zirconium oxide (zirconia) and third (81) and fourth (82) joints made from Fer-Chrome-Aluminum alloy of Fecralloy® type. 10. Module according to one of claims 1 to 9, the first seal consists of a mica washer having slots (611), the mica washer (610) being sandwiched between two washers (613, 614). ) glass-ceramic each respectively supported with the first and second interconnectors. 11. Module according to one of the preceding claims, comprising electrical contact elements, preferably metal grids (9, 10), between each of the electrodes and one or the other of the interconnectors. 12. Module according to one of the preceding claims, the metal component of the first and / or second interconnector being ferritic steel with about 20% chromium, preferably CROFER® 22APU or Fi 8TNb, or nickel-based type Inconel® 600 or Haynes® 230®. 13. EHT electrolysis or co-electrolysis reactor, SOEC type 30 comprising a stack of a plurality of modules (M1, M2) according to one of claims 1 to 2 and 4 to 12. Fuel cell SOFC type comprising a stack of a plurality of modules (M1, M2) according to one of claims 3 to 12. 15. EHT electrolysis or co-electrolysis reactor according to claim 13, or SOFC cell according to claim 14 , comprising mechanical interconnection means (11) interconnected between them adapted to prevent the opening of the modules but not to compress a compression interconnector on the other. 16. EHT electrolysis or co-electrolysis reactor, or SOFC cell according to claim 15, the mechanical assembly means comprising one or more bolts (11) mounted through in housings formed in the interconnectors, the head (110). each through bolt resting in a housing of one of the end interconnectors (5.1) of the stack and a nut (111) screwed onto the through bolt projecting from the other of the end interconnectors of the stack ( 5.3), the head and / or the nut bearing directly or indirectly on an electrical insulating sleeve (12) mounted in at least one of the housing. 17. The method of operation of an electrolysis or electrolysis EHT reactor according to claim 13 or 15 to 16 wherein: - the supply ducts (50) of the first interconnector (5.1) are supplied with steam. water or a mixture of water vapor and another gas selected from carbon dioxide and nitrogen dioxide and simultaneously the feed ducts (58) in equilibrium gas, the pressure of the steam or the mixture supplied being substantially equal to that of the equilibration gas; the hydrogen or the hydrogen and the carbon monoxide or nitrogen produced are recovered by electrolysis or co-electrolysis of the water vapor and simultaneously the balancing gas, in their respective recovery duct ( 59, 58). 18. Operating method according to claim 17, wherein the supply ducts (51) of the second interconnector (5.2) is supplied with draining gas, such as air, the pressure of the draining gas supplied being substantially equal to that of the balancing gas and the product oxygen is recovered. 19. The method of operation of a SOFC fuel cell according to one of claims 14 to 16 wherein: - the supply ducts of the first interconnector fuel is fed, such as hydrogen or methane, and simultaneously the balancing gas supply ducts; the supply ducts of the second interconnector are supplied with air or oxygen, the pressure of the supplied fuel and air or oxygen being substantially equal to that of the equilibration gas; the surplus fuel, the balancing gas, the water produced on the one hand and the surplus air or oxygen on the other hand, are recovered in their respective recovery ducts. 20. Operating method according to one of claims 17 to 19, wherein the temperature of the equilibrium gas is adjusted so that the latter regulates the operating temperature of the electrolysis or co-electrolysis reactor EHT or the SOFC fuel cell. 21. The method of operation according to one of claims 17 to 20, wherein the balancing gas is air, a neutral gas, hydrogen and / or water vapor. 22. The operating method according to claim 21, wherein: - any leakage of the fuel or products feeding or leaving the electrolysis / co-electrolysis reactor or the SOFC fuel cell is detected by analyzing the flow rate of the fuel. balancing gas mixture at the outlet of its recovery duct (58), then - it then adjusts the air flow as a balancing gas input of its supply duct to burn leaks detected.
    类似技术:
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    FR3057277A1|2018-04-13|WATER VAPOR GENERATOR, FOR ELECTROLYSIS OR WATER CO-ELECTROLYSIS REACTOR | OR FUEL CELL | HAVING PRESSURIZED OPERATION
    FR3090214A1|2020-06-19|Clamping plate for water electrolysis or co-electrolysis reactor | or fuel cell |, Associated manufacturing method
    同族专利:
    公开号 | 公开日
    DK3234227T3|2019-01-21|
    EP3234227B1|2018-10-03|
    US20170362724A1|2017-12-21|
    US10494729B2|2019-12-03|
    JP6479988B2|2019-03-06|
    JP2018507318A|2018-03-15|
    EP3234227A1|2017-10-25|
    FR3030893B1|2017-01-20|
    WO2016096752A1|2016-06-23|
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    CN107470803B|2017-08-08|2019-03-08|上海电器陶瓷厂有限公司|A kind of mica sheet skeleton|
    CN109485044A|2017-09-12|2019-03-19|陈志强|Submarine fresh water air safeguards system and its method|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1462699A|FR3030893B1|2014-12-18|2014-12-18|ELEMENTARY PATTERN FOR ELECTROLYSIS OR CO-ELECTROLYSIS REACTOROR FUEL CELLWITH PRESSURE OPERATION|FR1462699A| FR3030893B1|2014-12-18|2014-12-18|ELEMENTARY PATTERN FOR ELECTROLYSIS OR CO-ELECTROLYSIS REACTOROR FUEL CELLWITH PRESSURE OPERATION|
    JP2017532885A| JP6479988B2|2014-12-18|2015-12-14|Basic unit for water electrolysis or co-electrolysis reactoror fuel celloperating under pressure|
    US15/536,383| US10494729B2|2014-12-18|2015-12-14|Elementary unit for reactor performing water electrolysis or co-electrolysisor fuel celloperating under pressure|
    PCT/EP2015/079636| WO2016096752A1|2014-12-18|2015-12-14|Unit cell for reactor performing water electrolysis or co-electrolysisor fuel celloperating under pressure|
    DK15808431.9T| DK3234227T3|2014-12-18|2015-12-14|DEVICE GROUP FOR A WATER ELECTROLYSE OR -CO ELECTROLYCLE REACTOROR FUEL CELLWITH OPERATING UNDER PRESSURE|
    EP15808431.9A| EP3234227B1|2014-12-18|2015-12-14|Unit cell for reactor performing water electrolysis or co-electrolysisor fuel celloperating under pressure|
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