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    • 专利摘要:
    The invention relates to the production of a heat transfer gas circuit dedicated to the regulation / thermal management of the stack of an EHT reactor or of a SOFC fuel cell by removing certain cells from certain zones of the reactor. stacking to replace them with electrical contact elements that can pass the heat transfer gas.
    公开号:FR3038916A1
    申请号:FR1556727
    申请日:2015-07-16
    公开日:2017-01-20
    发明作者:Magali Reytier；Philippe Szynal
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    METHODS OF (CO) ELECTROLYSIS OF WATER (SOEC) OR PRODUCTION OF HIGH TEMPERATURE ELECTRICITY WITH INTEGRATED EXCHANGERS AS REACTOR STACK (EHT) OR FUEL CELL (SOFC) )
    Technical area
    The present invention relates to the field of solid oxide fuel cells (SOFC) and that of the electrolysis of water at high temperature (EHT, or EVHT for electrolysis of steam vapor). High Temperature Electrolysis (HTE), also known as HTSE (High Temperature Steam Electrolysis), also known as Solid Oxide Electrolysis Cell (SOEC). More particularly, the invention relates to novel methods of operating a SOEC-type high temperature water electrolysis (EHT) reactor to produce hydrogen H2 from H2O water vapor or co-electrolysis of CO2 carbon dioxide and H2O water to produce synthesis gas (mixture of CO and H2), or a SOFC type fuel cell stacked elementary electrochemical cells.
    Although described with reference mainly to the application of electrolysis of water at high temperature, the invention is equally applicable to the co-electrolysis of CO2 carbon dioxide and water H2O, or to a SOFC fuel cell fueled with H2 or methane CH4, as fuel and air or oxygen O2 as the oxidant.
    PRIOR ART The electrolysis of water an electrolytic reaction which decomposes the water into dioxygen and gaseous dihydrogen with the aid of an electric current according to the reaction:
    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 the electrolysis at high temperature, it is known to use a SOEC electrolyser (acronym for "Solid Oxide Electrolyte Cell"), consisting of a stack of elementary patterns each comprising a cell electrolysis to solid oxides, 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 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 hydrogen gas H2 and oxygen ions. The hydrogen is collected and discharged at the outlet of the steam / hydrogen compartment. Oxygen 02 ions migrate through the electrolyte and recombine in oxygen at the interface between the electrolyte and the oxygen electrode (anode).
    As shown diagrammatically 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. The two electrodes (cathode and anode) 2 , 4 are electronic conductors, 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 T electrolyser is then called anionic electrolyzer.
    The electrochemical reactions are at the interface between each of the electronic conductors and the ionic conductor. At cathode 2, the half-reaction is as follows:
    At anode 4, the half-reaction is as follows:
    The electrolyte 3 interposed between the two electrodes 2, 4 is the place of migration of 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 water vapor. 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.
    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).
    An electrolysis reactor or electrolyser of high temperature water (EHT) thus comprises at least one, generally a plurality of electrolysis cells stacked on each other, each elementary cell being formed of an electrolyte, a cathode and an anode, the electrolyte being interposed between the anode and the cathode.
    The fluidic and electrical interconnection devices, which are electronic conductors, are in electrical contact with one or more electrodes in general provide the power supply and collection functions and define one or more gas circulation compartments. More specifically, an interconnector provides electrical contact by one of its faces with the cathode of a cell and the other of its faces with the anode of the adjacent cell.
    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 using a draining gas.
    FIG. 2 represents an exploded view of elementary modules constituting the electrochemical stages of a high temperature steam electrolyser according to the state of the art. This electrolyser EHT comprises a plurality of elementary electrolysis cells Cl, Cl ... of solid oxide type (SOEC) stacked alternately with interconnectors 5. Each cell Cl, Cl ... 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 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. The interconnector 5 ensures the passage of the current between 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.
    FIG. 3 represents an exploded view of elementary modules constituting the electrochemical stages of a SOLC fuel cell according to the state of the art: the same elementary patterns as those of FIG. 2 are implemented for a SOLC fuel cell with the cells of elementary cells C1, C2 and the interconnectors 5. The cathodes 2.1, 2.2 ... of the electrolyser EHT are then used as SOLC stack anodes and the anodes 4.1, 4.2 ... of the EHT electrolysers are used in cathodes in SOLC batteries. Thus, in SOLC battery operation, the injection of oxygen-containing air into each elemental pattern is done in the cathode compartment SOLC 51. The collection of the water produced at the SOLC anode is carried out in the anode compartment SOLC 50 downstream of the cell C1, C2, after recombination of the water therewith with H2 hydrogen injected at the anode 2.2 into each anode compartment upstream of the cell C1, C2. The current produced during the oxidation of hydrogen to water vapor is collected by the interconnectors 5.
    Thus, in a SOLC solid oxide fuel cell, the cells C1, C2, and interconnectors used are the same components, but the operation is the reverse of that of an EHT electrolyser as just explained. with an inverted flow direction, with air supplying the SOFC cathode compartments and hydrogen as fuel that supplies the SOFC anode compartments.
    Satisfactory operation of an EHT electrolyser or of a SOFC fuel cell requires, among other things, the following essential functions: AJ good electrical insulation between two adjacent interconnects in the stack, otherwise the elementary electrochemical cell interposed between the two interconnectors, B / a good seal between the two separate compartments, ie anodic and cathodic, under penalty of recombination of the gases produced leading to a drop in efficiency and especially the appearance of hot spots damaging T electrolyser, C / a good distribution of gas both 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.
    In addition, the operating point selected for the electrolysis reactor or the SOFC cell also fixes the thermal conditions in the stack. Indeed, for the electrolyses carried out at high temperature, the zlH energy necessary for the dissociation of the input molecule (H 2 O or CO 2) can be provided in electrical form and / or heat. The thermal energy supplied Q is then defined as a function of the voltage U at the terminals of each electrolysis cell by the relation:
    where U is the electrical voltage, I is the electric current and F is the Faraday constant.
    Thus, three operating regimes for electrolysis or co-electrolysis, corresponding to three different thermal modes for stacking cells, are defined: the so-called autothermal mode in which the imposed voltage Uimp is equal to Æ1 / 2F. The heat consumed by the dissociation reaction is completely compensated by the different electrical resistances of the electrolyser T (irreversibilities). The electrolyser does not need any particular thermal management while remaining stable in temperature. the so-called endothermic mode in which the imposed voltage Uimp is less than AH / 2F. The electrolyser consumes more heat than the electrical losses within it. This necessary heat must then be provided by another means, otherwise its temperature will drop irretrievably. the so-called exothermic mode in which the imposed voltage Uimp is greater than zlH / 2F. Electrolysis consumes less heat than electric losses by Joule effect. This release of heat within the electrolyser must then be evacuated by another means, otherwise its temperature will increase unacceptably.
    The operation of a battery fueled with CFL methane requires precautions. In fact, the internal reforming reaction, according to the CH4 + H2O-OFb + CO equation, catalyzed by the cermet, generally in nickel-zirconia of the SOFC anode fed with CFL, is highly endothermic, whereas the reaction of Oxidation of hydrogen within the cell is highly exothermic. Without any particular precaution, this requires managing large thermal gradients in the stack, between the inlet and the outlet of the gases, these significant thermal gradients can be unacceptable because inducing high mechanical stresses.
    Thus, the electrochemical reactions necessary for the operation of this type of electrolyser stack or SOFC fuel cell stack can be carried out under various electrical and thermal conditions, each having its own advantages and disadvantages.
    In particular, in the endothermic mode for electrolysis, less electricity is consumed but less hydrogen is produced and heat must be supplied to the stack. The point of this operating point lies in the availability of an inexpensive heat source. Everything depends then on the nature, the temperature of this thermal source and the design of the interconnector making it possible to value this heat at best. In contrast, the exothermic mode for electrolysis as for the battery leads to a significant production of either hydrogen or electricity, but it is necessary to cool the stack, which can be difficult to achieve. Only a suitable interconnector design can allow cooling. The interest of this exothermic mode then depends a lot on the cost of electricity and the use of excess heat.
    An important constraint is to better manage these thermal operating conditions of a fuel cell (SOFC) or an electrolyser (EHT).
    Indeed, whatever the mode considered, the thermal gradients within the stack can be very large, which generates high or very high mechanical stresses that can lead to the breakage of cells and / or joints. In addition, if the stack is not well cooled, it is possible to reach temperatures that are too high, particularly for the seals.
    However, the internal elements of the SOFC stack or the electrolyser, especially the elementary cells, are made at least partly of ceramic, they are therefore very sensitive to temperature gradients and are not able to withstand a shock thermal, nor a too great thermal gradient (a few tens of degrees between the entry and the exit of the gases).
    In addition, to ensure the longevity of the battery or the electrolyser and its proper operation, it is preferable to ensure a distribution of the temperature within the reactor, as homogeneous as possible. Temperatures varying from not more than 10 to 20 ° C are typically sought throughout the stack.
    Different control strategies / thermal management of an EHT electrolyser stack or SOFC stack have already been implemented.
    Beforehand, it is important to specify that the high operating temperatures of EHT electrolyser or SOFC stack prohibit any cooling by means of a liquid as is the case for electrolysers and proton exchange membrane fuel cells. as an electrolyte (PEM for "Protons Exchange Membrane" or "Polymer Electrolyte Membrane").
    Widely used solutions for the cooling of SOFC batteries, alternatively consist in: - carrying out a direct internal reforming within the cell, that is to say a possible conversion thanks to the catalytic activity of the anode, a mixture of methane and water according to the equation
    - lower the fuel utilization rate, - increase the air flow.
    The last two solutions mentioned aim to evacuate the heat by the gases, but this has a direct negative impact on the efficiency of the battery.
    It is also known from the patent application WO 2009/040335 to circulate the gases within the interconnection plates which then act as exchanger, this solution having the advantage of being able to be implemented both for SOFC battery operation and for an electrolyser.
    Some stacking architectures provide for the addition of tubes between the interconnect plates so as to circulate a gas in order to evacuate the calories: this is patent application WO2005 / 122302. Other architectures, as described in the patent application US 2006/0105213, have intercohnectors with fins projecting outwardly of 1 stack to provide additional heat exchange with the external environment.
    Finally, the small thickness of the interconnect sheets limits the possibilities of cooling by radiation and therefore leads to thicken some sheets, as is described for example in the patent application WO2013 / 060869.
    This makes it possible to increase the predominant heat exchange by radiation and / or to be able to circulate other fluids within this type of thick plate, as described in US Pat. No. 4,574,112, but has a significant negative impact on the cost of stacking as for the tubes between plates or exchange fins reported.
    Moreover, a stack of elementary patterns in an EHT electrolyser or in an SOFC cell also has different boundary conditions from one pattern to another adjacent one. In particular, the elementary patterns close to the ends of the stack can conveniently exchange heat with the external environment, which allows to manage their temperature to a certain extent.
    On the other hand, the elementary patterns in the center of the stack have no possible heat exchange with the external environment. For these reasons in the center of the stack, only the gases brought into these areas can therefore be used to manage the thermal.
    There is therefore a need to improve the electrolysis or co-electrolysis reactors and the SOFC fuel cells operating at high temperature, in particular in order to limit the thermal gradients within their stack in order to increase their service life. , while reducing the cost of performing the stack, in particular by avoiding any addition of material or additional parts, such as thick interconnection plates and / or tubes and / or fins added.
    An object of the invention is to respond at least in part to this need.
    Presentation of the invention
    To this end, the invention relates, under a first alternative, to a high temperature electrolysis reactor comprising an alternating stack of two distinct groups of stages including: a group of a plurality of stages, called electrochemical stages, each consisting of a SOEC solid oxide type electrolysis cell formed of a cathode, an anode and an electrolyte interposed between the cathode and the anode, and two interconnectors each adapted to provide a electrical and fluidic interconnection, arranged on either side of the elementary cell, - a group of at least one stage, said stage (s) of thermal regulation constituted (s) of at least one electrical contact element passing through the gases and two interconnectors, each adapted to achieve an electrical and fluidic interconnection, arranged on either side of the contact element, the floor interconnectors Electrochemical s and the thermal stage (s) being adapted for both: • circulating steam or a mixture of H2O and water vapor through the stack; carbon dioxide CO2, a draining gas such as air, and a heat-transfer gas, • recover hydrogen H2 produced or synthesis gas (mixture of carbon monoxide CO and hydrogen H2) produced at the cathodes of the cells the oxygen O 2 produces at the anodes of the cells and, where appropriate, the draining gas, and the heat-transfer gas at the outlet of the elements, the interconnectors of the electrochemical stages being furthermore adapted to distribute both the water vapor or the mixture of water vapor H2O and carbon dioxide CO2, to the cathodes of the cells, and the draining gas to the anodes of the cells, while the interconnectors of (the) stage (s) of thermal regulation are adapted to distribute only the gas coolant to 1 'element (s) of electrical contact allowing the gases to pass. The invention also relates, under a second alternative, to a high temperature fuel cell (SOFC) comprising an alternating stack of two distinct groups of stages including: a group of a plurality of stages, called electrochemical stages, each consisting of an SOFC solid oxide type elementary electrochemical cell formed of a cathode, an anode and an electrolyte interposed between the cathode and the anode, and two interconnectors, each adapted to provide an electrical and fluidic interconnection , arranged on either side of the elementary cell, a group of at least one stage, called a thermal regulation stage (s) constituted by at least one electrical contact element allowing the gases to pass through and two interconnectors, each adapted to achieve an electrical and fluidic interconnection, arranged on either side of the contact element, the interconnectors of the stages electrochemical and of (s) the thermal stage (s) being adapted for both: • circulating through the stack, a fuel, an oxidizer, such as air, and a heat-transfer gas, Recovering the excess fuel and the produced water produced at the anodes of the cells, the surplus of oxidant at the cathodes of the cells and, and the heat transfer gas at the outlet of the elements, the interconnectors of the electrochemical stages being furthermore adapted to distribute at the same time the fuel at the anodes of the cells, and the oxidant at the anodes of the cells, while the interconnectors of the heat-regulation stage (s) are adapted to distribute only the heat-transfer gas to the element (s) electrical contact letting through the gases.
    Preferably, the electrical contact element passing through the gas is a metal gate. The element may also consist of discrete metal wires, a porous conductive electronic substrate ...
    According to an advantageous embodiment, the interconnectors of the electrochemical stages each consist of a device consisting of three plane plates, elongated along two axes of symmetry orthogonal to each other, one of the end plates being intended to come into mechanical contact with the plan of a cathode of one elementary cell and the other of the end plates being intended to come into mechanical contact with the plane of an anode of an adjacent elementary cell, in which device: - the parts of the sheet central and one of the end plates, said first end plate are not drilled while the central portion of the other end plate, said second end plate is pierced, - each of the three flat sheets is breakthrough, on the periphery of its central part, six lights, the first to fourth lights of each sheet being elongated on a corresponding length at a portion of the length of the central portion along one of the X axes of the sheets and being distributed in pairs on either side of said X axis, while the fifth and sixth lights are elongated over a corresponding length substantially along the length of the central portion along the other of the Y axes, the first end plate further comprises a seventh and an eighth light arranged symmetrically on either side of the X axis, within its first to fourth lights, and elongated along a length corresponding substantially to the length of the central portion along the X axis, the second of the end plates, further comprises a seventh and eighth lights arranged symmetrically on both sides other of the Y axis inside respectively its fifth and sixth light, and elongated along a length substantially corresponding to the length of the central portion according to the Y axis, and, the first, third, fifth and sixth lights of the central plate are enlarged respectively with respect to the first, third, fifth and sixth lights of each end plate, while the second and fourth light of the three plates are of substantially identical dimensions to each other, all the enlarged lights of the central plate have in their widened portion tabs of sheets spaced apart from each other forming a comb, each of the slots defined between the edge of an enlarged slot and a tongue or between two consecutive tongues opening on one of the inner lumens of the first or second end plate, the three sheets are laminated and assembled together such that: • the sheet metal tabs form spacer spacers between first and second sheets end respectively between the first and seventh lights of the pr the end plate, between the third and eighth lights of the first end plate, between the fifth and seventh lumens of the second end plate, and between the sixth and eighth lights of the second end plate, each of the first to sixth lumens of one of the three plates is in fluid communication individually with one of the corresponding first to sixth lumens of the other two laminations, respectively, the first or alternatively the second lumen of the first end plate is in fluid communication with the seventh light of the first end sheet through the slots the first enlarged light of the central sheet, the third or alternatively the fourth light of the first end sheet is in fluid communication with the eighth light from the first end sheet through the slots of the a third enlarged light of the central plate, • the fifth and the seventh lights of the second end plate are in fluid communication through the slots of the fifth enlarged light of the central plate, • the sixth and eighth lights of the second end sheet is in fluid communication through the slots of the sixth enlarged light of the central sheet.
    According to this mode, at least one of the two interconnectors of the thermal regulation stages consists of the same device as the interconnectors of the electrochemical stages, but does not include the seventh and eighth lights of the second end plate.
    Advantageously, the two interconnectors of the same electrochemical stage are each constituted from three identical flat sheets but with the central plate of one of the interconnectors turned upside down with respect to the central plate of the other of the interconnectors.
    According to an advantageous variant, it is possible to provide a number of thermal regulation stages different from the number of electrochemical stages.
    It is also possible to provide a number of thermal regulation stages higher than the center of the stack than on the ends of the stack.
    According to an advantageous characteristic, no thermal regulation stage is visible from outside the stack.
    Thus, the invention essentially consists in creating a heat transfer gas circuit dedicated to the regulation / thermal management of the stack of an EHT reactor or of a SOFC fuel cell by removing certain cells from certain zones of the stacking to replace them with electrical contact elements that can pass the heat transfer gas.
    In other words, a new type of stack is created in an EHT reactor or an SOFC fuel cell in which most of the usual electrochemical stages dedicated to the (co) electrolysis of the water vapor are stored. or to the production of electricity by the battery, and they are added floors with thermal control function instead of electrochemical stages to regulate the thermal reactions in these areas.
    Compared to thermal regulation solutions according to the state of the art, the invention makes it possible not to have to make specific interconnectors with additions of tubes or with plate thicknesses or with cooling fins in contact with outside.
    In particular, in the advantageous embodiment of interconnectors with three laminated flat sheets and assembled together, it suffices: in the interconnectors dedicated to the electrochemical stages to turn up / down the central plate of an interconnector relative to that of an adjacent interconnector; in the interconnectors dedicated to the thermal regulation stages, to eliminate the supply and recovery lights either in draining gas or in oxidant. A stack is thus obtained at a lower cost, all the interconnectors of which are made with the same design of three flat sheets.
    Thus, it is possible to realize all the interconnectors, whether they are dedicated to electrochemical stages or those of thermal regulation, on the same production tool and with the same production lines. In other words, the thermal control stages according to the invention are made with the same manufacturing, assembly and assembly tool as in a stack that does not integrate these stages.
    Advantageously, the heat-transfer gas may be either the fuel, such as the water vapor in (co-) electrolysis operation mode, or the draining gas or the oxidant in the SOFC battery operating mode. For the two operating modes, SOFC or SOEC, it is planned to choose a porous material of the electrical contact that takes into account the oxidizing or reducing nature of the atmosphere of the heat transfer gas.
    It is then possible to supply / recover heat transfer gas both for a group of electrochemical stages and for a group of thermal regulation stages adjacent to the electrochemical stages, or in parallel while keeping the clarinets separated from one another. another, either in series by connecting them to one another on the outside of the stack. The invention does not alter the reversibility of a stack reactor which can be used both as an electrolysis or co-electrolysis reactor and as an SOFC cell with hydrogen or methane as fuel.
    In summary, the EHT reactors, SOFC fuel cells and their operating methods according to the invention have many features and advantages, among which we can mention: - regulation / management of the thermal of a stack since it can be targeted in the quasi-adiabatic reaction zones at the center of the stack, - series coupling of the heat-transfer gas with the H2 / H2O feed gas of the cells to preheat or cool the electrochemical stages, - design changes at the level of the thermal control stages at lower cost since these modifications consist of the replacement of solid oxide cells by electrical contact elements, such as metal grids, and with regard to the interconnectors dedicated solely to the non-drilling of feed lights and combustion gas recovery and therefore there are no constraints on the realization of interconnectors with thick plates, or with specific heat transfer tubes, - Achievements of the set of less expensive interconnectors compared to those of the solutions according to the state of the art, because the means of manufacture, the range of manufacture and are identical for all laminated and assembled flat sheet interconnectors. The subject of the invention is also a process for electrolysis at high temperature of the water vapor H2O, or for co-electrolysis of the water vapor H2O and carbon dioxide CO2, implemented in a reactor according to a previously described according to which: - from the interconnectors of the electrochemical stages, steam (EEb (l)) or a mixture of water vapor H2O and carbon dioxide CO2, are fed as fuel, and the (1c) distributes to the cathodes of the cells, then the hydrogen product Eb (SH2 (1)) or the synthesis gas (mixture of carbon monoxide CO and hydrogen Eb) is recovered at the outlet of the cathodes; from the interconnectors of the electrochemical stages, a draining gas such as air, (E (02)), and is distributed to the anodes of the cells, then the oxygen O 2 produced and, where appropriate, the draining gas are recovered ( S (02)) at the outlet of the anodes, - from the stage interconnectors s, a heat transfer gas (EH2 (2)) and distributes it to the electrical contact elements, then it is recovered at the output of the elements.
    According to an advantageous variant, the heat-transfer gas (EH2 (2)) is the fuel (water vapor H2O, or mixture of water vapor H2O and hydrogen H2, or mixture of water vapor H2O and of dioxide of water carbon CO2) or the draining gas, such as air, (E (02)). The subject of the invention is also a method for producing electricity at high temperature, implemented in a solid oxide fuel cell (SOFC) described above, according to which: - electrochemical stages are supplied from the interconnectors, the fuel (EH2 (1)), and it is distributed to the anodes of the cells, then the excess fuel and the produced water (SH2 (1)) are recovered at the outlet of the anodes, - the oxidant is supplied from the interconnectors of the electrochemical stages such as air, (E (02)), and is distributed to the cathodes of the cells, then the surplus of oxidant S (O 2) is recovered at the cathode output, - regulator stages are fed from the interconnectors. thermal, a heat transfer gas (EH2 (2)) and distributes it to the electrical contact elements, then it is recovered at the output of the elements.
    The fuel is preferably hydrogen or methane (CH4).
    Advantageously, the supply of the fuel gas is connected in series with that of the heat transfer gas.
    According to one variant, the supply of the fuel gas may be in parallel ("coflow" in English) with that of the heat-transfer gas.
    Alternatively, the supply of the fuel gas is counter-current ("counterflow" in English) of that of the heat transfer gas.
    Advantageously, it is possible to implement an exothermic or endothermic chemical reaction between the heat-transfer gas and the electrical contact elements.
    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 ", ie a cell in which the electrolyte and the oxygen electrode (anode) are arranged on the thicker hydrogen or carbon monoxide (cathode) electrode which therefore serves as a support .
    DETAILED DESCRIPTION Other advantages and characteristics of the invention will emerge more clearly on reading the detailed description of exemplary embodiments of the invention, given by way of non-limiting illustration with reference to the following figures among which: FIG. 1 is a schematic view showing the operating principle of a water electrolyser at high temperature; FIG. 2 is an exploded diagrammatic view of part of a high temperature steam electrolyser comprising interconnectors according to the state of the art; FIG. 3 is an exploded diagrammatic view of FIG. a portion of a high temperature SOFC fuel cell comprising interconnectors according to the state of the art; - Figure 4 in section of an electrolysis reactor implementing a high temperature electrolysis process according to a embodiment of the invention; FIG. 5 is an exploded view of a part of an electrolysis reactor according to the invention with an electrolysis stage adjacent to a thermal regulation stage, FIGS. 6A and 6B are exploded views of an interconnector of an electrolysis stage according to the invention which allows a supply / recovery of water vapor and hydrogen produced, and a supply / recovery of heat transfer gas the figures showing l feeding, distribution and recovery of water vapor and hydrogen produced in FIG. 6A and heat transfer gas in FIG. 6B, FIG. 6C is an exploded view of the interconnector according to FIGS. 6A and 6B, showing the supply, distribution and recovery of the draining gas and oxygen produced, - Figure 7A is a front view of an end plate of an interconnector according to Figure 6A, showing the supply, the distribution and recovery of water vapor and hydrogen produced; FIG. 7B is a front view of an end plate of an interconnector according to FIG. 6B, showing the supply, distribution and the recovery of the coolant gas according to the invention, - Figure 7C is a front view of an end plate of an interconnector according to Figure 6A or 6B, showing the supply, distribution and recovery of the draining gas and oxygen produced FIG. 7D is a perspective view of an interconnector according to FIG. 6A or 6B; FIG. 8 is an exploded view of an interconnector of a thermal regulation stage according to the invention, this FIG. absence of light for the supply, distribution and recovery of the draining gas and oxygen at the temperature control stage, - Figures 9A and 9B are detailed views of a portion of an interconnector according to the invention.
    It is specified here that in all of Figures 1 to 8, the symbols and the feed arrows on the one hand water vapor H2O, distribution and recovery of hydrogen H₂ and oxygen O₂ and the current are shown for the sake of clarity and precision, to illustrate the operation of a state of the art water vapor electrolysis reactor and a steam electrolysis reactor according to the present invention. invention.
    It is also specified that all the electrolysers described are of the solid oxide type (SOEC), operating at high temperature. Thus, all the constituents (anode / electrolyte / cathode) of an electrolysis cell are ceramics. The high operating temperature of an electrolyser (electrolysis reactor) is typically between 600 ° C and 950 ° 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 the table below.
    BOARD
    Figures 1 to 3 have already been described in detail in the preamble. They are not so below.
    By convention, and in order to facilitate the reading of the circulations of the gases in the different figures, the following symbols are used: - EH2 (1): designates the circulation through the stack of water vapor as "fuel" feeding the electrolysis cells C1, C2; - SH2 (1): designates the circulation through the stack of hydrogen produced by the electrolysis cells Cl, C2; - EH2 (2): designates the circulation through the stack of heat transfer gas supplying the thermal control stages; - SH2 (2): designates the circulation through the stack of heat transfer gas at the output of the thermal control stages; -E (02): denotes the circulation through the stack of the draining gas supplying the electrolysis cells Cl, C2; -S (02): denotes the circulation through the stack of oxygen produced at the electrolysis cells Cl, C2.
    In order to improve the management of the thermal operations of the electrolysis reactor of the electrochemical stages, more particularly those of the center of the stack which have no possible exchange with the external environment, the inventors have thought judiciously to integrate stages of thermal regulation within the stack by implementing planar plate interconnectors very little modified in their structure compared to those dedicated to the electrochemical stages and by arranging electrical contact elements allowing the gases to pass in place of the 'electrolysis.
    Thus, as illustrated in FIG. 4, the following steps are carried out simultaneously in the stack according to the invention: electrochemical stages are fed from the interconnectors 5.1, 5.2, the water vapor EH2 (1) as that fuel, and distributes it to the cathodes of the electrolysis cells C1, C2, then the hydrogen H2 product SH2 (1) is recovered at the output of the cathodes 2.1, 2.2, - is supplied from the interconnectors 5.1, 5.2 stages electrochemical, a draining gas such as air, E (02), and is distributed to the anodes 4.1, 4.2 of the cells, then recovering the O2 oxygen produced and optionally the draining gas S (02) output anodes, - it is fed, from the interconnectors 5.2, 5.3 stages of thermal regulation, a heat transfer gas EH2 (2) and is distributed to the electrical contact elements 14, and is recovered at the output of these elements 14 SH2 (2 ).
    Thus, according to the invention, most of the usual electrochemical stages of an EHT reactor stack, which are dedicated to the electrolysis of water vapor, are conserved and thermally controlled stages are added thereto in place and placing electrochemical stages in order to regulate the thermal reactions in these zones.
    According to the invention, provision is made for the circuit of the thermal regulation stages to be swept by a heat-reducing gas which is sufficiently reducing in order to prevent the oxidation of the contact elements. Thus, the coolant can advantageously be a mixture of water vapor and heat transfer. 'hydrogen. In this case, the hydrogen is present at least 10% to prevent oxidation of the contact elements 14, in particular in the form of a nickel grid.
    FIG. 5 schematically shows part of a high-temperature solid oxide electrolyser (SOEC) according to the invention.
    This electrolysis electrolysis reactor comprises an alternating stack of a SOEC type electrolysis cell (Cl) formed of a cathode 2.1, 2.2, an anode 4.1, 4.2 and an electrolyte 3.1, 3.2, inserted between the cathode and the anode, and a metal gate 14.
    This metal grid ensures electrical continuity in series through the thermal regulation stage. The electrochemical stage comprises two electrical and fluidic interconnectors 5.1, 5.2 arranged on either side of the elementary cell C1 with the cathode in electrical contact with the underside of the interconnector of the top 5.1 and the anode in electrical contact with the upper face of the interconnector below 5.2. The thermal control stage also comprises two electrical and fluidic interconnectors 5.2, 5.3, of which the above 5.2 is common with the electrochemical stage. The two interconnectors 5.2, 5.3 are arranged on either side of the metal gate 14.
    As shown in FIG. 5, isolation and sealing frames 9 are also provided to ensure electrical insulation between interconnectors 5.1 and 5.2 on the one hand and between interconnectors 5.2, 5.3 on the other hand. It should be noted that between the two interconnectors 5.2 and 5.3 the frame 9 is used above all to achieve sealing, the electrical insulation is not required on the floor dedicated to thermal management.
    Each frame 9 is pierced with lights 99 adapted to accommodate the fastening tie rods of the stack, as well as seals 10 provided for sealing around the supply ports for gases H2O, air and for recovering the gases produced H2. O2 with Air, as well as clarinets dedicated to heat transfer gas
    A contact layer 11, such as a nickel metal grid, makes it possible to ensure contact between the cathode of the cell C1 and the interconnector 5.1 from above.
    Another seal 12 is further provided at the periphery of the anode of the cell to seal the product oxygen. The assembly of the stack comprising the electrolysis cell Cl and the metal gate 11 for the heat transfer gas is traversed by the same electric current.
    In the reactor according to the invention, all the cathodic compartments 50 of the electrochemical stages in which the fed water vapor H2O circulates and the hydrogen produced H2 communicate with each other.
    Similarly, all thermal control stages in which the heat transfer gas circulates, communicate in them.
    According to the invention, an interconnector 5.3 dedicated to a thermal regulation stage is different from an interconnector 5.1 dedicated to an electrochemical stage in order to be able to perform only a supply of heat transfer gas, without introduction of oxidant, at a metal gate 14.
    FIGS. 6A to 6C each explode an interconnector 5.1 or 5.2 of an electrochemical stage according to the invention making it possible to ensure both: the supply of H2O water vapor as "fuel", the circulation water vapor and hydrogen produced in the cell C1, the recovery of the hydrogen produced, as well as the supply and recovery of oxygen O2 produced within the stack of a reactor d electrolysis, the supply of heat-transfer gas, the circulation of this heat-transfer gas at a metal gate 14 and its recovery having circulated on a metal gate 14 within the stack of an electrolysis reactor.
    Each interconnector 5.1, 5.2 dedicated to an electrochemical stage makes it possible to ensure a circulation of the gas (H2O / H2) to the cathodes of the cross-flow cells at 90 ° with the circulation of the recovered gas (02) and the draining gas at the anode cells. The interconnector 5.1 or 5.2 consists of three flat sheets 6, 7, 8 elongated along two axes of symmetry (X, Y) orthogonal to each other, the flat sheets being laminated and assembled together by welding. A central plate 7 is interposed between a first 6 and a second 8 end plates.
    The first end plate 6 is intended to come into mechanical contact with the plane of a cathode 2.1 of the elemental electrolysis cell C1 and the central plate 7 is intended to come into mechanical contact with the plane of an anode 4.1. an adjacent elementary electrolysis cell, each of the two adjacent elementary electrolysis cells (C1, C2) of SOEC type being formed of a cathode 2.1, 2.2, an anode 4.1, 4.2 and an electrolyte 3.1 , 3.2 interposed between the cathode and the anode.
    Each of the three flat sheets 6, 7, 8 comprises a central portion 60, 70, 80.
    The central portions 60, 70 of the central plate 7 and the first end plate 6 are non-pierced while that 80 of the second end plate 80 is pierced.
    Each sheet 6, 7, 8 is pierced, at the periphery of its central part, with six slots 61, 62, 63, 64, 65, 66; 71, 72, 73, 74, 75, 66; 81, 82, 83, 84, 85, 86.
    The first 61, 71, 81 to fourth 64, 74, 84 lights of each sheet are elongated over a length corresponding to a portion of the length of the central portion 60, 70, 80 along one of the X axes of the sheets and are distributed in pairs on either side of said X axis.
    The fifth 65, 75, 85 light is elongated over a length substantially corresponding to the length of the central portion 60, 70, 80 along the other of the Y axes.
    The sixth 66, 76, 86 light is elongated over a length substantially corresponding to the length of the central portion 60, 70, 80 along the other of the Y axes.
    The first end plate 6 further comprises a seventh 67 and eighth 68 lights arranged symmetrically on either side of the axis X, inside its first to fourth lights 61 to 64, and are elongated on a length corresponding substantially to the length of the central portion along the axis X.
    The second end plate 8 further comprises a seventh 87 light and eighth 88 light arranged symmetrically on either side of the Y axis, respectively inside its fifth 85 light and sixth light 86, and elongated over a length substantially corresponding to the length of the central portion along said axis Y.
    As can be seen in FIG. 6A, the first 71, third 73, fifth 75 and sixth 76 lumens of the central plate 7 are enlarged relative to the first 61, 81, third 63, 83, fifth 65, 85 and sixth 66, respectively. lights of each end plate 6, 8.
    The second 62, 72, 82 and fourth 64, 74, 84 lights of the three sheets are of substantially identical dimensions to each other.
    The laminating and the assembly of the three sheets 6, 7, 8 between them are performed such that: • each of the first to sixth 61 to 66 lumens of one of the three sheets is in fluid communication individually respectively with one of the first at sixth 71 to 76 and 81 to 86 corresponding lumens of the two other plates 7, 8. • the first lumen 61 of the first end plate 6 is in fluid communication with the seventh light 67 of the first end plate 6 by through the first lumen 71 of the central plate 7, • the third lumen 63 of the first end plate 6 is in fluid communication with the eighth lumen 68 of the first end plate 6 through the third light 73 of the central plate 7, • the fifth 85 and the seventh 87 lights of the second 8 end plate are in fluid communication through the fifth 75 light of the central plate 7, the sixth 86 and the eighth 88 lumens of the second end plate 8 are in fluid communication through the sixth light 76 of the central plate 7.
    FIGS. 9A and 9B show in detail the production of the comb formed by the sheet tongues 710 at the widened slot 71 of the central plate and its arrangement between the two end plates 6, 8 in order to allow the feeding of an electrolysis cell, here in H2O water vapor or a metal gate 14 at a temperature control stage as detailed below. Thus, the formed comb 710, 711 allows water vapor to pass from the supply clarinet 61, 71, 81 to the dispensing slot 67 by passing through the space between the two end plates 6, 8 The thickness of the central plate 7 at the level of this comb 710, 711 gives it a spacer function and thus guarantees the height of the passage for the water vapor in the space between the end plates 6, 8 Such a passage of the gases according to the invention from the inside of the interconnector 5.1 has the advantage of releasing a flat surface for producing the seals. In addition, thanks to these comb forms for the enlarged slots 71, 75, a homogeneous distribution of each gas (H 2 O, Air) is obtained on each electrolysis cell and on each metal grid of the thermal stage, and thanks to these comb forms for enlarged slits 73, 76 recovery of product gas (H2, O2) or heat transfer gas. These distributions or recoveries homogeneous or otherwise uniform in flow are shown in the various figures 6A to 8, in the form of small arrows spaced from each other.
    To realize the interconnector 5.2 shown in FIG. 6B, which makes it possible both to bring the draining gas at the level of the cell C1 and the heat-transfer gas at the level of the metal gate 14, the same three flat plates 6, 7, 8 are used as those used for the realization of Γinterconnecteur 5.1 but by proceeding only to a reversal of the central plate 7 up-down before lamination and assembly with the two end plates 6, 8.
    Thus, in the interconnector 5.2, the three plates 6, 7, 8 are laminated and assembled together such that: • each of the first to sixth 61 to 66 lumens of one of the three sheets is in fluid communication individually with the one of the first to sixth 71 to 76 and 81 to 86 corresponding lights of the other two sheets 7, 8, • the second light 62 of the first 6 end plate is in fluid communication with the seventh 67 light of the first 6 sheet metal at the end through the third 73 lumen of the central plate 7, the fourth lumen 64 of the first end plate 6 is in fluid communication with the eighth light 68 of the first end plate 6 through of the first light 71 of the central plate 7, the fifth 85 and the seventh 87 lights of the second end plate 8 are in fluid communication through the fifth 75 of the central plate 7, the sixth 86 and the eighth 88 lumens of the second end plate 8 are in fluid communication via the sixth 76 of the central plate 7.
    To produce the interconnector 5.3 shown in FIG. 8, which makes it possible not to bring draining gas or oxygen or to recover oxidizing gas at the level of the metal grid 14, the same three flat sheets 6, 7, 8 as used for the realization of interconnectors 5.1 and 5.2 retaining all the lights dedicated to the supply / recovery of gases except the lights 87, 88 which are deleted.
    In other words, an interconnector 5.3 is created dedicated to a thermal regulation stage starting exactly from the same plane plates 6, 7, 8 constituting the interconnectors 5.1, 5.2 dedicated to an electrochemical stage and removing only the lights 87, 88 or slots usually dedicated to the function of supplying draining gas and recovering O 2 oxygen produced.
    Thus, according to the invention, using an identical interconnector in its laminated and assembled flat sheet structure and in its thicknesses and shapes to those dedicated to the electrochemical stages, a stage is created dedicated to the thermal regulation.
    Thanks to the invention, an alternating stack of thermal regulation stages and electrochemical stages is thus obtained, the thermal regulation of which, in particular at the center of the stack, is very efficient and whose production cost is lower compared with the solutions. according to the state of the art since all interconnectors 5.1, 5.2, 5.3 are made with the same flat sheets 6, 7, 8 and therefore according to the same manufacturing lines and some electrolysis cells are replaced by metal grids which ensure electrical continuity through the stack.
    6A to 8, the method of operation of an electrolysis reactor according to the invention as just described is described with reference to FIGS.
    The first 61, 71, 81 water vapor lights EH2 (1) of the interconnects 5.1 to 5.3 and the second 62, 72, 82 lumens of the interconnector 5.1 to 5.3 are fed with EH2 heat transfer gas (2).
    The heat transfer gas EH2 (2) passes through the interconnector 5.1 without being distributed to the cathode 2.1 of the cell C1. It supplies the lights 62, 73, and 82 of the interconnector 5.2.
    Similarly, the water vapor EH2 (1) passes through the interconnector 5.2 without being distributed on the metal grid 14.
    The path within a 5.1 interconnector, the injected water vapor and the hydrogen produced is shown schematically in FIGS. 6A and 7A.
    The path within an interconnector 5.2 of the heat transfer gas within an interconnector 5.2 is shown schematically in FIGS. 6B and 7B.
    In addition, the fifth 65, 75, 85 light of the three plates 8 of each interconnector 5.1, 5.2, 5.3 is supplied with a draining gas E (02), such as air.
    The path of the air as the injected draining gas and the oxygen produced within a 5.1 or 5.2 interconnector is shown schematically in FIG. 6C.
    Due to the absence of the lights 87, 88 within the interconnector 5.3, the draining gas is not distributed / recovered on the metal gate 14.
    The hydrogen product SH2 (1) is thus recovered by the electrolysis of the water vapor at the level of the cell C1, in the third 63, 73, 83 lumens of the interconnector 5.1.
    The circulating heat transfer gas SH2 (2) is recovered separately for thermal management purposes at the level of the metal gate 14, in the fourth 64, 84 end plate lights and the first light 71 of the interconnector 5.2. .
    At the same time, the oxygen O 2 product S (O 2) is recovered in the sixth 66, 76, 86 lights of the three plates 8 of each interconnector 5.1, 5.2. The supply of water vapor and the recovery of hydrogen produced as well as the draining gas supply and the oxygen recovery product shown in FIGS. 6A to 6C constitute a co-current circulation of fuel / heat transfer gas. a C1 cell relative to the adjacent metal grid 14, and crossed current with the flow of gas draining / oxygen product common.
    With the two types of interconnectors 5.1, 5.2 it is also possible, as an alternative, to carry out a countercurrent flow of fuel / heat transfer gas of a cell C1 relative to the adjacent metal grid 14, and to cross current with the flow of draining gas / oxygen produced.
    The three flat sheets 6, 7, 8 constituting each interconnector 5.1, 5.2, 5.3 according to the invention are flat metal thin plates, drilled and assembled together by welding. Preferably, the thin sheets are sheets with a thickness of less than 3 mm, typically of the order of 0.2 mm. All welds between sheets produced during manufacture, apart from any operation of the electrolyser, can advantageously be carried out using a laser transparency technique, which is possible because of the small thickness of the thin sheets, typically of the order of 0. , 2 mm.
    Advantageously, all the sheets are made of ferritic steel with an order of 20% chromium, preferably made of CROFER® 22APU or FT18TNb, based on Inconel® 600 or Haynes® type nickel in thicknesses typically between 0.1 and 1 mm. . The assembly by lines of welds ls around the lights between flat sheets 6, 7, 8 ensures a good seal during the operation of the electrolyser between the water vapor EFb (1) fed to the interconnectors 5.1 as "fuel" , the heat transfer gas EFb (2) fed to the interconnectors 5.2, 5.3 as thermal management, the hydrogen SFb (1) recovered at the interconnectors 5.1, the heat transfer gas SFb (2)
    recovered at the interconnectors 5.2, the draining gas supplied E (02) and oxygen S (O2) recovered. The weld lines are illustrated in FIGS. 10A to 10C
    As illustrated in all of Figures 5 to 8, the three sheets 6, 7, 8 are pierced at their periphery with additional lights 69, 79, 89 adapted to accommodate tie rods. These tie rods make it possible to apply a holding force to the stacking of the various components of both the electrochemical stages and the thermal control stages of the electrolysis reactor. Other variants and improvements may be envisaged within the scope of the invention.
    Thus, if in the illustrated embodiment, the heat transfer gas is of the water vapor type with hydrogen, it can equally well be envisaged that the draining gas is also the heat transfer gas. More generally, the heat-transfer gas may be any gas, provided that it is adapted to the material (s) of the contact elements 14, that is to say that it does not oxidize these latter.
    It could also be used to make a dedicated interconnector, to laminate and assemble three flat sheets such as those 6, 7, 8 illustrated but provided to remove the lights 67, 68 of T interconnector 5.2 dedicated to the supply of the steam / hydrogen and the recovery of hydrogen produced and maintain 87 and 88 on the interconnector 5.3 at a temperature control stage. According to this variant, the thermal regulation would be done by the draining gas (or oxidizing gas in SOFC stack). In this case, the metal gate 14 is either a grid resistant to oxidation, or an electrical contact provided directly by welding to one another two successive interconnectors 5.2, 5.3. The welds between these two interconnectors 5.2, 5.3 must then ensure the sealing and the passage of the current.
    The electrochemical stages and the thermal control stages can be in parallel if the gas supply / recovery clarinets remain independent or in series if they are connected to each other outside the stack.
    The series connection between electrochemical stages and thermal control stages effectively preheats water vapor dedicated to the electrolysis of water before entering the cathodes of the electrolysis cells.
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    1. High temperature electrolysis reactor (EHT) comprising an alternating stack of two distinct groups of stages including: - a group of a plurality of stages, called electrochemical stages, each consisting of an elementary electrolysis cell (Cl, C2, C3) SOEC solid oxide type formed of a cathode (2.1, 2.2, ...), an anode (4.1, 4.2, ...) and an electrolyte (3.1, 3.2 ...) interposed between the cathode and the anode, and two interconnectors (5.1, 5.2), each adapted for the electrical and fluidic interconnection, arranged on either side of the elementary cell (C1, C2), a group of at least one stage, called a thermal regulation stage (s) constituted by at least one electrical contact element (14) allowing the gases to pass and two interconnectors (5.2, 5.3) each adapted to the electrical and fluidic interconnection, arranged on either side of the contact element, the interconnectors of the electrochemical stages and the thermal stage (s) being adapted for both: • circulating water vapor (EH2 (1)) or a mixture of water vapor H2O and carbon dioxide CO2, a draining gas, such as air, (E (02)), and a heat-transfer gas (EH2 (2)), • recover H2 hydrogen produced (SH2 (1)) or the synthesis gas (mixture of carbon monoxide CO and hydrogen H 2) produced at the cathodes of the cells, the oxygen O 2 produced (S (O 2)) at the anodes of the cells and, if appropriate, the draining gas , and the heat-transfer gas (SH2 (2)) at the outlet of the elements (14), the interconnectors of the electrochemical stages being further adapted to dispense both the water vapor (EH2 (1)) or the steam mixture. water H2O and carbon dioxide CO2, to the cathodes of the cells, and the draining gas (E (02)) to the anodes of the cells, while the interconnectors of (the) stage (s) of thermal regulation are adapted to distribute only the heat transfer gas to 1 '(the) element (s) of electrical contact (14) passing through the gases.
    [2" id="c-fr-0002]
    2. High temperature fuel cell (SOFC) comprising an alternating stack of two distinct groups of stages including: a group of a plurality of stages, called electrochemical stages, each consisting of an elementary electrochemical cell (Cl, C2, C3) SOFC solid oxide type formed of a cathode (2.1, 2.2, ...), an anode (4.1, 4.2, ...) and an electrolyte (3.1, 3.2 ... ) interposed between the cathode and the anode, and two interconnectors (5.1, 5.2) each adapted for the electrical and fluidic interconnection and arranged on either side of the elementary cell (C1, C2), - a group of at least one stage, said stage (s) of thermal regulation constituted (s) of at least one electrical contact element (14) allowing the passage of gases and two interconnectors (5.2, 5.3) each adapted for the electrical interconnection and fluidic, arranged on both sides of the contact element, the interconnectors of the electrochemical stages and of (s) the thermal stage (s) being adapted for both: • circulating through the stack, a fuel (EH2 (1)), an oxidizer, such as air, (E (02)), and a heat transfer gas (EEh (2)), • recover the surplus fuel and produced water (SEh (l)) at the anodes of the cells, the surplus of oxidant (S (02)) )) to the cathodes of the cells and, and the heat-transfer gas (SEh (2)) at the outlet of the elements (14), the interconnectors of the electrochemical stages being further adapted to distribute both the fuel (EEh (l)) to the anodes cells, and the oxidant, (E (02)) to the anodes of the cells, while the interconnectors of (the) temperature control stage (s) are adapted to distribute only the heat transfer gas to 1 '(the) element (s) electrical contact (14) allowing the gas to pass.
    [3" id="c-fr-0003]
    3. High temperature electrolysis reactor (EHT) or high temperature fuel cell (SOFC) according to claim 1 or 2, the gas-permeable electrical contact element being a metal gate.
    [4" id="c-fr-0004]
    4. High temperature electrolysis reactor (EHT) or high temperature fuel cell (SOFC) according to one of claims 1 to 3, the interconnectors of the electrochemical stages each consisting of a device consisting of three flat plates (6, 7, 8), elongated along two axes of symmetry (X, Y) orthogonal to one another, one of the end plates being intended to come into mechanical contact with the plane of a cathode (2) of a cell ( C2) and the other of the end plates being intended to come into mechanical contact with the plane of an anode (4) of an adjacent elementary cell (C1), in which: - the central parts (60, 70) of the central plate (7) and one of the end plates, said first end plate, (6) are not drilled while the central portion (8) of the other end plate, called second end plate (8) is pierced (80), - each of the three planar holes (6, 7, 8) is pierced at the periphery of its central part with six slots (61, 62, 63, 64, 65, 66; 71, 72, 73, 74, 75, 76; 81, 82, 83, 84, 85, 86), the first to fourth lumens (61 to 64; 71 to 74; 81 to 84) of each sheet being elongated along a length corresponding to a portion of the length of the central portion. along one of the X axes of the sheets and being distributed in pairs on either side of said X axis, while the fifth and sixth (65, 75, 85; 66.76, 86) lights are elongated along a length substantially corresponding to the length of the central portion along the other of the Y axes, - the first end plate (6), further comprises a seventh (67) and an eighth (68) lights arranged symmetrically on both sides. other of the axis X, inside its first to fourth lumens (61, 62, 63, 64), and elongated along a length substantially corresponding to the length of the central portion along the axis X, - the second (8) end plates, further comprises a seventh (87) and an eighth (88) lights arrangement are symmetrically on either side of the Y axis within respectively its fifth (85) and sixth (86) lumens, and elongated along a length substantially corresponding to the length of the central portion along said Y axis , and, - the first (71), third (73), fifth (75) and sixth lights of the central plate (7) are widened relative to the first (61, 81), third (63, 83), fifth (65, 85) and sixth (66, 86) lights of each end plate, while the second (62, 72, 82) and fourth (64, 74, 84) light of the three sheets are of substantially identical dimensions between they, - all the enlarged lights (71, 73, 75, 76) of the central plate (7) comprise in their enlarged part, tabs of metal sheets spaced from each other forming a comb, each of the slots defined between the edge an enlarged slot (71, 73, 75, 76) and a tongue or between two tongues consecutive iives opening on one of the inner lights of the first (6) or second (8) end sheet, - the three sheets (6, 7, 8) are laminated and assembled together such that: • the sheet metal tabs form spacers spacing between first (6) and second (8) end plates respectively between the first (61) and seventh (67) lumens of the first end sheet (6), between the third (63) and eighth (68) lights of the first end plate (6), between the fifth (85) and seventh (87) lumens of the second end plate (8), and between the sixth (86) and eighth (88) lights of the second end plate (8), • each of the first to sixth lumens (61 to 66) of one of the three sheets is in fluid communication individually with one of the first to sixth lumens respectively (71 to 76 ; 81 to 86) of the two other sheets, • the first (61) or alternatively the second (62) light of the first (6) end plate is in fluid communication with the seventh (66) light of the first (6) ) end plate through the slots the first (71) enlarged light of the central plate (7), • the third (63) or alternatively the fourth (64) light of the first (6) end plate is in fluid communication with the eighth (68) lumen of the first (6) end plate through the slots of the third (73) enlarged light of the central plate (7), • the fifth (85) and the seventh (87) lights of the second (8) end plate are in fluid communication through the slots of the fifth (75) enlarged light of the central plate (7), • the sixth (86) and the eighth (88) ) lights of the second (8) end plate are in fluid communication e through the slots of the sixth (76) enlarged light of the central plate (7).
    [5" id="c-fr-0005]
    5. High temperature electrolysis reactor (EHT) or high temperature fuel cell (SOFC) according to claim 4, at least one of the two interconnectors of the thermal control stages being formed from the three plates that the interconnectors stages electrochemical, but do not include the seventh (87) and eighth (88) lights of the second end sheet (8).
    [6" id="c-fr-0006]
    6. High temperature electrolysis reactor (EHT) or high temperature fuel cell (SOFC) according to claim 4 or 5, the two interconnectors of the same electrochemical stage (5.1, 5.2) are each constituted from three identical flat sheets (6, 7, 8), but with the central plate of one of the interconnectors turned upside down with respect to the central plate of the other of the interconnectors.
    [7" id="c-fr-0007]
    7. High temperature electrolysis reactor (EHT) or high temperature fuel cell (SOFC) according to one of the preceding claims, comprising a number of thermal control stages different from the number of electrochemical stages.
    [8" id="c-fr-0008]
    8. High temperature electrolysis reactor (EHT) or high temperature fuel cell (SOFC) according to one of the preceding claims, comprising a number of thermal regulation stages greater than the center of the stack that on the ends of the stacking.
    [9" id="c-fr-0009]
    9. High temperature electrolysis reactor (EHT) or high temperature fuel cell (SOFC) according to one of the preceding claims, wherein (which) no thermal regulation stage is visible from outside the stack .
    [10" id="c-fr-0010]
    10. A method of high temperature electrolysis of water vapor H2O, or co-electrolysis of water vapor H2O and carbon dioxide CO2, implemented in a reactor according to one of claims 1 or 3 to 9, according to which: - electrochemical stages, water vapor (EH2 (1)) or a mixture of water vapor H2O and carbon dioxide CO2 are supplied from the interconnectors (5.1, 5.2), as fuel, and it is (the) distributed to the cathodes of the cells, then the hydrogen H2 produced (SH2 (1)) or the synthesis gas (mixture of carbon monoxide CO and hydrogen H2) are recovered as output cathodes, - is fed from the interconnectors (5.1, 5.2) electrochemical stages, a draining gas, such as air, (E (02)), and distributed to the anodes of the cells, then recovering the oxygen O2 produced and optionally the draining gas (S (02)) at the outlet of the anodes, - is fed, from the interconnectors (5.2, 5.3) of the thermal regulation stages, a heat transfer gas (EH2 (2)) and distributes it to the electrical contact elements (14), and then retrieves the output of the elements (14).
    [11" id="c-fr-0011]
    11. A method of electrolysis at high temperature of water vapor H2O, or co-electrolysis of water vapor H2O and carbon dioxide CO2 according to claim 10, wherein the heat-transfer gas (EH2 (2) ) is the fuel (water vapor H2O, or mixture of water vapor H2O and hydrogen H2, or mixture of water vapor H2O and carbon dioxide CO2) or the draining gas, such as air, (E (02)).
    [12" id="c-fr-0012]
    12. A method for producing high temperature electricity, implemented in a solid oxide fuel cell (SOFC) according to one of claims 3 to 9, wherein: - is supplied from the interconnectors (5.1, 5.2) electrochemical stages, the fuel (EH2 (1)), and it is distributed to the anodes of the cells, then the excess fuel and the produced water (SH2 (1)) are recovered at the outlet of the anodes, interconnectors (5.1, 5.2) of the electrochemical stages the oxidant such as air, (E (02)), and distributes it to the cathodes of the cells, then the surplus of oxidant S (O 2) is recovered at the output of the cathodes - From the interconnectors (5.2, 5.3) are supplied thermal regulation stages, a heat transfer gas (EEh (2)) and distributed to the electrical contact elements (14), and then recovered at the output of the elements (14). ).
    [13" id="c-fr-0013]
    13. A method of producing high temperature electricity according to claim 12, the fuel being hydrogen or methane (CH4).
    [14" id="c-fr-0014]
    14. Process for the high temperature electrolysis of water vapor H2O, or co-electrolysis of water vapor H2O and carbon dioxide CO2, according to one of claims 10 or 11, and production process. high-temperature electricity according to one of claims 13 or 12, wherein the supply of the fuel gas is connected in series with that of the heat-transfer gas.
    [15" id="c-fr-0015]
    15. A method of electrolysis at high temperature of water vapor H2O, or co-electrolysis of water vapor H2O and carbon dioxide CO2, according to one of claims 10, 11, or 14, and high temperature electricity production method according to one of claims 12, 13 or 14, wherein the supply of the fuel gas is in parallel with that of the heat transfer gas.
    [16" id="c-fr-0016]
    16. A method for the high temperature electrolysis of water vapor H20, or co-electrolysis of water vapor H20 and carbon dioxide CO2, according to one of claims 10, 11 or 14, and the method high-temperature electricity production system according to one of claims 12, 13 or 14, wherein the supply of the fuel gas is counter-current to that of the heat-transfer gas.
    [17" id="c-fr-0017]
    17. A method of electrolysis at high temperature of the water vapor H20, or of the co-electrolysis of the water vapor H20 and the carbon dioxide CO2, according to one of claims 10, 11 or 14 to 16, and method for producing high temperature electricity according to one of claims 12, 13 or 14 to 16, according to which an exothermic or endothermic chemical reaction is carried out between the heat-transfer gas and the electrical contact elements (14).
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    同族专利:
    公开号 | 公开日
    JP6620236B2|2019-12-11|
    JP2018528329A|2018-09-27|
    FR3038916B1|2017-07-28|
    US20180202055A1|2018-07-19|
    CA2992130C|2020-11-24|
    US10597788B2|2020-03-24|
    DK3322839T3|2021-07-26|
    EP3322839B1|2021-04-28|
    CA2992130A1|2017-01-19|
    EP3322839A1|2018-05-23|
    WO2017009238A1|2017-01-19|
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    法律状态:
    2016-07-29| PLFP| Fee payment|Year of fee payment: 2 |
    2017-01-20| PLSC| Publication of the preliminary search report|Effective date: 20170120 |
    2017-06-30| PLFP| Fee payment|Year of fee payment: 3 |
    2018-07-27| PLFP| Fee payment|Year of fee payment: 4 |
    2019-07-31| PLFP| Fee payment|Year of fee payment: 5 |
    2020-07-31| PLFP| Fee payment|Year of fee payment: 6 |
    2021-07-29| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1556727A|FR3038916B1|2015-07-16|2015-07-16|METHODS OFELECTROLYSIS OF WATEROR PRODUCTION OF HIGH TEMPERATURE ELECTRICITY WITH INTEGRATED EXCHANGERS AS REACTOR STACKOR FUEL CELL)|FR1556727A| FR3038916B1|2015-07-16|2015-07-16|METHODS OFELECTROLYSIS OF WATEROR PRODUCTION OF HIGH TEMPERATURE ELECTRICITY WITH INTEGRATED EXCHANGERS AS REACTOR STACKOR FUEL CELL)|
    JP2018521695A| JP6620236B2|2015-07-16|2016-07-08|Method forelectrolysisor power generation of water at high temperatures using exchangers integrated as reactor stackor fuel cellstages|
    DK16736471.0T| DK3322839T3|2015-07-16|2016-07-08|PROCEDURE FORELECTROLYSIS OF WATER OR FOR THE PRODUCTION OF ELECTRICITY AT HIGH TEMPERATURE WITH INTEGRATED EXCHANGERS AS STEPS TO A STACK REACTORS OR A FUEL CELL|
    EP16736471.0A| EP3322839B1|2015-07-16|2016-07-08|Methods for electrolysis of water or for producing electricity at a high temperature with exchangers incorporated as stages of a reactor stack or a fuel cell|
    PCT/EP2016/066304| WO2017009238A1|2015-07-16|2016-07-08|Methods for electrolysis of wateror for producing electricity at a high temperature with exchangers incorporated as stages of a reactor stackor a fuel cell |
    CA2992130A| CA2992130C|2015-07-16|2016-07-08|Methods for electrolysis of wateror for producing electricity at a high temperature with exchangers incorporated as stages of a reactor stackor a fuel cell |
    US15/744,144| US10597788B2|2015-07-16|2016-07-08|Methods for electrolysis of wateror for producing electricity at a high temperature with exchangers incorporated as stages of a reactor stackor a fuel cell |
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