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    • 专利摘要:
    The main object of the invention is an assembly (80) comprising a SOEC / SOFC solid oxide stack (20) and a clamping system (60) of the stack (20). This assembly (80) further comprises an overheating system (40) of the inlet gases of the stack (20) comprising: a heating plate (61) integrated in the thickness of at least one of the clamping plates upper (45) and lower (46) clamping system (60); an upper or lower terminal plate for overheating the gases (65, 43, 66, 44), comprising a circulation circuit for the gases to be heated; and an inlet duct (62) for the gases to be heated.
    公开号:FR3073093A1
    申请号:FR1760114
    申请日:2017-10-26
    公开日:2019-05-03
    发明作者:Michel Planque；Charlotte Bernard；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:

    ASSEMBLY OF A SOEC / SOFC-TYPE SOLID OXIDE STACK AND A TIGHTENING SYSTEM WITH INTEGRATED GAS OVERHEATING SYSTEM
    DESCRIPTION
    TECHNICAL AREA
    The present invention relates to the general field of electrolysis of water at high temperature (EHT), in particular the electrolysis of water vapor at high temperature (EVHT), respectively designated by the English designations “High Temperature Electrolysis ”(HTE) and“ High Temperature Steam Electrolysis ”(HTSE), for the electrolysis of carbon dioxide (CO 2 ), or even the co-electrolysis of high temperature water (EHT) with carbon dioxide carbon (CO 2 ).
    More specifically, the invention relates to the field of high temperature solid oxide electrolysers, usually designated by the acronym SOEC (for "Solid Oxide Electrolyzer Cell" in English).
    It also relates to the field of high-temperature solid oxide fuel cells, usually designated by the acronym SOFC (for “Solid Oxide Fuel Cells”).
    Thus, more generally, the invention relates to the field of solid oxide stacks of the SOEC / SOFC type operating at high temperature.
    More specifically, the invention relates to an assembly comprising a solid oxide stack of SOEC / SOFC type and a system for clamping the stack with an integrated system for overheating the gases at the inlet of the stack, as well as a method for manufacture of such a gas overheating system.
    PRIOR STATE OF THE ART
    As part of a high temperature solid oxide electrolyser of the SOEC type, this involves transforming, by means of an electric current, within the same electrochemical device, the water vapor (H 2 O ) into dihydrogen (H 2 ) and dioxygen (O 2 ), and / or to convert carbon dioxide (CO 2 ) into carbon monoxide (CO) and dioxygen (O 2 ). In the context of a high-temperature solid oxide fuel cell of the SOFC type, the operation is reversed to produce an electric current and heat by being supplied with dihydrogen (H 2 ) and dioxygen (O 2 ), typically in air and natural gas, namely by methane (CH 4 ). For the sake of simplicity, the following description favors the operation of a high temperature solid oxide electrolyser of the SOEC type carrying out the electrolysis of water. However, this operation is applicable to the electrolysis of carbon dioxide (CO 2 ), or even the co-electrolysis of water at high temperature (EHT) with carbon dioxide (CO 2 ). In addition, this operation can be transposed to the case of a high-temperature solid oxide fuel cell of the SOFC type.
    To carry out the electrolysis of water, it is advantageous to carry it out at high temperature, typically between 600 and 1000 ° C., because it is more advantageous to electrolyze water vapor than liquid water. and because part of the energy necessary for the reaction can be provided by heat, which is cheaper than electricity.
    To carry out the electrolysis of water at high temperature (EHT), a high temperature solid oxide electrolyser of the SOEC type consists of a stack of elementary patterns each comprising a solid oxide electrolysis cell, or also an electrochemical cell, consisting of three anode / electrolyte / cathode layers superposed one on the other, and interconnection plates made of metal alloys, also called bipolar plates or interconnectors. Each electrochemical cell is enclosed between two interconnection plates. A high temperature solid oxide electrolyser of the SOEC type is then an alternating stack of electrochemical cells and interconnectors. A high temperature solid oxide fuel cell of the SOFC type consists of the same type of stack of elementary patterns. Since this high temperature technology is reversible, the same stack can operate in electrolysis mode and produce hydrogen and oxygen from water and electricity, or in fuel cell mode and produce electricity at from hydrogen and oxygen.
    Each electrochemical cell corresponds to an electrolyte / electrode assembly, which is typically a multilayer ceramic assembly, the electrolyte of which is formed by a central ion-conducting layer, this layer being solid, dense and tight, and sandwiched between the two porous layers. forming the electrodes. It should be noted that additional layers may exist, but which only serve to improve one or more of the layers already described.
    The interconnection devices, electrical and fluidic, are electronic conductors which ensure, from an electrical point of view, the connection of each electrochemical cell of elementary pattern in the stack of elementary patterns, guaranteeing the electrical contact between a face and the cathode of one cell and between the other face and the anode of the next cell, and from a fluid point of view, thus combining the production of each of the cells. The interconnectors thus ensure the functions of supply and collection of electric current and delimit gas circulation compartments, for distribution and / or collection.
    More specifically, the main function of the interconnectors is to ensure the passage of electric current but also the circulation of gases in the vicinity of each cell (namely: injected water vapor, hydrogen and oxygen extracted for EHT electrolysis; air and fuel (hydrogen injected and water extracted for a SOFC cell), and to separate the anode and cathode compartments of two adjacent cells, which are the gas circulation compartments on the side of the anodes and cathodes of the cells respectively.
    In particular, for a SOEC type high temperature solid oxide electrolyser, the cathode compartment comprises water vapor and hydrogen, product of the electrochemical reaction, while the anode compartment comprises a draining gas, if present, and oxygen, another product of the electrochemical reaction. For a high temperature solid oxide fuel cell of the SOFC type, the anode compartment comprises the fuel, while the cathode compartment comprises the oxidizer.
    To carry out the electrolysis of high temperature water vapor (EHT), water vapor (H 2 O) is injected into the cathode compartment. Under the effect of the electric current applied to the cell, the dissociation of water molecules in the form of vapor is carried out at the interface between the hydrogen electrode (cathode) and the electrolyte: this dissociation produces dihydrogen gas ( H 2 ) and oxygen ions (O 2 ). Dihydrogen (H2) is collected and evacuated at the outlet of the hydrogen compartment. Oxygen ions (O 2 ) migrate through the electrolyte and recombine into dioxygen (O2) at the interface between the electrolyte and the oxygen electrode (anode). A draining gas, such as air, can circulate at the level of the anode and thus collect the oxygen generated in gaseous form at the anode.
    To ensure the operation of a solid oxide fuel cell (SOFC), air (oxygen) is injected into the cathode compartment of the cell and hydrogen is injected into the anode compartment. The oxygen in the air will dissociate into O 2 ions. These ions will migrate in the electrolyte from the cathode to the anode to oxidize the hydrogen and form water with simultaneous production of electricity. In SOFC cells, as in SOEC electrolysis, water vapor is found in the dihydrogen compartment (H 2 ). Only the polarity is reversed.
    By way of illustration, FIG. 1 represents a schematic view showing the operating principle of a high temperature solid oxide electrolyser of the SOEC type. The function of such an electrolyser is to transform water vapor into hydrogen and oxygen according to the following electrochemical reaction:
    H 2 O-> 2 H 2 + O 2 .
    This reaction is carried out electrochemically in the cells of the electrolyser. As shown diagrammatically in FIG. 1, each elementary electrolysis cell 1 is formed by a cathode 2 and an anode 4, placed on either side of a solid electrolyte 3. The two electrodes (cathode and anode) 2 and 4 are electronic and / or ionic conductors, made of porous material, and the electrolyte 3 is gas tight, electronic insulator and ionic conductor. The electrolyte 3 can in particular be an anionic conductor, more precisely an anionic conductor of O 2 ions and the electrolyser is then called anionic electrolyser, as opposed to proton electrolytes (H + ).
    The electrochemical reactions take place at the interface between each of the electronic conductors and the ionic conductor.
    At cathode 2, the half-reaction is as follows:
    H 2 O + 4 e 2 H 2 + 2 O 2 .
    At anode 4, the half-reaction is as follows:
    O 2 O 2 + 4th.
    The electrolyte 3, inserted between the two electrodes 2 and 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 entering the cathode can be accompanied by hydrogen H 2 and the hydrogen produced and recovered at the outlet can be accompanied by water vapor. Likewise, as illustrated in dotted 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 playing the role of thermal regulator.
    An elementary electrolyser, or electrolysis reactor, consists of an elementary cell as described above, with a cathode 2, an electrolyte 3, and an anode 4, and two interconnectors which provide the electrical distribution functions, hydraulic and thermal.
    To increase the flow rates of hydrogen and oxygen produced, it is known to stack several elementary electrolysis cells on top of each other by separating them by interconnectors. The assembly is positioned between two end interconnection plates which support the electrical supplies and gas supplies of the electrolyser (electrolysis reactor).
    A high temperature solid oxide electrolyser of the SOEC type thus comprises at least one, generally a plurality of electrolysis cells stacked on top of each other, each elementary cell being formed of an electrolyte, a cathode and a anode, the electrolyte being interposed between the anode and the cathode.
    As indicated above, the fluidic and electrical interconnection devices which are in electrical contact with one or more electrodes generally provide the functions of supplying and collecting electrical current and delimit one or more compartments for the circulation of gases.
    Thus, the so-called cathode compartment has the function of distributing electric current and water vapor as well as recovering the hydrogen at the cathode in contact.
    The 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 patterns of a high temperature solid oxide electrolyser of the SOEC type according to the prior art. This electrolyser comprises a plurality of elementary electrolysis cells Cl, C2, of solid oxide type (SOEC), stacked alternately with interconnectors 5. Each cell Cl, C2 consists of a cathode 2.1, 2.2 and an anode (only the anode
    4.2 of cell C2 is shown), between which an electrolyte is placed (only electrolyte 3.2 of cell C2 is shown).
    The interconnector 5 is a metal alloy component which ensures the separation between the cathode 50 and anode 51 compartments, defined by the volumes comprised 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 takes place in the cathode compartment 50. The collection of the hydrogen produced and of the residual water vapor at the cathode 2.1, 2.2 is carried out in the cathode compartment 50 downstream of cell C1, C2 after dissociation of the water vapor by the latter. The oxygen produced at the anode 4.2 is collected in the anode compartment 51 downstream of the cell C1, C2 after dissociation of the water vapor by the latter. The interconnector 5 ensures the passage of 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.
    The operating conditions of a high temperature solid oxide chlorinator (SOEC) being very close to those of a solid oxide fuel cell (SOFC), the same technological constraints are found.
    Thus, the proper functioning of such solid oxide stacks of the SOEC / SOFC type operating at high temperature mainly requires satisfying the points set out below.
    First of all, it is necessary to have electrical insulation between two successive interconnectors on pain of short-circuiting the electrochemical cell, but also a good electrical contact and a sufficient contact surface between a cell and an interconnector. The lowest possible ohmic resistance is sought between cells and interconnectors.
    Furthermore, it is necessary to have a seal between the anode and cathode compartments on pain of having a recombination of the gases produced resulting in a reduction in yield and above all the appearance of hot spots damaging the stack.
    Finally, it is essential to have a good distribution of gases both at the inlet and at the recovery of the products under penalty of loss of yield, inhomogeneity of pressure and temperature within the various elementary patterns, or even prohibitive degradations of the electrochemical cells.
    The incoming and outgoing gases in a high temperature electrolysis (SOEC) or fuel cell (SOFC) stack operating at high temperature can be managed by means of suitable devices of an oven such as that illustrated with reference to the figure 3.
    The oven 10 thus comprises cold parts PF and hot parts PC, the latter comprising the oven bottom 11, a looped tube 12 for managing the gas inlets and outlets and the stack 20, also called “stack”, d '' high temperature electrolysis (SOEC) or fuel cell (SOFC).
    Conventionally, there are two main techniques for overheating the inlet gases in a high temperature electrolysis (SOEC) or fuel cell (SOFC) stack.
    First of all, as shown diagrammatically by the looped tube 12 in FIG. 3, it is possible to use lengths of tube wound in line with the heating resistors of an oven 10 in the hot part PC. The gases will have been previously brought to a temperature of approximately 500 ° C. at the outlet of the exchangers if this is provided for by the system. Then, this or these overheating tubes 12 of the gases make it possible to gain approximately 300 ° C. more by using the thermal radiation of the resistances of the oven 10 and of the stack 20, before being introduced into the stack 20.
    Furthermore, it is also known to pass the gases through electric heaters 30 such as that shown in FIG. 4. Such an electric heater 30 is similar to a solid assembly comprising an inertial mass 31 of steel, a heating resistor 32 and a gas pipe 33 wound on the inertial mass 31. In FIG. 4 are also shown the incoming gases GE and the outgoing gases GS. These electric drivers 30 are responsible for bringing the incoming gases GE from 20 ° C. to a temperature of around 800 ° C. before the introduction of the outgoing gases GS into the stack 20.
    The proper functioning of these two main techniques set out above requires a very precise temperature at the input of the stack or stack 20 in order to guarantee the proper functioning of the assembly.
    The first technique which, after passing the gases through the exchangers, recovers the radiation from the furnace resistances to raise the gases to the right temperature at the inlet of the stack therefore requires windings with a length of approximately 3 m, which leads to the disadvantage of adding complexity to the bends to ensure that the tubes arrive in the right places in a confined space, and this significantly increases the size of the furnace. The implementation is therefore complicated because it is necessary to be precise and because the tubes, typically of diameter 10/12 in 316L stainless steel or Inconel 600, are very rigid. Furthermore, the fact of making gas overheating loops takes up a lot of space, and inevitably interferes with the current leads, the thermocouple passages, and the electrolyser outlet tubes, which often leads to shortening these lines. due to lack of space in the oven. In addition, the same bending job must be repeated with each new stack, because the dismantling of the connection of these loops is destructive.
    As a general rule, to obtain the correct temperature at the inlet to stack 20, and for an internal diameter of tube 12 of approximately 10 mm, a developed length of approximately 3 m is required per gas line at the inlet, typically H 2 O and N 2 O 2 , with a flow rate between 5 and 15 Nm 3 / s. This length of approximately 3 m, which saves approximately 300 ° C, works equally well in high temperature electrolysis stacking (SOEC) or fuel cell (SOFC) mode, and guarantees the correct input temperature of stack.
    In addition, it is necessary to carry out an expensive and lengthy treatment of these gas lines by deposition of alumina in order to avoid pollution due to oxidation when 316L stainless steel is used. These particles (chromium, vanadium, ...) can be fixed on this cell, and thus reduce the performance of the stack of solid oxides of the SOEC / SOFC type.
    Furthermore, the second technique requires a superheater 30 by gas inlets. However, these are massive assemblies which take up a lot of space while there is an increasing tendency to go towards compact systems. There are therefore as many electric superheaters as there are gas inlets, which, within the framework of the integration of the peripheral elements in an oven, poses serious problems. There is therefore a need to place the gas outlet of this electric heater 30 as close as possible to the entrances to the stack in order to avoid tracing of the line by heating arm.
    STATEMENT OF THE INVENTION
    The object of the invention is to at least partially remedy the needs mentioned above and the drawbacks relating to the embodiments of the prior art.
    It aims in particular to achieve a design of an integrated stack (or stack) / gas overheating system for a high temperature electrolysis (SOEC) or fuel cell (SOFC) stack, and more specifically to realize, at the very heart of the stack, partly hot, a compact system for overheating the inlet gases of the stack, without adding any thickness. This system must therefore be able to be integrated into the stack having a “Plug & Play” (PnP) type character, or of the “branch and use” type, as described in French patent application FR 3 045 215 A1.
    According to one of its aspects, the subject of the invention is therefore an assembly comprising:
    - a solid oxide stack of SOEC / SOFC type operating at high temperature, comprising:
    a plurality of electrochemical cells each formed by a cathode, an anode and an electrolyte interposed between the cathode and the anode, and a plurality of intermediate interconnectors each arranged between two adjacent electrochemical cells,
    - an upper end plate and a lower end plate, between which the plurality of electrochemical cells and the plurality of intermediate interconnectors are enclosed,
    - a clamping system for the SOEC / SOFC type solid oxide stack, comprising an upper clamping plate and a lower clamping plate, between which the SOEC / SOFC type solid oxide stack is enclosed, characterized in that that it also includes:
    - a system for overheating the gases entering the SOEC / SOFC type solid oxide stack, comprising:
    - at least one heating plate integrated into the thickness of at least one of the upper and lower clamping plates allowing the heating of the gases to be heated,
    - at least one upper gas overheating end plate, positioned between the upper clamping plate and the SOEC / SOFC type solid oxide stack, and / or a lower gas overheating end plate, positioned between the clamping plate bottom and the solid oxide stack of SOEC / SOFC type, each gas overheating end plate comprising a gas circulation circuit from a first end, at the level of which the gases to be heated reach a second end, at the level from which the heated gases escape towards the stack,
    - at least one inlet gas duct to be heated communicating with the first end of a gas overheating end plate, so that a flow of gas to be heated entering said at least one inlet duct circulates in the gas circulation circuit, from the first end to the second end to reach the entry of the SOEC / SOFC type solid oxide stack.
    Thanks to the invention, it is possible to dispense with tubular windings complicated to implement, as described above in connection with the first technique of gas overheating, by means of an innovative and compact geometry compared to nearly 2 meters, or even 3.6 meters, of bent tubes in the oven enclosure by gas line. We therefore obtain a significant gain in terms of space. It is an integration in the stack because there is no additional piece added.
    In addition, the overheating system according to the invention being part of the stack, it is possible to avoid redoing the tubular windings with each new stack while the system of tubular loops according to the first technique of the prior art is not not recoverable.
    Advantageously, the overheating system according to the invention can be reused for other stacks.
    In addition, it can be easy to put thermocouples at the outlet of the superheating system according to the invention in order to know with precision the temperature of entry of the gases into the stack, whereas for the tubes according to the prior art, it is more complicated due to the lack of space and the curved geometries of the windings.
    Furthermore, the path of the gas within the overheating system according to the invention is facilitated by the sinusoidal geometry allowing good continuity in the incoming gas flow while limiting the pressure losses.
    In addition, any treatment by deposition of alumina is to be carried out only once inside the overheating system to avoid pollution by evaporation of chromium and other elements.
    The overheating system according to the invention may also include one or more of the following characteristics taken in isolation or according to any possible technical combination.
    The gas circulation circuit can preferably extend in a sinusoidal form, or in a serpentine form, from the first end towards the second end, the amplitude of the sinusoidal waves being regular or not. Alternatively, other forms are possible.
    According to a first embodiment of the invention, said at least one upper end plate for gas overheating and / or said at least one lower end plate for gas overheating can be respectively positioned between the upper clamping plate and the end plate upper, and between the lower clamping plate and the lower end plate.
    In particular, the gas overheating end plate or plates can be positioned between two electrical insulation plates, in particular made of mica.
    According to a second embodiment of the invention, said at least one upper end plate for gas overheating and / or said at least one lower end plate for gas overheating can be formed respectively by the upper end plate and the lower end plate , which comprises a gas circulation circuit from a first end, at the level of which the gases to be heated reach, towards a second end, at the level of which the heated gases escape towards the stack.
    Each gas overheating system can then comprise at least one closing plate, in particular two closing plates on either side of the upper gas overheating end plate and / or of the gas overheating lower end plate, for close the gas circulation circuit.
    Furthermore, the gas overheating system can also comprise at least one outlet pipe for recovering the gases at the outlet of the SOEC / SOFC type solid oxide stack.
    In addition, each clamping plate of the clamping system can comprise at least one clamping orifice, the clamping system further comprising:
    - at least one clamping rod intended to extend through a clamping orifice of the upper clamping plate and through a corresponding clamping orifice of the lower clamping plate to allow assembly between them of upper and lower clamping plates,
    clamping means at each clamping orifice of the upper and lower clamping plates intended to cooperate with said at least one clamping rod to allow the assembly of upper and lower clamping plates between them,
    - Optionally at least one electrical insulation plate intended to be located between the stack of solid oxides of the SOEC / SOFC type and at least one of the upper and lower clamping plates.
    Furthermore, the subject of the invention is also, according to another of its aspects, a method of manufacturing at least one gas overheating system at the input of a SOEC / SOFC type solid oxide stack of an assembly as defined above, characterized in that it comprises the step of machining a lower gas superheat end plate and / or an upper gas superheat end plate to form a gas circulation circuit.
    The method may further include the step of attaching, by a method of laser welding by transparency, a closure plate on the circulation circuit of the lower gas overheating end plate and / or the overheating end plate upper gases, in particular two closing plates on either side of the lower gas overheating end plate and / or of the upper gas overheating end plate.
    The assembly and the manufacturing method according to the invention may include any of the characteristics set out in the description, taken in isolation or in any technically possible combination with other characteristics.
    BRIEF DESCRIPTION OF THE DRAWINGS
    The invention will be better understood on reading the detailed description which follows, of non-limiting examples of implementation thereof, as well as on examining the figures, schematic and partial, of the appended drawing, on which :
    FIG. 1 is a schematic view showing the operating principle of a high temperature solid oxide electrolyser (SOEC),
    FIG. 2 is an exploded schematic view of part of a high temperature solid oxide electrolyser (SOEC) comprising interconnectors according to the prior art,
    FIG. 3 illustrates the principle of the architecture of an oven on which a high temperature electrolysis stack (SOEC) or a fuel cell stack (SOFC) operating at high temperature is placed,
    FIG. 4 illustrates the principle of an electric gas heater according to the prior art,
    - Figure 5 shows, in perspective, a first example of an assembly according to the invention comprising a solid oxide stack of SOEC / SOFC type and a clamping system of the stack, further comprising two systems for overheating gases, respectively in the upper position and in the lower position, with the gas overheating end plate of each system taken between the stack end plate and the clamping plate,
    - Figure 6 shows, in perspective, a second example of an assembly according to the invention comprising a solid oxide stack of SOEC / SOFC type and a clamping system of the stack, further comprising two systems for overheating gases, respectively in the upper position and in the lower position, with the gas overheating end plate of each system integrated in the concept of the stack end plate,
    FIGS. 7 and 8 are partial sectional and perspective views of the second overall example of FIG. 6, without the presence of the stack,
    FIG. 9 represents, in perspective, an example of a gas overheating end plate of an assembly in accordance with the invention, which can be distinct from the stack end plate as according to the example of FIG. 5 or be integrated into the stack end plate as in the example of FIG. 6, and
    - Figure 10 shows the gas overheating end plate of the figure with the presence of a closing plate reported by laser welding.
    Throughout these figures, identical references may designate identical or analogous elements.
    In addition, the different parts shown in the figures are not necessarily shown on a uniform scale, to make the figures more readable.
    DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
    FIGS. 1 to 4 have already been described previously in the part relating to the state of the prior art and to the technical context of the invention. It is specified that, for FIGS. 1 and 2, the symbols and arrows for supplying water vapor H 2 O, for distributing and recovering dihydrogen H 2 , oxygen O 2 , air and electric current, are shown for clarity and precision, to illustrate the operation of the devices shown.
    In addition, it should be noted that all the constituents (anode / electrolyte / cathode) of a given electrochemical cell are preferably ceramics. The operating temperature of a high temperature SOEC / SOFC type stack is moreover typically between 600 and 1000 ° C.
    In addition, the possible terms “upper” and “lower” are to be understood here according to the normal direction of orientation of a SOEC / SOFC type stack when in its configuration of use.
    With reference to FIG. 5, a first example of an assembly 80 has been illustrated, comprising a stack 20 of solid oxides of the SOEC / SOFC type according to the invention and a clamping system 60, further comprising two superheating systems 40 of the gas, respectively in the upper position and in the lower position, with the gas overheating end plate 65, 66 of each system taken between the stack end plate 43, 44 and the clamping plate 45, 46.
    Furthermore, with reference to FIGS. 6, 7 and 8, a second example of an assembly 80 has been illustrated comprising a stack 20 of solid oxides of the SOEC / SOFC type according to the invention and a clamping system 60, further comprising two gas superheating systems 40, respectively in the upper position and in the lower position, with the gas superheating end plate 43, 44 corresponding to the stack end plate 43, 44.
    In other words, it is therefore possible to implement the invention according to these two embodiments: the first, in which the gas overheating end plate 65, 66 is pressed between a clamping plate 45, 46 and an end plate stack 43, 44; the second, in which the gas overheating end plate corresponds directly to a stack end plate 43, 44, the gas circulation circuit, single-channel circuit, being integrated in this stack end plate 43, 44.
    Each superheating system 40 makes it possible to heat the gases at the inlet of the stack 20 of the SOEC / SOFC type associated with an oven 10, as described previously with reference to FIG. 3.
    Among the different modes of heat transfer in the zone of the furnace 10, the predominant mode at these temperature levels, ie between 650 and 800 ° C., corresponds to radiative exchanges by radiation. The other transfer mode is then thermal conduction, and this is the one that the invention implements because it has the advantage of creating less heat loss to the outside. It is the mode of heat transfer caused by a temperature difference between two regions of the same medium or between two media in contact without appreciable displacement of material. The use of heating plates 61, as described below, for the overheating systems 40 makes it possible to recover the thermal conduction and to raise the gases to the correct temperature.
    Advantageously, the assembly 80 according to the invention has a structure similar to that of the assembly described in French patent application FR 3 045 215 A1, except for the presence here of a gas overheating system, it that is to say that the stack 20 has a “Plug & Play” type character (PnP).
    Also, in common with the two embodiments of the invention, and as visible in FIGS. 5 to 8, each assembly 80 comprises a stack 20 of solid oxides of the SOEC / SOFC type operating at high temperature.
    This stack 20 comprises a plurality of electrochemical cells 41 each formed by a cathode, an anode and an electrolyte interposed between the cathode and the anode, and a plurality of intermediate interconnectors 42 each arranged between two electrochemical cells 41 adjacent. This set of electrochemical cells 41 and intermediate interconnectors 42 can also be designated by “stack”.
    In addition, the stack 20 comprises an upper end plate 43 and a lower end plate 44, respectively also called upper stack end plate 43 and lower stack end plate 44, between which the plurality of electrochemical cells 41 and the plurality of intermediate interconnectors 42 are enclosed, ie between which is the stack.
    Furthermore, the assembly 80 also includes a clamping system 60 for the stack 20 of solid oxides of the SOEC / SOFC type, comprising an upper clamping plate 45 and a lower clamping plate 46, between which the stack 20 to solid oxides of SOEC / SOFC type is enclosed.
    Each clamping plate 45, 46 of the clamping system 60 has four clamping holes 54.
    In addition, the clamping system 60 further comprises four clamping rods extending through a clamping orifice 54 of the upper clamping plate 45 and through a corresponding clamping orifice 54 of the clamping plate lower 46 to allow the assembly between the upper 45 and lower 46 clamping plates.
    The clamping system 60 further comprises clamping means 56, 57, 58 at each clamping orifice 54 of the upper 45 and lower 46 clamping plates cooperating with the clamping rods 55 to allow the assembly of the plates upper 45 and lower 46.
    More specifically, the clamping means comprise, at each clamping orifice 54 of the upper clamping plate 45, a first clamping nut cooperating with the corresponding clamping rod 55 inserted through the clamping orifice 54. more, the clamping means comprise, at each clamping orifice 54 of the lower clamping plate 46, a second clamping nut 57 associated with a clamping washer 58, these cooperating with the corresponding clamping rod 55 inserted through the clamping orifice 54. The clamping washer 58 is located between the second clamping nut 57 and the lower clamping plate 46.
    Furthermore, in accordance with the invention, the assembly 80 further comprises a superheating system 40 for the upper GS gases and a lower superheating system for the GS gases at the inlet of the stack 20 of solid oxides of SOEC / SOFC type.
    Each upper or lower overheating system 40 comprises a heating plate 61 integrated into the thickness of the upper 45 or lower clamping plate 46 so as to allow the heating of the gases to be heated GE.
    In addition, each upper or lower superheating system 40 has an upper or lower gas overheating end plate. The upper end plate for gas overheating 65, 43 is positioned between the upper clamping plate 45 and the stack 20 of solid oxides of SOEC / SOFC type, the lower gas overheating plate 66, 44 is positioned between the plate for lower clamp 46 and stack 20 of solid oxides of the SOEC / SOFC type.
    More specifically, with reference to FIG. 5, the first embodiment provides that the gas overheating end plate 65, 66 is independent of the stack end plate 43, 44.
    Thus, the upper end plate for gas overheating 65 is located between the upper clamping plate 45 and the upper end plate for stack 43. Likewise, the lower end plate for gas overheating 66 is located between the lower clamping plate 46 and the lower stack plate 44.
    Advantageously, each gas overheating end plate 65, 66 is taken between two electrical insulation plates 59, made of mica. These electrical insulation plates 59 play the role of electrical insulation wedges. In the absence of these, the clamping system being preferably metallic, it would cause an overall short circuit between the top and the bottom of the stack 20.
    On the other hand, with reference to FIGS. 6 to 8, the second embodiment provides that the gas overheating end plate corresponds to the stack end plate 43, 44. In other words, the gas circulation circuit C is formed in the usual stack end plate 43, 44.
    This type of stack end plate 43, 44 conventionally has two functions: taking the sandwich stack; receive the stack inlet / outlet pipes, as well as the thermocouples, especially at the level of the bottom stack end plate 44.
    Thus, the second embodiment of the invention adds the function of using this plate to overheat the gases entering the stack.
    It should be noted that each stack end plate 43, 44 and / or each gas overheating end plate 65, 66 can be made for example from high temperature ferritic stainless steel, such as Crofer® 22 APU.
    In the two embodiments, respectively according to FIG. 5 and according to FIGS. 6 to 8, the upper gas superheat end plate 43 or 65 is identical to the lower gas superheat end plate 44 or 66. However, it could to be otherwise. The geometry of the plates can be modified as required, but their operating principle remains the same.
    Thus, as can be seen in particular in FIGS. 8 and 9, the gases to be heated GE penetrate into an inlet conduit 62 and reach the first end PI of a single-channel gas circulation circuit C of the gas overheating end plate 65, 43. FIG. 9 shows the upper gas overheating end plate 65 or 43 but the principle is the same for the lower gas overheating end plate 66 or 44.
    Once at the first end PI, the gases follow the sinusoidal, or serpentine, path of the circulation circuit C as according to the arrows F shown in FIG. 9 until reaching the second end P2 at the level of which the heated gases GS, via the heating plate 61, escape towards the stack 20. The total length traveled by the gases in the circulation circuit C, in other words the length between the first PI and second P2 ends , is for example of the order of 2 m. By way of example, the pressure drop calculated with respect to this configuration is of the order of 81 mbar for a channel of 5 mm × 5 mm over a length of 2 m.
    The overall shape of the circulation circuit C, that is to say the overall shape of the envelope in which the circulation circuit C is contained, can be of any type, being for example square, rounded or even rectangular like c 'is the case for the example of Figure 9 with an upper gas overheating end plate 43 or 65 also rectangular.
    The circulation circuit C can be obtained by machining, for example by means of a numerically controlled milling machine or any other suitable machining system in order to obtain the desired geometry. In all cases, the section of the single channel forming the circulation circuit C and its length must be optimized to properly overheat the gases while minimizing pressure drops.
    Furthermore, as can be seen in FIGS. 8 and 9 in particular, each GS gas overheating system 40 comprises an outlet duct TS for recovering the gases at the outlet of the stack 20 of solid oxides of SOEC / SOFC type, passing through the plate corresponding gas overheating terminal.
    In addition, in the first embodiment of the invention according to the example in FIG. 5, no closing of the upper gas overheating end plates 65 and lower 66 is necessary since two electrical insulation plates 19, produced in mica, are positioned on either side of each gas overheating end plate 65 and 66, namely a plate for closing the channels of the top and bottom stack end plate, and the other plate for the electrical insulation.
    On the other hand, in the second embodiment of the invention according to the example of FIGS. 6 to 8, each overheating system 40 comprises at least one closing plate 48 in particular two closing plates 48 on either side of the gas overheating end plate 43 or 44, to close the circulation circuit C, as shown in figure 10.
    The closure plate (s) 48 are preferably added laser welded by transparency. The laser welding technique allows the welding of metals by the characteristics of laser technology: with the high energy density and fineness of the laser beam, the targeted areas start to melt and are then quickly welded by cooling. This results in a solid weld on a reduced surface.
    As illustrated in FIG. 10, the laser welding by transparency must preferably follow the contour Ct, or laser closing line, as shown in order to be able to force the gases to follow the complete path.
    Of course, the invention is not limited to the exemplary embodiments which have just been described. Various modifications can be made by those skilled in the art.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    1. Set (80), comprising:
    - a stack (20) of solid oxides of the SOEC / SOFC type operating at high temperature, comprising:
    - a plurality of electrochemical cells (41) each formed by a cathode, an anode and an electrolyte interposed between the cathode and the anode, and a plurality of intermediate interconnectors (42) each arranged between two electrochemical cells (41) adjacent,
    - an upper end plate (43) and a lower end plate (44), between which the plurality of electrochemical cells (41) and the plurality of intermediate interconnectors (42) are enclosed,
    - a clamping system (60) of the stack (20) of solid oxides of SOEC / SOFC type, comprising an upper clamping plate (45) and a lower clamping plate (46), between which the stack (20 ) with solid oxides of the SOEC / SOFC type is enclosed, characterized in that it also comprises:
    - a gas overheating system (40) (GS) at the input of the SOEC / SOFC type solid oxide stack (20), comprising:
    - at least one heating plate (61) integrated in the thickness of at least one of the upper (45) and lower (46) clamping plates allowing the heating of the gases to be heated (GE),
    - at least one upper gas overheating end plate (65, 43), positioned between the upper clamping plate (45) and the stack (20) of solid oxides of SOEC / SOFC type, and / or a lower end plate superheat gas (66, 44), positioned between the lower clamping plate (46) and the stack (20) of solid oxides of SOEC / SOFC type, each end gas overheating plate (65, 43, 66, 44) comprising a gas circulation circuit (C) from a first end (PI), at the level of which the gases to be heated (GE) arrive, towards a second end (P2), at the level of which the gases escape reheated (GS) towards the stack (20),
    - at least one inlet duct (62) for the gases to be heated (GE) communicating with the first end (PI) of a gas overheating end plate (65, 43, 66, 44), so that a flow of gas to be heated (GE) entering said at least one inlet duct (62) circulates in the gas circulation circuit (C), from the first end (PI) to the second end (P2) to reach l entry of the stack (20) of solid oxides of SOEC / SOFC type.
    [2" id="c-fr-0002]
    2. Assembly according to claim 1, characterized in that the gas circulation circuit (C) extends in a sinusoidal form from the first end (PI) to the second end (P2).
    [3" id="c-fr-0003]
    3. Assembly according to claim 1 or 2, characterized in that said at least one upper end plate for gas overheating (65) and / or said at least one lower end plate for gas overheating (66) are respectively positioned between the upper clamping plate (45) and the upper end plate (43), and between the lower clamping plate (46) and the lower end plate (44).
    [4" id="c-fr-0004]
    4. An assembly according to claim 3, characterized in that the terminal or gas overheating plates (65, 66) are positioned between two electrical insulation plates (59), in particular made of mica.
    [5" id="c-fr-0005]
    5. Assembly according to claim 1 or 2, characterized in that said at least one upper end plate for gas overheating (43) and / or said at least one lower end plate for gas overheating (44) are respectively formed by the upper end plate (43) and the lower end plate (44), which have a gas circulation circuit (C) from a first end (PI), at the level of which the gases to be heated (GE) reach a second end (P2), at which level the heated gases (GS) escape towards the stack (20).
    [6" id="c-fr-0006]
    6. An assembly according to claim 5, characterized in that each gas overheating system (40) comprises at least one closing plate (48), in particular two closing plates (48) on either side of the end plate upper gas superheat (43) and / or lower gas superheat end plate (44), to close the gas circulation circuit (C).
    [7" id="c-fr-0007]
    7. Assembly according to any one of the preceding claims, characterized in that the gas overheating system (40) (GS) further comprises at least one outlet duct (TS) for recovering the gases at the outlet of the stack (20) with solid oxides of SOEC / SOFC type.
    [8" id="c-fr-0008]
    8. Assembly according to any one of the preceding claims, characterized in that each clamping plate (45, 46) of the clamping system (60) comprises at least one clamping orifice (54), the clamping system (60) further comprising:
    - at least one clamping rod (55) intended to extend through a clamping orifice (54) of the upper clamping plate (45) and through a corresponding clamping orifice (54) of the lower clamping plate (46) to allow the assembly between them of the upper (45) and lower (46) clamping plates,
    - clamping means (56, 57, 58) at each clamping orifice (54) of the upper (45) and lower (46) clamping plates intended to cooperate with said at least one clamping rod (55) for allow the assembly of upper (45) and lower (46) clamping plates,
    - optionally at least one electrical insulation plate (19) intended to be located between the stack (20) of solid oxides of the SOEC / SOFC type and at least one of the upper (45) and lower (46) clamping plates ).
    [9" id="c-fr-0009]
    9. Method for manufacturing at least one superheating system (40) for gases (GS) at the input of a stack (20) of solid oxides of SOEC / SOFC type of an assembly (80) according to any one of the preceding claims, characterized in that it comprises the step of machining an end plate for lower gas overheating
    5 (44, 66) and / or an upper gas overheating end plate (43, 65) to form a gas circulation circuit (C).
    [10" id="c-fr-0010]
    10. The method of claim 9, characterized in that it comprises the step of reporting, by a laser welding process by transparency, a
    10 closure plate (48) on the circulation circuit (C) of the lower gas superheat end plate (44, 66) and / or the upper gas superheat end plate (43, 65), in particular two plates closure (48) on either side of the lower gas superheat end plate (44, 66) and / or the upper gas superheat end plate (43, 65).
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    同族专利:
    公开号 | 公开日
    DK3679620T3|2021-10-25|
    JP2021500472A|2021-01-07|
    EP3679620A1|2020-07-15|
    US20200313217A1|2020-10-01|
    EP3679620B1|2021-08-11|
    CA3078768A1|2019-05-02|
    WO2019081866A1|2019-05-02|
    FR3073093B1|2022-02-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2004077587A2|2003-02-27|2004-09-10|Forschungszentrum Jülich GmbH|Production of a high-temperature fuel cell stack|
    WO2005060028A2|2003-12-17|2005-06-30|Honda Motor Co., Ltd.|Fuel cell and fuel cell stack|
    EP1705741A1|2005-03-21|2006-09-27|Sulzer Hexis AG|High temperature fuel cells installation and clamping assembly for fuel cell stack|
    EP3035430A1|2014-12-19|2016-06-22|Hexis AG|Fuel cell module|
    FR3045215A1|2015-12-15|2017-06-16|Commissariat Energie Atomique|AUTONOMOUS SELF-CONTAINING SYSTEM OF SOEC / SOFC HIGH-TEMPERATURE SOLID OXIDE STACK|FR3104833B1|2019-12-12|2021-12-03|Commissariat Energie Atomique|Clamping plate integrating a heating element and electrochemical device comprising it|
    DE102020205881A1|2020-05-11|2021-11-11|Robert Bosch Gesellschaft mit beschränkter Haftung|Heatable current collecting plate and cell stack with heatable current collecting plate|
    DE102020205884A1|2020-05-11|2021-11-11|Robert Bosch Gesellschaft mit beschränkter Haftung|Cell stack with heatable end plate|
    法律状态:
    2019-05-03| PLSC| Publication of the preliminary search report|Effective date: 20190503 |
    2019-10-31| PLFP| Fee payment|Year of fee payment: 3 |
    2020-10-30| PLFP| Fee payment|Year of fee payment: 4 |
    2021-10-29| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1760114A|FR3073093B1|2017-10-26|2017-10-26|ASSEMBLY OF A SOEC/SOFC TYPE SOLID OXIDE STACK AND A CLAMPING SYSTEM WITH INTEGRATED GAS SUPERHEATING SYSTEM|
    FR1760114|2017-10-26|FR1760114A| FR3073093B1|2017-10-26|2017-10-26|ASSEMBLY OF A SOEC/SOFC TYPE SOLID OXIDE STACK AND A CLAMPING SYSTEM WITH INTEGRATED GAS SUPERHEATING SYSTEM|
    CA3078768A| CA3078768A1|2017-10-26|2018-10-26|Assembly comprising a soec/sofc-type solid oxide stack and a clamping system with an integrated gas superheating system|
    PCT/FR2018/052663| WO2019081866A1|2017-10-26|2018-10-26|Assembly comprising a soec/sofc-type solid oxide stack and a clamping system with an integrated gas superheating system|
    JP2020522303A| JP2021500472A|2017-10-26|2018-10-26|Assembly with SOEC / SOFC type solid oxide stack and clamp system with integrated gas overheating system|
    EP18800734.8A| EP3679620B1|2017-10-26|2018-10-26|Stack assembly of solid oxide cells soec/sofc and tightening system with an integrated overheat system of the gases|
    DK18800734.8T| DK3679620T3|2017-10-26|2018-10-26|Unit with a stack of solid oxides of SOEC / SOFC type and with a clamping system with an integrated system for overheating the gases|
    US16/758,176| US20200313217A1|2017-10-26|2018-10-26|Assembly comprising a soec/sofc-type solid oxide stack and a clamping system with an integrated gas superheating system|
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