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    • 专利摘要:
    The present invention relates to a seal (20) that can be used to be mounted in contact with two metal surfaces (28 and 29) of an electrochemical device, particularly of the solid oxide fuel cell ("SOFC") type or electrolyzer. high temperature solid oxide water vapor ("SOEC"). This seal comprises: - a sealing means (21) of the seal comprising at least one glass-type material, and - an electrically insulating supporting means (24) which supports the sealing means and which has two main faces (22). and 23) parallel, an outer peripheral edge (22a) and an inner peripheral edge (23a), the seal being adapted to be mounted against these surfaces by these main faces, which are covered with the sealing means. According to the invention, the sealing means partitions the support means between these inner and outer edges by extending continuously from one of the main faces to the other through the support means, so that the means of sealing directly connects these staves to one another.
    公开号:FR3014246A1
    申请号:FR1362100
    申请日:2013-12-04
    公开日:2015-06-05
    发明作者:Iorio Stephane Di；Bruno Oresic；Julien Petit；Magali Reytier
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] SEAL FOR ELECTROCHEMICAL DEVICE, METHOD FOR MANUFACTURING AND ASSEMBLING JOINT, AND DEVICE.
    [0002] The present invention relates to a seal that can be used in an electrochemical device, a method for manufacturing and assembling the seal in this device and such a device. The invention is particularly applicable to devices forming solid oxide fuel cells ("SOFC" for short for "Solid Oxide Fuel Cell") and electrolyzers of water vapor at high temperature to solid oxides ( "SOEC" abbreviated in English, for "Solid Oxide Electrolyser Cell", these solid oxide electrolysers being electrolyzers generically known in English under the abbreviations "HTE" or "HTSE" respectively for "High Temperature Electrolysis" or "High Temperature Steam Electrolysis "and French EHT or EVHT). In a known manner, the electrochemical devices of the "SOEC" and "SOFC" type require high-quality seals in the different chambers that compose them to be efficient. If the seals are of good quality, then all the gas sent is used by the "SOEC" devices and all the gases produced are recovered for the "SOEC", and it is furthermore avoided for these devices to mix the gases used or products which would strongly penalize the performance and durability of these devices. These electrochemical devices usually comprise: at least one cell consisting of a hydrogen electrode-electrolyte-oxygen electrode assembly and defining two chambers, at least two electrical contact elements with each cell, at least two metal interconnectors which bring about the stream and distribute the gases (eg water vapor, oxygen, dihydrogen, carbon dioxide and optionally a carrier gas such as nitrogen or air) to the electrodes and which provide the junction between two adjacent cells, and - electrically insulative seals to avoid short circuits, comprising first seals sealing between the two chambers of each cell, second seals sealing between the inlet and the outlet gas inlets and third seals sealing the device with the outside. In a SOEC type electrochemical device, the water molecule is dissociated in hydrogen to the hydrogen electrode (cathode), the O 2 ions migrate through the electrolyte to recombine on the oxygen electrode side (anode). oxygen. The or each "SOEC" cell thus produces dihydrogen by dissociating water molecules. In an SOFC type electrochemical device, the oxygen is reduced to the oxygen electrode (cathode), the O 2 ions migrate through the electrolyte. An oxidation reaction then takes place at the hydrogen electrode (anode) and the or each "SOFC" cell thus produces electricity and water by combining dihydrogen and oxygen. The sealing of SOEC and SOFC devices is thus one of the most critical points in operation. Indeed, if part of the hydrogen produced in a "SOEC" device, for example, flows partially outward of the device instead of being completely recovered because of a leakage, the efficiency of the device is reduced. In addition, if the two chambers of a cell of a SOEC or SOFC device communicate with each other, then the mixing of gases that takes place leads to a loss of efficiency of the devices, to hot spots and to a decrease in their life. For "SOEC" devices, it can be considered that a seal is satisfactory when 97% of the dihydrogen produced is recovered at the outlet of the device, good when this recovery rate is 99% and excellent when this level is greater than 99, 9%. In addition to the recovery rate, the quality of a seal can be evaluated by considering its resistance to overpressure. A tightness resistant to 50 mbar (or 5000 Pa) is suitable, it is good when it resists 200 mbar (or 20000 Pa) and excellent at 500 mbar (or 50000 Pa). The duration of this resistance is also an important parameter, it being specified that a tightness that can withstand only a few minutes has little value, the durations targeted being of the order of several thousand hours. It is known that a seal for "SOEC" or "SOFC" devices can be achieved by means of compressive seals, ie which, in order to perform their sealing function, must be subjected to compression forces that deform these seals, which by putting themselves in place establish ao sealing. This deformation of the joints can be reversible (e.g. elastic polymer seal for low temperatures) or irreversible (e.g. plastic deformation of metallic materials). These compressive seals are most often dense, which may in this case be polymeric or metallic, or porous, for example mica seals, the compressive force making it possible in this latter case to fill the open internal pores of the porous material to avoid leaks in its thickness. A major disadvantage of metal-type compressive seals is that they do not guarantee electrical insulation between the metal interconnects, and especially that they require very high load levels to be effective. As for the porous electrical insulating compressive joints such as mica seals, they have the disadvantage of requiring compressive stresses greater than those tolerated by the "SOFC" and "SOEC" stacks to obtain satisfactory seals and are not watertight. in their thickness. In addition, the mica seals pose the problem of the expansion coefficients of the materials in contact which must be as close as possible. It is also known that the seal can be achieved using seals made of glass. Specially developed glasses for "SOEC" and "SOFC" applications include those of the G018 family (marketed by Schott), set up and crystallized at temperatures above the operating temperatures of the stack. Then the temperature is lowered to the operating temperature so that the glass seal becomes more rigid, which allows it to be able to withstand operating pressures. A major drawback of the use of glass gaskets in "SOEC" and "SOFC" devices is that if these seals are too thick, they will not withstand high overpressures (a few millibars - ie hundreds of Pa - are sufficient to flow a glass joint of the order of 1 mm thick). Indeed, it is known that a glass seal must have the lowest possible thickness to limit its flow under pressure because at its temperature of use, the glass of this seal is never completely solidified which can cause it to flow (ie to be "flushed out") under the effect of pressure under the laws of flow of a fluid between two walls with a high flow velocity and a the overpressure resistance time reduced in proportion, thus leading to a leakage loss. In conclusion, for the same overpressure, the life of a glass joint will be longer as its thickness will be reduced and its support surface important. In practice, the dimensional control of the glass joints is complex since it is also essential to keep the parts of the stack in contact in order to allow good circulation of the electric current, ie the interconnectors, electrical contact elements and cell (s). ). Another disadvantage of these known glass seals is that if the seal glass establishes a seal between two metal scopes but is too thin, then there is a risk of a short circuit in the device because the glass reacts. with the metal carried to form oxides which may become conductive, as indicated in the article by VAC Haanappel et al., Behavior of various glass-ceramic sealants with ferritic steels under simulated SOFC stack conditions, Journal of Power Sources 150 (2005) 86-100. As described in EP-A2-2 522 639, it is possible to alternatively use glass-ceramic glasses which have a structure which can crystallize with time, which increases the rigidity of the glass. This solution is however not optimal, because the overpressure resistance of these vitroceramic joints may be insufficient. In order to provide a solution to the aforementioned problems of dimensioning glass joints, recent attempts have been made to combine a glass sealing layer and a compressive material such as a mica in the same composite joint in order to reduce the stress. necessary compression and / or improve the results obtained with respect to a joint consisting of this single compressive material. For example, document US-A1-2009 / 0311570 discloses a composite seal for an electrochemical device consisting of a mica sealed by glass deposited in contact with it. Disadvantages of this composite seal reside in the leaks observed in the thickness of the mica, in the difficulty of controlling the amount of glass to be deposited because the height between the metal surfaces subjected to dimensional variations conditions the spreading of the glass, and in keeping the glass on the mica which is generally weak. One can also cite the document WO-A1-2005 / 024280 which has a composite joint where the glass is infiltrated in a mica, which improves the properties of a mica compressive joint but has the disadvantage of requiring a complex process and very difficult to implement because of the reduced size of the pores of mica which makes problematic the infiltration of glass into the pores of a mica already shaped. It is also possible to cite WO-A1-2013 / 144167 which has a composite joint consisting of a solid and continuous ceramic core covered with glass on its two main faces, and the document US-A1-2010 / 0068602 which presents a composite glass / support plate for example mica in which the glass covers only the two main faces of the plate, which is optionally machined surface on these two faces. A disadvantage of this latter seal is that it does not block gas leaks in its thickness. Finally, WO-A2-2004 / 059761 discloses a composite joint with various constituents such as fibers and ceramic powder, glass and a binder. A disadvantage of this seal is that it requires a long series of steps to be shaped and consists of components that can pollute the chambers to be sealed and whose diversity gives the joint an uncontrolled expansion coefficient and risk of break. An object of the present invention is to provide a seal that can be used to be mounted in contact with two metal surfaces of an electrochemical device, in particular of the "SOFC" or "SOEC" type, the seal comprising: sealing the seal comprising at least one glass-ceramic material, and - an electrically insulating support means which supports the sealing means and which has two parallel main faces, an outer peripheral edge and an inner peripheral edge, the seal being adapted to be mounted against these surfaces by these main faces, which are at least partially covered by the sealing means, which overcomes all the aforementioned drawbacks by representing a practical solution, simple to implement and 20 expensive to the aforementioned problems and to obtain an excellent seal especially for cell ules of high area may for example be of the order of 120 x 120 to 150 x 150 mm2 and with operating temperatures typically between 600 and 900 ° C. For this purpose, a seal according to the invention is such that the sealing means partitions the support means between said inner peripheral edge and said outer peripheral edge by continuously extending from one of said main faces to the other through the support means, so that the means for sealing directly connects these litters to each other. By "inner peripheral edge" and "outer peripheral edge" is meant respectively in the present description an edge extending along the inner and outer perimeters which may be independently of one another elliptical (eg circular, then being circumferential edges) or polygonal (for example square), by way of example and not limitation. It will be noted that this transverse partitioning through the support means by the sealing means, which thus bears on these two opposite faces, makes it possible to seal the gas leaks in the thickness of the seal, to control the quantity deposited glass material by managing its overflows, to position this material exactly where it is needed and, finally, to create a seal metal / material type glass / metal of excellent quality. Due to this watertight partitioning of the support means, it is possible to produce the latter in a non-watertight material such as a porous material, as will be explained hereinafter. Note also that this structure of the joints according to the invention allows great simplicity in their implementation within the electrochemical device and advantageously require a single component 15 providing a satisfactory seal, which is said glass-type material whose coefficient of expansion is very close to that of metal scopes which has the advantage of not penalizing the seal obtained by thermal cycling. It should further be noted that this watertight partitioning makes it possible to eliminate the gas leaks in the wafer of the material of the support means, and to prevent that oxidation of the adjacent metal surfaces can create a short circuit in the device because the thickness of the glass-like or glass-ceramic material is important. According to another characteristic of the invention, the support means may comprise a one-piece frame of a porous material which is machined to define surfaces pierced through the frame forming at least one through channel of predetermined geometry receiving the means of sealing, said at least one channel filled with the sealing means forming at least one watertight partition extending continuously from one of said main faces to the other. It will be noted that the or each channel thus machined makes it possible to precisely position in an optimum configuration (ie exactly at the predetermined locations required) the glass-type material of the sealing means within the support means, which advantageously consists of this one-piece frame. . This vitreous material (or vitroceramic, therefore partially crystalline) then forms one or bulkhead (s) waterproof (s) adhering excellently to metal surfaces, which increases the strength of the or each partition. The dimensions of the or each watertight partition (ie transverse height measured perpendicular to the main faces of the frame and width measured parallel to these faces) are completely controlled since they correspond to those of the holes or cuts initially made on the frame, and the it is thus possible to produce partitions each having a small width (typically 1 mm) which provides a small footprint with the formation of several watertight partitions. It will also be noted that, where the or each watertight partition is contained by the material of the support frame (mica for example), it must necessarily flow between this frame and the facing metal seats. Since this sliding is very difficult, a confinement of the glass-type sealing means is thus obtained which provides an excellent seal, which can be maintained for pressures greater than 1 bar (ie greater than 105 Pa). The or each channel pierced in the frame is adapted to receive the overflow of the sealing means during the implementation phase of the or each seal of the "SOEC" or "SOFC" device according to the invention at a higher temperature. to that of operation, this overflow forming the aforementioned bulkhead between the two metal surfaces. As will be explained in more detail below, it will be further appreciated that a seal according to the invention may be prepared prior to mounting the device and its eventual stack of cells. According to another characteristic of the invention, said surfaces of said at least one channel may be generally perpendicular to said main faces and extend in a generally concentric peripheral direction to said inner and outer peripheral edges, continuously or discontinuously along said peripheral direction, tabs constituted by said frame being able to be formed on either side of said at least one channel for connecting the latter to the remainder of the frame or to another said adjacent channel, each tab having a volume smaller than that of said at least one channel.
    [0003] By "globally concentric peripheral direction" is meant in the present description a direction surrounding said inner peripheral edge of the frame in the form of one or more straight lines (eg in the form of dashes and / or dotted lines), curves and / or broken, seen in section in a plane internal to the frame parallel to its main faces (ie seen in a median horizontal plane inside the frame). Note that these tabs consist of uncut parts of the frame that maintain this frame in one piece, thus avoiding the assembly of several blocks whose precise positioning relative to each other would be impossible. These tongues are judiciously positioned to allow both the mechanical strength of the frame and the minimization of gas leaks within it. Preferably, said tongues are angularly radially offset on either side of said at least one channel, for example in a staggered arrangement, so as to maximize the length of the gas path distributed by interconnectors formed by said staves and / or the pressure drops for these gases through said porous material of said frame. By "radially" is meant in the present description a direction within the frame passing substantially through the center of the frame and perpendicular to the axis of symmetry of the frame. According to a first embodiment of the invention, said at least one watertight partition extends continuously in said peripheral direction (seen in a horizontal plane internal to the frame), said tabs extending on either side of said at least one channel respectively to said outer peripheral edge and to said inner peripheral edge. According to this first embodiment, a seal according to the invention may advantageously comprise at least two said concentric bulkheads which are connected two by two to each other by said radial tabs. According to a second embodiment of the invention, said at least one watertight partition extends discontinuously in said at least one peripheral direction (seen in a horizontal plane internal to the frame) by forming a plurality of partitioning portions that can be connected two by two together in this peripheral direction by said tongues. According to this second embodiment, a seal according to the invention may advantageously comprise: at least two said watertight partitions formed each of said plurality of partitioning portions housed in said channels passing through said frame which are machined according to rectilinear curvilinear geometries ( for example, like the aforementioned dashes), corrugated and / or in the form of broken lines and which are filled with the sealing means, or alternatively a multitude of said watertight partitions which are respectively formed of a multitude of holes (for example like the aforementioned dotted lines) passing through said frame, for example cylindrical, which form said machined channels at regular intervals between said inner peripheral edge and said outer peripheral edge and which are filled with the sealing means. With reference to this second embodiment of the invention, it will be noted that numerous line configurations may be used, in particular any pattern making it possible to maximize the length of the path of the gases flowing in the thickness of the frame, or even patterns of the type fractals. According to another preferred feature of the invention, said sealing means is based on glass or glass-ceramic (ie mainly comprising by weight or exclusively a glass paste), and said support means consists of a machined sheet a porous material forming said frame and selected from the group consisting of porous ceramics and porous minerals, preferably mica.
    [0004] It will be noted that, thanks to the sealed partitioning of the frame according to the present invention, it is not necessary that this frame be sealed, which allows the use of porous materials in general, such as: - porous ceramics (for example Macor which is a porous alumina). Indeed, an advantage of porous ceramics is that they are easily machinable, and generally less expensive when they are not 100% dense, or - porous mineral materials such as mica, which comprises in a known manner the group of alumino-silicate minerals having a lamellar structure (mica is relatively temperature stable, is an easy to machine, inexpensive and electrically insulating support) and exists under a large number of compounds among which the most common are biotites (eg of formula K2 (Mg, Fe) 2 (OH) 2 (AlSi3) io), Fuchsites (ie Biotites rich in iron), Lepidolites (eg of formula LiKAI, (01-1, F) 2 (Si205) 2) Muscovites (eg of formula KAl2 (OH) 2 (AlSi3010)) and Phlogopites (eg of formula (KMg3A1). (OH) Si401o). A method of manufacturing and assembling according to the invention a seal as defined above in an electrochemical device, in particular of the solid oxide fuel cell type ("SOFC") or the steam electrolyser with solid oxide high temperature ("SOEC"), comprising: a) a machining of the support means for piercing said at least one channel between said inner peripheral edge and said outer peripheral edge which extends continuously from one of said main faces to the other through the support means, b) a deposition of the sealing means, such as a glass paste (also called "slip"), on said main faces and in said at least one channel for the obtaining a blank of the joint before assembly, c) assembling the seal within a stack of at least one cell of the device at a temperature of between 600 ° C. and 900 ° C. and under an applied pressure of several kPa, to melt e the sealing means while putting it in place. It should be noted that the use according to the invention of a single piece forming each seal makes it possible to set up in one single step at a time almost all the joints of one stage of the stack during assembly. of the electrochemical device of the invention. An electrochemical device of the solid oxide fuel cell ("SOFC") type or high temperature solid oxide water vapor electrolyser ("SOEC") according to the invention comprises: - at least one cell which comprises an assembly hydrogen electrode-electrolyte-oxygen electrode and which delimits two chambers, - at least two elements of electrical contact with said at least one cell respectively positioned in contact with said electrodes, - at least two metallic surfaces forming interconnectors which distribute in said at least one cell an electric current and gases such as water vapor, dioxygen, dihydrogen and optionally a carrier gas and which, in the case of several said cells, provide the junction between them, and seals which are each mounted in contact with a pair of said interconnectors, and this device is characterized in that at least one n of these seals is as defined above in connection with the present invention. Advantageously, all of said seals are electrically insulating, these seals comprising first seals ensuring the sealing between the chambers of said at least one cell, second seals sealing between respective feeds of inlet gas and outlet gas and third seals sealing said at least one cell with the outside atmosphere, said second and third seals being according to the invention as defined above. Other characteristics, advantages and details of the present invention will emerge on reading the following description of several examples of embodiment of the invention, given for illustrative and not limiting, said description being made with reference to the accompanying drawings, among FIG. 1 is a partial diagrammatic view in a transverse half-section (in a vertical plane) of a SOEC or SOFC electrochemical device showing an example of a typical location of seals according to the invention. in this device, FIG. 2 is a partial schematic view in transverse half-section showing a first phase of the preparation of a composite joint according to the invention, for example included in the device of FIG. 1 and mounted in contact with two 3 is a partial schematic view in cross-sectional half-section showing a subsequent phase of the preparation of the gasket of the 2 in contact with the two interconnectors, FIG. 4 is a diagrammatic view in horizontal section of a seal according to said second embodiment of the invention, in a sectional plane internal to the joint which is parallel to the main faces of the latter, FIGS. 5 and 6 are each a photograph of a half of a joint according to said first embodiment of the invention, showing in FIG. 5 the filling of a circular channel of the support frame by the sealing means and in FIG. 6 the filling of another adjacent channel, FIG. 7 is a photograph identical to FIG. 6 but furthermore schematically illustrating by an arrow the interest of the tongues of the frame angularly offset for the path of the gases through the joint. 8, 9, 10 and 11 are diagrammatic views in horizontal section of different variants of a gasket according to said second embodiment of the invention, in a sectional plane internal to the gasket which is parallel to the main faces. 12 is a schematic view in horizontal section of a variant of a seal according to said first embodiment of the invention, in a sectional plane internal to the joint which is parallel to the main faces of the latter. FIG. 13 is a graph showing a current-voltage curve (IV) of a test on a SOEC device with a 120 × 120 mm 2 cell equipped with a gasket according to FIG. 2 with glass-filled mica frame. FIG. 14 is a graph showing the mass flow rates of dihydrogen produced and recovered as a function of time by this mica / glass seal of FIG. 12, under an overpressure of 500 mbar (50000 Pa) for the SOEC cell, and FIG. 15 is a horizontal cross-sectional photograph of the interior of a seal similar to that of FIG. 12, after disassembly of the "SOEC" cell following its operation to illustrate the barrier effect of the dioxygen and dihydrogen gases of two glass partitions of this joint . The electrochemical device 1 partially illustrated in the example of FIG. 1 comprises: - cells 2 each consisting of a hydrogen electrode-electrolyte-oxygen electrode assembly (not shown), - electrical contact elements 3 and 4 with each cell 2 delimiting two chambers 5 and 6 for it, - metal interconnectors 7, 8, 9, 10, 11, 12 which bring the current and distribute the gases (eg water vapor, oxygen, hydrogen, and optionally a carrier gas such as nitrogen or air) to the electrodes and which provide the junction between two adjacent cells 2, and - electrically insulating seals 13, 14, 15 to avoid any short circuit, comprising first seals 13 providing a seal between the two chambers 5 and 6 of each cell 2, second seals 14 sealing between the inlet and outlet gas inlets and the third seals 15 ensuring the sealing of the device with the outside. As can be seen in FIGS. 2 and 3, a seal 20 according to the invention is produced by depositing a sealing means 21, advantageously consisting of a glass paste, on the two parallel main faces 22 and 23 of a monobloc frame. Electrical insulation in sheet form for example mica (the faces 22 and 23 of the frame 24 are interconnected by an outer peripheral edge 22a and an inner peripheral edge 23a). According to the invention, this sheet 24 is previously machined so as to pierce therein one or more opening (s) through (s) 25, 26 of predetermined geometry (s) which open on these two faces 22 and 23. The glass 21 thus deposited fills the openings 25, 26 of the frame 24 to form glass-tight partitions 27 bearing on the interconnectors 28 and 29, such as those mentioned above with reference to the device 1 of Figure 1. As visible in FIG. Figure 4, tabs 33 consist of uncut portions (visible in white dash) of a frame 30 seal 34 according to the invention to maintain the frame 34 in one piece. If the blank (shown in white by openings 35, 36 of rectangular section filled with sealing glass 37, 38) was continuous, there would indeed be in this embodiment six pieces to be assembled instead of one and their precise positioning relative to each other would be impossible. The tongues 33 are judiciously positioned to allow both the mechanical strength of the frame 34 and the minimization of the gas leaks within it, and these tongues 33 generate a discontinuity of the sealed glass partitions 37, 38 filling the openings 35, 36 in the peripheral and / or transverse direction of the joint 30 incorporating this frame 34. Since the material preferably used for this frame 34 (eg a mica) is porous, each tongue 33 may be the seat of a gas leak in the thickness of the frame 34, which the Applicant has demonstrated in the photograph of FIG. 15. Indeed, this FIG. 15 shows that the smaller the tab, the smaller the passage section for the gases and the leakage of these gases from. as much smaller. But it should be noted that the tongues 33 must not be too small (ie not too thin or too narrow) not to break during handling of the frame 34. In this context, the geometry shown in Figure 4 is an example embodiment for minimizing the width of each tab 33 to minimize leakage in the seal 30.
    [0005] As illustrated in the photographs of FIGS. 5 to 7, a frame for a seal according to the invention is pierced according to at least one continuous or discontinuous line in the peripheral direction (eg circumferential), and preferably in multiple lines forming channels which once filled with glass (in white) define as many watertight partitions to completely prevent the passage of gases (see Figure 6). In addition, the tabs that connect the channels to each other are positioned angularly offset (ie staggered), so as to maximize the length of the gas in the frame (see arrow in Figure 7 schematically illustrating the sinuous course of gas through these tabs) and to increase the pressure losses within the joint. Thus, and with reference to FIGS. 8 and 9, a frame seal 44 made according to the example of FIG. 8 with staggered tabs 43 formed between impervious partition portions 47, 48 discontinuous in the peripheral direction, presents results. gas sealing much better than that of a seal 50 to frame 54 made according to Figure 9 with tabs 53 radially aligned between portions of sealed partition 57, 58 also discontinuous. As illustrated in FIG. 10, it is possible to provide alternatively in a frame 64 of a seal 60 according to the invention several rows of generally concentric channels which are each in non-straight lines (eg broken or corrugated) with tabs 63 of FIG. connection, to increase the size of the watertight bulkheads 67, 68 filling these channels and to control the mechanical strength of the frame 64. As illustrated in FIG. 11, instead of having cut lines, it is possible to have a joint 70 with a frame 74 pierced. a multitude of transverse holes 75 regularly spaced and for example of circular section. These glass holes 75 are filled to form as many watertight partitions 77 aligned for example in a multitude of concentric rows. These 30 holes 75 have the advantage of being easy to produce and arrange in the form of regular rows. The size limit of each hole 75 is given by the capillarity of the glass, which must fill the holes 75 without remaining on the surface.
    [0006] With reference to all of the aforementioned embodiments and embodiments of the invention, the sealing means used using a robot and a pneumatic syringe in the form of a glass paste are advantageously deposited by example of type G018 which is a mixture of commercial glass powder (eg a Schott G018-311 type glass powder mixed with an ethanol solvent and a terpineol-type binder). The glass paste is prepared in the laboratory from this commercial glass powder, and it is deposited on solid parts of the frame between two holes which, on the one hand, allows the glass to overflow into the openings or channels of the frame. according to a controlled overflow and, secondly, facilitates the deposit and allows the manipulation of the frame after this deposit. The glass is not deposited elsewhere because it could overflow into the gas supply zones of the stack of the electrochemical device. As it is easy to handle, it is easy to weigh the frame before and after the deposition of the glass paste, which makes it easy and precise to know the quantity of glass thus deposited. This quantity of deposited glass, which corresponds to the quantity necessary to fill the openings or channels of the support frame, is calculated as accurately as possible. The volume of the openings or channels to be filled is calculated and the exact amount of glass required for this filling is deposited. Often, the tolerances on the spacings between interconnectors are of the order of 50 pm. For a mica frame without a hole, an uncertainty of 50 μm in height over a glass height of 100 μm is very important since it is 50%, which generates overflows at undesired locations. With the grooves of the invention, as the volume of glass deposited in these grooves is important, these 50 pm will lead to only a few% of excess glass. Thus, the present invention makes the height variations on the rib chains much less critical.
    [0007] The Applicant has also carried out comparative tests not in accordance with the invention with parts cut in a mica frame not in a through manner, but recessed in this frame (i.e. transversely blind). These comparative tests have given for the "control" seal thus obtained filling these recessed portions of the experimental results significantly worse, namely a maximum pressure resistance of only 0.2 bar (20000 Pa) and no resistance to cycles thermal. To manufacture a gasket according to the invention, it is possible, for example, to use the following successive steps: - production of the electrical insulating frame, eg a mica sheet (for example of the thermophilic name 866® from the company Flexitallic) with a thickness of sheet between 0.1 mm and several mm. Alternatively, this frame may be made of any other machinable electrically insulating material; - Achieving the through openings from one main face to the other of the sheet by cutting the milling cutter, or alternatively by any other means giving a good surface finish such as laser, for example piece or cutter; - assembly of the frame, the glass paste and the cell (the glass paste is for example a mixture of Schott G018-311 glass powder, an ethanol solvent and a terpineol-type binder), being specified that the glass is deposited on the frame using a robot on the areas between two grooves for the first face and after drying in the open air for a few hours, the glass is deposited on the second face; mounting of the gasket thus obtained within the stack of the electrochemical device (see FIG. 1) at a temperature of the order of 900 ° C. (this temperature depends on the glass chosen, the temperature range to be used being given by the glass manufacturer) to melt the glass and put it in place. For this purpose, a charge of a few kPa is applied to the stack indifferently before or after the heating to set up the contact elements 3 and 4 of Figure 1. A small part of this load is used to put the glass in place since, the glass is not rigid at these temperatures, it offers only a very low resistance to crushing. The charge is maintained throughout the rest of the test, then the stack is cooled to its operating temperature (for example 800 ° C) to allow its operation. It should be noted that the use of a frame according to a given cutout 5 makes it possible to easily obtain a core supporting the glass-based sealing means forming a seal according to the invention, which makes it possible in particular to finely control the height of each glass partition by decreasing this height and, therefore, improve gasket effectiveness in terms of gas tightness compared to that achieved with larger glass heights. In addition, the use of a support frame according to the invention allows alternating barriers consisting of a glass partition and a glass-mica composite. The Applicant has demonstrated that these successive barriers have a positive effect on the gastightness in that they allow the loss of a barrier without loss of seal at the entire joint. FIG. 12 illustrates a test according to the invention carried out on a "SOEC" device with a 120 × 120 mm 2 cell, which consisted in imposing a current on a "SOEC" device comprising this cell, which was provided with a seal 80 according to the invention to frame 84 incorporating a glass bulkhead 87 and tabs 83. The excellent seal obtained allowed to send 100% of the gas sent to the cell. Thus, the current / voltage curve visible in FIG. 13 was obtained. It should be noted that if a portion of the gas sent did not reach the cell, then the curve IV would not be linear, contrary to what is shown in FIG. FIG. 13. The theoretical amount of dihydrogen (H2) produced as a function of the imposed stream was easily calculated, and the amount of dihydrogen recovered was measured. It turns out that 100% of the hydrogen produced was recovered even under 500 mbar (50000 Pa) of overpressure, as can be seen in FIG. 14. This test was carried out under more than 200 mbar (ie more than 20 000). Pa) for more than 400 hours of operation and the sealing was maintained during this time without it being altered. The seals obtained were therefore excellent. In addition, these seals have withstood more than 500 mbar (more than 50000 Pa) overpressure for several hours. Therefore, the test was stopped without these 50000 Pa overpressure have caused a loss of tightness. As shown in FIG. 14, 100% of the dihydrogen produced during an IV test is recovered under 50000 Pa of overpressure. The Applicant has shown in the photograph of FIG. 15 the "barrier" effect of the mica-glass composite gasket according to this example a. o of the invention during the dismantling of the cell used for this test. It can be seen in this figure 15 that: the dihydrogen colors the mica in gray / white. Thus, a white mica testifies to a hydrogenated atmosphere; and that the two chambers H2 and O2 are tight with respect to each other, since the hydrogen passes the first glass barrier in the retaining tongue but does not pass the second barrier (if a hydrogen leakage had existed, the mica would have been entirely colored, the dihydrogen diffusing very easily).
    权利要求:
    Claims (13)
    [0001]
    CLAIMS1) Gasket (13, 14, 15, 20, 30, 40, 50, 60, 70, 80) usable to be mounted in contact with two metal surfaces (7, 8, 9, 10, 11, 12, 28 and 29) of an electrochemical device (1) in particular of solid oxide fuel cell ("SOFC") type or high temperature solid oxide water vapor electrolyzer ("SOEC"), the seal comprising: sealing means (21) for sealing the joint comprising at least one glass-ceramic material, and electrically insulating support means (24, 34, 44, 54, 64, 74, 84) which supports the means sealing and which has two main faces (22 and 23) parallel, an outer peripheral edge (22a) and an inner peripheral edge (23a), the seal being adapted to be mounted against these surfaces by these main faces, which are covered at least partially of the sealing means, characterized in that the sealing means partitioning the support means between said inner peripheral edge and said outer peripheral edge by continuously extending from one of said major faces to the other through the support means, whereby the sealing means directly connects these worn to each other.
    [0002]
    2) A seal (13, 14, 15, 20, 30, 40, 50, 60, 70, 80) according to claim 1, characterized in that the support means (24, 34, 44, 54, 64, 74, 84) comprises a one-piece frame of a porous material which is machined to define surfaces pierced through the frame forming at least one through-channel (25 and 26, 35 and 36) of predetermined geometry receiving the sealing means ( 21), said at least one channel filled with the sealing means forming at least one watertight bulkhead (27, 37 and 38, 47 and 48, 57 and 58, 67 and 68, 77, 87) extending continuously from the one of said main faces (22) to the other (23).
    [0003]
    3) seal (13, 14, 15, 20, 30, 40, 50, 60, 70, 80) according to claim 2, characterized in that said surfaces of said at least one channel (25 and 26, 35 and 36) are generally perpendicular to said main faces (22 and 23) and extend in a generally concentric peripheral direction to said peripheral inner (23a) and outer (22a) edges, continuously or discontinuously along said peripheral direction, tongues (33 , 43, 53, 63, 83) constituted by said frame (24, 34, 44, 54, 64, 74, 84) being formed on either side of said at least one channel for connecting the latter to the rest of the frame or to another said adjacent channel, each tab having a volume smaller than that of said at least one channel.
    [0004]
    4) Joint (40, 60) according to claim 3, characterized in that said tongues (43, 63) are angularly radially offset on either side of said at least one channel (25, 26), for example according to a staggered arrangement, so as to maximize the length of the gas path distributed by interconnectors (28 and 29) formed by said scopes and / or pressure drops for these gases through said porous material of said frame (44, 64). 20
    [0005]
    5) Joint (80) according to claim 3 or 4, characterized in that said at least one watertight partition (87) extends continuously in said peripheral direction, said tongues (83) extending from both sides. other of said at least one channel respectively to said outer peripheral edge (22a) and to said inner peripheral edge (23a).
    [0006]
    6) Joint (20) according to claim 5, characterized in that it comprises at least two said bulkheads (27) concentric which are connected two by two together by said radial tabs (83). 30
    [0007]
    7) Joint (30, 40, 50, 60, 70) according to claim 3 or 4, characterized in that said at least one watertight bulkhead (47 and 48, 57 and 58, 67 and 68, 77) extends from discontinuously in said at least one peripheral direction by forming a plurality of partition portions (47 and 48, 57 and 58, 67 and 68, 77).
    [0008]
    8) seal (30, 40, 50, 60) according to claim 7, characterized in that it comprises at least two said bulkheads (47 and 48, 57 and 58, 67 and 68) formed each of said plurality of portions of partitioning (47 and 48, 57 and 58, 67 and 68) housed in said channels passing through said frame (34, 44, 54, 64) which are machined in curvilinear, rectilinear, wavy and / or line-like geometries broken and which are filled with sealing means (21), these partitioning portions being connected two by two in the peripheral direction by said tabs (33, 43, 53, 63).
    [0009]
    9) Joint (70) according to claim 7, characterized in that it comprises a plurality of said bulkheads (77) which are respectively formed of a plurality of holes (75) passing through said frame (74) for example cylindrical, which form said channels (75) machined at regular intervals between said inner peripheral edge (23a) and said outer peripheral edge (22a) and which are filled with the sealing means (21).
    [0010]
    10) Seal (13, 14, 15, 20, 30, 40, 50, 60, 70, 80) according to one of the preceding claims, characterized in that the sealing means (21) is based on glass or glass ceramic and in that the support means (24, 34, 44, 54, 64, 74, 84) consists of a machined sheet of a porous material selected from the group consisting of porous ceramics and porous minerals, of preferably mica.
    [0011]
    11) A method for manufacturing and assembling a seal (13, 14, 15, 20, 30, 40, 50, 60, 70, 80) according to one of the preceding claims in an electrochemical device (1), in particular of the type solid oxide fuel cell ("SOFC") or high temperature solid oxide water vapor electrolyser ("SOEC"), characterized in that the method comprises: a) machining of the support means (24, 34, 44, 54, 64, 74, 84) for piercing said at least one channel (25 and 26, 35 and 36) between said inner peripheral edge (23a) and said outer peripheral edge (22a) which extends continuously from the one of said main faces (22) to the other (23) through the support means, b) a deposit of the sealing means (21), such as a glass paste, on said main faces and in said at least one channel for obtaining a blank of the joint before assembly, c) a joint assembly within a stack of at least one cell (2) of the dispositi f at a temperature between 600 ° C and 900 ° C and under an applied pressure of several kPa, to melt the sealing means while putting it in place.
    [0012]
    An electrochemical device (1) of the solid oxide fuel cell ("SOFC") type or high temperature solid oxide water vapor electrolyser ("SOEC"), the device comprising: - at least one cell ( 2) which comprises a hydrogen electrode-electrolyte-oxygen electrode assembly and which delimits two chambers (5 and 6), - at least two electrical contact elements (3 and 4) with said at least one cell respectively positioned in contact with each other. Said electrodes, at least two metal surfaces (7, 8, 9, 10, 11, 12, 28 and 29) forming interconnectors which distribute in said at least one cell an electric current and gases such as steam, water, dioxygen, dihydrogen and optionally a carrier gas and which, in the case of several said cells, provide the junction between these, and - seals (13, 14, 15, 20, 30, 40, 50, 60, 70, 80) which are each mounted to the con tact of a pair of said interconnectors, characterized in that at least one of said joints is according to one of claims 1 to 10.
    [0013]
    13) Electrochemical device (1) according to claim 12, characterized in that all of said seals (13, 14, 15, 20, 30, 40, 50, 60, 70, 80) are electrically insulating and include first seals (13) sealing between the chambers of said at least one cell (2), second seals (14) sealing between respective inlet and outlet gas feeds and third seals ( 15) sealing said at least one cell with the outside atmosphere, said second and third seals being according to one of claims 1 to 10.
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    同族专利:
    公开号 | 公开日
    US20160285113A1|2016-09-29|
    JP2017504929A|2017-02-09|
    DK3078071T3|2019-03-18|
    EP3078071B1|2018-11-28|
    US10651482B2|2020-05-12|
    CA2928784A1|2015-06-11|
    JP6572210B2|2019-09-04|
    EP3078071A1|2016-10-12|
    FR3014246B1|2016-01-01|
    WO2015083076A1|2015-06-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20040048137A1|2002-04-26|2004-03-11|Yeong-Shyung Chou|Advanced mica based seal and methods for making and using|
    US20100285394A1|2006-08-28|2010-11-11|Lee Jong-Ho|Hybrid sealing composite for flat solid oxide fuel cell stack|
    FR2988916A1|2012-03-27|2013-10-04|Commissariat Energie Atomique|SEALANT PRESERVING THE INTEGRITY OF ELECTROCHEMICAL CELLS, AND METHODS OF MAKING AND USING SAME|FR3056337A1|2016-09-22|2018-03-23|Commissariat A L'energie Atomique Et Aux Energies Alternatives|WATER ELECTROLYSIS REACTOROR FUEL CELLAT RATES OF USE OF WATER VAPOR OR RESPECTIVELY FUEL INCREASE|
    WO2019122631A1|2017-12-19|2019-06-27|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Interconnector with a rugged surface state for ensuring tightness|NL49618C|1936-05-14|
    JPH0582145A|1991-09-19|1993-04-02|Mitsubishi Heavy Ind Ltd|Seal material for fuel cell|
    DE10116046A1|2001-03-30|2002-10-24|Elringklinger Ag|poetry|
    CA2511673C|2002-12-24|2012-01-31|Global Thermoelectric Inc.|High temperature gas seals|
    US7470640B2|2006-04-11|2008-12-30|Corning Incorporated|Glass-ceramic seals for use in solid oxide fuel cells|
    DE102006058335A1|2006-12-11|2008-06-12|Staxera Gmbh|Fuel cell stack and gasket for a fuel cell stack and their manufacturing process|
    CA2724572A1|2008-06-17|2009-12-23|Battelle Memorial Institute|Sofc double seal with dimensional control for superior thermal cycle stability|
    US20130196253A1|2012-01-31|2013-08-01|Delphi Technologies, Inc.|Fuel cell stack having interlocking features to enhance adhesion of glass seal to sealing surfaces|JP6795894B2|2016-02-17|2020-12-02|株式会社チノー|How to assemble the electrochemical cell evaluation holder|
    FR3074970B1|2017-12-13|2019-12-06|Commissariat A L'energie Atomique Et Aux Energies Alternatives|ELECTROCHEMICAL REACTOR WITH HIGH TEMPERATURE PROTON EXCHANGE MEMBRANE SUITABLE FOR LOW TEMPERATURE STORAGE|
    FR3113443A1|2020-08-11|2022-02-18|Commissariat A L'energie Atomique Et Aux Energies Alternatives|Electrolysis or co-electrolysis reactoror fuel cellwith stacking of electrochemical cells by pre-assembled modules, associated production method.|
    法律状态:
    2015-12-31| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-29| PLFP| Fee payment|Year of fee payment: 4 |
    2018-01-02| PLFP| Fee payment|Year of fee payment: 5 |
    2018-12-31| PLFP| Fee payment|Year of fee payment: 6 |
    2019-12-31| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-28| PLFP| Fee payment|Year of fee payment: 8 |
    2021-12-31| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362100A|FR3014246B1|2013-12-04|2013-12-04|SEAL FOR ELECTROCHEMICAL DEVICE, METHOD FOR MANUFACTURING AND ASSEMBLING JOINT, AND DEVICE.|FR1362100A| FR3014246B1|2013-12-04|2013-12-04|SEAL FOR ELECTROCHEMICAL DEVICE, METHOD FOR MANUFACTURING AND ASSEMBLING JOINT, AND DEVICE.|
    DK14821853.0T| DK3078071T3|2013-12-04|2014-12-02|SEALING CONNECTION TO AN ELECTROCHEMICAL DEVICE AND PROCEDURE FOR MANUFACTURING AND ASSEMBLY OF THE CONNECTION AND DEVICE|
    PCT/IB2014/066518| WO2015083076A1|2013-12-04|2014-12-02|Seal for an electrochemical device, process for manufacturing and fitting the seal and this device|
    JP2016531989A| JP6572210B2|2013-12-04|2014-12-02|Seals for electrochemical devices, methods for manufacturing and fitting seals and the devices|
    CA2928784A| CA2928784A1|2013-12-04|2014-12-02|Seal for an electrochemical device, process for manufacturing and fitting the seal and this device|
    US15/037,158| US10651482B2|2013-12-04|2014-12-02|Electrochemical cell carrier seal and processes for manufacturing and fitting said seal|
    EP14821853.0A| EP3078071B1|2013-12-04|2014-12-02|Seal for an electrochemical device, process for manufacturing and fitting the seal and this device|
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