Patent Grant
10991956
The present invention relates to the field of solid oxide fuel cells (SOFCs) and that of high-temperature electrolysis of water (HTE, acronym for “high-temperature electrolysis” or else HTSE, acronym for “high-temperature steam electrolysis”) or of co-electrolysis of steam and carbon dioxide CO2, also using solid oxides (SOEC, acronym for “solid oxide electrolysis cell”).
The invention relates more particularly to a new design for the distribution of gases within a high-temperature water electrolysis or co-electrolysis (HTE) reactor of SOEC type, or a fuel cell of SOFC type, containing a stack of individual electrochemical cells, which makes it possible to attain high rates of use respectively of steam H2O or of fuel.
Although it is described mainly with reference to the application of high-temperature water electrolysis, the invention also applies to an SOFC fuel cell supplied with hydrogen H2 and/or with methane CH4 as fuel, and with air or oxygen O2 or air as oxidizer.
The electrolysis of water is an electrolytic reaction that decomposes water into gaseous dioxygen and dihydrogen by means of an electrical current, according to the reaction:
H2O→H2+½O2.
It is advantageous to carry out the electrolysis of water at high temperature, typically between 600 and 1000° C., as some of the energy required for the reaction can be supplied by heat, which is less expensive than electricity, and activation of the reaction is more efficient at high temperature and does not require a catalyst. It is known to use an SOEC (acronym of “solid oxide electrolysis cell”) electrolyzer to implement high-temperature electrolysis, said electrolyzer consisting of a stack of individual units that each comprise a solid oxide electrolysis cell, consisting of three anode/electrolyte/cathode layers superposed on one another, and of interconnecting plates made of metal alloys, also referred to as bipolar plates or interconnectors. The function of the interconnectors is both to let electric current pass and gases flow in the vicinity of each cell (injected steam and extracted hydrogen and oxygen in an HTE electrolyzer; injected air and hydrogen and extracted water in an SOFC fuel cell) and to separate the anode and cathode compartments, which are the gas-flow compartments on the anode side and the cathode side of the cells, respectively. To carry out high-temperature electrolysis (HTE) of steam, steam (H2O) is injected into the cathode compartment. Under the action of the current applied to the cell, dissociation of the water molecules in the form of steam takes place at the interface between the hydrogen electrode (cathode) and the electrolyte: this dissociation produces dihydrogen gas H2 and oxygen ions. The dihydrogen is collected and discharged at the outlet of the hydrogen compartment. The O2− oxygen ions migrate through the electrolyte and recombine into dioxygen at the interface between the electrolyte and the oxygen electrode (anode).
As shown schematically in
The electrochemical reactions take place at the interface between each of the electron conductors and the ion conductor.
At the cathode 2, the half-reaction is as follows:
2H2O+4e−→2H2+2O2−.
At the anode 4, the half-reaction is as follows:
2O2−→O2+4e−.
The electrolyte 3 inserted between the two electrodes 2, 4 is the site of migration of the O2− ions under the effect of the electrical field created by the difference in potential imposed between the anode 4 and the cathode 2.
As illustrated in brackets in
An individual electrolysis reactor consists of an individual cell as described above, with a cathode 2, an electrolyte 3 and an anode 4, and of two monopolar connectors which provide the electrical, hydraulic and thermal distribution functions.
In order to increase the flow rates of hydrogen and oxygen produced, it is known to stack several individual electrolysis cells on top of one another, separating them with interconnection devices, usually known as bipolar interconnection plates or interconnectors. The assembly is positioned between two end interconnection plates which bear the electrical supplies and gas supplies of the electrolyzer (electrolysis reactor).
A high-temperature water electrolyzer (HTE) thus comprises at least one, generally a plurality of, electrolysis cells stacked on top of one another, each individual cell being formed of an electrolyte, of a cathode and of an anode, the electrolyte being inserted between the anode and the cathode.
The fluidic and electrical interconnection devices, which are in electrical contact with one or more electrodes, generally provide the functions of introducing and collecting electrical current and delimit one or more gas flow compartments.
Thus, a “cathode” compartment has the role of distributing the electrical current and steam and also of recovering the hydrogen at the cathode in contact.
An “anode” compartment has the role of distributing the electrical current and also of recovering the oxygen produced at the anode in contact, optionally with the help of a draining gas.
The interconnector 5 is a component made of metal alloy, which provides the separation between the cathode compartment 50 and anode compartment 51, which are defined by the volumes between the interconnector 5 and the adjacent cathode 2.1 and between the interconnector 5 and the adjacent anode 4.2, respectively. It also provides distribution of the gases to the cells. Injection of steam into each individual unit takes place in the cathode compartment 50. Collection of the hydrogen produced and of the residual steam at the cathode 2.1, 2.2, . . . takes place in the cathode compartment 50 downstream of the cell C1, C2, . . . after dissociation of the steam by the latter. Collection of the oxygen produced at the anode 4.2 takes place in the anode compartment 51 downstream of the cell C1, C2, . . . after dissociation of the steam by the latter.
The interconnector 5 provides the passage of the current between the cells C1 and C2 by contact, preferably direct contact, with the adjacent electrodes, that is to say between the anode 4.2 and the cathode 2.1.
In a solid oxide fuel cell SOFC, according to the prior art, the cells C1, C2, . . . and interconnectors 5 used are the same components, but the operation is the reverse of that of an HTE electrolyzer such as has just been explained, with a reversed current direction, with air or oxygen O2 which supplies what have become cathode compartments and hydrogen and/or methane CH4 as fuel which supplies what have become anode compartments.
Satisfactory operation of an HTE electrolyzer requires, inter alia, the following essential functions:
A/ good electrical insulation between two adjacent interconnectors in the stack, otherwise the individual electrolysis cell inserted between the two interconnectors will be short-circuited,
B/ good leaktightness between the two separate compartments, i.e. anode and cathode compartments, otherwise the gases produced will recombine, resulting in a drop in yield and in particular in the appearance of hot spots which damage the electrolyzer,
C/ good distribution of the gases both at the inlet and on recovery of the gases produced, otherwise there will be a loss of yield, nonuniformity of pressure and nonuniformity of temperature within the various individual cells, or even unacceptable deterioration of the cells.
The high temperatures considerably complicate the fulfillment of the three abovementioned essential functions A/ to C/. In addition, the fragility of the solid oxide cells necessitates certain restrictive design measures so as to guarantee the mechanical integrity thereof.
Various designs already exist for simultaneously achieving the three essential functions A/ to C/.
Indeed, usually, these functions within an EHT electrolyzer are achieved according to the configuration shown schematically in
The top interconnector 5.1 is pierced with a conduit for supplying steam 52, which opens at the periphery of one side of the cathode 2, and with a conduit for recovering the hydrogen produced 54, which opens at the periphery of the cell on the side of the cathode 2 opposite the side on which the supply conduit opens, so as to distribute the steam supplied and the hydrogen produced, in the cathode compartment 50.
The bottom interconnector 5.2 is itself pierced with a conduit for supplying draining gas 53, such as air, on the cell on one side of the anode 4, and with a conduit for recovering the oxygen produced 55, which opens at the periphery of the cell on the side of the anode 4 opposite the side on which the supply conduit opens, so as to distribute the draining gas and the oxygen produced in the anode compartment 51.
A first seal 6 is arranged at the periphery of the individual cell and bears both against the top interconnector 51 and against the bottom interconnector. The role of this seal 6 is to provide leaktightness of the cathode compartment with respect to the outside.
A second seal 7 is arranged at the periphery of the anode 4 of the individual cell and bears both against the bottom interconnector 5.2 and against the electrolyte 3 of the cell. This second seal 7 makes it possible to provide leaktightness between cathode 50 and anode 51 compartments, the oxygen produced O2 and optionally the draining gas circulating within the latter.
Given the high operating temperature ranges of HTE electrolyzers and SOFC fuel cells, typically 600° C. to 1000° C., the seals are conventionally produced based on glass or glass-ceramic. A glass seal is in the pasty state at the operating temperature. At the design stage, it is necessary to take care not to expel the glass under the effect of a pressure difference applied to the seal. A glass-ceramic seal itself undergoes a thermal cycle in situ with the aim of causing it to crystallize and hence of limiting the flow thereof by endowing it with internal rigid elements at the operating temperature. As with the glass seal, it is necessary to take care not to expel the glass-ceramic before it is rigidified. In the configuration shown schematically in
A first electrical contact element 8 is in mechanical contact on the one hand with the interconnector 5.1 and on the other hand with the cathode 2.
A second electrical contact element 9 is in mechanical contact on the one hand with the anode 4 and on the other hand with the bottom interconnector 5.2.
Usually, the contact element 8 is a metal screen made of nickel which has the advantages of being an effective solution for ensuring the electrical continuity between the interconnector and cathode and the flow of the gases, and is relatively inexpensive. The element 9 cannot be a nickel screen since the atmosphere of this chamber is oxidizing and the nickel would be converted very rapidly into nickel oxide which is not conductive. One possible solution is to machine the interconnector 5.2 in order to create channels for distributing the gas between supply conduit 52 and recovery conduit 54.
In the configuration illustrated in
This configuration, with contact screen 8 and first seal 6 between cathode compartment 50 and outside of the stack, has several drawbacks.
Firstly, the inventors have been able to observe that some of the steam which is intended to supply the cathode is in fact not used, i.e. is not converted into hydrogen. Specifically, as illustrated in
Next, the arrangement of the second seal 7 supported by the dense electrolyte 3 at the periphery of the anode 4 places the cell C in an unstable position. This creates flexural stresses which give rise to a tensioning of certain parts of the cell during the clamping of the stack of the electrolyzer. Specifically, the second seal 7 becomes increasingly rigid over time, and the stresses applied to the stack result in tensile stresses due to this flexion which are damaging for each cell. The stresses of the clamping of the stack are represented in
The drawbacks explained above have repercussions for all the individual units of the stack.
There is therefore a need to find a novel configuration of an (HTE) electrolyzer of SOEC type or of a fuel cell of SOFC type with a stack, which makes it possible to achieve the aforementioned functions A/ to C/, in particular by avoiding the drawbacks of the configuration shown schematically in
One aim of the invention is to at least partially meet this need.
Another aim of the invention is to provide a novel configuration of an (HTE) electrolyzer of SOEC type or of a fuel cell of SOFC type which at least partly meets this need and which makes it possible to modify a minimum number of parts for producing the stack compared to those of the prior art.
To this end, the invention relates, in one of its aspects, and according to a first alternative, to a device, intended to form an individual unit of an electrolysis or co-electrolysis reactor of SOEC type, comprising:
a solid oxide individual electrolysis cell formed of a cathode, of an anode and of an electrolyte inserted between the cathode and the anode,
a first and a second electrical and fluid interconnector, each consisting of a component made of electron-conducting and gastight material, the first and second interconnectors being arranged on either side of the individual cell; the first interconnector being pierced with a conduit for supplying steam, which opens at the periphery of one side of the cathode, and with a conduit for recovering the hydrogen produced, which opens at the periphery of the cell on the side of the cathode opposite the side on which the supply conduit opens, so as to distribute the steam supplied and the hydrogen produced, in a compartment; the second interconnector being pierced with a conduit for recovering the oxygen produced, which opens at the periphery of the cell on the side of the anode so as to distribute the oxygen produced to the recovery conduit in a compartment;
a first electrical contact element, different from the interconnectors, which is in mechanical contact on the one hand with the first interconnector and on the other hand with the cathode; the first electrical contact element being a porous substrate.
According to the invention, the device comprises:
a first seal arranged at the periphery of the individual cell and bearing both against the first interconnector and against the second interconnector;
a second seal arranged at the periphery of the anode of the individual cell and bearing both against the second interconnector and against the electrolyte.
a third seal, inserted into the porous substrate of the first contact element, the seal bearing against the first interconnector and the cathode by being arranged at the periphery of the conduits for supplying steam and for recovering the hydrogen produced, respectively, thus delimiting the compartment for distributing the steam supplied and the hydrogen produced.
According to one feature of the invention, the second interconnector may be pierced with a conduit for supplying draining gas, such as air, on the cell on the side of the anode opposite to the side on which the conduit for recovering O2 opens, so as to distribute respectively the draining gas supplied and the oxygen produced, from the supply conduit to the recovery conduit.
According to one advantageous variant, the device comprises a second electrical contact element, which is in mechanical contact on the one hand with the anode and on the other hand with the second interconnector.
Another subject of the invention, according to a second alternative, is a device, intended to form an individual unit of a fuel cell of SOFC type, comprising:
a solid oxide individual electrochemical cell formed of an anode, of a cathode and of an electrolyte inserted between the cathode and the anode,
a first and a second electrical and fluid interconnector, each consisting of a component made of electron-conducting and gastight material, the first and second interconnectors being arranged on either side of the individual cell; the first interconnector being pierced with a conduit for supplying fuel, which opens at the periphery of one side of the anode, and with a conduit for recovering the water produced, which opens at the periphery of the cell on the side of the anode opposite the side on which the supply conduit opens, so as to distribute the fuel supplied and the water produced, respectively, in a compartment; the second interconnector being pierced with a conduit for supplying air or oxygen, which opens at the periphery of the cell on one side of the cathode and with a conduit for recovering the surplus air or oxygen, which opens at the periphery of the cell on the side of the cathode opposite the side on which the supply conduit opens, so as to distribute the air or oxygen to the recovery conduit in a compartment;
a first electrical contact, different from the interconnectors, which is in mechanical contact on the one hand with the first interconnector and on the other hand with the anode; the first electrical contact element being a porous substrate.
According to the invention, the device comprises:
a first seal arranged at the periphery of the individual cell and bearing both against the first interconnector and against the second interconnector;
a second seal arranged at the periphery of the cathode of the individual cell and bearing both against the second interconnector and against the electrolyte;
a third seal, inserted into the porous substrate of the first contact element, the seal bearing against the first interconnector and the anode by being arranged at the periphery of the conduits for supplying fuel and for recovering the water produced, respectively, thus delimiting the compartment for distributing the fuel supplied and the water produced.
The expression “arranged at the periphery of the conduits” is understood here and within the context of the invention to mean arranged at the periphery of the electrode beyond ducts for supplying and recovering the gases, the electrode being the cathode for a (co-)electrolysis reactor and the anode for an SOFC fuel cell.
According to an advantageous embodiment variant, the device comprises a second electrical contact element, which is in mechanical contact on the one hand with the cathode and on the other hand with the second interconnector.
Thus, the invention essentially consists in arranging a new seal, within a porous substrate which forms the contact element of each hydrogen H2 flow electrode (cathode for an SOEC reactor, anode for a fuel cell), and at the periphery of this electrode beyond the conduits for supplying the gas injected and for recovering the gases, in order to force the circulation of said gases into the sole working zone of the cell which corresponds to the electrochemically active surface of the H2 electrode. Thus, all of the gases injected (H2O, H2, CO2, CO, CH4, etc.), supplying either an electrolysis or co-electrolysis reactor, or an SOFC fuel cell, may be converted.
Hence, the maximum degree of conversion of the injected gases is increased, and may reach 100%.
According to one feature of the invention, the first and second seals may each be a bead based on glass and/or on glass-ceramic.
According to one advantageous embodiment of the invention, the seal arranged at the periphery of the conduits is moreover arranged substantially in a vertical line with the second seal, the first contact element being considered to be above the electrolyte, i.e. above the cathode of a (co-)electrolyzer and above an anode of an SOFC fuel cell. This arrangement limits the flexions of the cells in the stack and therefore the detrimental tensile mechanical stresses. Specifically, the porous substrate of the contact element has the same geometric surface area as the H2 electrode, which makes it possible to support the cell and to distribute the stresses over the entire surface thereof. And owing to the fact that the third seal is located in line with the second seal, the cell is no longer in an unstable position, and therefore no flexion is induced over the cells.
Thus, the judiously arranged seal according to the invention makes it possible to overcome the drawbacks of the configurations of an SOEC reactor or an SOFC fuel cell according to the prior art, by increasing the effectiveness of the distribution of the gases and by minimizing the mechanical stresses detrimental to the cells of the stack by limiting the flexions, while guaranteeing a good electrical contact between interconnector and cell.
According to one advantageous variant, the seal at the periphery of the conduits is a bead based on glass and/or on glass-ceramic inserted into the porous substrate of the first contact element. It is particularly advantageous to produce the seal according to the invention from a glass-ceramic bead. A glass-ceramic at room temperature is in the form of a paste which it is easy to cause to penetrate a porous metallic substrate such as a nickel screen. A rise in temperature of the seal to temperatures between 850 and 1000° C. will make it possible to melt the glass-ceramic which will be put in place while hot and conform to the shape of the substrate by filling the porosities, such as the meshes of the nickel screen, according to the continuous profile that it is desired to give thereto in order to obtain a leaktight seal. The temperature increase and decrease rates of the seal are preferably less than 5° C./min.
Once put in place, the seal is crystallized at the operating temperatures of the reactor or the fuel cell, typically between 600 and 850° C., and therefore prevents any passage of injected gases from the supply conduits (H2O, H2, CO2, CO, CH4, etc.) to the non-active zones of the H2 electrode at the periphery of the cells and beyond the conduits for supplying and recovering gases.
One advantageous example of the composition and use of the seal is the one described in patent FR3014246 B1.
According to one distinct variant, the seal at the periphery of the conduits may consist of a bead of solder inserted into the porous substrate of the first contact element. The solder may be inserted into the porous substrate before the positioning in the stack of an SOEC reactor or SOFC fuel cell.
Advantageously, the height of the seal at the periphery of the conduits is substantially the same as that of the porous substrate of the first contact element, while guaranteeing that this seal is indeed in contact with the first interconnector and the cathode of the electrolyzer or anode of the SOFC fuel cell.
Also advantageously, the porous substrate of the first contact element is a metal screen, such as a nickel screen. A nickel screen is a contact solution that is relatively inexpensive and effective as electrical contact element and element for distributing gases. Embedding a seal made of glass or of glass-ceramic or a solder within a nickel screen is not detrimental to the effectiveness of the latter and enables it to indeed remain in contact with the interconnector and the cell throughout the operating time of the SOEC reactor or SOFC fuel cell. In particular, the glass-ceramic retains an ability to be greatly deformed over several hours so as not to hinder the possible deformations of the nickel screen which occur when setting up the electrolyzer. For longer periods, of the order of a day and a week, the glass-ceramic, although rigidified by its internal structure, retains a certain flow capacity which makes it possible to accommodate the deformation of the nickel screen.
According to one advantageous feature, the porous substrate of the first electrical contact element has a surface area substantially identical to that of the electrode with which it is in contact.
More preferably, each interconnector consists of a plate or of an assembly of flat metal sheets, and has a thickness of between 0.1 and 10 mm.
Preferably, the plates or metal sheets constituting the interconnectors are made of ferritic steel containing approximately 20% chromium, preferably made of CROFER® 22APU or F18TNb or AISI 441, or based on nickel of Inconel® 600 or Haynes® type.
Preferably, the individual electrolysis cells are of cathode-supported type. The expression “cathode-supported cell” is understood here and within the context of the invention to mean the definition already given in the field of high-temperature electrolysis HTE of water, and denoted by the acronym CSC for “cathode-supported cell”, that is to say to mean a cell in which the electrolyte and the oxygen electrode (anode) are positioned on the thicker hydrogen electrode (cathode) which thus serves as support.
Another subject of the invention is an HTE electrolysis or co-electrolysis reactor, of SOEC type comprising a stack of a plurality of devices described above.
A final subject of the invention is a fuel cell of SOFC type comprising a stack of a plurality of devices described above.
The invention finally relates to a system comprising an aforementioned (co-)electrolysis reactor, that is able to operate reversibly as a fuel cell as described above and vice versa.
Other advantages and features of the invention will become more clearly apparent on reading the detailed description of examples of implementation of the invention, given by way of nonlimiting illustration with reference to the following figures, in which:
It is specified here that, in
It is also specified that, throughout the application, the terms “above”, “below”, “in a vertical line with”, “vertical”, “lower”, “upper”, “bottom”, “top”, “below” and “above” should be understood with reference to an SOEC electrolysis reactor or an SOFC fuel cell in the vertical configuration in operation, that is to say with the planes of interconnectors and electrochemical cells being horizontal, the O2 electrode below the H2 electrode.
It is also specified that all the electrolyzers described are of solid oxide type (SOEC, acronym of “solid oxide electrolysis cell”) operating at high temperature. Thus, all the constituents (anode/electrolyte/cathode) of an electrolysis cell are ceramics. The high operating temperature of an electrolyzer (electrolysis reactor) is typically between 600° C. and 1000° C.
Typically, the characteristics of an individual SOEC electrolysis cell suitable for the invention, of the cathode-supported (CSC) type, may be those indicated as follows in table 1 below.
All of the
This unit firstly repeats all of the components, with their relative arrangements, of the unit according to
The contact element 8 is here a nickel screen of the same surface area as the cathode 2.
According to the invention, a third seal 10 is provided in addition to the first seal 6 and second seal 7. This third seal 10 is inserted in the nickel screen 8, bears against the top interconnector 5.1 and the cathode 2 by being arranged at the periphery of the conduits for supplying steam 52, and for recovering the hydrogen produced 54, respectively.
The arrangement of the third seal 10 according to the invention thus delimiting the compartment 50 for distributing the steam supplied and the hydrogen produced which is restricted relative to the one from the prior art. Specifically, as shown by the arrows on the figures in
In order to produce the seal 10 according to the invention, a continuous bead of a glass-ceramic in the pasty state is deposited at ambient temperature on the surface of the nickel screen 8. Next, by passing beyond its glass transition temperature, between 850 and 1000° C., the paste melts and fills the meshes of the nickel screen 8 by conforming to the shape thereof. At the operating temperature of the electrolyzer, typically between 600 and 850° C., the glass-ceramic third seal 10 is crystallized.
The seal is deposited using a syringe and a deposition robot. The syringe pressure and the size of the needle are adjustable which makes it possible to obtain a deposited amount over a given time. The speed of advance of the arm of the robot is itself also adjustable. These parameters make it possible to meter the amount of glass/glass-ceramic deposited.
The temperature increase and decrease rates of the seal are preferably less than 5° C. min.
On the contrary, in the case of too low a deposited amount of glass-ceramic, the nickel screen 8 may not be completely leaktight, which would have the consequence of reintroducing at least some of the steam into the zones Z1 as in the prior art.
The inventors experimentally validated the effectiveness of a seal according to the invention.
They thus carried out comparative tests between a high-temperature electrolyzer according to the prior art and an electrolyzer according to the invention with exactly the same components arranged identically, the electrolyzer according to the invention being further provided with a glass seal 10 inserted in a nickel screen 8.
Each of the electrolyzers tested comprises a stack of 25 individual units with, for each cell, an active surface area of 100 cm2.
The flow rates of steam sent to the inlet of electrolyzers are 10.8 Nml/min and per cm2 of active surface area of the stack. Added to this steam is a hydrogen flow rate of 1.2 Nml/min/cm2, also sent to the inlet.
The electrolyzers were tested at an operating temperature of 800° C. The two electrolyzers have excellent leaktightness and 100% of the gases sent to the inlet are recovered at the outlet.
It emerges from this
An electrolyzer consumes the steam sent and converts it into hydrogen. When a polarization curve is produced, the current increases continuously which consumes more and more steam. The rate of use of the steam sent therefore increases during the polarization. When the residual steam in the active zones decreases, then the voltage within the electrolyzer increases greatly. This great increase in the voltage over the polarization curve is a marker indicating that most of the steam present in the active zones has been consumed. This great increase in voltage is referred to as “concentration overvoltage”. For the commercial electrochemical cells of the prior art, if the concentration overvoltages appear for values of less than 90% of the rate of steam use, it may be considered that a portion of the steam is not distributed in the active zones of the electrolyzer and that it is lost for the application.
It emerges from this
The electrolyzer according to the invention itself operates up to rates of use of at least 65% without the appearance of a concentration overvoltage. This tends to prove that the seal 10 according to the invention makes it possible to substantially improve the distribution of the gases within the stack. In this test, the rates of use greater than 65% were not tested. However, the increase of at least 20% in the maximum rate of use is already indicative of a marked improvement in the performance.
An additional test was carried out on another electrolyzer according to the invention with a single individual unit therefore provided with a single electrolysis cell having an active surface area of 100 cm2.
The flow rates injected at the cell inlet are here 10.8 Nml/min/cm2 of active surface area for the steam to which a hydrogen flow rate of 1.2 Nml/min/cm2 is added. The test is also carried out at a temperature of 800° C.
It is observed that this single-unit electrolyzer is perfectly leaktight and 100% of the gases sent are recovered at the outlet.
It emerges from this
Following the tests carried out, it is therefore possible to conclude that the additional seal 10 according to the invention makes it possible to distribute the steam in an optimal manner in the active zones of the cells and that therefore, unlike the configurations according to the prior art, no amount of steam is sent into non-active zones of the electrolyzer, such as the zones Z1 from
The invention is not limited to the aforementioned examples; in particular, features of the illustrated examples may be combined in variants that have not been illustrated.
Other variants and improvements may be envisaged within the context of the invention.
In particular, if the material inserted in the nickel screen 8 is a glass-ceramic in the examples described in detail above, it may be any material that opposes the passage of the gases and that may be readily shaped within a porous metallic substrate of a contact element. It may especially be a solder that seals the screen over its periphery, before or after its my placement within the stack.
Instead of a nickel screen, use may be made of other contact elements containing a porous substrate and that are electron conductors.
| Number | Date | Country | Kind |
|---|---|---|---|
| 16 58906 | Sep 2016 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/073839 | 9/20/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/055011 | 3/29/2018 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20030104262 | Kuroki et al. | Jun 2003 | A1 |
| 20050191539 | Yoshioka et al. | Sep 2005 | A1 |
| 20060275650 | Yamada et al. | Dec 2006 | A1 |
| 20160285113 | Di Iorio et al. | Sep 2016 | A1 |
| 20170362724 | Planque | Dec 2017 | A1 |
| Number | Date | Country |
|---|---|---|
| 1 296 394 | Mar 2003 | EP |
| 1 729 361 | Dec 2006 | EP |
| 3 014 246 | Jun 2015 | FR |
| 3 014 246 | Jan 2016 | FR |
| 2003-17092 | Jan 2003 | JP |
| 2005-243442 | Sep 2005 | JP |
| 2016-81813 | May 2016 | JP |
| Entry |
|---|
| Japanese Office Action dated Jun. 29, 2020 in Patent Application No. 2019-515580 (with English translation), 12 pages. |
| International Search Report dated Oct. 26, 2017 in PCT/EP2017/073839 filed on Sep. 20, 2017. |
| French Preliminary Search Report dated Feb. 8, 2017 in FR1658906 filed on Sep. 22, 2016. |
| Number | Date | Country | |
|---|---|---|---|
| 20190348691 A1 | Nov 2019 | US |
