EP2353202A1 - Plaque d'electrolyte a rigidité augmentée, et systeme electrochimique comportant une telle plaque d'électrolyte - Google Patents
Plaque d'electrolyte a rigidité augmentée, et systeme electrochimique comportant une telle plaque d'électrolyteInfo
- Publication number
- EP2353202A1 EP2353202A1 EP09745023A EP09745023A EP2353202A1 EP 2353202 A1 EP2353202 A1 EP 2353202A1 EP 09745023 A EP09745023 A EP 09745023A EP 09745023 A EP09745023 A EP 09745023A EP 2353202 A1 EP2353202 A1 EP 2353202A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ribs
- plate
- face
- electrolyte plate
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
- H01M8/1006—Corrugated, curved or wave-shaped MEA
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/122—Corrugated, curved or wave-shaped MEA
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an electrolyte plate with improved rigidity for fuel cells and for electrolysers, more particularly for high temperature fuel cells, type SOFC ("Solid oxide fuel cell”) and for high temperature electrolysers ( EHT).
- type SOFC Solid oxide fuel cell
- EHT high temperature electrolysers
- the electrolyte is ceramic.
- the life of a high temperature fuel cell or a high temperature electrolyzer is conditioned, in particular, by the mechanical strength of each cell, and more particularly by the mechanical strength of the electrolyte in the case of electrolyte cells. supports.
- the cells are subjected to mechanical loading during manufacture and during operation of the electrochemical system.
- mechanical loading is applied to the stack along its axis, during assembly of the electrochemical system.
- This Mechanical loading can be achieved by applying a predetermined force. This force will generate stresses and deformations in the system, especially at the cell level. Stresses that are too high can cause damage to the various layers, or even a break.
- the operation at high temperature strongly solicits the different layers. The damage of the different layers can reduce the performance of the electrochemical system, or even completely prevent its operation.
- a ceramic electrolyte plate for fuel cell or electrolyser of substantially planar shape having on both sides projections in the form of straight or curved lines.
- a plate having, on its two faces of larger surface, a structured relief in lines is produced, which makes it possible to increase significantly the rigidity of the electrolyte, and therefore of the cell as a whole.
- By loading imposed force it allows to lower the constraints suffered by the cell, and possibly to control the distribution.
- the lifetime of the electrochemical system composed of such cells is then increased.
- the projections of one face are in the form of straight lines parallel to each other, the projections of the other face are in the form of straight lines parallel to each other, the direction of the projections of a face then forms an angle with the direction of the projections on the other side.
- the main subject of the present invention is therefore an electrolyte plate for an electrochemical system comprising a first and a second opposite face of larger surfaces, each of these faces comprising ribs.
- the ribs of the first face are linear and substantially parallel to each other and the ribs of the second face are linear and substantially parallel to each other.
- the ribs of the first face may be substantially parallel to the ribs of the second face.
- Each rib of the second face may be contained in a plane orthogonal to the median plane of the plate containing a rib of the first face.
- the ribs of the first face are linear and form an angle with the ribs of the second face.
- the angle between the ribs of the first face and the ribs of the second face is between 60 ° and 90 °, and more preferably is equal to 90 °.
- the distance separating the ribs is advantageously very large relative to the transverse dimension of the ribs, the ratio between said distance and the transverse dimension being for example between 1 and 33, and preferably between 2 and 5.
- the ribs advantageously represent between 2% and 50% of the surface of a face, more particularly the ribs represent between 15% and 25% of the surface of a face.
- the electrolyte plate according to the present invention may have a thickness e between
- the present invention also relates to an electrochemical system comprising at least one cell comprising an electrolyte plate according to the present invention, an anode on one of the first and second faces and a cathode on the other of its faces.
- the electrochemical system may include a plurality of cells connected in series or in parallel by interconnecting plates disposed between an anode of a cell and a cathode of an adjacent cell.
- the electrochemical system can be a fuel cell, for example high temperature, type SOFC, or an electrolyzer, for example high temperature.
- FIG. 1 is a perspective view of an embodiment of an electrolyte plate according to the present invention.
- FIG. 2 is a sectional view along the plane A-A of the plate of FIG. 1;
- FIG. 3 is a perspective view of an alternative embodiment of an electrolyte plate of FIG. 1;
- FIG. 4 is a perspective view of another alternative embodiment of an electrolyte plate of FIG. 1;
- FIG. 5 is a perspective view of a particularly advantageous embodiment of an electrolyte plate according to the present invention
- FIGS. 6A and 6B respectively show the distribution of the stresses on a plate without relief and on a plate of FIG. 6,
- FIG. 7 is a longitudinal sectional view of a stack comprising electrolyte plates of FIG. 5.
- electrolyte plates that will be described have a rectangular parallelepiped shape, however, it is understood that plates having a disk shape or any other shape are not outside the scope of the present invention.
- an electrolyte plate 2 has a substantially planar shape of average plane P.
- the material of the electrolyte plate 2 is a ceramic.
- the plate 2 has the shape of a rectangular parallelepiped having a thickness e small compared to its width L and to its length 1.
- the plate has two faces 4 and 6 of larger surface, opposite to the average plane P.
- These two faces 4, 6 are intended to be facing one of anode and the other of a cathode, as can be seen in FIG.
- each face 4, 6 has a relief distributed over their entire surface.
- the relief is composed of linear ribs 8, 10 extending from one edge 2.1 of the plate to an opposite edge 2.2 of the plate.
- the ribs 4, 6 extend along the width.
- ribs in the present invention means lines protruding from the faces of the electrolyte plate, the lines being straight or curved. In the examples shown, the projecting lines are straight, but lines closed on themselves to form circles or broken lines forming zigzags are not outside the scope of the present invention. In the example shown, the ribs 8,
- the ribs 8 of the face 4 form pairs with the ribs 10 of the face 6, each pair of ribs being contained in a plane Q orthogonal to the plane P. This provision is also not limiting.
- a rib seen in cross section has a trapezoidal section isosceles, but it is understood that a rib having any trapezoidal section, a square section, rectangular or even a semicircle is not beyond the scope of the present invention.
- the trapezoidal section has a height H1, a small base of length L2, a large base of length L2 + 2L1.
- the ribs are distributed evenly on the faces 4, 6. The distance separating two edges of adjacent ribs is L3 and is constant over the entire plate.
- the thickness of the electrolyte plate varies. Indeed, it has a thickness e in the zones without rib and a thickness e 'at the ribs, e' being equal to e + 2Hl, the height of the two ribs adding to the thickness of the plate. It is then advantageous to have a very large dimension L3 in front of the other dimensions to reduce the electronic resistance of the plate.
- the ratio L3 / (L2 + 2L1) is between 1 and 33, and preferably between 2 and 5.
- the plate 102 has ribs 108, 110 extending along the length of the plate and no longer along its width.
- the orientation of the ribs, according to the length ( Figure 3) or the width ( Figure 1) is chosen according to the type of effort applied, as we shall see later.
- the ribs, and more generally the reliefs on both sides have the effect of increasing significantly the rigidity of the electrolyte plate without significantly increasing the thickness of the plate, which would be detrimental to the electronic resistance.
- E equi apparent equivalent stiffnesses
- the rigidity of a material is characterized by the linear relationship between the stress ⁇ applied and the elastic deformation ⁇ resulting from this stress.
- the Young's modulus E corresponds to the slope of this line.
- Ll (mm) L2 (mm) L3 (mm) Hl (mm) E e which Variation
- the present invention therefore makes it possible to produce more rigid plates while limiting their thickness.
- a plate 302 according to the invention can be seen in which the ribs 308, 310 of the two faces 304, 306 are no longer contained two by two in planes orthogonal to the median plane of the plate, but the ribs 308 and the ribs 310 are offset relative to each other, for example a half-step.
- FIG. 5 shows another embodiment of an electrolyte plate 402 according to the present invention, in which the ribs 408 situated on a face 404 do not have the same direction as the ribs 410 situated on the Another face 410.
- the ribs 408 are substantially parallel to each other, the ribs 410 are also substantially parallel to each other, and the ribs 408 form an angle with the ribs 410.
- the angle is advantageously between 60 ° and 90 °, and is preferably 90 °, as shown in Figure 4 in which the ribs 408 and the ribs 410 form an angle of 90 ° between them, drawing a lattice with square mesh. But it is understood that ribs intersecting at any angle in the range] 0; 90] is not outside the scope of the present invention. A lattice with lozenge mesh or parallelogram shape would then be defined.
- the ribs 408 of the upper face extend along the length and the ribs 410 of the underside extend along the width. But it can be provided that the ribs 408 of the upper face extend along the width and the ribs 410 of the lower face extend along the length.
- the apparent rigidity measured is equal to 264.5 GPa, which corresponds to an increase of 32%.
- FIG. 5 has the advantage over the configurations of FIGS. 1 and 2 of providing the same apparent rigidity as the biasing, both in the width direction and in the direction of the length of the plate. .
- the plate deforms homogeneously, which limits the risk of damage.
- the plates of Figures 1 and 2 offer different stiffnesses in the direction of stress.
- the cross configuration of Figure 5 provides increased stiffness of 30% in both directions, relative to a flat face plate.
- the plate according to Fig. 1 exhibits a 19% increase in stiffness for a bias in the length direction
- the plate according to Fig. 2 provides a 42% increase in the length direction.
- these plates are stressed in the width and not in the length, their apparent rigidity will vary: it will increase for the plate of Figure 1 and lower for the plate 2. Therefore, if the plates are requested in the two directions simultaneously with the same force, the difference in rigidity will lead to non-homogeneous deformation of the plate, which avoids the plate according to the present invention.
- FIGS. 6A and 6B show the distribution of stresses within a plate of the state of the art 502 and within a plate 402 of FIG. 5 according to the invention.
- the maximum stress values are in the ribs 408.
- the volume of the overloaded parts is therefore small.
- the present invention then makes it possible to modify the distribution of constraints within a cell.
- the location of the maximum stresses is shifted from the center of the plate to the ribs.
- the following dimensions can be given:
- the thickness e may be between 25 ⁇ m and 2 mm, and preferably may be equal to 200 ⁇ m; the height H1 of the ribs may be between 5 ⁇ m and 1.5 mm, and preferably may be equal to 50 ⁇ m; the dimension L1 may be between 10 ⁇ m and 1 mm, and preferably may be equal to 50 ⁇ m; the dimension L2 may be between 10 ⁇ m and 1 mm, and preferably may be equal to 350 ⁇ m; the dimension L3 may be between 10 ⁇ m and 1 mm, and preferably may be equal to 50 ⁇ m; it being understood that the quantities Ll, L2 and L3 preferably satisfy the relation: 1 ⁇ L3 / (L2 + 2L1) ⁇ 33
- An electrolyte plate may have the following external dimensions: in the case of a polygonal plate, it may be square in shape, the sides of which measure 150 mm. In the case of a disk-shaped plate, it may be of a diameter equal to 120 mm.
- the ceramic electrolyte plate may be made of ytered zirconia (YSZ), the oxygen electrode may be strontium doped lanthanum chromite (LSM), and the H2 electrode may be a cermet. nickel / ytered zirconia (Ni-YSZ).
- the material of the electrolyte plate may also be 8YSZ, 3YSZ, 10ScSZ, 1OScICeSZ, 1OScIASZ, 1OScIYSZ, 5YbSZ, BCY, BCZY, BCG, BZY, BCZG.
- the design of the shape of the plate, including the arrangement, distribution and dimensions of the relief can be obtained by finite element calculation.
- the electrolyte plate can be made according to the known techniques, for example by strip casting of a suspension of 3YSZ.
- the thickness of the front plate structuring takes into account the relief to be made, for example the height of the ribs.
- the structuring of the faces of the plate is carried out "raw" (that is to say before sintering), for example by means of a laser device whose movement can be programmed using a computer.
- the power of the beam should be sufficient to dig the surface without breaking the cell.
- a first structuring is performed on a first face, then the electrolyte plate is returned to allow structuring of the other side.
- the following steps are those of a conventional method of producing a cell, in particular the electrolyte plate is then sintered, then the electrodes are made, for example by screen printing, and then sintered in turn.
- the invention does not therefore imply a major modification of the manufacturing process of the cells since it only requires the addition of a single step: the structuring by laser beam.
- FIG. 7 shows an exemplary SOFC cell according to the present invention comprising a stack of C1, C2 cells each comprising a structured electrolyte plate similar to that of FIG. 5, an anode 14 and a cathode 16. cells are connected in series by interconnecting plates 18.
- the cells could also be connected in parallel.
- An electrolyser according to the present invention is of similar design to that of the battery of FIG. It is understood that the ribs of the same face may not have the same dimensions, as well as from one face to another.
- An SOFC cell can be used for the cogeneration of electricity and heat with high energy efficiency.
- An electrolyser according to the invention can be used for the production of dihydrogen with a good yield
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0857406A FR2938121B1 (fr) | 2008-10-30 | 2008-10-30 | Plaque d'electrolyte a rigidite augmentee, et systeme electrochimique comportant une telle plaque d'electrolyte |
PCT/EP2009/064192 WO2010049441A1 (fr) | 2008-10-30 | 2009-10-28 | Plaque d'electrolyte a rigidité augmentée, et systeme electrochimique comportant une telle plaque d'électrolyte |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2353202A1 true EP2353202A1 (fr) | 2011-08-10 |
Family
ID=40352241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09745023A Withdrawn EP2353202A1 (fr) | 2008-10-30 | 2009-10-28 | Plaque d'electrolyte a rigidité augmentée, et systeme electrochimique comportant une telle plaque d'électrolyte |
Country Status (4)
Country | Link |
---|---|
US (1) | US8889313B2 (fr) |
EP (1) | EP2353202A1 (fr) |
FR (1) | FR2938121B1 (fr) |
WO (1) | WO2010049441A1 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CL2009000893A1 (es) * | 2009-04-14 | 2009-08-28 | Ancor Tecmin S A | Estructura isobarica autosoportante conformada por un marco estructural hueco formado por tres materiales con un nucleo termoplastico hueco recubierto con capas de mantas de fibras de vidrio saturadas con resina, las que se cubren con un material compuesto polimerico termoestable, conformando un compuesto estructural resistente monolitico. |
FR2969179B1 (fr) | 2010-12-20 | 2013-02-08 | Commissariat Energie Atomique | Cellule de production d'hydrogene comprenant une cellule d'electrolyseur de la vapeur d'eau a haute temperature. |
FR2972572B1 (fr) | 2011-03-09 | 2013-04-12 | Commissariat Energie Atomique | Procede de preparation d'une electrode a air, ladite electrode ainsi obtenue et ses utilisations |
JP5554740B2 (ja) * | 2011-03-30 | 2014-07-23 | 株式会社日本触媒 | 固体酸化物形燃料電池用電解質シート |
FR2974452B1 (fr) | 2011-04-22 | 2014-04-04 | Commissariat Energie Atomique | Procede de preparation d'une demi-cellule electrochimique |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07161368A (ja) * | 1993-12-10 | 1995-06-23 | Yamaha Motor Co Ltd | 燃料電池 |
US6835488B2 (en) * | 2000-05-08 | 2004-12-28 | Honda Giken Kogyo Kabushiki Kaisha | Fuel cell with patterned electrolyte/electrode interface |
KR100409042B1 (ko) | 2001-02-24 | 2003-12-11 | (주)퓨얼셀 파워 | 막전극 접합체와 그 제조 방법 |
FR2828769A1 (fr) * | 2001-12-21 | 2003-02-21 | Commissariat Energie Atomique | Element de base d'une pile a combustible avec electrolyte tridimensionnel et son procede de fabrication |
US7067208B2 (en) | 2002-02-20 | 2006-06-27 | Ion America Corporation | Load matched power generation system including a solid oxide fuel cell and a heat pump and an optional turbine |
US7045234B2 (en) | 2002-08-14 | 2006-05-16 | Hewlett-Packard Development Company, L.P. | Fuel-cell integral multifunction heater and methods |
US7959780B2 (en) * | 2004-07-26 | 2011-06-14 | Emporia Capital Funding Llc | Textured ion exchange membranes |
-
2008
- 2008-10-30 FR FR0857406A patent/FR2938121B1/fr not_active Expired - Fee Related
-
2009
- 2009-10-28 EP EP09745023A patent/EP2353202A1/fr not_active Withdrawn
- 2009-10-28 US US13/126,602 patent/US8889313B2/en not_active Expired - Fee Related
- 2009-10-28 WO PCT/EP2009/064192 patent/WO2010049441A1/fr active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2010049441A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2938121A1 (fr) | 2010-05-07 |
US8889313B2 (en) | 2014-11-18 |
WO2010049441A1 (fr) | 2010-05-06 |
FR2938121B1 (fr) | 2011-04-01 |
US20110229786A1 (en) | 2011-09-22 |
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