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• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
  • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
• • 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
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/64—Burning or sintering processes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/8605—Porous electrodes
  • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/88—Processes of manufacture
  • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
  • H01M4/8882—Heat treatment, e.g. drying, baking
  • H01M4/8885—Sintering or firing
• • 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
  • H01M8/02—Details
• • 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
• • 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
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0094—Composites in the form of layered products, e.g. coatings
• • 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
• • 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
  • H01M8/126—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 cerium 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
  • H01M8/1266—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 bismuth 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 the field of solid oxide fuel cell (SOFC), but also the thermal barrier layer and the diffusion layer layer.
• SOFC solid oxide fuel cell
• a SOFC type cell is composed of an electrolyte sandwiched between a cathode and an anode.
• the oxidant, on the cathodic side (air, O 2 ), is reduced by the electrons coming from the anode, and the fuel (CH 4 , H 2 , methanol), anodic side, is oxidized by oxygen ions from the cathode.
• the fuel CH 4 , H 2 , methanol
• anodic side is oxidized by oxygen ions from the cathode.
• one of the two ions formed passes through the electrolyte to react with oxygen or hydrogen and thus form This reaction takes place at high temperature.
• YSZ yttrium zirconia
• cermet for the anode, that is to say a metallic ceramic where nickel is dispersed on stabilized zirconia (Ni-YSZ)
• Ni-YSZ stabilized zirconia
• perovskite of the type La x Sr y MnO 3 for the cathode.
• the high temperature operation of the cells generally between 80O 0 C and 1000 0 C, is imposed by the conduction property of the zirconia yttrié as electrolyte. Indeed, the electrolyte YSZ is certainly a good ionic conductor, but only at high temperature.
• the minimum thicknesses of dense electrolyte obtained by industrial processes are of the order of 10 to 15 micrometers, whereas at the laboratory scale, the best performances obtained with thin layers have been obtained. have been achieved with films 5 microns thick.
• the production of sealed membranes of 1 micron thickness or less and up to 3 micrometers would lower the operating temperature to 500 0 C for YSZ and 250 0 C for Ceo , 9Gdo, 10i, 95 or Nb-doped SrTiO 3 .
• Minh et al (5) have shown that ionic conductivity at grain boundaries is much lower for solid electrolyte materials tested. Thus, by developing crystallographically oriented electrolyte layers, disorientation at the grain boundaries can be greatly attenuated, thereby reducing the ionic conductivity and thereby reducing the resistance of the electrolyte.
• US 5,106,654 describes a method for tuning the expansion coefficients within the structure of an SOFC by the development of a tubular structure, in place of the conventional planar structures.
• Multilayers made from perovskites with a Lai_ x E x CoO.6NiO.4 O3 (E: rare earth) structure are deposited by screen printing and then subjected to heat treatment.
• the present invention is based on the implementation of the technique of deposition by CVD (chemical vapor deposition), and more specifically MO-CVD ("Metal Organic Chemical Vapor Deposition"), for the manufacture on a substrate of a membrane , in particular an electrolyte for SOFC batteries.
• CVD chemical vapor deposition
• MO-CVD Metal Organic Chemical Vapor Deposition
• Such an electrolyte is essentially made of yttriated zirconia (YSZ) but, in an original manner, comprises at least one heterogeneous trilayer of YSZ / X / YSZ sequence.
• the "three-layer” is called the stack of three layers.
• X is a different material from YSZ.
• the substrate on which the deposits are made is advantageously a cermet, in particular of Ni / NiO + YSZ composition.
• the material X deposited between the two layers of YSZ is not YSZ. It is advantageously chosen from the group comprising: Y 2 O 3 , CeO 2 : Gd, SrTiO 3 : Nb, Bi 2 O 3 , or a mixture of these materials.
• CVD deposition employs precursors selected from alkoxide precursors, ⁇ -diketonates, carboxylates, metal salts.
• the precursors used are the following:
• the interface layer between the two layers of YSZ advantageously has a thickness of between 10 and 100 nanometers, more advantageously equal to 50 nanometers.
• this heterostructure undergoes a heat treatment between 650 and 850 0 C, over a period of 1 to 5 hours, under an oxygen atmosphere of between 20 and 100% depending on the duration and temperature of the treatment.
• This allows on the one hand to completely oxygenate the cermet, and on the other hand, to allow the diffusion of the X layer within the two layers of YSZ under-doped X.
• this treatment makes it possible to remove the layer of X as such, and see the creation of a diffuse interface between the two layers of YSZ.
• At least one upper layer is then deposited in situ, without surface pollution. It is advantageously a layer of CeO 2 : Gd (10 to 20% by weight) (FIG 6) and / or STO: Nb (1 to 2% by mass). These two deposits are added in an upper layer and have the function of smoothing the stack.
• the YSZ layers can be obtained by homoepitaxy, consisting in making a stack of at least two layers of a similar nature and structure, the two layers being obtained by the same method.
• the deposit is stopped at the end of the formation of the first layer while maintaining the temperature resistance and under gas flow. This makes it possible to homogenize the grains on the surface of the layer and to repeat the deposit, under good conditions, of a second layer of YSZ on the first layer.
• This method more generally makes it possible to produce multilayer systems, or composites based on metal / oxide or mixed oxides.
• the whole process deposits and heat treatments
• CVD vapor phase
• the method according to the invention therefore leads to the production of a multilayer having at least the YSZ / X / YSZ pattern. Of course, this pattern can be repeated a specified number of times.
• the trilayer can be covered with a top layer of smoothing.
• the electrolyte obtained at the end of the process according to the invention has a total thickness advantageously less than 5 micrometers, even more advantageously less than or equal to 2, or even 1 micrometer.
• An SOFC type cell equipped with an electrolyte according to the invention has an operating temperature of between 500 and 800 ° C.
• Figure 1 schematizes the operating principle of a SOFC stack, through the representation of a single cell.
• FIG. 2 represents the diagram of the structure of the electrolyte of a SOFC cell according to the invention, consisting of a heterogeneous multilayer.
• FIG. 3 represents the schematic diagram of the structure of this same electrolyte, after heat treatment.
• FIG. 4 corresponds to two diffractograms of electrolytes YSZ and YSZAf 2 OsAfSZ on NiO cermet.
• FIG. 5 represents images obtained by scanning electron microscopy
• FIG. 6 is a sectional view of an electrolyte constituted by a heterogeneous multilayer stack according to the invention.
• FIG. 8 illustrates a CVD injection system for implementing the method according to the invention.
• the support consists of a Ni / NiO + YSZ cermet.
• the CVD deposition is performed using the CVD injection system (DLI-MOCVD for "Direct Liquid Injection Metal Organic Chemical Vapor Deposition"), shown in Figure 8.
• DLI-MOCVD Direct Liquid Injection Metal Organic Chemical Vapor Deposition
• a first chemical solution (A) consisting of 5% by weight of Y in Zr in THF is prepared and connected to an injector 1.
• FIG. 4 represents two diffractograms of the layers obtained before heat treatment: on the first, the width of the peaks makes it possible to estimate the size of the grains at 8 nanometers, which implies a greater density. The second makes it possible to verify that it is indeed a tricouche which has been formed.
• Figure 5 shows photos taken before heat treatment. The top views comparing YSZ, YSZAf 2 Os and YSZ / Y 2 OsA 7 SZ reveal that the deposit is smoother in the case of the trilayer.
• a first chemical solution (A) consisting of 8% by weight of Y in Zr in THF is prepared and connected to an injector 1.
• a second chemical solution (B) consisting of Ce (thd) 4 at 0.02M and Gd (thd) at 0.004M in THF is prepared and then connected to an injector 2.
• the growth rate is 2.6 ⁇ m / h
• Figure 7 shows a permeation similar to the best references for a total thickness made by MOCVD of 2 micrometers (instead of 5 micrometers for references).
• the resulting structure is a denser film leading to similar permeation performance for films two to three times finer for pure zirconia, and twice as good for the heterostructure YSZ / CeO 2 : GdAfSZ.
• a first chemical solution (A) consisting of 8% by weight of Y in Zr in THF is prepared and connected to an injector 1.
• the growth rate of 2 ⁇ m / h. 35 drops are injected under an argon flow only, then the reactive vector gas (O 2 ) is introduced gradually. Between the deposits, the injection being stopped, the system is evacuated to 0 Torr (Pa) and the samples undergo a gas flow O 2 / Ar 50/50 for 10 minutes.
• the Sr / Ti ratio is set at 1.28.

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