CA2596173C - A method for producing a reversible solid oxide fuel cell - Google Patents
A method for producing a reversible solid oxide fuel cell Download PDFInfo
- Publication number
- CA2596173C CA2596173C CA2596173A CA2596173A CA2596173C CA 2596173 C CA2596173 C CA 2596173C CA 2596173 A CA2596173 A CA 2596173A CA 2596173 A CA2596173 A CA 2596173A CA 2596173 C CA2596173 C CA 2596173C
- Authority
- CA
- Canada
- Prior art keywords
- layer
- anode
- cathode
- metallic support
- forming
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
-
- 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
-
- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
-
- 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
- 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
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Abstract
The present invention provides a method for producing a reversible solid oxide fuel cell, comprising the steps of: - providing a metallic support layer; -forming a cathode precursor layer on the metallic support layer; - forming an electrolyte layer on the cathode precursor layer; - sintering the obtained multilayer structure; - impregnating the cathode precursor layer so as to form a cathode layer; and - forming an anode layer on top of the electrolyte layer.
Furthermore, a reversible SOFC is provided which is obtainable by said method.
The method advantageously allows for a greater choice of anode materials, resulting in more freedom in cell design, depending on the desired application.
Furthermore, a reversible SOFC is provided which is obtainable by said method.
The method advantageously allows for a greater choice of anode materials, resulting in more freedom in cell design, depending on the desired application.
Description
A method for producing a reversible solid oxide fuel cell Field of the invention The present invention relates to a method for producing a reversible solid oxide fuel cell (SOFC/SOEC) comprising a metallic support, and to a reversible solid oxide fuel cell obtainable by said method.
Background art Solid oxide fuel cells (SOFCs) operate at high temperatures which are generally in the range of about 750 C to about 1000 C. These high temperatures are challenging to the materials employed, and are of particular concern with regard to the stability of the an-ode structures. For fuel oxidation, the so far preferred anode material comprises metallic nickel. Nickel is also preferred for reformed hydrocarbon fuel since it is a good catalyst for hydrocarbon reformation.
Manufacture processes suggested in the prior art include the provision of a support, the formation of an anode layer thereon, followed by the application of an electrolyte layer.
The so formed half cell is dried and afterwards sintered, often in a reducing atmosphere.
Finally, a cathode layer is formed thereon so as to obtain a complete cell.
However, during the sintering of the half cell, undesired reactions between the metal support and anode materials may occur, resulting in a negative impact on the overall cell performance. Moreover, in the prevalent anode supported design, oxidation of the anode is known to be detrimental for the cell performance. The above mentioned method con-stitutes some limitations on the anode material to be used.
US 2002/0048699 discloses a solid oxide fuel cell comprising a ferritic stainless steel substrate including a porous region and a non-porous region bounding the porous re-gion. A ferritic stainless steel bipolar plate is located under one surface of the porous region of the substrate and is sealingly attached to the non-porous region of the sub-strate above the porous region thereof. A first electrode layer is located over the other surface of the porous region of the substrate, an electrolyte layer is located over the first electrode layer and a second electrode layer is located over the electrolyte layer. While such a solid oxide fuel cell is relatively cheap and avoids the use of brittle seals, the SOFC it is not sufficiently robust. The teaching of US 2002/0048699 furthermore does not overcome the above mentioned problems related to the manufacturing process of the SOFC.
WO-A2-2005/122300 relates to a solid oxide fuel cell comprising a metallic support end-ing in a substantially pure electron conducting oxide, an active anode layer consisting of cathode support, a cathode layer, an electrolyte layer and an anode layer in this order.
The cathode is preferably applied employing a printing technique.
In view of the prior art, there is still a need for more freedom in choice of suitable materi-Obiect of the present invention It is the object of the present invention to provide a method for producing a reversible Brief description of the invention Said object is achieved by a method for producing a reversible solid oxide fuel cell, com-prising the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
Background art Solid oxide fuel cells (SOFCs) operate at high temperatures which are generally in the range of about 750 C to about 1000 C. These high temperatures are challenging to the materials employed, and are of particular concern with regard to the stability of the an-ode structures. For fuel oxidation, the so far preferred anode material comprises metallic nickel. Nickel is also preferred for reformed hydrocarbon fuel since it is a good catalyst for hydrocarbon reformation.
Manufacture processes suggested in the prior art include the provision of a support, the formation of an anode layer thereon, followed by the application of an electrolyte layer.
The so formed half cell is dried and afterwards sintered, often in a reducing atmosphere.
Finally, a cathode layer is formed thereon so as to obtain a complete cell.
However, during the sintering of the half cell, undesired reactions between the metal support and anode materials may occur, resulting in a negative impact on the overall cell performance. Moreover, in the prevalent anode supported design, oxidation of the anode is known to be detrimental for the cell performance. The above mentioned method con-stitutes some limitations on the anode material to be used.
US 2002/0048699 discloses a solid oxide fuel cell comprising a ferritic stainless steel substrate including a porous region and a non-porous region bounding the porous re-gion. A ferritic stainless steel bipolar plate is located under one surface of the porous region of the substrate and is sealingly attached to the non-porous region of the sub-strate above the porous region thereof. A first electrode layer is located over the other surface of the porous region of the substrate, an electrolyte layer is located over the first electrode layer and a second electrode layer is located over the electrolyte layer. While such a solid oxide fuel cell is relatively cheap and avoids the use of brittle seals, the SOFC it is not sufficiently robust. The teaching of US 2002/0048699 furthermore does not overcome the above mentioned problems related to the manufacturing process of the SOFC.
WO-A2-2005/122300 relates to a solid oxide fuel cell comprising a metallic support end-ing in a substantially pure electron conducting oxide, an active anode layer consisting of cathode support, a cathode layer, an electrolyte layer and an anode layer in this order.
The cathode is preferably applied employing a printing technique.
In view of the prior art, there is still a need for more freedom in choice of suitable materi-Obiect of the present invention It is the object of the present invention to provide a method for producing a reversible Brief description of the invention Said object is achieved by a method for producing a reversible solid oxide fuel cell, com-prising the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer so as to form a cathode layer; and - forming an anode layer on top of the electrolyte layer.
Said object is further achieved by a method for producing a reversible solid oxide fuel cell, comprising the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- forming an anode precursor layer on the electrolyte layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
Said object is finally achieved by a reversible solid oxide fuel cell, obtainable by the above methods.
In one embodiment, the anode is formed by impregnation of an anode precursor layer.
In one embodiment, there is provided a method for producing a reversible solid oxide fuel cell, comprising the steps of: providing a metallic support layer;
forming a cathode precursor layer on the metallic support layer; forming an electrolyte layer on the cathode precursor layer; forming an anode precursor layer on the electrolyte layer; sintering the obtained multilayer structure; impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
In one embodiment, the metallic support layer comprises a FeCrMx alloy, wherein Mx is selected from the group consisting of Ni, Ti, Ce, Mn, Mo, W, Co, La, Y, Al, or mixtures thereof, and from about 0 to about 50 vol% metal oxides.
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer so as to form a cathode layer; and - forming an anode layer on top of the electrolyte layer.
Said object is further achieved by a method for producing a reversible solid oxide fuel cell, comprising the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- forming an anode precursor layer on the electrolyte layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
Said object is finally achieved by a reversible solid oxide fuel cell, obtainable by the above methods.
In one embodiment, the anode is formed by impregnation of an anode precursor layer.
In one embodiment, there is provided a method for producing a reversible solid oxide fuel cell, comprising the steps of: providing a metallic support layer;
forming a cathode precursor layer on the metallic support layer; forming an electrolyte layer on the cathode precursor layer; forming an anode precursor layer on the electrolyte layer; sintering the obtained multilayer structure; impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
In one embodiment, the metallic support layer comprises a FeCrMx alloy, wherein Mx is selected from the group consisting of Ni, Ti, Ce, Mn, Mo, W, Co, La, Y, Al, or mixtures thereof, and from about 0 to about 50 vol% metal oxides.
In one embodiment, the metal oxide is selected from the group of doped zirconia, doped ceria, MgO, CaO, Sr0, Co0,, MnO, B203, CuOx, Zn02, VON, Cr203, FeO, Mo0,, W03, Ga203, A1203, Ti02, and mixtures thereof.
In one embodiment, the electrolyte layer comprises doped zirconia or doped ceria.
In one embodiment, the impregnation of the anode precursor layer is carried out with a solution comprising a nitrate selected from Ni, Ce and Gd nitrates, and mixtures thereof.
In one embodiment, the formed anode layer is a redox stable anode.
In one embodiment, the metallic support layer comprises an oxide layer on the surface thereof.
Figures The invention will in the following be explained with reference to the following Figures:
Fig. 1 illustrates a SOFC with a cathode impregnation layer.
Fig. 2 illustrates a SOFC with a double electrode impregnation layer.
Fig. 3 illustrates a SOFC with a cathode impregnation layer and a barrier layer.
Detailed description of the invention In the following, the invention will be described in more detail.
3a In a first embodiment, the method of the present invention comprises the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer so as to form a cathode layer; and - forming an anode layer on top of the electrolyte layer.
The metallic support layer is preferably a ferritic stainless steel support.
The use of a metallic support makes the cell more robust by increasing the mechanical strength and securing the redox stability. Furthermore, ferritic steels are comparatively cheap and the metallic support allows a cost effective large-scale production of the cell.
In a further preferred embodiment, the metallic support is a porous layer.
Porosity of the support may be achieved by adding pore formers during the manufacturing process of the support. The desired porosity can be fine tuned by the amount of pore formers add-ed.
According to the invention, the metallic support may comprise a FeCrMx alloy, wherein Mx is selected from the group consisting of Ni, Ti, Ce, Mn, Mo, W, Co, La, Y, Al, or mix-tures thereof. The concentrations of Mx in the alloy are preferably in amounts such that austenite formation is avoided. Preferably, the concentration of Mx is in the range of from about 0 to 15 parts by weight, and more preferably from about 0.1 to 10 parts by weight, based on the total weight of the alloy. Furthermore, the FeCrMx alloy preferably comprises from about 0 to about 50 vol% metal oxides, and more preferred from 0.5 to vol%. Suitable oxides include doped zirconia, doped ceria, Mg/Ca/Sr0, CoOx, MnO, B203, CuOx, Zn02, V0,, Cr203, FeO, MoOx, W03, Ga203, A1203, Ti02, and mixtures thereof. The addition of one or more of said oxides enhances the chemical bonding be-tween the electrode layer and the metal support, at the same time advantageously ad-30 justing the thermal expansion coefficient of the respective layers so as to reduce the TEC difference thereof. Also, said oxides may be used to control the sinterability and grain growth of the layer. In the case of, for example, Mg/Ca/Sr0, or CoOx, the TEC
difference will increase, whereas in case of, for example, Cr203, A1203, Ti02, zirconia and possibly ceria, the TEC will be reduced. Thus, the addition of the respective oxide can be used to design the TEC difference as desired.
In a further preferred embodiment, the FeCrMx porous support layer comprises an oxide layer on all internal and external surfaces. Said oxide layer may be formed by oxidation of the FeCrMx alloy itself in a suitable atmosphere. Alternatively, the oxide layer may be coated on the alloy. The oxide layer advantageously inhibits the corrosion of the metal.
Suitable oxide layers comprise, for example, Cr203, Ce02, LaCr03, SrTiO3, and mixtures thereof. The oxide layer may preferably furthermore be suitably doped, e.g. by alkaline earth oxides.
The thickness of the metallic support layer of the present invention is preferably in the range of about 200 to about 2000 pm, and more preferably of about 250 to about pm.
The electrode precursor layers are preferably formed from doped zirconia and/or doped ceria and/or a FeCrMx alloy, and in the case of a cathode precursor layer a material se-lected from the group consisting of lanthanum strontium manganate, lanthanide stron-tium manganate, lanthanide strontium iron cobalt oxide, (Y1-xCax)Fe1-yCoy03, (Gd1-xSrx)Fei_yCoy03, (Gd1,Cax)Fei_yCoy03, and mixtures thereof, may optionally be added.
More preferred is the precursor layer being formed from Sc-Y-Ga-Ce, zirconia doped with any of Sm, Gd, Y, any Ln element, CaO doped ceria, and mixtures thereof, and op-tionally a material as defined above. Also optionally, metals and metal alloys such as FeCrMx, Ni, NiCrMx, and the like, may be added, with Mx, being selected from the group consisting of Ni, Ti, Ce, Mn, Mo, W, Co, La, Y, Al, and mixtures thereof. In case of addi-tion of the metals or metal alloys, the layer will possess oxygen-ion conductivity due to the layer comprising doped zirconia/ceria, as well as electronic conductivity due to the metal. If the layer comprises doped ceria, the layer will also exhibit some electrocatalytic properties.
The electrode precursor layers are converted to the respective electrode layers by im-pregnation after sintering. If the precursor layer is converted into an anode, impregnation is conducted with, for example, Ni with or without doped ceria. Preferably, the impregna-tion of the anode precursor layer is carried out with a solution comprising a nitrates of Ni, Ce and Gd. If the precursor layer is converted into a cathode layer, the impregnation is preferably carried out with ferrites or cobaltites.
According to the invention, the final cathode layer preferably comprises a composite ma-terial comprising doped zirconia and/or doped ceria and/or a FeCrMx alloy, for example scandia and yttria stabilized zirconia (ScYSZ), and further a material selected from the group consisting of lanthanum strontium manganate (LSM), lanthanide strontium man-ganate (LnSrMn), lanthanide strontium iron cobalt oxide (LnSrFeCo), (Y1-xCax)Fe1-yC0y03, (Gdi-XSrOSFel-yCOy03 or (Gdi_xCax)sFei-yCoy03, and mixtures thereof.
It has been found that a cathode layer comprising said composite material exhibits a better cathode performance, as compared to other cathode materials known in the art.
The thickness of the cathode layer is preferably in the range of about 10 to about 100 pm, and more preferably of about 15 to about 40 pm.
In a further preferred embodiment, the cathode precursor layer may be a graded im-pregnation layer which is made from one or more of thin sheets comprising a mixture of electrolyte material and a metal alloy, such as the ones mentioned above. Each sheet may have varying grain sizes and pore sizes, and a thicknesses of about 10 to 50 pm.
The gradiation is achieved by, for example, laminating the metal support layer and vari-ous sheets, preferably 1 to 4 sheets, with different grain sizes and pore sizes by rolling or pressing. The resulting graded layer may, for example, have an average grain size ranging from about 5 to 10 pm in the sheet closest to the metal support layer, and about 1 pm in the sheet closest to the electrolyte layer.
The electrolyte layer preferably comprises doped zirconia or doped ceria. In a more pre-ferred embodiment, the electrolyte layer comprises a co-doped zirconia based oxygen ionic conductor. Said electrolyte layer has a higher oxygen ionic conductivity than a layer comprising pure YSZ, and a better long time stability than a layer comprising pure ScSZ.
Doped ceria may be used alternatively. Other suitable materials for the formation of the electrolyte layer include ionic conducting materials mentioned above for the electrode precursor layers, and also gallates and proton conducting electrolytes.
In one embodiment, the electrolyte layer comprises doped zirconia or doped ceria.
In one embodiment, the impregnation of the anode precursor layer is carried out with a solution comprising a nitrate selected from Ni, Ce and Gd nitrates, and mixtures thereof.
In one embodiment, the formed anode layer is a redox stable anode.
In one embodiment, the metallic support layer comprises an oxide layer on the surface thereof.
Figures The invention will in the following be explained with reference to the following Figures:
Fig. 1 illustrates a SOFC with a cathode impregnation layer.
Fig. 2 illustrates a SOFC with a double electrode impregnation layer.
Fig. 3 illustrates a SOFC with a cathode impregnation layer and a barrier layer.
Detailed description of the invention In the following, the invention will be described in more detail.
3a In a first embodiment, the method of the present invention comprises the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer so as to form a cathode layer; and - forming an anode layer on top of the electrolyte layer.
The metallic support layer is preferably a ferritic stainless steel support.
The use of a metallic support makes the cell more robust by increasing the mechanical strength and securing the redox stability. Furthermore, ferritic steels are comparatively cheap and the metallic support allows a cost effective large-scale production of the cell.
In a further preferred embodiment, the metallic support is a porous layer.
Porosity of the support may be achieved by adding pore formers during the manufacturing process of the support. The desired porosity can be fine tuned by the amount of pore formers add-ed.
According to the invention, the metallic support may comprise a FeCrMx alloy, wherein Mx is selected from the group consisting of Ni, Ti, Ce, Mn, Mo, W, Co, La, Y, Al, or mix-tures thereof. The concentrations of Mx in the alloy are preferably in amounts such that austenite formation is avoided. Preferably, the concentration of Mx is in the range of from about 0 to 15 parts by weight, and more preferably from about 0.1 to 10 parts by weight, based on the total weight of the alloy. Furthermore, the FeCrMx alloy preferably comprises from about 0 to about 50 vol% metal oxides, and more preferred from 0.5 to vol%. Suitable oxides include doped zirconia, doped ceria, Mg/Ca/Sr0, CoOx, MnO, B203, CuOx, Zn02, V0,, Cr203, FeO, MoOx, W03, Ga203, A1203, Ti02, and mixtures thereof. The addition of one or more of said oxides enhances the chemical bonding be-tween the electrode layer and the metal support, at the same time advantageously ad-30 justing the thermal expansion coefficient of the respective layers so as to reduce the TEC difference thereof. Also, said oxides may be used to control the sinterability and grain growth of the layer. In the case of, for example, Mg/Ca/Sr0, or CoOx, the TEC
difference will increase, whereas in case of, for example, Cr203, A1203, Ti02, zirconia and possibly ceria, the TEC will be reduced. Thus, the addition of the respective oxide can be used to design the TEC difference as desired.
In a further preferred embodiment, the FeCrMx porous support layer comprises an oxide layer on all internal and external surfaces. Said oxide layer may be formed by oxidation of the FeCrMx alloy itself in a suitable atmosphere. Alternatively, the oxide layer may be coated on the alloy. The oxide layer advantageously inhibits the corrosion of the metal.
Suitable oxide layers comprise, for example, Cr203, Ce02, LaCr03, SrTiO3, and mixtures thereof. The oxide layer may preferably furthermore be suitably doped, e.g. by alkaline earth oxides.
The thickness of the metallic support layer of the present invention is preferably in the range of about 200 to about 2000 pm, and more preferably of about 250 to about pm.
The electrode precursor layers are preferably formed from doped zirconia and/or doped ceria and/or a FeCrMx alloy, and in the case of a cathode precursor layer a material se-lected from the group consisting of lanthanum strontium manganate, lanthanide stron-tium manganate, lanthanide strontium iron cobalt oxide, (Y1-xCax)Fe1-yCoy03, (Gd1-xSrx)Fei_yCoy03, (Gd1,Cax)Fei_yCoy03, and mixtures thereof, may optionally be added.
More preferred is the precursor layer being formed from Sc-Y-Ga-Ce, zirconia doped with any of Sm, Gd, Y, any Ln element, CaO doped ceria, and mixtures thereof, and op-tionally a material as defined above. Also optionally, metals and metal alloys such as FeCrMx, Ni, NiCrMx, and the like, may be added, with Mx, being selected from the group consisting of Ni, Ti, Ce, Mn, Mo, W, Co, La, Y, Al, and mixtures thereof. In case of addi-tion of the metals or metal alloys, the layer will possess oxygen-ion conductivity due to the layer comprising doped zirconia/ceria, as well as electronic conductivity due to the metal. If the layer comprises doped ceria, the layer will also exhibit some electrocatalytic properties.
The electrode precursor layers are converted to the respective electrode layers by im-pregnation after sintering. If the precursor layer is converted into an anode, impregnation is conducted with, for example, Ni with or without doped ceria. Preferably, the impregna-tion of the anode precursor layer is carried out with a solution comprising a nitrates of Ni, Ce and Gd. If the precursor layer is converted into a cathode layer, the impregnation is preferably carried out with ferrites or cobaltites.
According to the invention, the final cathode layer preferably comprises a composite ma-terial comprising doped zirconia and/or doped ceria and/or a FeCrMx alloy, for example scandia and yttria stabilized zirconia (ScYSZ), and further a material selected from the group consisting of lanthanum strontium manganate (LSM), lanthanide strontium man-ganate (LnSrMn), lanthanide strontium iron cobalt oxide (LnSrFeCo), (Y1-xCax)Fe1-yC0y03, (Gdi-XSrOSFel-yCOy03 or (Gdi_xCax)sFei-yCoy03, and mixtures thereof.
It has been found that a cathode layer comprising said composite material exhibits a better cathode performance, as compared to other cathode materials known in the art.
The thickness of the cathode layer is preferably in the range of about 10 to about 100 pm, and more preferably of about 15 to about 40 pm.
In a further preferred embodiment, the cathode precursor layer may be a graded im-pregnation layer which is made from one or more of thin sheets comprising a mixture of electrolyte material and a metal alloy, such as the ones mentioned above. Each sheet may have varying grain sizes and pore sizes, and a thicknesses of about 10 to 50 pm.
The gradiation is achieved by, for example, laminating the metal support layer and vari-ous sheets, preferably 1 to 4 sheets, with different grain sizes and pore sizes by rolling or pressing. The resulting graded layer may, for example, have an average grain size ranging from about 5 to 10 pm in the sheet closest to the metal support layer, and about 1 pm in the sheet closest to the electrolyte layer.
The electrolyte layer preferably comprises doped zirconia or doped ceria. In a more pre-ferred embodiment, the electrolyte layer comprises a co-doped zirconia based oxygen ionic conductor. Said electrolyte layer has a higher oxygen ionic conductivity than a layer comprising pure YSZ, and a better long time stability than a layer comprising pure ScSZ.
Doped ceria may be used alternatively. Other suitable materials for the formation of the electrolyte layer include ionic conducting materials mentioned above for the electrode precursor layers, and also gallates and proton conducting electrolytes.
The thickness of the electrolyte layer of the present invention is preferably in the range of about 5 to about 50 pm, and more preferably of about 10 to about 25 pm.
In another preferred embodiment, the anode layer is directly formed on the sintered mul-tilayer structure comprising the metallic support layer, the cathode layer and the elcetro-lyte layer. Said anode layer is a porous layer comprising NiO and doped zirconia or doped ceria.
Alternatively, a redox stable anode may be deposited on the multilayer structure. The anode material of the redox stable anode comprises Ni-zirconia, Ni-ceria, or any other metal oxide with oxygen ion or proton conductivity, for example.
La(Sr)Ga(Mg)03_8, SrCe(Yb)03_8, BaZr(Y)03_8, or the like, which have the property of being able to with-stand redox cycling better than hitherto known anodes.
Surface passivation of Ni-surfaces of the redox stable anode is achieved by the compo-sition comprising at least one additional oxide that is stable both under SOFC
anode and cathode conditions, e.g. A1203, Ti02, Cr203, Sc203, VON, Ta0x, MnO, NbOx, CaO, Bi203, Ln0x, MgCr204, MgTiO3, CaA1204, LaA103, YbCr03, ErCr04, NM03, NiCr204, and mix-tures thereof. Preferred are TiO2 and Cr203.
If, for example, TiO2 or Cr203 is used, NiTi204 and NiCr204 are formed in the redox sta-ble anode layer during the sintering step. A redox stable microstructure is created during the initial reduction of the anode composition, leaving a percolating Ni structure with randomly distributed fine TiO2 particles (on average about 1 micrometer).
The addition of the oxides furthermore preferably results in a decrease of the thermal extension coefficient of the redox stable anode layer, which in turn strengthens the over-all mechanical stability of the layers and the resulting cell. Preferred oxides therefore are Cr203, Ti02, A1203, and Sc203.
The amount of NiO in the composition is preferably in the range of about 45 to 75 weight %, based on the total weight of the composition, and more preferred in the range of from about 50 to 65 wt%. The amount of doped zirconia, doped ceria and/or a metal oxide with an oxygen ion or proton conductivity in the composition is preferably in the range of about 25 to 55 weight %, based on the total weight of the composition, and more pref-erably in the range of from 40 to 45 wt%. As a preferred material, Zr1_xMx02_6 may be used, with M = Sc, Ce, Ga, or combinations thereof. Y may also be included. X
is in the range of about 0.05 to about 0.3. Also preferred is Ce1-xMx02.,5 with M = Ca, Sm, Gd, Y
and/or any Ln element, or combinations thereof. X is in the range of about 0.05 to about 0.3.
The amount of the at least one oxide in the composition is preferably in the range of about 1 to 25 weight %, based on the total weight of the composition, and more prefera-bly in the range of from about 2 to 10 wt%.
In a further preferred embodiment, the composition additionally comprises an oxide se-lected from the group consisting of A1203, Co304, Mn304, B203, CuO, ZnO, Fe304, M003, W03, Ga203, and mixtures thereof. The amount thereof in the composition is preferably in the range of about 0.1 to 5 weight %, based on the total weight of the composition, and more preferred in the range of from 0.2 to 2 wt%. The additional oxides are used as sintering aids to facilitate the reaction during the sintering step.
Other suitable materials for the metallic support layer, the electrode precursor layer, the electrolyte layer, and the anode and cathode layer may be selected.
The individual layers may be tape cast and subsequently laminated together.
Altema-tively, the individual layers may, for example, be rolled from a paste or the like. Other application methods of the respective layers include spraying, spray-painting, screen-printing; electrophoretic deposition (EPD), and pulsed laser deposition (PLD).
The sintering temperatures are preferably in the range of from about 900 to 1500 C, more preferably in the range of from about 1000 to 1300 C.
In a second embodiment of the present invention, a method for producing a reversible solid oxide fuel cell is provided, comprising the steps of:
- providing a metallic support layer;
In another preferred embodiment, the anode layer is directly formed on the sintered mul-tilayer structure comprising the metallic support layer, the cathode layer and the elcetro-lyte layer. Said anode layer is a porous layer comprising NiO and doped zirconia or doped ceria.
Alternatively, a redox stable anode may be deposited on the multilayer structure. The anode material of the redox stable anode comprises Ni-zirconia, Ni-ceria, or any other metal oxide with oxygen ion or proton conductivity, for example.
La(Sr)Ga(Mg)03_8, SrCe(Yb)03_8, BaZr(Y)03_8, or the like, which have the property of being able to with-stand redox cycling better than hitherto known anodes.
Surface passivation of Ni-surfaces of the redox stable anode is achieved by the compo-sition comprising at least one additional oxide that is stable both under SOFC
anode and cathode conditions, e.g. A1203, Ti02, Cr203, Sc203, VON, Ta0x, MnO, NbOx, CaO, Bi203, Ln0x, MgCr204, MgTiO3, CaA1204, LaA103, YbCr03, ErCr04, NM03, NiCr204, and mix-tures thereof. Preferred are TiO2 and Cr203.
If, for example, TiO2 or Cr203 is used, NiTi204 and NiCr204 are formed in the redox sta-ble anode layer during the sintering step. A redox stable microstructure is created during the initial reduction of the anode composition, leaving a percolating Ni structure with randomly distributed fine TiO2 particles (on average about 1 micrometer).
The addition of the oxides furthermore preferably results in a decrease of the thermal extension coefficient of the redox stable anode layer, which in turn strengthens the over-all mechanical stability of the layers and the resulting cell. Preferred oxides therefore are Cr203, Ti02, A1203, and Sc203.
The amount of NiO in the composition is preferably in the range of about 45 to 75 weight %, based on the total weight of the composition, and more preferred in the range of from about 50 to 65 wt%. The amount of doped zirconia, doped ceria and/or a metal oxide with an oxygen ion or proton conductivity in the composition is preferably in the range of about 25 to 55 weight %, based on the total weight of the composition, and more pref-erably in the range of from 40 to 45 wt%. As a preferred material, Zr1_xMx02_6 may be used, with M = Sc, Ce, Ga, or combinations thereof. Y may also be included. X
is in the range of about 0.05 to about 0.3. Also preferred is Ce1-xMx02.,5 with M = Ca, Sm, Gd, Y
and/or any Ln element, or combinations thereof. X is in the range of about 0.05 to about 0.3.
The amount of the at least one oxide in the composition is preferably in the range of about 1 to 25 weight %, based on the total weight of the composition, and more prefera-bly in the range of from about 2 to 10 wt%.
In a further preferred embodiment, the composition additionally comprises an oxide se-lected from the group consisting of A1203, Co304, Mn304, B203, CuO, ZnO, Fe304, M003, W03, Ga203, and mixtures thereof. The amount thereof in the composition is preferably in the range of about 0.1 to 5 weight %, based on the total weight of the composition, and more preferred in the range of from 0.2 to 2 wt%. The additional oxides are used as sintering aids to facilitate the reaction during the sintering step.
Other suitable materials for the metallic support layer, the electrode precursor layer, the electrolyte layer, and the anode and cathode layer may be selected.
The individual layers may be tape cast and subsequently laminated together.
Altema-tively, the individual layers may, for example, be rolled from a paste or the like. Other application methods of the respective layers include spraying, spray-painting, screen-printing; electrophoretic deposition (EPD), and pulsed laser deposition (PLD).
The sintering temperatures are preferably in the range of from about 900 to 1500 C, more preferably in the range of from about 1000 to 1300 C.
In a second embodiment of the present invention, a method for producing a reversible solid oxide fuel cell is provided, comprising the steps of:
- providing a metallic support layer;
WO 2006/082057 , , - forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- forming an anode precursor layer on the electrolyte layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
In this embodiment, the anode precursor layer is formed on the electrolyte layer prior to sintering. Thereby, a second sintering step may be omitted. After sintering, the respec-tive electrode layers are impregnated, as described further above. The layer not to be impregnated in the respective impregnation step is masked so as to allow different im-pregnation materials. After impregnating the first layer, said impregnated layer is masked, the other layer is demasked so as to be impregnated, and impregnating the second layer.
All other preferred embodiments described for the first embodiment of the method of the present invention also apply to the second embodiment of the method of the present invention.
The method may preferably include the step of providing a reaction barrier layer com-prising doped ceria. Said reaction barrier layer, if provided, is located between the elec-trolyte layer and the cathode layer. The thickness of the barrier layer is about 0.1 to about 1 pm. The barrier layer advantageously prevents diffusion of cations from the cathode layer into the electrolyte layer, thereby increasing the life time of the cathode layer.
Referring now to Figure 1, a cell in accordance with the present invention is illustrated comprising a metallic support 1, a precursor layer for impregnation of the cathode 2, an electrolyte layer 3, and an anode layer 4.
The cell illustrated in Figure 2 corresponds to the one of Figure 1 with the exception of an anode precursor layer 5.
- forming an electrolyte layer on the cathode precursor layer;
- forming an anode precursor layer on the electrolyte layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
In this embodiment, the anode precursor layer is formed on the electrolyte layer prior to sintering. Thereby, a second sintering step may be omitted. After sintering, the respec-tive electrode layers are impregnated, as described further above. The layer not to be impregnated in the respective impregnation step is masked so as to allow different im-pregnation materials. After impregnating the first layer, said impregnated layer is masked, the other layer is demasked so as to be impregnated, and impregnating the second layer.
All other preferred embodiments described for the first embodiment of the method of the present invention also apply to the second embodiment of the method of the present invention.
The method may preferably include the step of providing a reaction barrier layer com-prising doped ceria. Said reaction barrier layer, if provided, is located between the elec-trolyte layer and the cathode layer. The thickness of the barrier layer is about 0.1 to about 1 pm. The barrier layer advantageously prevents diffusion of cations from the cathode layer into the electrolyte layer, thereby increasing the life time of the cathode layer.
Referring now to Figure 1, a cell in accordance with the present invention is illustrated comprising a metallic support 1, a precursor layer for impregnation of the cathode 2, an electrolyte layer 3, and an anode layer 4.
The cell illustrated in Figure 2 corresponds to the one of Figure 1 with the exception of an anode precursor layer 5.
Referring to Figure 3, a cell is illustrated comprising a metallic support 1, a precursor layer for impregnation of the cathode 2, an electrolyte layer 3, an anode layer 4/5 and a barrier layer 6.
The present invention also provides a reversible solid oxide fuel cell, obtainable by the above described methods. Advantageously, the impregnation allows more freedom in design and material selection of the SOFC, thus allowing to fine tune the SOFC
design according to the desired application. Furthermore, the impregnation of the electrode lay-ers results in finely distributed catalyst particles on the surface of the pores, which in turn leads to an improved cell performance. The particles are preferably in the size range of nanoparticles, making the electrode performances even more effective.
Moreover, less catalytic material is needed since all material is applied to the surface of the layer struc-ture, where it can contribute to the electrode reaction.
The present invention provides the following advantages:
a) The method is less complicated than methods suggested in the prior art, since no cathode/metal support barrier layer is required;
b) The life time of the metallic support will be increased; during operation of SOFCs having the anode on the metallic support, the relatively high pH20 (>0.5 atm.) on the anode side may result in severe corrosion of the metal support. Having the cathode on the support side, the metal will only be exposed to air, which is less corrosive;
c) If the anode and cathode are impregnated after sintering, only one sintering step is required and the method can thus be made more cost effective;
d) The sintering step may be carried out without the presence of anode or cathode materials, hence negative reactions, such as coarsening, during sintering is not an issue;
e) Chemical reaction between electrode materials and the other cell materials can be prevented because the operational temperature of the final cell is lower than the sintering temperature;
f) Due to impregnation of the electrodes, the electrodes have high surface areas;
g) The composite structure of the impregnation layer(s) ensures a good mechanical bonding between electrolyte and metal support as well as good conductivity across the interfaces.
In the following, the invention will be illustrated by examples. Alternative embodiments and examples exist without departing from the scope of the present invention.
Examples Example 1:
Preparation of a reversible SOFC with porous cathode impregnation layer.
A metallic support layer was tape-cast from a powder suspension comprising a Fe22Cr alloy, followed by a drying step. The support layer had a thickness of 300 pm.
Thereon, a porous layer comprising Zr0.78Sc0.20110.0202_6 for later impregnation of the cathode was formed by spray painting. The layer had a thickness of 50 pm and a poros-ity of about 40% with an average pore size of about 1-3 pm. Then, an electrolyte layer comprising Zr078Sc0.206.0202_6 was formed thereon, also by spray painting. The electro-lyte layer was formed from doped zirconia and had a thickness of about 10 pm.
The obtained multi-layer structure was dried, followed by sintering under reducing condi-tions at about 1300 C.
After sintering a nitrate solution of (Gdo.1Ce0.9)02-8 and (La0.6Sro.4.98(C00.2Fe0.8)03_8 was impregnated in to the cathode precursor layer by vacuum infiltration. The nitrates were subsequently decomposed at 500 C for 2 hours. The impregnation procedure was re-peated 5 times.
Afterwards, an NiO - (Gdo.1Ce0.002_5 anode was spray deposited on the surface of the multilayer structure. The resulting anode had a volume concentration of about 45 % Ni and 55 % (Gdo.1Ce0.9)02-s=
Example 2 A metallic support layer was tape-cast from a powder suspension comprising a FeCrMn0.01 alloy, followed by a drying step. The support layer had a thickness of 400 pm.
After drying of the support layer, a layer for later electrode impregnation (layer 2, 50 mi-crometer) was deposited by screen-printing an ink comprising a 1:1 volume mixture of Zr0.78Sc0.20Y0.02Zr2-5 and a Fe24CrMn0.01 The layer had a thickness of 50 pm.
Finally an electrolyte layer comprising Zr0.78Sc0.20Y0.0202-6 was deposited by spray painting.
The multilayer structure was sintered and the cathode impregnated as described in Ex-ample 1.
After sintering a redox stable anode was deposited by spray painting a suspension of NiO - Zr0.78Sc020Y0.02a2.6 - 1102. (52:43:5 weight %, respectively), followed by an addi-tional sintering step at about 1000 C in air. During sintering of the anode, NiTi204 was formed in the anode structure. The redox stable microstructure was created during the initial reduction of the anode, leaving a percolating Ni structure with randomly distributed fine TiO2 particles (¨ 1 pm).
Example 3:
Same method as in Example 2, but with the composition for the redox stable anode comprising pre-reacted NiT1O3 before processing.
Example 4:
Same method as in Example 2, but with the composition for the redox stable anode comprising NiCr204 before processing.
Example 5:
Same method as in Example 2, but with the composition for the redox stable anode comprising a mixture of pre-reacted NiTiO3 and NiCr204 to control the coverage of the nickel surfaces.
Example 6:
Same method as in Example 2, but with the composition for the redox stable anode comprising Sc203 as the added oxide.
Example 7:
Same method as in Example 2, but with the composition for the redox stable anode comprising NiTiO3 along with an equal molar amount of Sar03. During sintering, the following reaction took place. NiTiO3 + (SrLa)Zr03 = MO + (SrLa)TiO3+ Zr02.
Example 8:
Same method as in Example 2, but with the composition for the redox stable anode comprising doped ceria instead of zirconia.
Example 9 Same as Example 1, wherein the support sheet was obtained by tape-casting a Fe22CrTi0.04 alloy powder suspension mixed with 5 vol% Zr0.94Y0.06a2-6-The cell was completed as described in Example 2.
Example 10 A metallic support layer was tape-cast from a powder suspension comprising a Fe22Cr alloy, followed by a drying step. The support layer had a thickness of 400 pm.
A graded impregnation precursor layer was formed thereon from three thin sheets com-prising Zr0.78Sc0.20Y0.02Zr2_6 and a Fe22Cr alloy. The sheets with varying grain sizes and varying pore sizes, having a thicknesses of about 20 pm were manufactured by tape-casting respective powder suspensions. The cell structure was made by laminating the metal support sheet and the three impregnation precursor layers sheets by rolling and WO 2006/082057 , _ PCT/EP2006/000920 pressing. The obtained impregnation layer had a graded structure with pore size of from pm in the layer directly on top of the metal support layer, and a pore size of 2 pm at the layer on which the electrolyte layer was formed.
5 The cell was completed as described in Example 1.
Example 11 As Example 1, but with the addition of A1203 as a sintering additive so as to control the 10 shrinkage.
The cell was completed as described in Example 1.
Example 12 A half-cell as described in Example 1 was manufactured, wherein additionally a GdoiCe0.9)02.6 cathode/electrolyte barrier layer having a thickness of 0.5 pm was ap-plied.
The cell was completed as described in Example 1.
Example 13 A metallic support layer was formed by rolling a Fe22CrNd0.02Ti0.03 alloy paste, fol-lowed by a drying step. The support layer had a thickness of 800 pm.
A layer for cathode impregnation having a thickness of 30 pm, and an electrolyte layer having a thickness of 10 pm were deposited by spray painting. Both layers were formed from a composition of (Gdo.iCe0.9)02_6. After sintering, a nitrate solution of Ni, La, Sr, Co and Fe was impregnated into the porous ceria layer by vacuum infiltration.
After drying and cleaning of the electrolyte surface, a NiO-(SmoiCe0.9)02.6 anode was deposited by screen printing.
Example 14 A support was manufactured as explained in Example 1. After drying of the support, a layer for cathode impregnation, having a thickness of 70 pm, a Zr0.78Sc0.201/0.0202_6 elec-trolyte layer having a thickness of 10 pm, and finally another layer for anode impregna-tion having a thickness of 30 pm, were deposited by spray painting. Both impregnation layers were formed from a composition of Zr078Sc0.20Y0.0202..5 and 40 volc/0 Fe22Cr pow-der with an approximate porosity of -40%.
Samples were subsequently punched out in the desired dimensions, and the samples were sintered under controlled reducing conditions. The metal support layer was masked, and a solution of Ni- Ce-, Gd-nitrates was impregnated into the anode impreg-nation precursor layer by vacuum infiltration. The resulting anode will had a volume con-centration of 40% Ni and 60% (Gdo.iCeo.9)02_6. After drying, the mask was removed, the anode layer masked and a nitrate solution used to impregnate the cathode precursor layer by vacuum infiltration so that the resulting cathode composition was (Gdo.6Sro.4)o.99(C00.2Fe0.8)03-45.
Example 15 A cell structure was manufactured as described in Example 1. The cathode layer was formed by pressure impregnation of a nano-sized suspension of (LacoSro.4)o.99(C00.2Fe0.8)03-6.
The present invention also provides a reversible solid oxide fuel cell, obtainable by the above described methods. Advantageously, the impregnation allows more freedom in design and material selection of the SOFC, thus allowing to fine tune the SOFC
design according to the desired application. Furthermore, the impregnation of the electrode lay-ers results in finely distributed catalyst particles on the surface of the pores, which in turn leads to an improved cell performance. The particles are preferably in the size range of nanoparticles, making the electrode performances even more effective.
Moreover, less catalytic material is needed since all material is applied to the surface of the layer struc-ture, where it can contribute to the electrode reaction.
The present invention provides the following advantages:
a) The method is less complicated than methods suggested in the prior art, since no cathode/metal support barrier layer is required;
b) The life time of the metallic support will be increased; during operation of SOFCs having the anode on the metallic support, the relatively high pH20 (>0.5 atm.) on the anode side may result in severe corrosion of the metal support. Having the cathode on the support side, the metal will only be exposed to air, which is less corrosive;
c) If the anode and cathode are impregnated after sintering, only one sintering step is required and the method can thus be made more cost effective;
d) The sintering step may be carried out without the presence of anode or cathode materials, hence negative reactions, such as coarsening, during sintering is not an issue;
e) Chemical reaction between electrode materials and the other cell materials can be prevented because the operational temperature of the final cell is lower than the sintering temperature;
f) Due to impregnation of the electrodes, the electrodes have high surface areas;
g) The composite structure of the impregnation layer(s) ensures a good mechanical bonding between electrolyte and metal support as well as good conductivity across the interfaces.
In the following, the invention will be illustrated by examples. Alternative embodiments and examples exist without departing from the scope of the present invention.
Examples Example 1:
Preparation of a reversible SOFC with porous cathode impregnation layer.
A metallic support layer was tape-cast from a powder suspension comprising a Fe22Cr alloy, followed by a drying step. The support layer had a thickness of 300 pm.
Thereon, a porous layer comprising Zr0.78Sc0.20110.0202_6 for later impregnation of the cathode was formed by spray painting. The layer had a thickness of 50 pm and a poros-ity of about 40% with an average pore size of about 1-3 pm. Then, an electrolyte layer comprising Zr078Sc0.206.0202_6 was formed thereon, also by spray painting. The electro-lyte layer was formed from doped zirconia and had a thickness of about 10 pm.
The obtained multi-layer structure was dried, followed by sintering under reducing condi-tions at about 1300 C.
After sintering a nitrate solution of (Gdo.1Ce0.9)02-8 and (La0.6Sro.4.98(C00.2Fe0.8)03_8 was impregnated in to the cathode precursor layer by vacuum infiltration. The nitrates were subsequently decomposed at 500 C for 2 hours. The impregnation procedure was re-peated 5 times.
Afterwards, an NiO - (Gdo.1Ce0.002_5 anode was spray deposited on the surface of the multilayer structure. The resulting anode had a volume concentration of about 45 % Ni and 55 % (Gdo.1Ce0.9)02-s=
Example 2 A metallic support layer was tape-cast from a powder suspension comprising a FeCrMn0.01 alloy, followed by a drying step. The support layer had a thickness of 400 pm.
After drying of the support layer, a layer for later electrode impregnation (layer 2, 50 mi-crometer) was deposited by screen-printing an ink comprising a 1:1 volume mixture of Zr0.78Sc0.20Y0.02Zr2-5 and a Fe24CrMn0.01 The layer had a thickness of 50 pm.
Finally an electrolyte layer comprising Zr0.78Sc0.20Y0.0202-6 was deposited by spray painting.
The multilayer structure was sintered and the cathode impregnated as described in Ex-ample 1.
After sintering a redox stable anode was deposited by spray painting a suspension of NiO - Zr0.78Sc020Y0.02a2.6 - 1102. (52:43:5 weight %, respectively), followed by an addi-tional sintering step at about 1000 C in air. During sintering of the anode, NiTi204 was formed in the anode structure. The redox stable microstructure was created during the initial reduction of the anode, leaving a percolating Ni structure with randomly distributed fine TiO2 particles (¨ 1 pm).
Example 3:
Same method as in Example 2, but with the composition for the redox stable anode comprising pre-reacted NiT1O3 before processing.
Example 4:
Same method as in Example 2, but with the composition for the redox stable anode comprising NiCr204 before processing.
Example 5:
Same method as in Example 2, but with the composition for the redox stable anode comprising a mixture of pre-reacted NiTiO3 and NiCr204 to control the coverage of the nickel surfaces.
Example 6:
Same method as in Example 2, but with the composition for the redox stable anode comprising Sc203 as the added oxide.
Example 7:
Same method as in Example 2, but with the composition for the redox stable anode comprising NiTiO3 along with an equal molar amount of Sar03. During sintering, the following reaction took place. NiTiO3 + (SrLa)Zr03 = MO + (SrLa)TiO3+ Zr02.
Example 8:
Same method as in Example 2, but with the composition for the redox stable anode comprising doped ceria instead of zirconia.
Example 9 Same as Example 1, wherein the support sheet was obtained by tape-casting a Fe22CrTi0.04 alloy powder suspension mixed with 5 vol% Zr0.94Y0.06a2-6-The cell was completed as described in Example 2.
Example 10 A metallic support layer was tape-cast from a powder suspension comprising a Fe22Cr alloy, followed by a drying step. The support layer had a thickness of 400 pm.
A graded impregnation precursor layer was formed thereon from three thin sheets com-prising Zr0.78Sc0.20Y0.02Zr2_6 and a Fe22Cr alloy. The sheets with varying grain sizes and varying pore sizes, having a thicknesses of about 20 pm were manufactured by tape-casting respective powder suspensions. The cell structure was made by laminating the metal support sheet and the three impregnation precursor layers sheets by rolling and WO 2006/082057 , _ PCT/EP2006/000920 pressing. The obtained impregnation layer had a graded structure with pore size of from pm in the layer directly on top of the metal support layer, and a pore size of 2 pm at the layer on which the electrolyte layer was formed.
5 The cell was completed as described in Example 1.
Example 11 As Example 1, but with the addition of A1203 as a sintering additive so as to control the 10 shrinkage.
The cell was completed as described in Example 1.
Example 12 A half-cell as described in Example 1 was manufactured, wherein additionally a GdoiCe0.9)02.6 cathode/electrolyte barrier layer having a thickness of 0.5 pm was ap-plied.
The cell was completed as described in Example 1.
Example 13 A metallic support layer was formed by rolling a Fe22CrNd0.02Ti0.03 alloy paste, fol-lowed by a drying step. The support layer had a thickness of 800 pm.
A layer for cathode impregnation having a thickness of 30 pm, and an electrolyte layer having a thickness of 10 pm were deposited by spray painting. Both layers were formed from a composition of (Gdo.iCe0.9)02_6. After sintering, a nitrate solution of Ni, La, Sr, Co and Fe was impregnated into the porous ceria layer by vacuum infiltration.
After drying and cleaning of the electrolyte surface, a NiO-(SmoiCe0.9)02.6 anode was deposited by screen printing.
Example 14 A support was manufactured as explained in Example 1. After drying of the support, a layer for cathode impregnation, having a thickness of 70 pm, a Zr0.78Sc0.201/0.0202_6 elec-trolyte layer having a thickness of 10 pm, and finally another layer for anode impregna-tion having a thickness of 30 pm, were deposited by spray painting. Both impregnation layers were formed from a composition of Zr078Sc0.20Y0.0202..5 and 40 volc/0 Fe22Cr pow-der with an approximate porosity of -40%.
Samples were subsequently punched out in the desired dimensions, and the samples were sintered under controlled reducing conditions. The metal support layer was masked, and a solution of Ni- Ce-, Gd-nitrates was impregnated into the anode impreg-nation precursor layer by vacuum infiltration. The resulting anode will had a volume con-centration of 40% Ni and 60% (Gdo.iCeo.9)02_6. After drying, the mask was removed, the anode layer masked and a nitrate solution used to impregnate the cathode precursor layer by vacuum infiltration so that the resulting cathode composition was (Gdo.6Sro.4)o.99(C00.2Fe0.8)03-45.
Example 15 A cell structure was manufactured as described in Example 1. The cathode layer was formed by pressure impregnation of a nano-sized suspension of (LacoSro.4)o.99(C00.2Fe0.8)03-6.
Claims (10)
1. A method for producing a reversible solid oxide fuel cell, comprising the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer so as to form a cathode layer; and - forming an anode layer on top of the electrolyte layer.
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer so as to form a cathode layer; and - forming an anode layer on top of the electrolyte layer.
2. The method of claim 1, wherein the anode is formed by impregnation of an anode precursor layer.
3. A method for producing a reversible solid oxide fuel cell, comprising the steps of:
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- forming an anode precursor layer on the electrolyte layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
- providing a metallic support layer;
- forming a cathode precursor layer on the metallic support layer;
- forming an electrolyte layer on the cathode precursor layer;
- forming an anode precursor layer on the electrolyte layer;
- sintering the obtained multilayer structure;
- impregnating the cathode precursor layer and the anode precursor layer so as to form a cathode layer and an anode layer.
4. The method of any one of claims 1 to 3, wherein the metallic support layer comprises a FeCrMx alloy, wherein Mx is selected from the group consisting of Ni, Ti, Ce, Mn, Mo, W, Co, La, Y, Al, or mixtures thereof, and from about 0 to about 50 vol% metal oxides.
5. The method of claim 4, wherein the metal oxide is selected from the group of doped zirconia, doped ceria, MgO, CaO, SrO, CoO x, MnO x, B2O3, CuO x, ZnO2, VO x, Cr2O3, FeO x, MoO x, WO3, Ga2O3, Al2O3, TiO2, and mixtures thereof.
6. The method of any one of claims 1 to 5, wherein the electrolyte layer comprises doped zirconia or doped ceria.
7. The method of any one of claims 2 to 6, wherein the impregnation of the anode precursor layer is carried out with a solution comprising a nitrate selected from Ni, Ce and Gd nitrates, and mixtures thereof.
8. The method of any one of claims 1 to 7, wherein the formed anode layer is a redox stable anode.
9. The method of any one of claims 1 to 8, wherein the metallic support layer comprises an oxide layer on the surface thereof.
10. A reversible solid oxide fuel cell, obtained by the method of any one of claims 1 to 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA200500159 | 2005-02-02 | ||
| DKPA200500159 | 2005-02-02 | ||
| PCT/EP2006/000920 WO2006082057A2 (en) | 2005-02-02 | 2006-02-02 | A method for producing a reversible solid oxid fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2596173A1 CA2596173A1 (en) | 2006-08-10 |
| CA2596173C true CA2596173C (en) | 2013-10-01 |
Family
ID=36648477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2596173A Expired - Fee Related CA2596173C (en) | 2005-02-02 | 2006-02-02 | A method for producing a reversible solid oxide fuel cell |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US7601183B2 (en) |
| EP (1) | EP1844517B1 (en) |
| JP (1) | JP5208518B2 (en) |
| AT (1) | ATE465526T1 (en) |
| AU (1) | AU2006210103B2 (en) |
| CA (1) | CA2596173C (en) |
| DE (1) | DE602006013786D1 (en) |
| DK (1) | DK1844517T3 (en) |
| ES (1) | ES2342489T3 (en) |
| NO (1) | NO20073872L (en) |
| WO (1) | WO2006082057A2 (en) |
Families Citing this family (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1985397B (en) | 2004-06-10 | 2012-07-04 | 丹麦科技大学 | Solid oxide fuel cell |
| JP2008522370A (en) | 2004-11-30 | 2008-06-26 | ザ、リージェンツ、オブ、ザ、ユニバーシティ、オブ、カリフォルニア | Sealed joint structure for electrochemical devices |
| CN100568598C (en) | 2004-12-28 | 2009-12-09 | 丹麦科技大学 | Make metal and glass, metal and metal or metal and the ceramic method that is connected |
| KR100924700B1 (en) | 2005-01-12 | 2009-11-03 | 테크니칼 유니버시티 오브 덴마크 | The method producing multilayer structures whose shrinkage and porosity are controlled during sintering, multilayer structures produced by the said method, and SOFC including the said multilayer structures |
| AU2006208619B2 (en) | 2005-01-31 | 2009-06-04 | Technical University Of Denmark | Redox-stable anode |
| EP1760817B1 (en) * | 2005-08-31 | 2013-08-21 | Technical University of Denmark | Reversible solid oxide fuell cell stack and method for preparing same |
| ES2292313B1 (en) * | 2005-09-27 | 2009-02-16 | Ikerlan, S. Coop. | SOLID OXIDE FUEL CELL WITH FERRITIC SUPPORT. |
| JP2009544502A (en) | 2006-07-28 | 2009-12-17 | ザ、リージェンツ、オブ、ザ、ユニバーシティ、オブ、カリフォルニア | Jointed concentric tubes |
| CN100479245C (en) * | 2006-08-29 | 2009-04-15 | 中国科学院上海硅酸盐研究所 | Prepartion method of anode supported compound membrane of solid electrolyte in mesothermal fuel cell of soild oxide |
| US10615444B2 (en) | 2006-10-18 | 2020-04-07 | Bloom Energy Corporation | Anode with high redox stability |
| WO2008048445A2 (en) | 2006-10-18 | 2008-04-24 | Bloom Energy Corporation | Anode with remarkable stability under conditions of extreme fuel starvation |
| EP1928049A1 (en) * | 2006-11-23 | 2008-06-04 | Technical University of Denmark | Thin solid oxide cell |
| EP2378599B1 (en) * | 2006-11-23 | 2012-10-31 | Technical University of Denmark | Method for the manufacture of reversible solid oxide cells |
| JP5112711B2 (en) * | 2007-02-09 | 2013-01-09 | 日本電信電話株式会社 | Method for producing electrode for solid oxide fuel cell and solid oxide fuel cell |
| US20080261099A1 (en) | 2007-04-13 | 2008-10-23 | Bloom Energy Corporation | Heterogeneous ceramic composite SOFC electrolyte |
| BRPI0814362A2 (en) * | 2007-07-25 | 2015-01-27 | Univ California | INTERCONNECTION STRUCTURE FOR HIGH TEMPERATURE ELECTROCHEMICAL DEVICE AND METHOD FOR MAKING IT |
| ES2375407T3 (en) * | 2007-08-31 | 2012-02-29 | Technical University Of Denmark | SEPARATION OF IMPURITY PHASES OF ELECTROCHEMICAL DEVICES. |
| EP2662917A1 (en) * | 2007-08-31 | 2013-11-13 | Technical University of Denmark | Anode supported solid oxide fuel cell |
| EP2031675B1 (en) * | 2007-08-31 | 2011-08-03 | Technical University of Denmark | Ceria and stainless steel based electrodes |
| EP2104165A1 (en) | 2008-03-18 | 2009-09-23 | The Technical University of Denmark | An all ceramics solid oxide fuel cell |
| EP2103582A1 (en) * | 2008-03-18 | 2009-09-23 | Technical University of Denmark | A method for producing a multilayer structure |
| AU2008354733B2 (en) | 2008-04-18 | 2013-10-03 | The Regents Of The University Of California | Integrated seal for high-temperature electrochemical device |
| DE102008049712A1 (en) * | 2008-09-30 | 2010-04-01 | Siemens Aktiengesellschaft | Planar high-temperature fuel cell |
| FR2938270B1 (en) * | 2008-11-12 | 2013-10-18 | Commissariat Energie Atomique | METAL OR POROUS METAL ALLOY SUBSTRATE, PROCESS FOR PREPARING THE SAME, AND EHT OR SOFC METAL SUPPORT CELLS COMPRISING THE SUBSTRATE |
| ES1069849Y (en) | 2008-12-19 | 2009-09-14 | Coprecitec Sl | "REGULATION VALVE FOR A GAS COOKING DEVICE" |
| KR20100093957A (en) * | 2009-02-17 | 2010-08-26 | 삼성전자주식회사 | Fuel electrode material, process for preparing composite and solid oxide fuel cells using composite |
| JP2010192288A (en) * | 2009-02-19 | 2010-09-02 | Honda Motor Co Ltd | Electrolyte, electrode assembly, and their manufacturing method |
| DE102009015794B3 (en) * | 2009-03-26 | 2010-07-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Contact element for an electrically conductive connection between an anode and an interconnector of a high-temperature fuel cell |
| EP2244322A1 (en) | 2009-04-24 | 2010-10-27 | Technical University of Denmark | Composite oxygen electrode and method for preparing same |
| US8617763B2 (en) | 2009-08-12 | 2013-12-31 | Bloom Energy Corporation | Internal reforming anode for solid oxide fuel cells |
| KR101761346B1 (en) * | 2009-10-16 | 2017-07-25 | 인하대학교 산학협력단 | Fuel electrode material and solid oxide fuel cells using composite |
| EP2333883A1 (en) * | 2009-11-18 | 2011-06-15 | Forschungszentrum Jülich Gmbh (FJZ) | Anode for a high temperature fuel cell and production of same |
| EP2519472B1 (en) * | 2009-12-29 | 2018-07-25 | 3M Innovative Properties Company | Zirconia-based particles doped with a lanthanide element |
| JP5323269B2 (en) | 2010-01-26 | 2013-10-23 | ブルーム エナジー コーポレーション | Fuel cell components, especially electrolyte materials for solid oxide fuel cells |
| JP4773589B1 (en) * | 2010-06-15 | 2011-09-14 | 日本碍子株式会社 | Fuel cell |
| US8440362B2 (en) | 2010-09-24 | 2013-05-14 | Bloom Energy Corporation | Fuel cell mechanical components |
| US9642192B2 (en) * | 2011-08-04 | 2017-05-02 | Fuelcell Energy, Inc. | Method and manufacturing assembly for sintering fuel cell electrodes and impregnating porous electrodes with electrolyte powders by induction heating for mass production |
| US9236627B1 (en) * | 2011-09-29 | 2016-01-12 | University Of South Carolina | Solid oxide redox flow battery |
| WO2014081716A1 (en) | 2012-11-20 | 2014-05-30 | Bloom Energy Corporation | Doped scandia stabilized zirconia electrolyte compositions |
| US8658311B2 (en) * | 2012-12-07 | 2014-02-25 | Bruce S. Kang | High temperature rechargeable battery for greenhouse gas decomposition and oxygen generation |
| EP2936596B1 (en) * | 2012-12-19 | 2019-06-12 | LG Fuel Cell Systems Inc. | Fuel cell system with interconnect |
| US20140272665A1 (en) * | 2013-03-13 | 2014-09-18 | Redox Power Systems, LLC | Ceramic Fuel Cell With Enhanced Flatness And Strength And Methods Of Making Same |
| US9755263B2 (en) | 2013-03-15 | 2017-09-05 | Bloom Energy Corporation | Fuel cell mechanical components |
| CA2906709A1 (en) | 2013-03-15 | 2014-09-18 | Lg Fuel Cell Systems, Inc. | Fuel cell system configured to capture chromium |
| JP5522870B1 (en) | 2013-04-12 | 2014-06-18 | 日本碍子株式会社 | Fuel cell |
| CN107078309A (en) | 2014-07-21 | 2017-08-18 | Lg燃料电池系统股份有限公司 | Composition for fuel cell electrode |
| RU2571824C1 (en) * | 2014-11-12 | 2015-12-20 | Общество с ограниченной ответственностью "Газпром трансгаз Томск" (ООО "Газпром трансгаз Томск") | Method of making solid oxide fuel cell on metal base |
| US10651496B2 (en) | 2015-03-06 | 2020-05-12 | Bloom Energy Corporation | Modular pad for a fuel cell system |
| US10115973B2 (en) | 2015-10-28 | 2018-10-30 | Lg Fuel Cell Systems Inc. | Composition of a nickelate composite cathode for a fuel cell |
| US10680251B2 (en) | 2017-08-28 | 2020-06-09 | Bloom Energy Corporation | SOFC including redox-tolerant anode electrode and system including the same |
| CN107611461A (en) * | 2017-09-30 | 2018-01-19 | 福州大学 | A kind of preparation method of SOFC |
| CN111063898B (en) * | 2019-12-20 | 2021-03-30 | 中国矿业大学 | Battery anode reforming layer material, preparation method and power generation method of battery anode reforming layer material for solid oxide fuel battery |
| CN113764709A (en) * | 2020-12-31 | 2021-12-07 | 厦门大学 | Secondary fuel cell based on composite material |
| CN114016072A (en) * | 2021-12-15 | 2022-02-08 | 中国科学院大连化学物理研究所 | Solid oxide electrolytic cell |
| CN114583226A (en) * | 2022-03-31 | 2022-06-03 | 中国科学技术大学先进技术研究院 | Metal-supported proton conductor solid oxide cell and preparation method thereof |
Family Cites Families (81)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2019732A1 (en) | 1969-04-21 | 1970-11-26 | Minnesota Mining & Mfg | Metal powder filter |
| US4218985A (en) | 1972-08-10 | 1980-08-26 | Jones Allen Jr | Steering and stabilization apparatus for torpedo |
| US4702971A (en) * | 1986-05-28 | 1987-10-27 | Westinghouse Electric Corp. | Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells |
| US4957673A (en) | 1988-02-01 | 1990-09-18 | California Institute Of Technology | Multilayer ceramic oxide solid electrolyte for fuel cells and electrolysis cells and method for fabrication thereof |
| US5021304A (en) * | 1989-03-22 | 1991-06-04 | Westinghouse Electric Corp. | Modified cermet fuel electrodes for solid oxide electrochemical cells |
| EP0424732A1 (en) | 1989-10-27 | 1991-05-02 | Asea Brown Boveri Ag | Current conduction element for stacked hightemperature fuel cells and method of manufacture |
| EP0446680A1 (en) | 1990-03-15 | 1991-09-18 | Asea Brown Boveri Ag | Current collector for conducting current between neighbouring piled high temperature fuel cells |
| DK167163B1 (en) | 1991-02-13 | 1993-09-06 | Risoe Forskningscenter | FAST OXIDE FUEL CELLS FOR OXIDATION OF CH4 |
| JPH05135787A (en) * | 1991-03-28 | 1993-06-01 | Ngk Insulators Ltd | Manufacture of solid electrolyte film and manufacture of solid electrolyte fuel cell |
| DE4237602A1 (en) | 1992-11-06 | 1994-05-11 | Siemens Ag | High temperature fuel cell stack and process for its manufacture |
| US5368667A (en) | 1993-01-29 | 1994-11-29 | Alliedsignal Inc. | Preparation of devices that include a thin ceramic layer |
| DK94393D0 (en) | 1993-08-18 | 1993-08-18 | Risoe Forskningscenter | PROCEDURE FOR THE PREPARATION OF CALCIUM-DOPED LANTHANCHROMITE |
| US5592686A (en) | 1995-07-25 | 1997-01-07 | Third; Christine E. | Porous metal structures and processes for their production |
| US5670270A (en) | 1995-11-16 | 1997-09-23 | The Dow Chemical Company | Electrode structure for solid state electrochemical devices |
| DE19547700C2 (en) | 1995-12-20 | 1998-09-17 | Forschungszentrum Juelich Gmbh | Electrode substrate for a fuel cell |
| AUPN876896A0 (en) | 1996-03-18 | 1996-04-18 | Ceramic Fuel Cells Limited | An electrical interconnect for a planar fuel cell |
| AU3110197A (en) | 1996-11-11 | 1998-06-03 | Gorina, Liliya Fedorovna | Method for manufacturing a single unit high temperature fuel cell and its components: a cathode, an electrolyte, an anode, a current conductor, and interface and insulating layers |
| DE19650704C2 (en) | 1996-12-06 | 2000-09-14 | Forschungszentrum Juelich Gmbh | Connection element for fuel cells |
| DE19710345C1 (en) | 1997-03-13 | 1999-01-21 | Forschungszentrum Juelich Gmbh | Material for electrical contact layers between an electrode of a high-temperature fuel cell and a connecting element |
| US6210612B1 (en) | 1997-03-31 | 2001-04-03 | Pouvair Corporation | Method for the manufacture of porous ceramic articles |
| DE19782271T1 (en) | 1997-04-30 | 2000-04-27 | Dow Chemical Co | Electrode structure for solid electrochemical devices |
| US6099985A (en) | 1997-07-03 | 2000-08-08 | Gas Research Institute | SOFC anode for enhanced performance stability and method for manufacturing same |
| DE59702857D1 (en) | 1997-09-11 | 2001-02-08 | Sulzer Hexis Ag Winterthur | Electrochemically active element for a solid oxide fuel cell |
| US5908713A (en) | 1997-09-22 | 1999-06-01 | Siemens Westinghouse Power Corporation | Sintered electrode for solid oxide fuel cells |
| WO1999056899A1 (en) | 1998-05-04 | 1999-11-11 | Colorado School Of Mines | Porous metal-containing materials, method of manufacture and products incorporating or made from the materials |
| DE19836132B4 (en) | 1998-08-10 | 2006-11-23 | Siemens Ag | High temperature solid electrolyte fuel cell (SOFC) for a wide operating temperature range |
| US6458170B1 (en) | 1998-12-03 | 2002-10-01 | The Regents Of The University Of California | Method for making thin, flat, dense membranes on porous substrates |
| US6248468B1 (en) | 1998-12-31 | 2001-06-19 | Siemens Westinghouse Power Corporation | Fuel electrode containing pre-sintered nickel/zirconia for a solid oxide fuel cell |
| JP3230156B2 (en) * | 1999-01-06 | 2001-11-19 | 三菱マテリアル株式会社 | Electrode of solid oxide fuel cell and method of manufacturing the same |
| US6589680B1 (en) | 1999-03-03 | 2003-07-08 | The Trustees Of The University Of Pennsylvania | Method for solid oxide fuel cell anode preparation |
| JP4207218B2 (en) | 1999-06-29 | 2009-01-14 | 住友電気工業株式会社 | Metal porous body, method for producing the same, and metal composite using the same |
| US6605316B1 (en) * | 1999-07-31 | 2003-08-12 | The Regents Of The University Of California | Structures and fabrication techniques for solid state electrochemical devices |
| US6682842B1 (en) | 1999-07-31 | 2004-01-27 | The Regents Of The University Of California | Composite electrode/electrolyte structure |
| DK174654B1 (en) | 2000-02-02 | 2003-08-11 | Topsoe Haldor As | Solid oxide fuel cell and its applications |
| CA2614620C (en) | 2000-05-10 | 2010-02-02 | Alberta Research Council Inc. | Production of hollow ceramic membranes by electrophoretic deposition |
| DE10025108A1 (en) | 2000-05-20 | 2001-11-29 | Forschungszentrum Juelich Gmbh | High temperature material |
| AU2001280467A1 (en) | 2000-07-25 | 2002-02-05 | Bae Systems | Cmos sram cell with prescribed power-on data state |
| GB2368450B (en) | 2000-10-25 | 2004-05-19 | Imperial College | Fuel cells |
| US8007954B2 (en) | 2000-11-09 | 2011-08-30 | The Trustees Of The University Of Pennsylvania | Use of sulfur-containing fuels for direct oxidation fuel cells |
| FR2817860B1 (en) | 2000-12-07 | 2003-09-12 | Air Liquide | PROCESS FOR THE PREPARATION OF A LOW THICKNESS CERAMIC MATERIAL WITH CONTROLLED SURFACE POROSITY GRADIENT, CERAMIC MATERIAL OBTAINED, ELECTROCHEMICAL CELL AND CERAMIC MEMBRANE COMPRISING THE SAME |
| US20020127455A1 (en) | 2001-03-08 | 2002-09-12 | The Regents Of The University Of California | Ceria-based solid oxide fuel cells |
| US7709124B2 (en) | 2001-04-10 | 2010-05-04 | Northwestern University | Direct hydrocarbon fuel cells |
| JP3841149B2 (en) | 2001-05-01 | 2006-11-01 | 日産自動車株式会社 | Single cell for solid oxide fuel cell |
| AT4810U1 (en) | 2001-05-31 | 2001-11-26 | Plansee Ag | CURRENT COLLECTOR FOR SOFC FUEL CELLS |
| FR2826956B1 (en) | 2001-07-04 | 2004-05-28 | Air Liquide | PROCESS FOR PREPARING A LOW THICKNESS CERAMIC COMPOSITION WITH TWO MATERIALS, COMPOSITION OBTAINED, ELECTROCHEMICAL CELL AND MEMBRANE COMPRISING IT |
| US6772501B2 (en) | 2001-07-23 | 2004-08-10 | Itn Energy Systems, Inc. | Apparatus and method for the design and manufacture of thin-film electrochemical devices |
| US6653009B2 (en) | 2001-10-19 | 2003-11-25 | Sarnoff Corporation | Solid oxide fuel cells and interconnectors |
| JP2003132906A (en) | 2001-10-24 | 2003-05-09 | Nissan Motor Co Ltd | Single cell for fuel cell and solid electrolytic fuel cell |
| DE10161538B4 (en) | 2001-12-10 | 2004-09-09 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Carrier for an electrochemical functional unit of a high-temperature fuel cell and high-temperature fuel cell |
| US6893762B2 (en) | 2002-01-16 | 2005-05-17 | Alberta Research Council, Inc. | Metal-supported tubular micro-fuel cell |
| US6824907B2 (en) | 2002-01-16 | 2004-11-30 | Alberta Reasearch Council, Inc. | Tubular solid oxide fuel cell stack |
| US8114551B2 (en) | 2002-03-04 | 2012-02-14 | Sulzer Hexis Ag | Porous structured body for a fuel cell anode |
| GB2386126B (en) | 2002-03-06 | 2006-03-08 | Ceres Power Ltd | Forming an impermeable sintered ceramic electrolyte layer on a metallic foil substrate for solid oxide fuel cell |
| DK1624520T3 (en) | 2002-03-27 | 2012-01-02 | Topsoe Fuel Cell As | Thin Film Solid Oxide Fuel Cell (SOFC) and Method of Preparation |
| AU2003256251A1 (en) | 2002-04-24 | 2003-11-10 | The Regents Of The University Of California | Planar electrochemical device assembly |
| JP2004259643A (en) * | 2003-02-27 | 2004-09-16 | Sanyo Electric Co Ltd | Solid oxide fuel cell |
| KR101067226B1 (en) | 2002-05-29 | 2011-09-22 | 산요덴키가부시키가이샤 | Solid Oxide Fuel Cell |
| KR20050036914A (en) | 2002-06-06 | 2005-04-20 | 트러스티스 오브 더 유니버시티 오브 펜실바니아 | Ceramic anodes and method of producing the same |
| US20030232230A1 (en) | 2002-06-12 | 2003-12-18 | Carter John David | Solid oxide fuel cell with enhanced mechanical and electrical properties |
| US6843960B2 (en) | 2002-06-12 | 2005-01-18 | The University Of Chicago | Compositionally graded metallic plates for planar solid oxide fuel cells |
| US20030235752A1 (en) | 2002-06-24 | 2003-12-25 | England Diane M. | Oxygen getters for anode protection in a solid-oxide fuel cell stack |
| JP3976181B2 (en) | 2002-07-19 | 2007-09-12 | 東邦瓦斯株式会社 | Solid oxide fuel cell single cell and solid oxide fuel cell using the same |
| GB0217794D0 (en) | 2002-08-01 | 2002-09-11 | Univ St Andrews | Fuel cell electrodes |
| US20040121222A1 (en) | 2002-09-10 | 2004-06-24 | Partho Sarkar | Crack-resistant anode-supported fuel cell |
| US7285350B2 (en) | 2002-09-27 | 2007-10-23 | Questair Technologies Inc. | Enhanced solid oxide fuel cell systems |
| NL1021547C2 (en) * | 2002-09-27 | 2004-04-20 | Stichting Energie | Electrode-supported fuel cell. |
| US6843406B2 (en) | 2002-09-27 | 2005-01-18 | Battelle Memorial Institute | Gas-tight metal/ceramic or metal/metal seals for applications in high temperature electrochemical devices and method of making |
| DE10302122A1 (en) | 2003-01-21 | 2004-07-29 | Elringklinger Ag | Multi cell fuel stack has sealing between cells provided by layer of insulation and layer of sealing material |
| US6958196B2 (en) * | 2003-02-21 | 2005-10-25 | Trustees Of The University Of Pennsylvania | Porous electrode, solid oxide fuel cell, and method of producing the same |
| DE10309968A1 (en) | 2003-03-07 | 2004-09-23 | Forschungszentrum Jülich GmbH | Method for producing a layer system comprising a metallic carrier and an anode functional layer |
| GB2422479B (en) | 2003-04-15 | 2006-12-13 | Ceres Power Ltd | Solid oxide fuel cell with a novel substrate and a method for fabricating the same |
| JP4027836B2 (en) | 2003-04-16 | 2007-12-26 | 東京瓦斯株式会社 | Method for producing solid oxide fuel cell |
| AU2004272186B8 (en) | 2003-09-10 | 2010-02-18 | Btu International, Inc | Process for solid oxide fuel cell manufacture |
| UA83400C2 (en) | 2003-12-02 | 2008-07-10 | Нанодайнемікс, Інк. | Solid oxide fuel cells (sofc) with cermet electrolite and method for their manufacturing |
| CN1985397B (en) | 2004-06-10 | 2012-07-04 | 丹麦科技大学 | Solid oxide fuel cell |
| US20060024547A1 (en) | 2004-07-27 | 2006-02-02 | David Waldbillig | Anode supported sofc with an electrode multifunctional layer |
| CN100568598C (en) | 2004-12-28 | 2009-12-09 | 丹麦科技大学 | Make metal and glass, metal and metal or metal and the ceramic method that is connected |
| KR100924700B1 (en) | 2005-01-12 | 2009-11-03 | 테크니칼 유니버시티 오브 덴마크 | The method producing multilayer structures whose shrinkage and porosity are controlled during sintering, multilayer structures produced by the said method, and SOFC including the said multilayer structures |
| AU2006208619B2 (en) | 2005-01-31 | 2009-06-04 | Technical University Of Denmark | Redox-stable anode |
| EP1760817B1 (en) | 2005-08-31 | 2013-08-21 | Technical University of Denmark | Reversible solid oxide fuell cell stack and method for preparing same |
| EP2378599B1 (en) | 2006-11-23 | 2012-10-31 | Technical University of Denmark | Method for the manufacture of reversible solid oxide cells |
-
2006
- 2006-02-02 EP EP06706590A patent/EP1844517B1/en not_active Not-in-force
- 2006-02-02 AT AT06706590T patent/ATE465526T1/en not_active IP Right Cessation
- 2006-02-02 DK DK06706590.4T patent/DK1844517T3/en active
- 2006-02-02 AU AU2006210103A patent/AU2006210103B2/en not_active Ceased
- 2006-02-02 US US11/814,356 patent/US7601183B2/en not_active Expired - Fee Related
- 2006-02-02 JP JP2007552603A patent/JP5208518B2/en not_active Expired - Fee Related
- 2006-02-02 WO PCT/EP2006/000920 patent/WO2006082057A2/en active Application Filing
- 2006-02-02 ES ES06706590T patent/ES2342489T3/en active Active
- 2006-02-02 CA CA2596173A patent/CA2596173C/en not_active Expired - Fee Related
- 2006-02-02 DE DE602006013786T patent/DE602006013786D1/en active Active
-
2007
- 2007-07-24 NO NO20073872A patent/NO20073872L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU2006210103A1 (en) | 2006-08-10 |
| WO2006082057A2 (en) | 2006-08-10 |
| US7601183B2 (en) | 2009-10-13 |
| CA2596173A1 (en) | 2006-08-10 |
| EP1844517B1 (en) | 2010-04-21 |
| US20080118635A1 (en) | 2008-05-22 |
| JP2008529226A (en) | 2008-07-31 |
| DK1844517T3 (en) | 2010-07-19 |
| EP1844517A2 (en) | 2007-10-17 |
| AU2006210103B2 (en) | 2010-07-15 |
| WO2006082057A3 (en) | 2006-12-28 |
| ATE465526T1 (en) | 2010-05-15 |
| JP5208518B2 (en) | 2013-06-12 |
| NO20073872L (en) | 2007-08-31 |
| DE602006013786D1 (en) | 2010-06-02 |
| ES2342489T3 (en) | 2010-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2596173C (en) | A method for producing a reversible solid oxide fuel cell | |
| US7745031B2 (en) | Solid oxide fuel cell | |
| US8298721B2 (en) | Metal supported solid oxide fuel cell | |
| CN101796676B (en) | Removal of impurity phases from electrochemical devices | |
| CA2595854C (en) | Redox stable anode | |
| RU2537561C2 (en) | Composite oxygen electrode and method of obtaining thereof | |
| US20080299436A1 (en) | Composite ceramic electrolyte structure and method of forming; and related articles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20160202 |