CA2428275C - Solid oxide electrolyte fuel cell - Google Patents
Solid oxide electrolyte fuel cell Download PDFInfo
- Publication number
- CA2428275C CA2428275C CA002428275A CA2428275A CA2428275C CA 2428275 C CA2428275 C CA 2428275C CA 002428275 A CA002428275 A CA 002428275A CA 2428275 A CA2428275 A CA 2428275A CA 2428275 C CA2428275 C CA 2428275C
- Authority
- CA
- Canada
- Prior art keywords
- fuel
- support substrate
- fuel cell
- electrode layer
- cell according
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
- H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
-
- 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
- H01M8/1286—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
-
- 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
- H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
- H01M8/0217—Complex oxides, optionally doped, of the type AMO3, A being an alkaline earth metal or rare earth metal and M being a metal, e.g. perovskites
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
A fuel cell comprising a gas-permeable and electrically conducting support substrate having a fuel gas passage formed therein; a fuel-electrode layer formed on said substrate; a solid electrolytic layer formed on said support substrate so as to cover said fuel-electrode layer and containing ZrO2 in which rare earth elements are existing in the form of solid solutions; and an oxygen-electrode provided on the solid electrolytic layer so as to face said fuel-electrode layer; wherein said support substrate is formed of a metal of the iron family and/or an oxide of a metal of the iron family, and a rare-earth oxide containing at least one kind of element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr. The invention brings a coefficient of thermal expansion of the support substrate close to that of the solid electrolytic layer, and prevents a reduction in the performance of the solid electrolyte caused by the diffusion of elements from the support substrate.
Description
SOLID OXIDE ELECTROLYTE FUEL CELL
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a fuel cell and to a fuel cell assembly.
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a fuel cell and to a fuel cell assembly.
2. Description of the Related Art To obtain energy of the next generation, there have recently been proposed a variety of fuel cells by containing a stack of fuel cells in a container.
Fig. 3 is a diagram illustrating a stack of conventional solid oxide fuel cells. In this stack of cells, a plurality of fuel cells 1 are regularly arranged, a collector member 5 made of a metal felt is interposed between one fuel cell la and another neighboring fuel cell lb, and a fuel-electrode 7 of one fuel-cell la is electrically connected to an oxygen-electrode (air-electrode) 11 of another fuel cell lb.
The fuel celll (la, 1b) is constituted by a solid electrolyte 9 and the oxygen-electrode 11 composed of electrically conducting ceramics, that are provided in this order on the outer peripheral surface of the fuel-electrode of a cylindrical cermet (of which the interior serves as a fuel gas passage). An interconnect 13 is provided on the surface of the fuel-electrode 7 covered with neither the solid electrolyte 9 nor the oxygen-electrode 11. As will be obvious from Fig. 3, the interconnect 13 is electrically corinected to the fuel-electrode 7 so will not to be connected to the oxygen-electrode 11.
The interconnect 13 is made of electrically conducting ceramics which is subject to be little degraded with an oxygen-containing gas such as a fuel gas or the air. The electrically conducting ceramics must be so dense as to reliably shut the fuel aas flowing inside the fuel-electrode 7 off the oxygen-containing gas flowing outside the oxygen-electrode 11.
The collector member 5 provided between the neighboring fuel cells ia and lb is electrically connected to the fuel-electrode 7 of the one fuel cell la through the interconnect 13, and is further directly connected to the oxygen-electrode 11 of the other fuel cell lb, so that the neighboring fuel cells are connected together in series.
A fuel cell assembly is constituted by containing the cell stack having the above-mentioned structure in a container, and generates electricity at 600 to 1000 C by flowing the fuel gas (hydrogen) into the fuel rod 7 and flowing the air (oxygen) into the oxygen-electrode 11.
In the fuel cell constituting the above-mentioned fuel cell assembly, in general, the fuel-electrode 7 is formed of Ni and yttria stabilized zirconia (YSZ), the solid electrolyte 9 is formed of Zr02(YSZ) containing Y203, and the oxygen-electrode 11 is constituted by a perovskite composite oxide of the type of lanthanum manganate.
As a method of producina the above fuel cell, there has been known a so-called co-firing method which forms the fuel cell by co-firing the fuel-electrode 7 and the solid electrolyte 9. The co-firing method is a very simple process requiring a decreased number of steps for production, featuring increased yield in the production of cells, and is advantageous for decreasing the cost.
However, the conventional fuel cells are accompanied by such problems that the fuel-electrode 7 is cracked when the fuel-electrode 7 and the solid electrolyte 9 are co-fired, and the solid electrolyte 9 peels off the fuel-electrode 7 which is a support member. That is, the solid electrolyte 9 is formed of Zr0g containing Y203 having a coefficient of thermal expansion of 10.8 x 10-6/ C. Here, however, the fuel-electrode 7 supporting the solid electrolyte 9 contains Ni having a coefficient of thermal expansion of 16.3 x 10-6 / C which is very larger than that of YSZ. At the time of co-firing, therefore, there develops a large difference in the thermal expansion between the solid electrolyte 9 and the fuel-electrode 7 supporting it.
As a result, there occur such problems as cracking of the fuel-electrode 7 and peeling of the solid electrolyte 9.
In order to solve the above problems, further, it has been proposed to use mulite (3A1203 = 2Si 0,,) and spinel (MgAl2O9, CaAl20s) and to form the fuel-electrode 7 by using them in combination with Ni (see Japanese Unexamined Patent Publication (Kokai) No. 29574/1995).
According to the above proposal, the coefficient of thermal expansion of the fuel-electrode 7 is brought close to the coefficient of thermal expansion of the solid electrolyte 9, making it possible to suppress the occurrence of cracks in the fuel-electrode 7 and the peeling of the fuel-electrode 7 from the solid electrolyte 9 at the time of co-firing. There, however, arises a new problem in that the components such as Mg, A1 and Si in the fuel-electrode diffuse into the solid electrolyte 9 at the time of co-firing, whereby the ionic conductivity of the solid electrolyte 9 decreases and the generating performance of the fuel cell decreases.
SUMMARY OF THE INVENTION
It is therefore an object of the present inverition to provide a fuel cell which not only effectively suppresses the occurrence of cracks in the fuel-electrode and the peeling of the solid electrolyte at the time of co-firing but also suppresses the reduction of performance such as a decrease in the ionic conductivity caused by the diffusion of elements into the solid electrolyte, and which can be inexpensively produced by the co-firing method.
According to the present invention, there is provided a fuel cell unit comprising:
a gas-permeable and electrically conducting support substrate having at least one fuel gas passage formed therein;
a fuel-electrode layer formed on the support substrate;
a solid electrolytic layer formed on the fuel-electrode layer so as to cover the fuel-electrode layer and containing Zr02 in which at least one rare earth element is present in the form of a solid solution; and an oxygen-electrode provided on the solid electrolytic layer so as to face the fuel-electrode layer;
wherein:
the support substrate is formed of (a) a metal of the iron family and/or an oxide of a metal of the iron family, and (b) a rare-earth oxide containing at least one element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr; and the rare-earth oxide is contained in an amount of 35 to 65% by volume in the support substrate.
Namely, in the present invention, the support substrate in each of the members constituting the cell is formed by a metal of the iron family or an oxide thereof (such as Ni or NiO) and a particular rare-earth oxide in a 4a particular amount, and makes it possible to effectively avoid various inconveniences caused by the co-firing.
For example, the above rare-earth oxide in the support substrate does not almost form a solid solution with, or does not almost react with, the metal of the iron family or with the oxide thereof during the firing or during the generation of electricity. Besides, the rare-earth oxide has a coefficient of thermal expansion which is very smaller than the coefficient of thermal expansion (about 10.8 x 10-6/ C) of Zr02 (hereinafter ~
often referred to as stabilized zirconia) in which rare earth elements are existing in the form of solid solutions in the solid electrolytic layer or in the fuel-electrode layer. For example, Y203 or Yb203 has a coefficient of thermal expansion of about 8.14 x 10-6/ C.
By controlling the content of the rare--earth oxide such as Y203 or Z'b203r therefore, it is allowed to bring the coefficient of thermal expansion of the support substrate close to the coefficient of thermal expansion of the solid electrolytic layer or of the fuel-electrode layer and, hence, to effectively suppress the occurrence of cracks or peeling caused by a difference in the coefficient of thermal expansion.
Besides, the metal of the iron family, the oxides thereof and the particular rare-earth oxide constituting the support substrate all tend to be diffused little.
Even when the support substrate and the solid electrolytic layer are co-fired, therefore, the rare earth element is effectively suppressed from diffusing into the solid electrolytic layer avoiding adverse effect on the ionic conductivity of the solid electrolytic layer. Even if the rare earth element has diffused during the co-firing, the effect of diffusion of the rare earth element in the solid electrolyte can be minimized since the soli-d electrolytic layer has been constituted by Zr02 (stabilized zirconia) in which rare-earth oxides such as Y203 and Yb203 have been contained in the form of solid solutions.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a transverse sectional view illustrating a fuel cell according to the present invention;
Fig. 2 is a transverse sectional view illustrating a celi stack formed by a plurality of fuel cells; and Fig. 3 is a transverse sectional view illustrating a cell stack constituted by conventional fuel cells.
DETAILED DESCRIPTI0N OF THE iIVVENTI0N
In Fig. 1 which is a transverse sectional view of a fuel cell of the present invention, the fuel cell which is generally designated at 30 has a support substrate 31_ which is flat in cross section and is of an elliptic cylindrical shape as viewed generally. A plurality of fuel gas passages 31a are formed maintaining a suitable distance in the support substrate 31. The fuel cell 30 has a structure in which various kinds of members are provided on the support substrate 31. A plurality of the above fuel cells 30 are connected to each other in series through collector members 40 as shown in Fig. 2 thereby to form a cell stack for constituting a fuel cell assembly.
As will be understood from the shape shown in Fig.
1, the support substrate 31 comprises a flat portion A
and arcuate portions B at both ends of the flat portion A. Both surfaces of the flat portion A are formed nearly in parallel with each other, a fuel-electrode layer 32 is so provided as to cover one surface of the flat portion A and the arcuate portions B on both sides, and a dense solid electrolytic layer 33 is laminated so as to cover the fuel-electrode layer 32. An oxygen-electrode 34 is laminated on the solid electrolytic layer 33 from one surface of the flat portion A toward the arcuate portions B on both sides so as to face the fuel-electrode layer 32. An interconnect 35 is formed on the other surface of the flat portion A on where neither the fuel-electrode layer 32 nor the solid electrode layer 33 has been laminated. As is obvious Trom Fig. 1, the fuel-electrode layer 32 and the solid electrolytic layer 33 are extending up to both sides of the interconr,ect 35, so that the surface of the support substrate 31 is not exposed to the outer side.
Iri the fuel CEIl Cf the above StrUCtUre, a pOrt10 of the fuel-eiectrode layer 32 facing the oxygen-electrode 34 works as the fuel-electrode to generate electricity. Namely, the oxygen-containing gas such as the air is supplied to the outside of the oxygen-electrode 34, the fuel gas (hydrogen) =..s supplied to the gas passages in the support substrate 31, and the temperature is elevated up to a predetermined operation temperature, whereby the electrode reaction of the following formula (1) takes places on the oxygen-electrode 34, and the electrode reaction of, for example, the following formula (2) takes place on a port=~on of the fuel-electrode layer 32 that serves as the fuel-electrode to thereby generate electricity, Oxygen-electrode: 1/202 + 2e- - 02- (solid electrolyte) --- (1) Fuel-electrode: 02- (solid electrolyte) + H2 --+ H20 +
2e --- (2) The electric current produced by the above generation is collected through the interconnect 35 mounted on the support substrate 31.
(Support Substrate 3"1) In the fuel cell 30 of the present invention having the above structure, the support substrate 31 must be gas-permeable to permit the permeation of the fuel gas to the fuel-electrode layer 32, and must be electrically conducting to collect electricity through the interconnect. In order to satisfy the above requirements and to alleviate inconvenience caused by co-firing, the support substrate 31 is constituted by a metal component of the iron family and a particular rare-earth oxide.
The metal component of the iron family -s to impart electrically conducting property to the support substrate 31, and may be a simple metal of the iron family, an oxide of the metal of the iron family, an alloy of the metal of the iron family or an oxide of the alloy. The metal of the iron family may be iron, nickel or cobalt, and any one of them may be used in the present invention. From the standpoint of cost and stability in the fuel gas, however, it is desired that Ni and/or Ni0 '~~~_s contained as the component of the iron family.
The rare-earth oxide component is used for bringing the coefficient of thermal expansion of the support substrate 31 close to that of the stabilized zirconia forming the solid electrolytic layer 33. In order to maintain a high electronic conduct__vity and to prevent diffusion into the solid electrolytic layer 33, therefore, an oxide containing at least one kind of ra_Ve earth element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr is used in combination with the above componerlt of the iron family.
Concrete examp_es of the rare-earth oxide include Y203r LU203r Yb203, Tm203, Er203, ho203r DY203r Gd203, Sm203 and Pr203. Among them, however, Y203 and Yb203 are particularly desired since they are inexpensive.
From the standpoint of bringing the coefficient of thermal expansion of the support substrate 31 close to that of the stabilized zirconia, ir.i particular, it is desired in the present invention that the above component of the iron family is contained in an amount of from 35 to 65% by volume in the support substrate 31 and that the rare-earth oxide is contained in an amount of from 35 to 65% by volume in the support substrate 31.
The support substrate 31 may further contain other metal components and oxide compcnents in a range in which they do not impair the required properties.
It is essential that the support substrate 31 constituted by --he above metal component of the iron family and. the rare-earth oxide has fuel gas-permeating property and, hence, has an open porosity which is not usually smaller than 30% and, particularly, in a range of from 35 to 50%. It is further desired that the support substrate 31 has an electronic conductivity of not smaller than 300 S/cm and, particularly, not smaller than 440 S/cm.
It _J1s desired that the support substrate 31 has the flat portion A of a length of, usually, from 15 to 35 mm, has the arcuate porticns B of a length (length of arc) of from about 3 to about 8 mm, and has a thickness (gap between both surfaces of the flat portion A) of from about 2.5 to about 5 mm.
(Fuel-electrode Layer 32) In the present invention, the fuel-electrode layer 32 is for producing the electrode reaction of the above formula (2) and is by itse.lf formed of known porous and electrically ccnducting ceramics. For example, the fuel-electrode layer 32 is formed of Zr02 in which rare earth elements are contained in the form of solid solutions and Ni and/or NiO. As Zr02 (stabilized zirconia) in which rare earth elements are contained in the form of solid soiutions, there can be used those described below that have been used for the formation of the solid electrolytic iayer 33.
It is desired that the fuel-electrode layer 32 contains the stabilized zirconia in an amount in a range of from 35 to 65% by volume, and contains Ni or NiO in an amount in a range of from 65 to 315% by volume. It is further desired that the fuel-electrode layer 32 has an open porosity of not smaller than 15% and, particuiarly, in a range of from 20 to 40%, and has a thickness of from 1 to 30 4m. When the fuel-electrode layer 32 is too thin, the performance may decrease. When it is too thick, on the other hand, peeling may occur between the solid electrolytic layer 33 and the fuel-electrode layer 32 due to a difference in the thermal expansion.
In the example of .7ig. 1, the fuel-electrode layer 32 is extending up to both sides of the intrconnector 35. The fuel-electrode, however, needs be formed at a 5 position facing the oxygen-electrode 34. Therefore, the fuel-electrode layer 32 may be formed, for example, on only the flat portion A on the side where the oxygen-electrode 34 is provided. The fuel-electrode layer 32 may further be formed over the whole circumference of 10 the support substrate 31. In the present invention, it is desired that the solid electrolytic layer 33 as a whole is formed on the fuel-electrode layer 32 in order to increase the junction strength between the solid electrolytic layer 33 and the support substrate 31.
(Solid Electrolytic Layer 33) The solid electrolytic layer 33 on the fuel-electrode laye-- 32 is usually formed of dense ceramics comprising Zr02 in which 3 to 15o by mol of rare earth elements are contained in the form of solid solutions (called stabilized zirconia). As the rare earth elements, there can be exemplified Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
Among them, however, Y and Yb are desired since they are inexpensive.
It is desired that the stabilized zirconia ceramics forming the solid electrolytic layer 33 has a relative density (according to Archimedes' method) of not smaller than 93% and, particularly, not smaller than 95% from the standpoint of preventing the permeation of gas and has a thickness of from 10 to 100 pm.
(Oxygen-electrode 34) The oxygen-electrode 34 is formed of electrically conducting ceramics which is a perovskite-type oxide of the so-called AB03 type. As the perovskite-type oxide, there can be preferably used at least one kind of perovskite-type oxide of a. transition metal and, particularly, an LaMn03-type oxide having La on the A-site, an La-Fe03-type oxide or an LaCoO3-type oxide and, particularly, the LaFeO3-type oxide from the standpoint of a high electrically conducting property at ari operation temperature of from about 600 to about 1000 C.
In the above perovskite-type oxide, La and Sr may exist on the A-site and, besides, Fe as well as Co and Mn may exist on the B-site.
The oxygen-electrode 34 must be gas-permeable. It is, therefore, desired that the electrically conducting ceramics (perovskite-type oxide) forming the oxygen-electrode 34 has an open porosity of not smaller than 20% and, particularly, in a range of from 30 to 50%.
It is desired that the oxygen-electrode 34 has a thickness of from 30 to 100 pm frorn the standpoint of collecting electricity.
(Interconnect 35) The interconnect 35 formed on the support substrate 31 at a position facing the oxygen-electrode 34 comprises electrically conducting ceramics, and must have resistance against reduction and oxidation since it comes in contact with the fuel gas (hydrogen) and the oxygen-containing gas. As the above electrically conducting ceramics, there is usually used a perovskite oxide (LaCr03 oxide) of the type of lanthanum chromite.
In order to prevent the leakage of the fuel gas passing through the inside o- the support substrate 31 and of the oxygen-containing gas passing through the outside of the support substrate 31, further, the electrically conducting ceramics must be dense and must desirably have a relative density of, for example, not smaller than 93% and, particularly, not smaller than 95%.
It is desired that the interconnect 35 has a thyckness of from 10 to 200 pm from the standpoint of preventing the leakage of gas and electric resistance.
When its thickness is smaller than this range, the gas tends to leak. When the thickness is greater than this range, on the other hand, the electric resistance becomes so great that the function for collecting electricity may decrease due to a drop in the potential.
As is obvious from Fig. 1, further, the dense solid electrolytic layer 33 is intimately adhered onto both sides of the interconnect 35 to prevent the leakage of gas. In order to enhance the sealing performance, further, a junction layer (not shown) of, for example, Y203 may be provided between both side surfaces of the intrconnector 35 and the solid electrolytic layer 33.
It is desired that a P-type semiconductor layer 39 is formed on the outer surface (upper surface) of the interconnect 35. Namely, in a cell stack (see Fig. 2) assembled by the fuel cells the electrically conducting collector member 40 is connected to the interconnect 35.
If the collector member 40 is directly connected to the interconnect 35, however, the potential decreases to a large degree due to the non-ohmic contact, and electricity-collecting performance decreases. With the collector member 40 being connected to the interconnect 35 via the P-type semiconductor layer 39, however, the ohmic connection is established between the two, whereby a drop in the potential decreases, a drop in the electricity-collecting performance is effectively alleviated, and an electric current of, for example, from the oxygen-electrode 34 of from one fuel cell 30 is efficiently transferred to the support substrate 31 of the other fuel cell 30. As the P-type semiconductor of this kind, there can be exemplified a perovskite oxide of a transition metal. Concretely speaking, there can be used P-type semiconductor ceramics having an electron conductivitv greater than that of the LaCr03 oxide constituting the interconnect 35, for example, at least the one of the ~aMn03 oxide, LaFe03 oxide or LaCo03 oxide in which Mn, Fe or Co is present on the B-site. It is desired that the P-type semiconductor layer 39 has a thickness of, usually, in a range of from 30 to 100 um.
The interconnect 35 can be directly formed on the flat bortion A of the support substrate 31 on the side where the solid electrolytic layer 33 has not been formed. On this portion, too, however, the fuel-electrode layer 32 may be formed, and the 4-Interconnect 35 may be formed on the fuel-electrode layer 32. That is, the fuel-electrode layer 32 may be formed on the whole circumference of the support substrate 31, and the interconnect 35 may be formed on the fuel-electrode layer 32. Namely, formation of the interconnect 35 on the support substrate 31 via the fuel-electrode layer 32 is advantageous from the standpoint of suppressing a drop of potential on the interface between the support substrate 31 and the interconnect 35.
(Fabrication of the Fuel Cell) The fuel cel-l having the above-mentioned structure is fabricated as described below.
First, a powder of a metal of the iron family such as Ni or of an oxide thereof, a powder of a rare-earth oxide such as Y203r an organic binder and a solvent are mixed together to prepare a slurry thereof. The slurry is extrusion-molded to obtain a support substrate which is, then, dried.
Next, the materials for forming the fuel-electrode layer (Ni or Ni0 powder and stabilized zirconia powder), an organic binder and a solvent are mixed together to prepare a slurry from which a sheet is prepared for forming the fuel-electrode layer. Instead of preparing the sheet for the fuel-electrode layer, further, a paste obtained by dispersing the fuel-electrode-forming materials in a solvent may be applied onto a predetermined position of the support substrate-forming molded body obtained above followed by drying to form a coating layer for forming the fuel-electrode layer.
Further, the stabilized zirconia powder, the organic binder and the solvent are mixed together to prepare a slurry. By using this slurry, a sheet is prepared for forming the solid electrolytic layer.
The support substrate-forming molded body obtained above, the sheet for the fuel-electrode and the sheet for the solid electrolytic layer are larninated to const-tute a layer structure shown in, -For example, Fig.
1, and are dried. Here, when the coating layer for the fuel-electrode layer has been formed on the surface of the support substrate-forming molded body, the sheet for the solid electrolytic layer only may be laminated on the support substrate-forming molded body and may be dried.
Then, the material for the interconnect (e.g., LaCrO3 oxide powder), the organic binder and the solvent are mixed together to prepare a slurry thereof, and a sheet is prepared for forming the interconnect.
The sheet for forming the interconnect is further laminated on a predetermined position of the laminate obtained above, thereby to prepare a laminate for firing.
The laminate for firing is subjected to the processing for removing the binder and is co-fired in an oxygen-containing atmosphere at 1300 to 1600 C. The obtained sinterec. body is coated at a predetermined position with a paste containing a material for forming the oxygen-electrode (e.g., LaFe03 oxide powder) and a solvent and., as required, with a paste containing a material for forming the P-type semiconductor layer (e.g., LaFe03 oxide powder) and a solvent by dipping or the like, and is fired at 1000 to 1300 C to produce the fuel cell 30 of the present invention having the structure shown in Fig. 1.
When Ni alone is used for the formation of the 5 support substrate 31 and the fuel-electrode layer 32, Ni is oxidized into Ni0 due to the firing in the oxygen-containing atmosphere. As required, however, the reduction processing may be effected to return Ni0 back to Ni. Besides, NiO is exposed to the reducing 10 atmosphere while generating electricity and is returned back to Ni.
(Cell Stack) Referring to Fig. 2, the cell stack is constituted by a set of a plurality of the above-mentioned fuel 15 cells 30 which are connected to each other in series with the collector member 40 constituted by a metal felt and/or a metal plate interposed among the fuel cells 30 neighboring up and down. Namely, the support substrate 31 of one fuel cell 30 is electrically connected to the oxygen-electrode 34 of the other fuel cell 30 through the interconnect- 35, P-type semiconductor layer 39 and cotlector member 40. As shown in Fig. 2, further, the cell stacks are arranged side by side, and the neighboring cell stacks are connected in series through an electrically conducting member 42.
The fuel cell assembly of the present invention is constituted by containing the cell stack of Fig. 2 in a container. The container is provided with introduction pipes for introducing the fuel gas such as hydrogen into the fuel cell 30 from an external unit and with introduction pipes for introducing the oxygen-containing gas such as the air into external space of the fuel cell 30. When heated at a predetermined temperature (e.g., 600 to 900 C), the fuel cells generate electricity, and the fuel gas and the oxygen-containing gas after used are discharged out of the container.
The present invention is in no way limited to the above embodiment only but can be modified in a variety o-F other ways without modifying the gist of the invention. For example, the support substrate 31 may be formed in a cylindrical shape, or an intermediate layer having a suitable degree of electronic conductivity may be formed between the oxygen-electrode 34 and the solid electrolytic layer 33.
In the fuel unit of the present invention, the fuel-electrode layer, the solid electrolytic layer and the oxygen-electrode are provided on the support substrate formed by using a metal of the iron family such as Ni or an oxide thereof and a particular rare-earth oxide such as Y203 to effectively alleviate inconvenience such as peeling of the solid electrolytic layer and the occurrence of cracks due to a difference in the thermal expansion. That is, the coefficient of thermal expansion is brought close to that of the support substrate. Therefore, the fuel cell unit of the present invention is produced by co-firing inexpensively and maintaining a high yield.
Further, the particular rare-earth oxide such as Y203 existing in the support substrate diffuses little in the solid electrolytic layer at the time of co-firing and does not adversely affect the ionic conductivity of the solid electrolyte or the electronic conductivity of the electrode of the oxygen side. Besides, the solid electrolytic layer itself has been constituted by Zr02 in which rare earth elements such as Y203 and Yb203 have been contained in the form of solid solutions.
Therefore, even if the rare-earth oxides in the support substrate diffuse into the solid electrolytic layer at the time of co-firing, their effect is minimized. The rare-earth oxides such as Y203 and Yb203 present in the support substrate are used for stabilizing the zirconia that forms the solid electrolytic layer. Therefore, the fuel cell of the present invention is advantageous since it can be produced by using smali. number of elements and at a low cost.
EEXAMP~ES
(Experiment 1) An Ni0 powder or an Ni powder having an average particle size of 0.5 um and rare-earth oxide powders (average particle sizes of 0.8 to 1.0 pm) shown in Tables 1 to 5 were mixed together such that the volume ratios after firing were as shown in Tables 1 to 5 (samples Nos. 1 to 92).
Further, composite rare-earth oxide powders (average particle sizes of 0.8 to 1.0 pm) shown in Table 6 and the above Ni or NiO powder were mixed together at ratios shown in Table 6 (samples Nos. 93 to 124).
The amounts of NiO powder in Tables 1 to 6 are those calculated as Ni. For example, sample No. i has a mean_ng in that the NiO powder and the Y203 powder were mixed together, and, after firing, NiO was 65% by volume calculated as Ni. and Y203 was 35% by volume.
The compositions of composite rare-earth oxide powders shown in. Table 6 are those found by being converted into weight ratios of stable oxides from the molar ratios (measured) of the constituent elements in the starting powders and by, further, being converted into volume ratios of stable oxides.
The above mixed powders were further mixed with a pore-imparting agent, an organic binder (polyvinyl alcohol) and water (solvent) to prepare slurries for the support substrate. The slurries were, then, extrusion-molded into rectangular parallelopiped articles, dried, put to the processing for removing the binder, and were fired in the atmosphere at 1500 C.
The obtained sintered bodies were machined into a -ength of 20 mm, measured for their coefficients of thermal expansion in the atmosphere and in a reducing atmosphere of an oxygen partial pressure of about 10-19 Pa at room temperature to 1000 C, and were further measured for their electric conductivities in a reducing atmosphere of an oxygen partial pressure of about 10-19 Pa at 1000 C based on the four-terminal method. The results were as shown in Tables 1 to 6.
As comparative examples, further, there were used a mixed powder (sample No. 13 of Table 1) of the NiO
powder having an average particle size of 0.5 pm and a YSZ (Y203, stabilized zirconia) having an average particle size of 0.4 um, and a mixed powder (sample No.
14 of Table 1) of the Ni0 powder having an average particle size of 0.5 um and a spinel (MgA1zO4) powder having an average particle size of 0.5 }im. These powders were mixed with a pore-imparting agent, an organic binder (polyvinyl alcohol) and water (solvent), were fired under the same conditions as those described above, and were measured for their coefficients of thermal expansion and electric conductivities. The results were as shown in Table 1.
>1 >
o 0 0 0 0 o c c o 0 0 0 0 0 N N f- CO -I O LI) LO 00 ~ I O I~ ~
~ U) ~-o lo Ln Ln ~n Ln cr ~ Ln Lr; i.c') u-) Ln Lt) 4-) =~ ~i U d lf) M r-i 3' ~ v--I N N M N -' ('') --1 =,-1 ~ U U) ('M M c~ M N N ~ r M M M N Cr N
0 r-i i-H r-I
O ko O
tt~ ~O N N ~ ~ N N M M N ~ N N
U ~ .
~ M M M C~ N N r-I -1 M M N
--I r-I c--I c-i r-A s-I c--1 -I r-i r-I r-I r--I r-I
rl O N o\o I
~ O~ I I I I I I I I OT CD N I
O o N
m Z~ r Ln Ln O O O O Ln Lq I I Ln 0 N Ul ~ ~ M '') ~I d ~.f~ ~ l9 ~9 N ~ -04 ~
J-+ ul 0) 010 - -I
I LC) I O ! O I Ln I O I Lf) I i U) ~
~ ~O l9 Ln M l9 N O
-ka N o10 O 0 ~ QQ C) O I m I O I O N ~ ~
4) ~ -1 N M ~t iS) kl9 t- Oo 6l O --1 ('14 M
i-I
v) z >1 U --( O -~ ~ O O C) O J O O C) O O C) O O O O C) C) CO CD O C) C) C) O C) C) O
S-I C) C!) ri N t-- m N rl tf) lfl r I r-I N!'- l9 rI Om lfl O M N oo ~-p -I
ri tn l9 -I
U LO ~.D Ln l_C) u,) L'7 d" -zt' L(7 lo Qv Ln L.p Ln Ln 1' z4' lo k9 ud Lf) L() Lf) L() L( i N ~
~--i O
W C) (D
~ S4 U
Ln tI')MN~o S) MMl`~Ln ~,D MN(,o to -,t'Mlfl J ~-9CV ('7l9~OMV' W . . . . . . . . . . . . . . . . .
4-= U Q (''1M(M(~NN--~NMMMMNNr r- N~~MC~I NNr r N
C) O -i r-I -- -1 r-~ r-f ri -! H i-I ri r~
'C' 41 OCD
~
N ~ 10~9MNC--l9d"sr,9~,oL1)MM[- C- -v b ~.Ou-) n M:Z"~~~~ Ln S-{ . . . . . . . . .
(MC~MMNNr-INM(~MMNNri'--INf''MC~MMNNr-Ic~N
~ ri r-I ri r; --i r-I rl ri rl c-I rl rl ri r-i r-i rl c-i rl '--I c-I rl ~-i c--I ri rl r-i rl N
~
Q) I ! l I I 1 l I I I I I { ILn~OOOO .c7~0 f'MMd',,z1'in Ln lfllOtn C4 ~D., ~4 N or C) 'Z:~ ri I I I I I I I I ILn LC~ O O O O lo Ln O I I I I I I I I I
O O' ['')Mv d'tP,Ln W lflt.C) ~-41 0) o\o - Ln Ln OOOCpLn Ln O I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 M~ d~ tI~ l9 l9 l.f) 9, 0 ~
T j or--I 1 L n I O I O I L n Ln i 1.n I O I O ILn :n Iu) I O 1 O ILn Ln ~ l0 lfl Ln M N QO Q0 Ln M (N ~ ~ U-) m N
Z 5:14 ~-1 N o10 r-I Ln I O I O ILn ILn Ln I O I O ILn I T) Ln I O I O ILn IU-) Q O0 l0 Q9 :.t) M N"0 lD Lr) m N l0 l9 U') M N
z a ri Lnl9[- 006lOriNM-:t'tf)l9[- 00610-INm d'11710(- OOCSIOc--I
Fig. 3 is a diagram illustrating a stack of conventional solid oxide fuel cells. In this stack of cells, a plurality of fuel cells 1 are regularly arranged, a collector member 5 made of a metal felt is interposed between one fuel cell la and another neighboring fuel cell lb, and a fuel-electrode 7 of one fuel-cell la is electrically connected to an oxygen-electrode (air-electrode) 11 of another fuel cell lb.
The fuel celll (la, 1b) is constituted by a solid electrolyte 9 and the oxygen-electrode 11 composed of electrically conducting ceramics, that are provided in this order on the outer peripheral surface of the fuel-electrode of a cylindrical cermet (of which the interior serves as a fuel gas passage). An interconnect 13 is provided on the surface of the fuel-electrode 7 covered with neither the solid electrolyte 9 nor the oxygen-electrode 11. As will be obvious from Fig. 3, the interconnect 13 is electrically corinected to the fuel-electrode 7 so will not to be connected to the oxygen-electrode 11.
The interconnect 13 is made of electrically conducting ceramics which is subject to be little degraded with an oxygen-containing gas such as a fuel gas or the air. The electrically conducting ceramics must be so dense as to reliably shut the fuel aas flowing inside the fuel-electrode 7 off the oxygen-containing gas flowing outside the oxygen-electrode 11.
The collector member 5 provided between the neighboring fuel cells ia and lb is electrically connected to the fuel-electrode 7 of the one fuel cell la through the interconnect 13, and is further directly connected to the oxygen-electrode 11 of the other fuel cell lb, so that the neighboring fuel cells are connected together in series.
A fuel cell assembly is constituted by containing the cell stack having the above-mentioned structure in a container, and generates electricity at 600 to 1000 C by flowing the fuel gas (hydrogen) into the fuel rod 7 and flowing the air (oxygen) into the oxygen-electrode 11.
In the fuel cell constituting the above-mentioned fuel cell assembly, in general, the fuel-electrode 7 is formed of Ni and yttria stabilized zirconia (YSZ), the solid electrolyte 9 is formed of Zr02(YSZ) containing Y203, and the oxygen-electrode 11 is constituted by a perovskite composite oxide of the type of lanthanum manganate.
As a method of producina the above fuel cell, there has been known a so-called co-firing method which forms the fuel cell by co-firing the fuel-electrode 7 and the solid electrolyte 9. The co-firing method is a very simple process requiring a decreased number of steps for production, featuring increased yield in the production of cells, and is advantageous for decreasing the cost.
However, the conventional fuel cells are accompanied by such problems that the fuel-electrode 7 is cracked when the fuel-electrode 7 and the solid electrolyte 9 are co-fired, and the solid electrolyte 9 peels off the fuel-electrode 7 which is a support member. That is, the solid electrolyte 9 is formed of Zr0g containing Y203 having a coefficient of thermal expansion of 10.8 x 10-6/ C. Here, however, the fuel-electrode 7 supporting the solid electrolyte 9 contains Ni having a coefficient of thermal expansion of 16.3 x 10-6 / C which is very larger than that of YSZ. At the time of co-firing, therefore, there develops a large difference in the thermal expansion between the solid electrolyte 9 and the fuel-electrode 7 supporting it.
As a result, there occur such problems as cracking of the fuel-electrode 7 and peeling of the solid electrolyte 9.
In order to solve the above problems, further, it has been proposed to use mulite (3A1203 = 2Si 0,,) and spinel (MgAl2O9, CaAl20s) and to form the fuel-electrode 7 by using them in combination with Ni (see Japanese Unexamined Patent Publication (Kokai) No. 29574/1995).
According to the above proposal, the coefficient of thermal expansion of the fuel-electrode 7 is brought close to the coefficient of thermal expansion of the solid electrolyte 9, making it possible to suppress the occurrence of cracks in the fuel-electrode 7 and the peeling of the fuel-electrode 7 from the solid electrolyte 9 at the time of co-firing. There, however, arises a new problem in that the components such as Mg, A1 and Si in the fuel-electrode diffuse into the solid electrolyte 9 at the time of co-firing, whereby the ionic conductivity of the solid electrolyte 9 decreases and the generating performance of the fuel cell decreases.
SUMMARY OF THE INVENTION
It is therefore an object of the present inverition to provide a fuel cell which not only effectively suppresses the occurrence of cracks in the fuel-electrode and the peeling of the solid electrolyte at the time of co-firing but also suppresses the reduction of performance such as a decrease in the ionic conductivity caused by the diffusion of elements into the solid electrolyte, and which can be inexpensively produced by the co-firing method.
According to the present invention, there is provided a fuel cell unit comprising:
a gas-permeable and electrically conducting support substrate having at least one fuel gas passage formed therein;
a fuel-electrode layer formed on the support substrate;
a solid electrolytic layer formed on the fuel-electrode layer so as to cover the fuel-electrode layer and containing Zr02 in which at least one rare earth element is present in the form of a solid solution; and an oxygen-electrode provided on the solid electrolytic layer so as to face the fuel-electrode layer;
wherein:
the support substrate is formed of (a) a metal of the iron family and/or an oxide of a metal of the iron family, and (b) a rare-earth oxide containing at least one element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr; and the rare-earth oxide is contained in an amount of 35 to 65% by volume in the support substrate.
Namely, in the present invention, the support substrate in each of the members constituting the cell is formed by a metal of the iron family or an oxide thereof (such as Ni or NiO) and a particular rare-earth oxide in a 4a particular amount, and makes it possible to effectively avoid various inconveniences caused by the co-firing.
For example, the above rare-earth oxide in the support substrate does not almost form a solid solution with, or does not almost react with, the metal of the iron family or with the oxide thereof during the firing or during the generation of electricity. Besides, the rare-earth oxide has a coefficient of thermal expansion which is very smaller than the coefficient of thermal expansion (about 10.8 x 10-6/ C) of Zr02 (hereinafter ~
often referred to as stabilized zirconia) in which rare earth elements are existing in the form of solid solutions in the solid electrolytic layer or in the fuel-electrode layer. For example, Y203 or Yb203 has a coefficient of thermal expansion of about 8.14 x 10-6/ C.
By controlling the content of the rare--earth oxide such as Y203 or Z'b203r therefore, it is allowed to bring the coefficient of thermal expansion of the support substrate close to the coefficient of thermal expansion of the solid electrolytic layer or of the fuel-electrode layer and, hence, to effectively suppress the occurrence of cracks or peeling caused by a difference in the coefficient of thermal expansion.
Besides, the metal of the iron family, the oxides thereof and the particular rare-earth oxide constituting the support substrate all tend to be diffused little.
Even when the support substrate and the solid electrolytic layer are co-fired, therefore, the rare earth element is effectively suppressed from diffusing into the solid electrolytic layer avoiding adverse effect on the ionic conductivity of the solid electrolytic layer. Even if the rare earth element has diffused during the co-firing, the effect of diffusion of the rare earth element in the solid electrolyte can be minimized since the soli-d electrolytic layer has been constituted by Zr02 (stabilized zirconia) in which rare-earth oxides such as Y203 and Yb203 have been contained in the form of solid solutions.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a transverse sectional view illustrating a fuel cell according to the present invention;
Fig. 2 is a transverse sectional view illustrating a celi stack formed by a plurality of fuel cells; and Fig. 3 is a transverse sectional view illustrating a cell stack constituted by conventional fuel cells.
DETAILED DESCRIPTI0N OF THE iIVVENTI0N
In Fig. 1 which is a transverse sectional view of a fuel cell of the present invention, the fuel cell which is generally designated at 30 has a support substrate 31_ which is flat in cross section and is of an elliptic cylindrical shape as viewed generally. A plurality of fuel gas passages 31a are formed maintaining a suitable distance in the support substrate 31. The fuel cell 30 has a structure in which various kinds of members are provided on the support substrate 31. A plurality of the above fuel cells 30 are connected to each other in series through collector members 40 as shown in Fig. 2 thereby to form a cell stack for constituting a fuel cell assembly.
As will be understood from the shape shown in Fig.
1, the support substrate 31 comprises a flat portion A
and arcuate portions B at both ends of the flat portion A. Both surfaces of the flat portion A are formed nearly in parallel with each other, a fuel-electrode layer 32 is so provided as to cover one surface of the flat portion A and the arcuate portions B on both sides, and a dense solid electrolytic layer 33 is laminated so as to cover the fuel-electrode layer 32. An oxygen-electrode 34 is laminated on the solid electrolytic layer 33 from one surface of the flat portion A toward the arcuate portions B on both sides so as to face the fuel-electrode layer 32. An interconnect 35 is formed on the other surface of the flat portion A on where neither the fuel-electrode layer 32 nor the solid electrode layer 33 has been laminated. As is obvious Trom Fig. 1, the fuel-electrode layer 32 and the solid electrolytic layer 33 are extending up to both sides of the interconr,ect 35, so that the surface of the support substrate 31 is not exposed to the outer side.
Iri the fuel CEIl Cf the above StrUCtUre, a pOrt10 of the fuel-eiectrode layer 32 facing the oxygen-electrode 34 works as the fuel-electrode to generate electricity. Namely, the oxygen-containing gas such as the air is supplied to the outside of the oxygen-electrode 34, the fuel gas (hydrogen) =..s supplied to the gas passages in the support substrate 31, and the temperature is elevated up to a predetermined operation temperature, whereby the electrode reaction of the following formula (1) takes places on the oxygen-electrode 34, and the electrode reaction of, for example, the following formula (2) takes place on a port=~on of the fuel-electrode layer 32 that serves as the fuel-electrode to thereby generate electricity, Oxygen-electrode: 1/202 + 2e- - 02- (solid electrolyte) --- (1) Fuel-electrode: 02- (solid electrolyte) + H2 --+ H20 +
2e --- (2) The electric current produced by the above generation is collected through the interconnect 35 mounted on the support substrate 31.
(Support Substrate 3"1) In the fuel cell 30 of the present invention having the above structure, the support substrate 31 must be gas-permeable to permit the permeation of the fuel gas to the fuel-electrode layer 32, and must be electrically conducting to collect electricity through the interconnect. In order to satisfy the above requirements and to alleviate inconvenience caused by co-firing, the support substrate 31 is constituted by a metal component of the iron family and a particular rare-earth oxide.
The metal component of the iron family -s to impart electrically conducting property to the support substrate 31, and may be a simple metal of the iron family, an oxide of the metal of the iron family, an alloy of the metal of the iron family or an oxide of the alloy. The metal of the iron family may be iron, nickel or cobalt, and any one of them may be used in the present invention. From the standpoint of cost and stability in the fuel gas, however, it is desired that Ni and/or Ni0 '~~~_s contained as the component of the iron family.
The rare-earth oxide component is used for bringing the coefficient of thermal expansion of the support substrate 31 close to that of the stabilized zirconia forming the solid electrolytic layer 33. In order to maintain a high electronic conduct__vity and to prevent diffusion into the solid electrolytic layer 33, therefore, an oxide containing at least one kind of ra_Ve earth element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr is used in combination with the above componerlt of the iron family.
Concrete examp_es of the rare-earth oxide include Y203r LU203r Yb203, Tm203, Er203, ho203r DY203r Gd203, Sm203 and Pr203. Among them, however, Y203 and Yb203 are particularly desired since they are inexpensive.
From the standpoint of bringing the coefficient of thermal expansion of the support substrate 31 close to that of the stabilized zirconia, ir.i particular, it is desired in the present invention that the above component of the iron family is contained in an amount of from 35 to 65% by volume in the support substrate 31 and that the rare-earth oxide is contained in an amount of from 35 to 65% by volume in the support substrate 31.
The support substrate 31 may further contain other metal components and oxide compcnents in a range in which they do not impair the required properties.
It is essential that the support substrate 31 constituted by --he above metal component of the iron family and. the rare-earth oxide has fuel gas-permeating property and, hence, has an open porosity which is not usually smaller than 30% and, particularly, in a range of from 35 to 50%. It is further desired that the support substrate 31 has an electronic conductivity of not smaller than 300 S/cm and, particularly, not smaller than 440 S/cm.
It _J1s desired that the support substrate 31 has the flat portion A of a length of, usually, from 15 to 35 mm, has the arcuate porticns B of a length (length of arc) of from about 3 to about 8 mm, and has a thickness (gap between both surfaces of the flat portion A) of from about 2.5 to about 5 mm.
(Fuel-electrode Layer 32) In the present invention, the fuel-electrode layer 32 is for producing the electrode reaction of the above formula (2) and is by itse.lf formed of known porous and electrically ccnducting ceramics. For example, the fuel-electrode layer 32 is formed of Zr02 in which rare earth elements are contained in the form of solid solutions and Ni and/or NiO. As Zr02 (stabilized zirconia) in which rare earth elements are contained in the form of solid soiutions, there can be used those described below that have been used for the formation of the solid electrolytic iayer 33.
It is desired that the fuel-electrode layer 32 contains the stabilized zirconia in an amount in a range of from 35 to 65% by volume, and contains Ni or NiO in an amount in a range of from 65 to 315% by volume. It is further desired that the fuel-electrode layer 32 has an open porosity of not smaller than 15% and, particuiarly, in a range of from 20 to 40%, and has a thickness of from 1 to 30 4m. When the fuel-electrode layer 32 is too thin, the performance may decrease. When it is too thick, on the other hand, peeling may occur between the solid electrolytic layer 33 and the fuel-electrode layer 32 due to a difference in the thermal expansion.
In the example of .7ig. 1, the fuel-electrode layer 32 is extending up to both sides of the intrconnector 35. The fuel-electrode, however, needs be formed at a 5 position facing the oxygen-electrode 34. Therefore, the fuel-electrode layer 32 may be formed, for example, on only the flat portion A on the side where the oxygen-electrode 34 is provided. The fuel-electrode layer 32 may further be formed over the whole circumference of 10 the support substrate 31. In the present invention, it is desired that the solid electrolytic layer 33 as a whole is formed on the fuel-electrode layer 32 in order to increase the junction strength between the solid electrolytic layer 33 and the support substrate 31.
(Solid Electrolytic Layer 33) The solid electrolytic layer 33 on the fuel-electrode laye-- 32 is usually formed of dense ceramics comprising Zr02 in which 3 to 15o by mol of rare earth elements are contained in the form of solid solutions (called stabilized zirconia). As the rare earth elements, there can be exemplified Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
Among them, however, Y and Yb are desired since they are inexpensive.
It is desired that the stabilized zirconia ceramics forming the solid electrolytic layer 33 has a relative density (according to Archimedes' method) of not smaller than 93% and, particularly, not smaller than 95% from the standpoint of preventing the permeation of gas and has a thickness of from 10 to 100 pm.
(Oxygen-electrode 34) The oxygen-electrode 34 is formed of electrically conducting ceramics which is a perovskite-type oxide of the so-called AB03 type. As the perovskite-type oxide, there can be preferably used at least one kind of perovskite-type oxide of a. transition metal and, particularly, an LaMn03-type oxide having La on the A-site, an La-Fe03-type oxide or an LaCoO3-type oxide and, particularly, the LaFeO3-type oxide from the standpoint of a high electrically conducting property at ari operation temperature of from about 600 to about 1000 C.
In the above perovskite-type oxide, La and Sr may exist on the A-site and, besides, Fe as well as Co and Mn may exist on the B-site.
The oxygen-electrode 34 must be gas-permeable. It is, therefore, desired that the electrically conducting ceramics (perovskite-type oxide) forming the oxygen-electrode 34 has an open porosity of not smaller than 20% and, particularly, in a range of from 30 to 50%.
It is desired that the oxygen-electrode 34 has a thickness of from 30 to 100 pm frorn the standpoint of collecting electricity.
(Interconnect 35) The interconnect 35 formed on the support substrate 31 at a position facing the oxygen-electrode 34 comprises electrically conducting ceramics, and must have resistance against reduction and oxidation since it comes in contact with the fuel gas (hydrogen) and the oxygen-containing gas. As the above electrically conducting ceramics, there is usually used a perovskite oxide (LaCr03 oxide) of the type of lanthanum chromite.
In order to prevent the leakage of the fuel gas passing through the inside o- the support substrate 31 and of the oxygen-containing gas passing through the outside of the support substrate 31, further, the electrically conducting ceramics must be dense and must desirably have a relative density of, for example, not smaller than 93% and, particularly, not smaller than 95%.
It is desired that the interconnect 35 has a thyckness of from 10 to 200 pm from the standpoint of preventing the leakage of gas and electric resistance.
When its thickness is smaller than this range, the gas tends to leak. When the thickness is greater than this range, on the other hand, the electric resistance becomes so great that the function for collecting electricity may decrease due to a drop in the potential.
As is obvious from Fig. 1, further, the dense solid electrolytic layer 33 is intimately adhered onto both sides of the interconnect 35 to prevent the leakage of gas. In order to enhance the sealing performance, further, a junction layer (not shown) of, for example, Y203 may be provided between both side surfaces of the intrconnector 35 and the solid electrolytic layer 33.
It is desired that a P-type semiconductor layer 39 is formed on the outer surface (upper surface) of the interconnect 35. Namely, in a cell stack (see Fig. 2) assembled by the fuel cells the electrically conducting collector member 40 is connected to the interconnect 35.
If the collector member 40 is directly connected to the interconnect 35, however, the potential decreases to a large degree due to the non-ohmic contact, and electricity-collecting performance decreases. With the collector member 40 being connected to the interconnect 35 via the P-type semiconductor layer 39, however, the ohmic connection is established between the two, whereby a drop in the potential decreases, a drop in the electricity-collecting performance is effectively alleviated, and an electric current of, for example, from the oxygen-electrode 34 of from one fuel cell 30 is efficiently transferred to the support substrate 31 of the other fuel cell 30. As the P-type semiconductor of this kind, there can be exemplified a perovskite oxide of a transition metal. Concretely speaking, there can be used P-type semiconductor ceramics having an electron conductivitv greater than that of the LaCr03 oxide constituting the interconnect 35, for example, at least the one of the ~aMn03 oxide, LaFe03 oxide or LaCo03 oxide in which Mn, Fe or Co is present on the B-site. It is desired that the P-type semiconductor layer 39 has a thickness of, usually, in a range of from 30 to 100 um.
The interconnect 35 can be directly formed on the flat bortion A of the support substrate 31 on the side where the solid electrolytic layer 33 has not been formed. On this portion, too, however, the fuel-electrode layer 32 may be formed, and the 4-Interconnect 35 may be formed on the fuel-electrode layer 32. That is, the fuel-electrode layer 32 may be formed on the whole circumference of the support substrate 31, and the interconnect 35 may be formed on the fuel-electrode layer 32. Namely, formation of the interconnect 35 on the support substrate 31 via the fuel-electrode layer 32 is advantageous from the standpoint of suppressing a drop of potential on the interface between the support substrate 31 and the interconnect 35.
(Fabrication of the Fuel Cell) The fuel cel-l having the above-mentioned structure is fabricated as described below.
First, a powder of a metal of the iron family such as Ni or of an oxide thereof, a powder of a rare-earth oxide such as Y203r an organic binder and a solvent are mixed together to prepare a slurry thereof. The slurry is extrusion-molded to obtain a support substrate which is, then, dried.
Next, the materials for forming the fuel-electrode layer (Ni or Ni0 powder and stabilized zirconia powder), an organic binder and a solvent are mixed together to prepare a slurry from which a sheet is prepared for forming the fuel-electrode layer. Instead of preparing the sheet for the fuel-electrode layer, further, a paste obtained by dispersing the fuel-electrode-forming materials in a solvent may be applied onto a predetermined position of the support substrate-forming molded body obtained above followed by drying to form a coating layer for forming the fuel-electrode layer.
Further, the stabilized zirconia powder, the organic binder and the solvent are mixed together to prepare a slurry. By using this slurry, a sheet is prepared for forming the solid electrolytic layer.
The support substrate-forming molded body obtained above, the sheet for the fuel-electrode and the sheet for the solid electrolytic layer are larninated to const-tute a layer structure shown in, -For example, Fig.
1, and are dried. Here, when the coating layer for the fuel-electrode layer has been formed on the surface of the support substrate-forming molded body, the sheet for the solid electrolytic layer only may be laminated on the support substrate-forming molded body and may be dried.
Then, the material for the interconnect (e.g., LaCrO3 oxide powder), the organic binder and the solvent are mixed together to prepare a slurry thereof, and a sheet is prepared for forming the interconnect.
The sheet for forming the interconnect is further laminated on a predetermined position of the laminate obtained above, thereby to prepare a laminate for firing.
The laminate for firing is subjected to the processing for removing the binder and is co-fired in an oxygen-containing atmosphere at 1300 to 1600 C. The obtained sinterec. body is coated at a predetermined position with a paste containing a material for forming the oxygen-electrode (e.g., LaFe03 oxide powder) and a solvent and., as required, with a paste containing a material for forming the P-type semiconductor layer (e.g., LaFe03 oxide powder) and a solvent by dipping or the like, and is fired at 1000 to 1300 C to produce the fuel cell 30 of the present invention having the structure shown in Fig. 1.
When Ni alone is used for the formation of the 5 support substrate 31 and the fuel-electrode layer 32, Ni is oxidized into Ni0 due to the firing in the oxygen-containing atmosphere. As required, however, the reduction processing may be effected to return Ni0 back to Ni. Besides, NiO is exposed to the reducing 10 atmosphere while generating electricity and is returned back to Ni.
(Cell Stack) Referring to Fig. 2, the cell stack is constituted by a set of a plurality of the above-mentioned fuel 15 cells 30 which are connected to each other in series with the collector member 40 constituted by a metal felt and/or a metal plate interposed among the fuel cells 30 neighboring up and down. Namely, the support substrate 31 of one fuel cell 30 is electrically connected to the oxygen-electrode 34 of the other fuel cell 30 through the interconnect- 35, P-type semiconductor layer 39 and cotlector member 40. As shown in Fig. 2, further, the cell stacks are arranged side by side, and the neighboring cell stacks are connected in series through an electrically conducting member 42.
The fuel cell assembly of the present invention is constituted by containing the cell stack of Fig. 2 in a container. The container is provided with introduction pipes for introducing the fuel gas such as hydrogen into the fuel cell 30 from an external unit and with introduction pipes for introducing the oxygen-containing gas such as the air into external space of the fuel cell 30. When heated at a predetermined temperature (e.g., 600 to 900 C), the fuel cells generate electricity, and the fuel gas and the oxygen-containing gas after used are discharged out of the container.
The present invention is in no way limited to the above embodiment only but can be modified in a variety o-F other ways without modifying the gist of the invention. For example, the support substrate 31 may be formed in a cylindrical shape, or an intermediate layer having a suitable degree of electronic conductivity may be formed between the oxygen-electrode 34 and the solid electrolytic layer 33.
In the fuel unit of the present invention, the fuel-electrode layer, the solid electrolytic layer and the oxygen-electrode are provided on the support substrate formed by using a metal of the iron family such as Ni or an oxide thereof and a particular rare-earth oxide such as Y203 to effectively alleviate inconvenience such as peeling of the solid electrolytic layer and the occurrence of cracks due to a difference in the thermal expansion. That is, the coefficient of thermal expansion is brought close to that of the support substrate. Therefore, the fuel cell unit of the present invention is produced by co-firing inexpensively and maintaining a high yield.
Further, the particular rare-earth oxide such as Y203 existing in the support substrate diffuses little in the solid electrolytic layer at the time of co-firing and does not adversely affect the ionic conductivity of the solid electrolyte or the electronic conductivity of the electrode of the oxygen side. Besides, the solid electrolytic layer itself has been constituted by Zr02 in which rare earth elements such as Y203 and Yb203 have been contained in the form of solid solutions.
Therefore, even if the rare-earth oxides in the support substrate diffuse into the solid electrolytic layer at the time of co-firing, their effect is minimized. The rare-earth oxides such as Y203 and Yb203 present in the support substrate are used for stabilizing the zirconia that forms the solid electrolytic layer. Therefore, the fuel cell of the present invention is advantageous since it can be produced by using smali. number of elements and at a low cost.
EEXAMP~ES
(Experiment 1) An Ni0 powder or an Ni powder having an average particle size of 0.5 um and rare-earth oxide powders (average particle sizes of 0.8 to 1.0 pm) shown in Tables 1 to 5 were mixed together such that the volume ratios after firing were as shown in Tables 1 to 5 (samples Nos. 1 to 92).
Further, composite rare-earth oxide powders (average particle sizes of 0.8 to 1.0 pm) shown in Table 6 and the above Ni or NiO powder were mixed together at ratios shown in Table 6 (samples Nos. 93 to 124).
The amounts of NiO powder in Tables 1 to 6 are those calculated as Ni. For example, sample No. i has a mean_ng in that the NiO powder and the Y203 powder were mixed together, and, after firing, NiO was 65% by volume calculated as Ni. and Y203 was 35% by volume.
The compositions of composite rare-earth oxide powders shown in. Table 6 are those found by being converted into weight ratios of stable oxides from the molar ratios (measured) of the constituent elements in the starting powders and by, further, being converted into volume ratios of stable oxides.
The above mixed powders were further mixed with a pore-imparting agent, an organic binder (polyvinyl alcohol) and water (solvent) to prepare slurries for the support substrate. The slurries were, then, extrusion-molded into rectangular parallelopiped articles, dried, put to the processing for removing the binder, and were fired in the atmosphere at 1500 C.
The obtained sintered bodies were machined into a -ength of 20 mm, measured for their coefficients of thermal expansion in the atmosphere and in a reducing atmosphere of an oxygen partial pressure of about 10-19 Pa at room temperature to 1000 C, and were further measured for their electric conductivities in a reducing atmosphere of an oxygen partial pressure of about 10-19 Pa at 1000 C based on the four-terminal method. The results were as shown in Tables 1 to 6.
As comparative examples, further, there were used a mixed powder (sample No. 13 of Table 1) of the NiO
powder having an average particle size of 0.5 pm and a YSZ (Y203, stabilized zirconia) having an average particle size of 0.4 um, and a mixed powder (sample No.
14 of Table 1) of the Ni0 powder having an average particle size of 0.5 um and a spinel (MgA1zO4) powder having an average particle size of 0.5 }im. These powders were mixed with a pore-imparting agent, an organic binder (polyvinyl alcohol) and water (solvent), were fired under the same conditions as those described above, and were measured for their coefficients of thermal expansion and electric conductivities. The results were as shown in Table 1.
>1 >
o 0 0 0 0 o c c o 0 0 0 0 0 N N f- CO -I O LI) LO 00 ~ I O I~ ~
~ U) ~-o lo Ln Ln ~n Ln cr ~ Ln Lr; i.c') u-) Ln Lt) 4-) =~ ~i U d lf) M r-i 3' ~ v--I N N M N -' ('') --1 =,-1 ~ U U) ('M M c~ M N N ~ r M M M N Cr N
0 r-i i-H r-I
O ko O
tt~ ~O N N ~ ~ N N M M N ~ N N
U ~ .
~ M M M C~ N N r-I -1 M M N
--I r-I c--I c-i r-A s-I c--1 -I r-i r-I r-I r--I r-I
rl O N o\o I
~ O~ I I I I I I I I OT CD N I
O o N
m Z~ r Ln Ln O O O O Ln Lq I I Ln 0 N Ul ~ ~ M '') ~I d ~.f~ ~ l9 ~9 N ~ -04 ~
J-+ ul 0) 010 - -I
I LC) I O ! O I Ln I O I Lf) I i U) ~
~ ~O l9 Ln M l9 N O
-ka N o10 O 0 ~ QQ C) O I m I O I O N ~ ~
4) ~ -1 N M ~t iS) kl9 t- Oo 6l O --1 ('14 M
i-I
v) z >1 U --( O -~ ~ O O C) O J O O C) O O C) O O O O C) C) CO CD O C) C) C) O C) C) O
S-I C) C!) ri N t-- m N rl tf) lfl r I r-I N!'- l9 rI Om lfl O M N oo ~-p -I
ri tn l9 -I
U LO ~.D Ln l_C) u,) L'7 d" -zt' L(7 lo Qv Ln L.p Ln Ln 1' z4' lo k9 ud Lf) L() Lf) L() L( i N ~
~--i O
W C) (D
~ S4 U
Ln tI')MN~o S) MMl`~Ln ~,D MN(,o to -,t'Mlfl J ~-9CV ('7l9~OMV' W . . . . . . . . . . . . . . . . .
4-= U Q (''1M(M(~NN--~NMMMMNNr r- N~~MC~I NNr r N
C) O -i r-I -- -1 r-~ r-f ri -! H i-I ri r~
'C' 41 OCD
~
N ~ 10~9MNC--l9d"sr,9~,oL1)MM[- C- -v b ~.Ou-) n M:Z"~~~~ Ln S-{ . . . . . . . . .
(MC~MMNNr-INM(~MMNNri'--INf''MC~MMNNr-Ic~N
~ ri r-I ri r; --i r-I rl ri rl c-I rl rl ri r-i r-i rl c-i rl '--I c-I rl ~-i c--I ri rl r-i rl N
~
Q) I ! l I I 1 l I I I I I { ILn~OOOO .c7~0 f'MMd',,z1'in Ln lfllOtn C4 ~D., ~4 N or C) 'Z:~ ri I I I I I I I I ILn LC~ O O O O lo Ln O I I I I I I I I I
O O' ['')Mv d'tP,Ln W lflt.C) ~-41 0) o\o - Ln Ln OOOCpLn Ln O I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 M~ d~ tI~ l9 l9 l.f) 9, 0 ~
T j or--I 1 L n I O I O I L n Ln i 1.n I O I O ILn :n Iu) I O 1 O ILn Ln ~ l0 lfl Ln M N QO Q0 Ln M (N ~ ~ U-) m N
Z 5:14 ~-1 N o10 r-I Ln I O I O ILn ILn Ln I O I O ILn I T) Ln I O I O ILn IU-) Q O0 l0 Q9 :.t) M N"0 lD Lr) m N l0 l9 U') M N
z a ri Lnl9[- 006lOriNM-:t'tf)l9[- 00610-INm d'11710(- OOCSIOc--I
7- rlrirlriNNNNNNNNNNM0-) MP'iIn MMM(Y) M`t d' ~ 2 ~
O --i =r ~
O O O O O O O O O O O O O O O O O O O O O O O O O O O
M NNOJC- Or-IIQIflOr0 00 lONOlOf- 61NNOJt- NOLf)"C r-I
QdlflLn Lt tncr:,^Ln9b tnLn=)Ln zsz, ~~ Q4~d Ln LntS)L7:v Zrt.C) - O
W U
a-%
~4 U
~ 0) ~
~ lOt.n Oc-iC- t.nt.>7lOlOd'4I'i061Ll7zTCY`M d'IOC- M-I[- 19C- --.J'l9 44 =r; . . . . . . . . . . . . c' .
U ln t'M <~ (~'1 ('') N N. r-I I N. (M (~' i c'~ N N N M tM N M f'~) M ') N N
ri r 1 N
O -i r-i -I ~ r-I r-l rl ~-I r-i r-i r-i '-I ~-i ri r-I r-I r-I r-I c-i ri rl ~-I ri ~-I rl `-I rl O
nzi t>5 ~.o cn cMlo Lr)19Lc')l9lOtt)NNLt)~c'ncMtt)r- loM(>7~Ow tn uo lo ~4 M M . . . . . . . . . . . . . N -~ . . . . . . .
~ ()l7NN -I - NM(~MMN iN C7MM(~) NNrI N
c=-1 r-I r-~ ~-I '-I ri i-I r-~ r-I r-I '--I ~-I c- r-i r-I ~-~ ~-I '-I ~--~ r-I c-1 ~-I rl i-I r--I c-i c--f ~
L+
M ~-I
N ~'~--II I I I 1 11 11 1 1 1 1 1 l I i ILntn0000Lf7Ln0 c. O>0 ~ Mm dzz tI)Lf)lQ W Lf) ~4 r 0) 010 (~ "0 r=I 1 I I 1 1 I 1 1Lf) Ln O O O O Lf) n O 1 1 1 1 1 1 1 1 Z" Q~I MMd crtl7tf)10 ~0S) '-I
~ D\0 n'ZSr-1 LnLn 0000u-) Ln 0 I I I I I I I I I I I{{ I I I
O~~' M M-i' ~' i.f) LC) LO ~ tn ~4 U o\o -I ILn I O O ILo tS') I Ln I O O 1>n Ln I tt') O 1 O ILr, Ln ~ OR l9 l0 Ln M N t-0 ~O tI) C*') (N l0 ~D Ln (n N
la N o1o I
u ) I O I O I t1) ( L n L n I O I O I u'? ILnLQI O I O ILnI L1) O~0I l~ l0 Uf) (~') N l0 ~O L() M N lfl l0 ~ C+7 N
(D
-i N( d t-nIOC- CO 6l0t-INMcf Ln LO[- cc OIOc--ICV <'')d" Ln IS)f' OJ
cY' zl' d" C" :zj' cI' 'Cr d' Ln Ln Ln L7 Ln Lf) Ln Ln LC) Lf') ~-O k9 k,.o lfl LO lo l9 ~-O LO
ol 2 ~
~
U ~=' -~ ~
O ~ ~ O p O O O O O O O G) O O O O O O O O
I U M H w l9 c- N l0 Q9 O N --I ,M [- r-I CV I.n Ln r=-I
J U] LO w II) Ll) L.-) Ln -- d' Lo l4 lO 1I) Lf) Lo lS) 3' d LS) U -U
I o U
L
=rl S1 r ~C~ 6l cc l.9 ct ts~ Ln C` i C IZI' (n Ln IZi' ~t ~r . . . . . . . , . . . . . .
44 =H
4-1 U C~ M n') M (*') M M N N M M c~ c~'",, M N. N r-I r-I N
0 -0 0 r-i c-( c--I t-I c-i r-I c-l c-{ --! f! c-i c-: .--1 r-a r-I r-l ~--I
r--I
~
U O C) -rl x N p 61 t- C- t1) iC) Q4 LO ;;t+ LC7 L(') t'M l0 T) C') t.C) ~4 c7' M M M M (`') N N M C`'M M M M N N r-I f--I N
c--I i-i r-I s--I r-~i i-I ri r-I -I c--I r--I '--! r--I r-1 -1 +--I
E-~
~4 ~ Q o1a T3 ~-I I f I I 1 I I I 1 L7 Lo O O O p tn Ln O
a O 0 M M zi' zt' Ln ! n l.0 lS~ tf) Q, M N o\O
~ -1 O O O O LO iS) C) I I i I I I I I I
I ~ ~
~ M f'~ 1' G, tl') tf) l.o ~9 I) ~
~ 010 ~3 r I I Ln 1 O I C) I tn u) I Ln I p I p I Ln U=) H O > l0 C0 Uf ) M CN l9 11.0 LC) M N
Z R, ~-Jl N o10 ~ r I if) 1 O I O I U) I Ln Ln I O I O I un I Ln ~
I C~ ~9 L~ M N l9 l9 L) C~ N
N
r-i ~ 6 C) -I N M d Ln l9 f'- Co 6l C) ~-1 CV M lz~!' .f) l9 l0 r-= f- L- C`` C^~ t ^ l f- ['- Oo co Oo Oo co Oo OD
UD z ~
~
u ---i ~ 'r+ J
O O O O O O
O U
U ~ n ~ s) ~ s 0 O ~
O
U
N 4}
-rl O
-~-i 4-4 QO C5l O lf) O
-ri co ~
O~ OJ ~
~ZV Lr) Lf~
~
~
~
LnI
O I I I O C
~ ~
~
~-4 O o\o O'O - I I O O I
-n Ln S-;
N o\o O .r) ~-r) ~ I
~a4 Q o\0 Z~ r C i C I O
Ln Ln ~ o\o O 3 O ~.Or) ~ , ~ O
Ln N I
~ C 00 61 (D cc 00 W Ol 6l 61 -Y
k k ~ -x v) z U
OI
=~
~-I U ~'. 000000000000'0000000000CO0000000J0 41 ~:~NMk-0 P r-iOlOLn ,-=INQ0 IUr-IO[- I0 NN^~9r-iO'I" klo r--INt- C- r-iNU)t.() ~,9 t9 lI) Ln !=) j-) cr LC) ~ lfl t-f) !n LI) LJ') ct t' lQ l0 i.n ts') I.f) i.f) ct T' ~p l0 u') lt~ II'7 Ln i, cP' to ~ 0) in d" O NLn m M l- Ln N MLr-, c9' N :~" ~n d' N M Ln d' Lo Ln I-- ~O
~t' (''') lO lo ,O l0 ~ O111IU~ MMMMNN,--Ir-IMMMMNNrir-iMMMNNr-i r-IMMMMNN-Irl ~4- O r-=I c--i r-I ,-I c-=i t-I r--I r-I c-I r-I r-I r-i r- r--I -i ,-I t-I r-=-I r-=I ,-I -i r-I r-i r-I r--I r-i c=--I r-i rti i-i r--I r--I
~
N N ~4j S) LD r-I N lt) Ln C'm M t- l9 Cm Mk9 t1) t) kl9 ~.D rl M.r) '1) t-n cr OD t'ct iJ) t~ Co al 01 ~ O ( R MMMMNC\? -IrIMMMMNNc-Ic-IMMMCMNN -Ir-IMMMMNN -r-F"i rH r-1 t-i r-~ -I r-I c-I ,--i r--I r==~ r-i r-I r--I rl r-=~ r-I ,-I r-I
r-I r-i r-i r--i r-I f-I t-i t-I
U.~
D`O ~A ' -I q) -I - r- - i-- -- r-i rH rl r-i r--I r-I r-I l9 l0 l0 lq l~ ~9 l0 l9 N N
N N N N N N
O
-r-I
MI
O ~NI OOOOOOOOr --Ir-I -i*c-Ir-I -INNNNNNNNCQCOC>O0 OJCOM M
~r IZr IZr IZr ~4 tti ~ 'T OOOOOOOONNNNNCVNCV ~~~~Ln Lf)un Ln >II ~M ~M ~t ~I ~1 d V Q
H
O; MI
O ci tt7Lf) tf-) Ln tl-) LO tnt.f)OJODCOCO0J00 oOC0COCOCOCOCOC00oMNNNNNNNN
- r --i - r - c c ~C" J C7 d d MMMMMMMM
=rI
U) O
OOOOOOOOO
U ~i MM~~MMMM~O C) OOO ``O N~N~N~N~ (N vN ~N~N~M M M M M M M M
~ o\o N =t-~ -I
~ ~ ~
U) C) u-) Ln O O O O Ln L-n tI) tI) O O o OLn Ln Ln tI) O O O CO tf) lC) a) tf) O O (D O tS) I;
~~~ MM~T;t Ln tnl9lUMmd*~t'ullnlOl9mMct ~rtf)tf~~OIOMM-r:J"tl~~lolfl o~ax ~4 ~- I I O f O I I I O I O I I n I O I O I L n I I O 1 O I L) ~ O0 k-9 to Ln M 1,9 lfl LI) M l9 lo Ln M ~,9 C,0 Ln M
~7- 04 i ~ 01 Ln I O I O iLn I:t) f O f O ILo I t.C) I O I O ILn ILo I O I O I Ln I
O Cc ~9 l0 Ln M Q9 l0 t-r) (n Q0 "C) uM ~) l9 l.9 u'-) M
z o.
4) M tnl0 [~ Co6lOr-1Nr')crUn LCf- OJdIO -INMl.n l0 ('~M610 r-INm-4"
a1 61 61 01 61C316100000CO0000r-4 r=--I r-Ir-l -lrirfCNNNNN
I r-i r-1 r--~ r-i ,-I r=~ r--I r-I rl rl r-I r-f r=-I r- ,-1 r-I ,-1 ,-~ r-I
r-I r-I r-i ,-1 r-i rl When the Ni0 powder and the Ni powder are used as starting powders, it is learned from Table 1 above that use of the Y203 powder or the Yb203 powder in a suitable amount brings the coefficient of thermal expansion of 5 the sintered body (support substrate) close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte. 7t is further learned that the electronic conductivity of the support substrate decreases with an increase in the amount of Y203 or Yb203 10 but an excellent electronic conductivity is obtained so far as the amount thereof _ies within a. range of from 35 to 65% by volume.
It is, on the other hand, learned that the sintered body of sample No. 13(comparative example) has a 15 coefficient of thermal expansion that is considerably greater than the coefficient of thermal expansion of the solid electrolyte.
The sintered body of sample No. 14(comparative example) has a coefficient of thermal expansion that is 20 close to the coefficient of therma~~~ expansion of the solid electrolyte to a fair degree and exhibits a favorable electronic conductivity but permits the element to be diffused as will be ciescr.ibed later.
When the NiO powder and the Ni. powder are used as 25 starting powders, further, it is learned from Tables 2 to 4 above that use of the LU203 powder, Tm203 powder, Er203 powder, Ho203 powder, Dy203 powder, Gd203 powder, Sm203 powder and Pr203 powder in a suitable amount brings the coefficient of thermal expansion of the sintered body (support substrate) close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolvte. It is further learned that the electronic conductivity of the sintered body (support substrate) decreases with an increase in the amount of the above rare-earth oxides but an excellent electronic conductivity is maintained. so far as the amount thereof lies within a range of from 35 to 65% by volume.
Tt is further learned from Tabie 5 that when the Nd203 powder, CeO2 powder, and La203 powcier are used as the rare-earth oxides (samples Nos. 87 to 92,comparative examples), the sintered body (support substrate) exhibits excellent electronic conductivity but exhibits coefficients o-f thermal expansion which are very greater than the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte.
It is learried from Table 6 that even when two or more kinds of the rare-earth oxide powders are used in combination, the coefficient of thermal expansion of the sintered body (support substrate) can be brought close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte by adjusting their amounts. It is further learned that the e~~ectronic conductivity of the sintered body decreases with an increase in the amount thereof but an excellent electronic conductivity is maintained so far as the amount thereof lies within a range of from 35 to 65% by volume.
(Experiment 2) The sample powders used in Experiment 1 were extrusion-molded in the same manner as in Experiment 1 to obtain flat molded bodies for the support substrate, which were, then, dried.
Next, a sheet for forming the fuel-electrode layer was prepared by using a slurry of a mixture of the Zr02 (YSZ) powder containing 8% by mol of Y203, Ni0 powder, organic binder (acrylic resin) and solvent (toluene).
There was further prepared a sheet for the solid electrolytic layer by using a slurry of a mixture of the above YSZ powder, organic binder (acrylic resin) and toluene. These sheets were laminated one upon the other.
The laminated sheets were wound on the molded body for the support substrate in a manner that both ends thereof were spaced apart maintaining a predetermined distance (see Fig. 1), and were dried.
On the other hand, a sheet for forming the interconnect was prepared by using the LaCrO3 oxide powder having an average particle size of 2pm, organic binder (acrylic resin) and solvent (toluene). The sheet was, then, lamirlateci on the exposed portion of the molded body for the support substrate on which the laminated sheets have been wound, thereby to obtain a laminated sheet for firing comprising the molded body for the support substrate, sheet for the fuel-electrode layer and sheet for the solid electrolytic layer.
Next, the laminated sheet for sintering was put to the processing for removing the birlder and was co-fired in the atmosphere at 1500 C.
The obtained sintered body was immersed in a paste comprising an Lao.6SrG,4Co0,2Feo,803 powder having an average particie size of 2 um and a solvent (normal -caraffin) to form a coating layer for oxygen-electrode on the surface of the solid electrolytic layer that has been sintered. At the same time, the above paste was applied onto the outer surface of the interconnect that has been sintered to thereby form a coating layer for the P-type semiconductor followed by firing at 1150 C to produce a fuel cell unit as shown ir: Fig. 1 (sample Nos.
125 to 248).
In the thus produced fuel cells, the flat portion A
of the support substrate possessed a length of 26 mm, the arcuate portions B possessed a length of 3.5 mm, the uel-electrode layer possessed a thickness of 10 pm, the solid electrolytic layer possessed a thickness of 40 pm, the oxygen-electrode possessed a thickness of 50 um, the interconnect possessed a thickness of 50 }im and the P-type semiconductor layer possessed a thickness of 50 um.
The fuel cells corresponding to the above samples Ncs. 13 and 14 of comparative examples are the samples Nos. 137 and 138.
Sectional surfaces of the solid electrolytic layers of the obtained fuel cells were analyzed by EPMA to confirm elernents that have diffused from the support substrates. Further, a hydrogen gas was supplied into the gas passages of the support substrates, and the air was supplied to the outer side of the fuel cells (to the outer surfaces of the oxygen-electrodes) to generate electricity at 850 C for 100 hours. The fuel cell units were then cooled and were immersed in water while pressurizing the interiors thereof to observe the leakage of gas, cracks in the fuel-electrode layers and peeling of the solid electrolytic layers from the fuel-electrode layers.
Further, the generating performance per a fuel cell was measured at 850 G after 100 hours have passed. The results were as shown in Tables 7 to 12.
Table 7 Sample Sample Diffusion Cracks Generating No. No. in into solid and performance Table 1 electrolyte peeling W/cm2 125 1 no no 0.45 126 2 no no 0.41 127 3 no no 0.39 128 4 no no 0.42 129 5 no no 0.37 130 6 no no 0.40 131 7 no no 0.37 132 8 no no 0.36 133 9 no no 0.37 134 10 no no 0.35 135 11 no no 0.38 136 12 no no 0.37 *137 *13 no yes 0.25 *138 *14 yes Al,Mg no 0.19 *: outside the scope of the invention Table 8 Sample Sample Diffusion Cracks Generating No. iio. in into solid and performance Table 2 electrolyte peeling W/cm2 139 15 no no 0.45 140 16 no no 0.42 141 17 no no 0.40 142 18 no no 0.38 143 19 no no 0.39 144 20 no no 0.39 145 21 no no 0.36 146 22 no no 0.36 147 23 no no 0.40 148 24 no no 0.44 149 25 no no 0.43 150 26 no no 0.43 i51 27 no no 0.42 152 28 no no 0.39 153 29 no no 0.40 154 30 no no 0.36 155 31 no no 0.36 156 32 no no 0.39 157 33 no no 0.44 158 34 no no 0.45 159 35 no no 0.41 160 36 no no 0.42 161 37 no no 0.39 162 38 no no 0.39 163 39 no no 0.36 164 40 no no 0.36 165 41 no no 0.41 31.
Table 9 Sample Sample Diffusion Cracks Generating No. No. in into solid and performance Table 3 electrolyte peeling W/cmz 166 42 no no 0.45 167 43 no no 0.44 168 44 no no 0.42 169 45 no no 0.42 170 46 no no 0.39 171 47 no no 0.38 172 48 no no 0.35 173 49 no no 0.35 174 50 nc no 0.40 175 51 no no 0.44 176 52 no no 0.44 177 53 no no 0.4L
178 54 no no 0.42 179 55 no no 0.38 180 56 no no 0.39 181 57 no no 0.36 182 58 no no 0.36 183 59 no no 0.39 184 60 no no 0.45 185 61 no no 0.44 186 62 no no 0.42 187 63 no no 0.42 1-88 64 no no 0.38 189 65 no no 0.38 190 66 no no 0.36 191 67 no no 0.35 192 68 no no 0.41 Table 10 Sample Sampi-e Diffusion Cracks Generating No. No. in into solid and performance Table 4 electrolyte peeling WIcm2 193 69 no no 0.45 194 70 no no 0.45 195 7i no no 0.42 196 72 no no 0.42 197 73 no no 0.38 198 74 no no 0.38 199 75 no no 0.35 200 76 no no 0.35 201 77 no no 0.39 202 78 no no 0.44 203 79 no no 0.44 204 80 no no 0.42 205 81 no no 0.42 206 82 no no 0.39 207 83 no no 0.39 208 84 no no 0.35 209 85 no no 0.35 210 86 no no 0.40 Table 11 Sample Sample Diffusion C:facks Generating No. No. in into sol:d and performance Table 5 electrolyte peeling W/cm`
*211 *87 no yes -*212 *88 no yes -*213 *89 no yes -*214 *90 nc> yes -*215 *9~ no yes *216 *92 no yes -*: outside the scope of the invention Table 12 Sample Sample Diffusion Cracks Generating No. No. in into solid and performance Table 6 electrolyte peeling W/cm2 217 93 no no 0.45 218 94 no no 0.45 219 95 no no 0.42 220 96 no no 0.41 221 97 no no 0.39 222 98 no no 0.40 223 99 no no 0.36 224 100 no no 0.36 225 101 no no 0.45 226 102 no no 0.44 227 103 no no 0.42 228 104 no no 0.42 229 105 no no 0.40 230 106 no no 0.39 231 107 no nc 0.36 232 108 no no 0.35 233 109 no no 0.44 234 110 no no 0.45 235 111 no no 0.42 236 112 no no 0.41 237 113 no no 0.38 238 114 no no 0.39 239 115 no no 0.35 240 116 no no 0.35 241 117 no no 0.44 242 118 no no 0.45 243 119 no no 0.42 244 120 no no 0.41 245 121 no no 0.39 246 122 no no 0.40 247 123 no no 0.35 248 124 no no 0.35 In the fuel cell samples Nos. 125 to 136 and 139 to 210 as will be understood from the results of Tables 7 to 12, there were observed no cracks in the fue.1-electrode layers and no peeling of the solid 5 electrolytic layers from the fuel-electrode layers.
Further, no elements diffused, and the generating performance was as good as not smaller zhan 0.35 W/cm'.
In the samples Nos. 125 to 136 and 139 to 210, on the other hand, the differences in the coefficient of 10 thermal expansion were relatively small between the support substrate and the solid electrolytic layer, and there were observed no cracks in the fuel-electrode layers or the peeling of the solid electrolytic layers from the fuel-electrode layers. From the standpoint of 15 long-term reliability, however, it is desired that the amount of the particular rare-earth oxide in the support substrate is better iarge in a range in which it does not impair the electronic conductivity of the support substrate and is, desirably, from 35 to 65% by volume 20 and, particularly, from 40 to 65% by volume.
In the sample No. 137 of comparative example, no diffusion was observed but the difference in the coefficient of thermal expansion was so great between the support substrate and the solid electrolytic layer 25 that cracks occurred in the fuel-electrode layer.
In the sample No. 138 of comparative example, there were observed no cracks in the fuel-electrode layer and no peeling of the solid electrolytic laver from the fuel-electrode layer. However, diffusion of Mg and Al 30 was seen in the solid electrolytic layer, and the generating performance after the power generation of 100 hours was as low as 0.19 W/cm2.
From the results of Table 11, further, no diffusion was seen in the samples Nos. 211 to 216 that were 35 comparative examples. However, differences in the coefficient of thermal expansion were so great between the support substrate and the solid electrolytic layer that cracks occurred in the fuel-electrode layer.
Tt is learned from Table 12 tnat even in the samples Nos. 217 to 248 (present invent~-on) using the composite rare-earth oxides as rare earth powders, the coefficients of t-hermal expansion of the support substrates can be brought close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte by adjusting the amounts of the composite rare-earth oxides, making it possible to suppress the occurrence of cracks in the fuel-electrode layers. Because of the same reason, further, there is observed no peeling of the solid electrolyte from the fuel-electrode layer.
O --i =r ~
O O O O O O O O O O O O O O O O O O O O O O O O O O O
M NNOJC- Or-IIQIflOr0 00 lONOlOf- 61NNOJt- NOLf)"C r-I
QdlflLn Lt tncr:,^Ln9b tnLn=)Ln zsz, ~~ Q4~d Ln LntS)L7:v Zrt.C) - O
W U
a-%
~4 U
~ 0) ~
~ lOt.n Oc-iC- t.nt.>7lOlOd'4I'i061Ll7zTCY`M d'IOC- M-I[- 19C- --.J'l9 44 =r; . . . . . . . . . . . . c' .
U ln t'M <~ (~'1 ('') N N. r-I I N. (M (~' i c'~ N N N M tM N M f'~) M ') N N
ri r 1 N
O -i r-i -I ~ r-I r-l rl ~-I r-i r-i r-i '-I ~-i ri r-I r-I r-I r-I c-i ri rl ~-I ri ~-I rl `-I rl O
nzi t>5 ~.o cn cMlo Lr)19Lc')l9lOtt)NNLt)~c'ncMtt)r- loM(>7~Ow tn uo lo ~4 M M . . . . . . . . . . . . . N -~ . . . . . . .
~ ()l7NN -I - NM(~MMN iN C7MM(~) NNrI N
c=-1 r-I r-~ ~-I '-I ri i-I r-~ r-I r-I '--I ~-I c- r-i r-I ~-~ ~-I '-I ~--~ r-I c-1 ~-I rl i-I r--I c-i c--f ~
L+
M ~-I
N ~'~--II I I I 1 11 11 1 1 1 1 1 l I i ILntn0000Lf7Ln0 c. O>0 ~ Mm dzz tI)Lf)lQ W Lf) ~4 r 0) 010 (~ "0 r=I 1 I I 1 1 I 1 1Lf) Ln O O O O Lf) n O 1 1 1 1 1 1 1 1 Z" Q~I MMd crtl7tf)10 ~0S) '-I
~ D\0 n'ZSr-1 LnLn 0000u-) Ln 0 I I I I I I I I I I I{{ I I I
O~~' M M-i' ~' i.f) LC) LO ~ tn ~4 U o\o -I ILn I O O ILo tS') I Ln I O O 1>n Ln I tt') O 1 O ILr, Ln ~ OR l9 l0 Ln M N t-0 ~O tI) C*') (N l0 ~D Ln (n N
la N o1o I
u ) I O I O I t1) ( L n L n I O I O I u'? ILnLQI O I O ILnI L1) O~0I l~ l0 Uf) (~') N l0 ~O L() M N lfl l0 ~ C+7 N
(D
-i N( d t-nIOC- CO 6l0t-INMcf Ln LO[- cc OIOc--ICV <'')d" Ln IS)f' OJ
cY' zl' d" C" :zj' cI' 'Cr d' Ln Ln Ln L7 Ln Lf) Ln Ln LC) Lf') ~-O k9 k,.o lfl LO lo l9 ~-O LO
ol 2 ~
~
U ~=' -~ ~
O ~ ~ O p O O O O O O O G) O O O O O O O O
I U M H w l9 c- N l0 Q9 O N --I ,M [- r-I CV I.n Ln r=-I
J U] LO w II) Ll) L.-) Ln -- d' Lo l4 lO 1I) Lf) Lo lS) 3' d LS) U -U
I o U
L
=rl S1 r ~C~ 6l cc l.9 ct ts~ Ln C` i C IZI' (n Ln IZi' ~t ~r . . . . . . . , . . . . . .
44 =H
4-1 U C~ M n') M (*') M M N N M M c~ c~'",, M N. N r-I r-I N
0 -0 0 r-i c-( c--I t-I c-i r-I c-l c-{ --! f! c-i c-: .--1 r-a r-I r-l ~--I
r--I
~
U O C) -rl x N p 61 t- C- t1) iC) Q4 LO ;;t+ LC7 L(') t'M l0 T) C') t.C) ~4 c7' M M M M (`') N N M C`'M M M M N N r-I f--I N
c--I i-i r-I s--I r-~i i-I ri r-I -I c--I r--I '--! r--I r-1 -1 +--I
E-~
~4 ~ Q o1a T3 ~-I I f I I 1 I I I 1 L7 Lo O O O p tn Ln O
a O 0 M M zi' zt' Ln ! n l.0 lS~ tf) Q, M N o\O
~ -1 O O O O LO iS) C) I I i I I I I I I
I ~ ~
~ M f'~ 1' G, tl') tf) l.o ~9 I) ~
~ 010 ~3 r I I Ln 1 O I C) I tn u) I Ln I p I p I Ln U=) H O > l0 C0 Uf ) M CN l9 11.0 LC) M N
Z R, ~-Jl N o10 ~ r I if) 1 O I O I U) I Ln Ln I O I O I un I Ln ~
I C~ ~9 L~ M N l9 l9 L) C~ N
N
r-i ~ 6 C) -I N M d Ln l9 f'- Co 6l C) ~-1 CV M lz~!' .f) l9 l0 r-= f- L- C`` C^~ t ^ l f- ['- Oo co Oo Oo co Oo OD
UD z ~
~
u ---i ~ 'r+ J
O O O O O O
O U
U ~ n ~ s) ~ s 0 O ~
O
U
N 4}
-rl O
-~-i 4-4 QO C5l O lf) O
-ri co ~
O~ OJ ~
~ZV Lr) Lf~
~
~
~
LnI
O I I I O C
~ ~
~
~-4 O o\o O'O - I I O O I
-n Ln S-;
N o\o O .r) ~-r) ~ I
~a4 Q o\0 Z~ r C i C I O
Ln Ln ~ o\o O 3 O ~.Or) ~ , ~ O
Ln N I
~ C 00 61 (D cc 00 W Ol 6l 61 -Y
k k ~ -x v) z U
OI
=~
~-I U ~'. 000000000000'0000000000CO0000000J0 41 ~:~NMk-0 P r-iOlOLn ,-=INQ0 IUr-IO[- I0 NN^~9r-iO'I" klo r--INt- C- r-iNU)t.() ~,9 t9 lI) Ln !=) j-) cr LC) ~ lfl t-f) !n LI) LJ') ct t' lQ l0 i.n ts') I.f) i.f) ct T' ~p l0 u') lt~ II'7 Ln i, cP' to ~ 0) in d" O NLn m M l- Ln N MLr-, c9' N :~" ~n d' N M Ln d' Lo Ln I-- ~O
~t' (''') lO lo ,O l0 ~ O111IU~ MMMMNN,--Ir-IMMMMNNrir-iMMMNNr-i r-IMMMMNN-Irl ~4- O r-=I c--i r-I ,-I c-=i t-I r--I r-I c-I r-I r-I r-i r- r--I -i ,-I t-I r-=-I r-=I ,-I -i r-I r-i r-I r--I r-i c=--I r-i rti i-i r--I r--I
~
N N ~4j S) LD r-I N lt) Ln C'm M t- l9 Cm Mk9 t1) t) kl9 ~.D rl M.r) '1) t-n cr OD t'ct iJ) t~ Co al 01 ~ O ( R MMMMNC\? -IrIMMMMNNc-Ic-IMMMCMNN -Ir-IMMMMNN -r-F"i rH r-1 t-i r-~ -I r-I c-I ,--i r--I r==~ r-i r-I r--I rl r-=~ r-I ,-I r-I
r-I r-i r-i r--i r-I f-I t-i t-I
U.~
D`O ~A ' -I q) -I - r- - i-- -- r-i rH rl r-i r--I r-I r-I l9 l0 l0 lq l~ ~9 l0 l9 N N
N N N N N N
O
-r-I
MI
O ~NI OOOOOOOOr --Ir-I -i*c-Ir-I -INNNNNNNNCQCOC>O0 OJCOM M
~r IZr IZr IZr ~4 tti ~ 'T OOOOOOOONNNNNCVNCV ~~~~Ln Lf)un Ln >II ~M ~M ~t ~I ~1 d V Q
H
O; MI
O ci tt7Lf) tf-) Ln tl-) LO tnt.f)OJODCOCO0J00 oOC0COCOCOCOCOC00oMNNNNNNNN
- r --i - r - c c ~C" J C7 d d MMMMMMMM
=rI
U) O
OOOOOOOOO
U ~i MM~~MMMM~O C) OOO ``O N~N~N~N~ (N vN ~N~N~M M M M M M M M
~ o\o N =t-~ -I
~ ~ ~
U) C) u-) Ln O O O O Ln L-n tI) tI) O O o OLn Ln Ln tI) O O O CO tf) lC) a) tf) O O (D O tS) I;
~~~ MM~T;t Ln tnl9lUMmd*~t'ullnlOl9mMct ~rtf)tf~~OIOMM-r:J"tl~~lolfl o~ax ~4 ~- I I O f O I I I O I O I I n I O I O I L n I I O 1 O I L) ~ O0 k-9 to Ln M 1,9 lfl LI) M l9 lo Ln M ~,9 C,0 Ln M
~7- 04 i ~ 01 Ln I O I O iLn I:t) f O f O ILo I t.C) I O I O ILn ILo I O I O I Ln I
O Cc ~9 l0 Ln M Q9 l0 t-r) (n Q0 "C) uM ~) l9 l.9 u'-) M
z o.
4) M tnl0 [~ Co6lOr-1Nr')crUn LCf- OJdIO -INMl.n l0 ('~M610 r-INm-4"
a1 61 61 01 61C316100000CO0000r-4 r=--I r-Ir-l -lrirfCNNNNN
I r-i r-1 r--~ r-i ,-I r=~ r--I r-I rl rl r-I r-f r=-I r- ,-1 r-I ,-1 ,-~ r-I
r-I r-I r-i ,-1 r-i rl When the Ni0 powder and the Ni powder are used as starting powders, it is learned from Table 1 above that use of the Y203 powder or the Yb203 powder in a suitable amount brings the coefficient of thermal expansion of 5 the sintered body (support substrate) close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte. 7t is further learned that the electronic conductivity of the support substrate decreases with an increase in the amount of Y203 or Yb203 10 but an excellent electronic conductivity is obtained so far as the amount thereof _ies within a. range of from 35 to 65% by volume.
It is, on the other hand, learned that the sintered body of sample No. 13(comparative example) has a 15 coefficient of thermal expansion that is considerably greater than the coefficient of thermal expansion of the solid electrolyte.
The sintered body of sample No. 14(comparative example) has a coefficient of thermal expansion that is 20 close to the coefficient of therma~~~ expansion of the solid electrolyte to a fair degree and exhibits a favorable electronic conductivity but permits the element to be diffused as will be ciescr.ibed later.
When the NiO powder and the Ni. powder are used as 25 starting powders, further, it is learned from Tables 2 to 4 above that use of the LU203 powder, Tm203 powder, Er203 powder, Ho203 powder, Dy203 powder, Gd203 powder, Sm203 powder and Pr203 powder in a suitable amount brings the coefficient of thermal expansion of the sintered body (support substrate) close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolvte. It is further learned that the electronic conductivity of the sintered body (support substrate) decreases with an increase in the amount of the above rare-earth oxides but an excellent electronic conductivity is maintained. so far as the amount thereof lies within a range of from 35 to 65% by volume.
Tt is further learned from Tabie 5 that when the Nd203 powder, CeO2 powder, and La203 powcier are used as the rare-earth oxides (samples Nos. 87 to 92,comparative examples), the sintered body (support substrate) exhibits excellent electronic conductivity but exhibits coefficients o-f thermal expansion which are very greater than the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte.
It is learried from Table 6 that even when two or more kinds of the rare-earth oxide powders are used in combination, the coefficient of thermal expansion of the sintered body (support substrate) can be brought close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte by adjusting their amounts. It is further learned that the e~~ectronic conductivity of the sintered body decreases with an increase in the amount thereof but an excellent electronic conductivity is maintained so far as the amount thereof lies within a range of from 35 to 65% by volume.
(Experiment 2) The sample powders used in Experiment 1 were extrusion-molded in the same manner as in Experiment 1 to obtain flat molded bodies for the support substrate, which were, then, dried.
Next, a sheet for forming the fuel-electrode layer was prepared by using a slurry of a mixture of the Zr02 (YSZ) powder containing 8% by mol of Y203, Ni0 powder, organic binder (acrylic resin) and solvent (toluene).
There was further prepared a sheet for the solid electrolytic layer by using a slurry of a mixture of the above YSZ powder, organic binder (acrylic resin) and toluene. These sheets were laminated one upon the other.
The laminated sheets were wound on the molded body for the support substrate in a manner that both ends thereof were spaced apart maintaining a predetermined distance (see Fig. 1), and were dried.
On the other hand, a sheet for forming the interconnect was prepared by using the LaCrO3 oxide powder having an average particle size of 2pm, organic binder (acrylic resin) and solvent (toluene). The sheet was, then, lamirlateci on the exposed portion of the molded body for the support substrate on which the laminated sheets have been wound, thereby to obtain a laminated sheet for firing comprising the molded body for the support substrate, sheet for the fuel-electrode layer and sheet for the solid electrolytic layer.
Next, the laminated sheet for sintering was put to the processing for removing the birlder and was co-fired in the atmosphere at 1500 C.
The obtained sintered body was immersed in a paste comprising an Lao.6SrG,4Co0,2Feo,803 powder having an average particie size of 2 um and a solvent (normal -caraffin) to form a coating layer for oxygen-electrode on the surface of the solid electrolytic layer that has been sintered. At the same time, the above paste was applied onto the outer surface of the interconnect that has been sintered to thereby form a coating layer for the P-type semiconductor followed by firing at 1150 C to produce a fuel cell unit as shown ir: Fig. 1 (sample Nos.
125 to 248).
In the thus produced fuel cells, the flat portion A
of the support substrate possessed a length of 26 mm, the arcuate portions B possessed a length of 3.5 mm, the uel-electrode layer possessed a thickness of 10 pm, the solid electrolytic layer possessed a thickness of 40 pm, the oxygen-electrode possessed a thickness of 50 um, the interconnect possessed a thickness of 50 }im and the P-type semiconductor layer possessed a thickness of 50 um.
The fuel cells corresponding to the above samples Ncs. 13 and 14 of comparative examples are the samples Nos. 137 and 138.
Sectional surfaces of the solid electrolytic layers of the obtained fuel cells were analyzed by EPMA to confirm elernents that have diffused from the support substrates. Further, a hydrogen gas was supplied into the gas passages of the support substrates, and the air was supplied to the outer side of the fuel cells (to the outer surfaces of the oxygen-electrodes) to generate electricity at 850 C for 100 hours. The fuel cell units were then cooled and were immersed in water while pressurizing the interiors thereof to observe the leakage of gas, cracks in the fuel-electrode layers and peeling of the solid electrolytic layers from the fuel-electrode layers.
Further, the generating performance per a fuel cell was measured at 850 G after 100 hours have passed. The results were as shown in Tables 7 to 12.
Table 7 Sample Sample Diffusion Cracks Generating No. No. in into solid and performance Table 1 electrolyte peeling W/cm2 125 1 no no 0.45 126 2 no no 0.41 127 3 no no 0.39 128 4 no no 0.42 129 5 no no 0.37 130 6 no no 0.40 131 7 no no 0.37 132 8 no no 0.36 133 9 no no 0.37 134 10 no no 0.35 135 11 no no 0.38 136 12 no no 0.37 *137 *13 no yes 0.25 *138 *14 yes Al,Mg no 0.19 *: outside the scope of the invention Table 8 Sample Sample Diffusion Cracks Generating No. iio. in into solid and performance Table 2 electrolyte peeling W/cm2 139 15 no no 0.45 140 16 no no 0.42 141 17 no no 0.40 142 18 no no 0.38 143 19 no no 0.39 144 20 no no 0.39 145 21 no no 0.36 146 22 no no 0.36 147 23 no no 0.40 148 24 no no 0.44 149 25 no no 0.43 150 26 no no 0.43 i51 27 no no 0.42 152 28 no no 0.39 153 29 no no 0.40 154 30 no no 0.36 155 31 no no 0.36 156 32 no no 0.39 157 33 no no 0.44 158 34 no no 0.45 159 35 no no 0.41 160 36 no no 0.42 161 37 no no 0.39 162 38 no no 0.39 163 39 no no 0.36 164 40 no no 0.36 165 41 no no 0.41 31.
Table 9 Sample Sample Diffusion Cracks Generating No. No. in into solid and performance Table 3 electrolyte peeling W/cmz 166 42 no no 0.45 167 43 no no 0.44 168 44 no no 0.42 169 45 no no 0.42 170 46 no no 0.39 171 47 no no 0.38 172 48 no no 0.35 173 49 no no 0.35 174 50 nc no 0.40 175 51 no no 0.44 176 52 no no 0.44 177 53 no no 0.4L
178 54 no no 0.42 179 55 no no 0.38 180 56 no no 0.39 181 57 no no 0.36 182 58 no no 0.36 183 59 no no 0.39 184 60 no no 0.45 185 61 no no 0.44 186 62 no no 0.42 187 63 no no 0.42 1-88 64 no no 0.38 189 65 no no 0.38 190 66 no no 0.36 191 67 no no 0.35 192 68 no no 0.41 Table 10 Sample Sampi-e Diffusion Cracks Generating No. No. in into solid and performance Table 4 electrolyte peeling WIcm2 193 69 no no 0.45 194 70 no no 0.45 195 7i no no 0.42 196 72 no no 0.42 197 73 no no 0.38 198 74 no no 0.38 199 75 no no 0.35 200 76 no no 0.35 201 77 no no 0.39 202 78 no no 0.44 203 79 no no 0.44 204 80 no no 0.42 205 81 no no 0.42 206 82 no no 0.39 207 83 no no 0.39 208 84 no no 0.35 209 85 no no 0.35 210 86 no no 0.40 Table 11 Sample Sample Diffusion C:facks Generating No. No. in into sol:d and performance Table 5 electrolyte peeling W/cm`
*211 *87 no yes -*212 *88 no yes -*213 *89 no yes -*214 *90 nc> yes -*215 *9~ no yes *216 *92 no yes -*: outside the scope of the invention Table 12 Sample Sample Diffusion Cracks Generating No. No. in into solid and performance Table 6 electrolyte peeling W/cm2 217 93 no no 0.45 218 94 no no 0.45 219 95 no no 0.42 220 96 no no 0.41 221 97 no no 0.39 222 98 no no 0.40 223 99 no no 0.36 224 100 no no 0.36 225 101 no no 0.45 226 102 no no 0.44 227 103 no no 0.42 228 104 no no 0.42 229 105 no no 0.40 230 106 no no 0.39 231 107 no nc 0.36 232 108 no no 0.35 233 109 no no 0.44 234 110 no no 0.45 235 111 no no 0.42 236 112 no no 0.41 237 113 no no 0.38 238 114 no no 0.39 239 115 no no 0.35 240 116 no no 0.35 241 117 no no 0.44 242 118 no no 0.45 243 119 no no 0.42 244 120 no no 0.41 245 121 no no 0.39 246 122 no no 0.40 247 123 no no 0.35 248 124 no no 0.35 In the fuel cell samples Nos. 125 to 136 and 139 to 210 as will be understood from the results of Tables 7 to 12, there were observed no cracks in the fue.1-electrode layers and no peeling of the solid 5 electrolytic layers from the fuel-electrode layers.
Further, no elements diffused, and the generating performance was as good as not smaller zhan 0.35 W/cm'.
In the samples Nos. 125 to 136 and 139 to 210, on the other hand, the differences in the coefficient of 10 thermal expansion were relatively small between the support substrate and the solid electrolytic layer, and there were observed no cracks in the fuel-electrode layers or the peeling of the solid electrolytic layers from the fuel-electrode layers. From the standpoint of 15 long-term reliability, however, it is desired that the amount of the particular rare-earth oxide in the support substrate is better iarge in a range in which it does not impair the electronic conductivity of the support substrate and is, desirably, from 35 to 65% by volume 20 and, particularly, from 40 to 65% by volume.
In the sample No. 137 of comparative example, no diffusion was observed but the difference in the coefficient of thermal expansion was so great between the support substrate and the solid electrolytic layer 25 that cracks occurred in the fuel-electrode layer.
In the sample No. 138 of comparative example, there were observed no cracks in the fuel-electrode layer and no peeling of the solid electrolytic laver from the fuel-electrode layer. However, diffusion of Mg and Al 30 was seen in the solid electrolytic layer, and the generating performance after the power generation of 100 hours was as low as 0.19 W/cm2.
From the results of Table 11, further, no diffusion was seen in the samples Nos. 211 to 216 that were 35 comparative examples. However, differences in the coefficient of thermal expansion were so great between the support substrate and the solid electrolytic layer that cracks occurred in the fuel-electrode layer.
Tt is learned from Table 12 tnat even in the samples Nos. 217 to 248 (present invent~-on) using the composite rare-earth oxides as rare earth powders, the coefficients of t-hermal expansion of the support substrates can be brought close to the coefficient of thermal expansion of 10.8 x 10-6 of the solid electrolyte by adjusting the amounts of the composite rare-earth oxides, making it possible to suppress the occurrence of cracks in the fuel-electrode layers. Because of the same reason, further, there is observed no peeling of the solid electrolyte from the fuel-electrode layer.
Claims (18)
1. A fuel cell comprising:
a gas-permeable and electrically conducting support substrate having at least one fuel gas passage formed therein;
a fuel-electrode layer formed on the support substrate;
a solid electrolytic layer formed on the fuel-electrode layer so as to cover the fuel-electrode layer and containing ZrO2 in which at least one rare earth element is present in the form of a solid solution; and an oxygen-electrode layer provided on the solid electrolytic layer so as to face the fuel-electrode layer wherein the support substrate is formed of (a) a metal of the iron family and/or an oxide of a metal of the iron family, and (b) a rare-earth oxide containing at least one rare-earth element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr, and the rare-earth oxide is contained in an amount of 35 to 65% by volume in the support substrate.
a gas-permeable and electrically conducting support substrate having at least one fuel gas passage formed therein;
a fuel-electrode layer formed on the support substrate;
a solid electrolytic layer formed on the fuel-electrode layer so as to cover the fuel-electrode layer and containing ZrO2 in which at least one rare earth element is present in the form of a solid solution; and an oxygen-electrode layer provided on the solid electrolytic layer so as to face the fuel-electrode layer wherein the support substrate is formed of (a) a metal of the iron family and/or an oxide of a metal of the iron family, and (b) a rare-earth oxide containing at least one rare-earth element selected from the group consisting of Y, Lu, Yb, Tm, Er, Ho, Dy, Gd, Sm and Pr, and the rare-earth oxide is contained in an amount of 35 to 65% by volume in the support substrate.
2. The fuel cell according to claim 1, wherein the metal of the iron group is Ni.
3. The fuel cell according to claim 1 or 2, wherein the rare-earth oxide (b) in the support substrate comprises at least one of Y2O3 and Yb2O3.
4. The fuel cell according to any one of claims 1 to 3, wherein the support substrate has an open porosity of 30 to 50% and an electric conductivity of not smaller than 300 S/cm.
5. The fuel cell according to any one of claims 1 to 4, wherein the fuel-electrode layer contains ZrO2 in which at least one of Ni and NiO as well as rare earth elements are existing in the form of solid solutions.
6. The fuel cell according to any one of claims 1 to 4, wherein the fuel-electrode layer contains 35 to 65% by volume of ZrO2 stabilized with the rare earth elements in the form of solid solutions and 65 to 35% by volume of at least one of Ni and NiO, has an open porosity of 15 to 40% and has a thickness of 1 to 30 µm.
7. The fuel cell according to any one of claims 1 to 6, wherein:
the oxygen-electrode layer is positioned on the surface of the support substrate on one side thereof;
an interconnect is provided on a surface of the support substrate on the other side thereof; and the fuel-electrode layer and the solid electrolytic layer are turning round up to both end portions of the interconnect.
the oxygen-electrode layer is positioned on the surface of the support substrate on one side thereof;
an interconnect is provided on a surface of the support substrate on the other side thereof; and the fuel-electrode layer and the solid electrolytic layer are turning round up to both end portions of the interconnect.
8. The fuel cell according to any one of claims 1 to 6 wherein:
the support substrate is flat in cross section, is of an elliptic cylindrical shape as viewed generally and comprises a flat portion and arcuate portions at both ends of the flat portion;
the flat portion has two parallel surfaces, whereby the fuel-electrode layer is positioned to cover one of the parallel surfaces and the arcuate portions of the support substrate;
the solid electrolytic layer is laminated to cover the fuel-electrode layer;
the oxygen-electrode layer is laminated on the solid electrolytic layer so as to face the fuel-electrode layer;
an interconnect is provided on the other parallel surface of the support substrate where neither the fuel-electrode layer nor the solid electrolytic layer is laminated; and the solid electrolytic layer is intimately adhered onto both sides of the interconnect to prevent leakage of any gas.
the support substrate is flat in cross section, is of an elliptic cylindrical shape as viewed generally and comprises a flat portion and arcuate portions at both ends of the flat portion;
the flat portion has two parallel surfaces, whereby the fuel-electrode layer is positioned to cover one of the parallel surfaces and the arcuate portions of the support substrate;
the solid electrolytic layer is laminated to cover the fuel-electrode layer;
the oxygen-electrode layer is laminated on the solid electrolytic layer so as to face the fuel-electrode layer;
an interconnect is provided on the other parallel surface of the support substrate where neither the fuel-electrode layer nor the solid electrolytic layer is laminated; and the solid electrolytic layer is intimately adhered onto both sides of the interconnect to prevent leakage of any gas.
9. The fuel cell according to claim 8, wherein the flat portion of the support substrate has a length of 15 - 35 mm and a thickness of 2.5 - 5 mm.
10. The fuel cell according to claim 7, 8 or 9, wherein the interconnect is made of perovskite lanthanum chromite LaCrO3 and has a relative density of at least 93%
and a thickness of 10 to 200 µm.
and a thickness of 10 to 200 µm.
11. The fuel cell according to any one of claims 1 to 10, wherein the oxygen-electrode layer is formed of porous electrically conducting ceramics composed of a perovskite oxide of ABO3 type having an A-site.
12. The fuel cell according to claim 11, wherein the perovskite oxide possesses La on the A-site of the ABO3 type.
13. The fuel cell according to claim 12, wherein the perovskite oxide is an La-MnO3 oxide, an La-CoO3 oxide or an La-FeO3 oxide, and the oxygen-electrode layer has a thickness of 30 to 100 µm.
14. The fuel cell according to any one of claims 1 to 13, wherein the solid electrolytic layer has a thickness of 10 to 100 µm and is formed of dense ceramics comprising ZrO2 which contains 3 to 15% by mol of the rare earth elements which are selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb an Lu, the dense ceramics having a relative density according to Archimedes' method of at least 93%.
15. The fuel cell according to claim 14, wherein the rare earth elements are Y and Yb'.
16. The fuel cell according to claim 7, 8, 9 or 10 which further comprises:
a P-type semiconductor ceramics layer on an outer surface of the interconnect.
a P-type semiconductor ceramics layer on an outer surface of the interconnect.
17. The fuel cell according to any one of claims 1 to 16, wherein a plurality of the fuel gas passages are formed maintaining a suitable distance from each other in the support substrate.
18. A fuel cell assembly comprising:
a container, and in the container, a cell stack of a structure in which a plurality of the fuel cells as defined in any one of claims 1 to 17 are connected together in series via a collector member.
a container, and in the container, a cell stack of a structure in which a plurality of the fuel cells as defined in any one of claims 1 to 17 are connected together in series via a collector member.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002156284 | 2002-05-29 | ||
| JP2002-156284 | 2002-05-29 | ||
| JP2002249800 | 2002-08-28 | ||
| JP2002-249800 | 2002-08-28 | ||
| DE10324396A DE10324396B4 (en) | 2002-05-29 | 2003-05-28 | Fuel cell and fuel cell assembly |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2428275A1 CA2428275A1 (en) | 2003-11-29 |
| CA2428275C true CA2428275C (en) | 2009-08-18 |
Family
ID=34139201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002428275A Expired - Fee Related CA2428275C (en) | 2002-05-29 | 2003-05-07 | Solid oxide electrolyte fuel cell |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US7351487B2 (en) |
| JP (1) | JP3996861B2 (en) |
| CA (1) | CA2428275C (en) |
| DE (1) | DE10324396B4 (en) |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4544872B2 (en) * | 2003-01-27 | 2010-09-15 | 京セラ株式会社 | Fuel cell and fuel cell |
| CA2459612C (en) * | 2003-02-28 | 2010-04-13 | Kyocera Corporation | Fuel cell |
| KR100648144B1 (en) * | 2005-09-15 | 2006-11-24 | 한국과학기술연구원 | High performance anode supported solid oxide fuel cell |
| JP4544975B2 (en) * | 2004-07-21 | 2010-09-15 | 京セラ株式会社 | Fuel cell and fuel cell |
| JP4912576B2 (en) * | 2004-08-31 | 2012-04-11 | 京セラ株式会社 | Fuel cell |
| EP1801905B1 (en) | 2004-09-13 | 2013-01-16 | Kyocera Corporation | Electrode support for fuel cell |
| US7527761B2 (en) * | 2004-12-15 | 2009-05-05 | Coorstek, Inc. | Preparation of yttria-stabilized zirconia reaction sintered products |
| US7833469B2 (en) * | 2004-12-15 | 2010-11-16 | Coorstek, Inc. | Preparation of yttria-stabilized zirconia reaction sintered products |
| ITMI20042468A1 (en) * | 2004-12-23 | 2005-03-23 | Eni Spa | METHOD FOR THE PREPARATION OF A NICKEL CERMET FOR COMBUSTIBLE CELLS WITH SOLID OXIDES |
| JP4931365B2 (en) * | 2005-04-20 | 2012-05-16 | 京セラ株式会社 | Support substrate for fuel cell, fuel cell, and fuel cell |
| KR101006420B1 (en) * | 2006-01-17 | 2011-01-06 | 오사까 가스 가부시키가이샤 | Cell for solid oxide fuel cell and manufacturing method thereof |
| JP5288686B2 (en) | 2006-01-27 | 2013-09-11 | 京セラ株式会社 | Conductive sintered body for fuel cell, fuel cell, fuel cell |
| EP2013936A2 (en) * | 2006-04-05 | 2009-01-14 | Saint-Gobain Ceramics and Plastics, Inc. | A sofc stack having a high temperature bonded ceramic interconnect and method for making same |
| JP4936801B2 (en) | 2006-06-22 | 2012-05-23 | ヤンマー株式会社 | Flat solid oxide fuel cell |
| DE102008009985B4 (en) * | 2008-02-19 | 2015-04-09 | Sunfire Gmbh | An electrolyte for an electrolyte-supported high-temperature fuel cell, method for its production, its use for an electrolyte-supported fuel cell and use of the fuel cell for a fuel cell stack |
| JP5238610B2 (en) * | 2009-05-27 | 2013-07-17 | 株式会社ノリタケカンパニーリミテド | Solid oxide fuel cell system and bonding material |
| JP2011054429A (en) * | 2009-09-02 | 2011-03-17 | Toyota Motor Corp | Fuel cell stack device |
| JP5331252B2 (en) | 2010-07-30 | 2013-10-30 | コリア インスティチュート オブ エナジー リサーチ | Flat tube type solid oxide cell stack |
| JP2012054015A (en) * | 2010-08-31 | 2012-03-15 | Kyocera Corp | Solid oxide fuel battery cell and fuel battery |
| FR2964664B1 (en) | 2010-09-13 | 2013-09-13 | Commissariat Energie Atomique | AQUEOUS INK FOR THE PRODUCTION OF HIGH TEMPERATURE ELECTROCHEMICAL CELL ELECTRODES |
| JP2012094427A (en) * | 2010-10-28 | 2012-05-17 | Kyocera Corp | Solid oxide fuel cell and fuel cell module |
| US20140087282A1 (en) * | 2011-05-18 | 2014-03-27 | Toto Ltd. | Solid oxide fuel cell and method for producing solid oxide fuel cell |
| WO2012165409A1 (en) | 2011-05-30 | 2012-12-06 | 京セラ株式会社 | Solid oxide fuel cell, fuel cell stack system, fuel cell module, and fuel cell system |
| JP5062789B1 (en) * | 2011-09-08 | 2012-10-31 | 日本碍子株式会社 | Solid oxide fuel cell |
| EP2772473B1 (en) | 2011-10-24 | 2019-01-02 | Kyocera Corporation | Ceramic sintered compact, high-temperature member, and electrochemical element |
| JP5502180B2 (en) * | 2011-11-24 | 2014-05-28 | 日本碍子株式会社 | Solid oxide fuel cell |
| US20130167723A1 (en) * | 2011-12-30 | 2013-07-04 | Industrial Technology Research Institute | Method for modifying porous substrate and modified porous substrate |
| KR101418071B1 (en) | 2012-04-06 | 2014-07-10 | 한국에너지기술연구원 | flat-tubular solid oxide cell stack |
| EP2980899B1 (en) | 2013-03-28 | 2018-04-25 | Kyocera Corporation | Solid-oxide electrolytic cell, cell stack device and electrolytic module, and electrolytic de vice |
| EP3016190B1 (en) * | 2013-06-27 | 2018-08-01 | Kyocera Corporation | Cell, cell stack, and module |
| KR101826821B1 (en) | 2015-04-06 | 2018-02-12 | 한국에너지기술연구원 | Mass flat-tubular cell stack and solid-oxide fuel cell or solid-oxide water electrolysis apparatus using the same |
| CN106299430B (en) * | 2015-05-28 | 2018-10-02 | 清华大学 | The application method of fuel cell |
| JP6560083B2 (en) * | 2015-09-25 | 2019-08-14 | 京セラ株式会社 | Cell, cell stack device, module, and module housing device |
| KR101891079B1 (en) * | 2016-10-28 | 2018-08-24 | 충북대학교 산학협력단 | Multi-layer structured inter-connector of solid oxide fuel cell |
| JP7027125B2 (en) * | 2017-11-02 | 2022-03-01 | 太陽誘電株式会社 | All-solid-state battery and its manufacturing method |
| JP7103783B2 (en) * | 2017-12-07 | 2022-07-20 | 株式会社ノリタケカンパニーリミテド | Joining material and joining body |
| EP4239730A1 (en) * | 2020-10-30 | 2023-09-06 | Kyocera Corporation | Cell, cell stack device, module, and module storage device |
| CN114583226B (en) * | 2022-03-31 | 2024-07-12 | 电堆科技(合肥)有限公司 | Metal-supported proton conductor solid oxide battery and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1922970A1 (en) * | 1968-05-13 | 1969-12-04 | Westinghouse Electric Corp | Fuel cell battery |
| DE2328050C3 (en) * | 1973-06-01 | 1978-10-05 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Catalyst for fuel electrodes of fuel elements |
| US4894297A (en) * | 1988-12-07 | 1990-01-16 | Westinghouse Electric Corp. | Electrochemical generator apparatus containing modified fuel electrodes for use with hydrocarbon fuels |
| JP2877259B2 (en) | 1991-03-07 | 1999-03-31 | 三菱重工業株式会社 | Fuel electrode material |
| US5391440A (en) * | 1994-02-14 | 1995-02-21 | Westinghouse Electric Corporation | Method of forming a leak proof plasma sprayed interconnection layer on an electrode of an electrochemical cell |
| JPH11329518A (en) * | 1998-05-21 | 1999-11-30 | Toshiba Battery Co Ltd | Battery device |
| US6916569B2 (en) * | 2000-11-23 | 2005-07-12 | Sulzer Hexis Ag | Fuel cell comprising a solid electrolyte layer |
| US6887361B1 (en) * | 2001-03-22 | 2005-05-03 | The Regents Of The University Of California | Method for making thin-film ceramic membrane on non-shrinking continuous or porous substrates by electrophoretic deposition |
-
2003
- 2003-02-26 JP JP2003049332A patent/JP3996861B2/en not_active Expired - Fee Related
- 2003-04-28 US US10/424,889 patent/US7351487B2/en not_active Expired - Lifetime
- 2003-05-07 CA CA002428275A patent/CA2428275C/en not_active Expired - Fee Related
- 2003-05-28 DE DE10324396A patent/DE10324396B4/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE10324396A8 (en) | 2005-05-04 |
| CA2428275A1 (en) | 2003-11-29 |
| JP3996861B2 (en) | 2007-10-24 |
| JP2004146334A (en) | 2004-05-20 |
| US7351487B2 (en) | 2008-04-01 |
| DE10324396B4 (en) | 2008-10-23 |
| US20030224240A1 (en) | 2003-12-04 |
| DE10324396A1 (en) | 2004-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2428275C (en) | Solid oxide electrolyte fuel cell | |
| US7645535B2 (en) | Method and materials for bonding electrodes to interconnect layers in solid oxide fuel cell stacks | |
| KR101475392B1 (en) | Titanate and metal interconnects for solid oxide fuel cells | |
| KR101608293B1 (en) | Fuel cell, cell stack, fuel cell module, and fuel cell device | |
| US20070037031A1 (en) | Cermet and ceramic interconnects for a solid oxide fuel cell | |
| AU2012271841B2 (en) | Fuel cell system with interconnect | |
| AU2014233440B2 (en) | Fuel cell system with interconnect | |
| EP2461405A1 (en) | Solid oxide fuel cell | |
| US8252366B2 (en) | Method for making toughened electrode-supported ceramic fuel cells | |
| CA2838962A1 (en) | Fuel cell system with interconnect | |
| JP4332639B2 (en) | Fuel cell and method for producing the same | |
| CA2459612C (en) | Fuel cell | |
| US10003088B2 (en) | Solid oxide fuel cell stack | |
| EP3038197A1 (en) | Ceramic substrate for electrochemical element, method for manufacturing same, fuel cell, and fuel cell stack | |
| JP4828104B2 (en) | Fuel cell | |
| EP3422448B1 (en) | Fuel cell power generation unit and fuel cell stack | |
| KR20190129841A (en) | Method for manufacturing electrochemical device and electrochemical device | |
| EP3152794A1 (en) | Fuel cell having flat-tubular anode | |
| CN111244498A (en) | Fuel cell and fuel cell stack | |
| JP4480377B2 (en) | Fuel cell and fuel cell | |
| US20160093910A1 (en) | Solid oxide fuel cell stack | |
| Stöver et al. | Recent developments in anode supported thin film SOFC at Research Centre Jülich | |
| US20100297527A1 (en) | Fast Ion Conducting Composite Electrolyte for Solid State Electrochemical Devices | |
| CA3161426C (en) | A bilayer hydrogen electrode for a solid-oxide electrochemical cell | |
| Stöver et al. | Processing and properties of advanced solid oxide fuel cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20170510 |