CN1591947A - Anode supported flat tubular solid oxide fuel battery and its mfg. method - Google Patents

Anode supported flat tubular solid oxide fuel battery and its mfg. method Download PDF

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Publication number
CN1591947A
CN1591947A CNA2004100576559A CN200410057655A CN1591947A CN 1591947 A CN1591947 A CN 1591947A CN A2004100576559 A CNA2004100576559 A CN A2004100576559A CN 200410057655 A CN200410057655 A CN 200410057655A CN 1591947 A CN1591947 A CN 1591947A
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China
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fuel cell
slurry
connector
powder
anode
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CN1332463C (en
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宋珞铉
申东烈
金钟熙
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Despu Co ltd
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Korea Institute of Energy Research KIER
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • 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
    • H01M8/002—Shape, form of a fuel cell
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • 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

Abstract

To provide a fuel electrode support type flat tube solid oxide fuel cell stack free from a trouble due to low electric power density while keeping an advantage of a cylindrical shape by constructing the stack in a flat structure and a cylindrical structure, and a method of effectively manufacturing the same. A fuel electrode support type flat tube solid oxide fuel cell stack includes a supporting tube having semicircular both ends and a flat center, an interlocking material covering the center of the flat upper plane of the supporting tube, a fuel cell composed of an electrolyte layer covering the outer peripheral surface of the supporting tube except for the interlocking material and an air electrode covering the outer peripheral surface of the electrolyte, and a connection plate composed of a lower part connection plate on which a gas channel for interlocking many fuel cells is formed in a laminated state, one or more intermediate connection plates and an upper connection plate.

Description

The flat tube shape solid-oxide fuel cell stack and the manufacture method thereof of anode-supported
Background of invention
1. invention field
The present invention relates to a kind of anode that uses as the flat tube shape solid-oxide fuel cell stack of supporter and make the method for this battery pile.More specifically, the present invention relates to a kind of flat tube shape solid-oxide fuel cell stack of anode-supported and make the method for this battery pile, this battery pile comprises the anode support tube with semicylinder part and plate part, thereby has the combining structure of tubular type and slab anode supporter.The advantage of the flat tube shape solid-oxide fuel cell stack of this anode-supported is: the fuel cell that constitutes battery pile seals easily, and has the power density of the per unit area of excellent thermal stress resistance and raising.
2. description of Related Art
Fuel cell is a kind of electric organ of high efficiency cleaning, wherein in alkyl material such as natural gas, coal gas or methyl alcohol in contained hydrogen and the air contained oxygen produce electrochemical reaction and produce electric energy.Fuel cell is divided into alkaline fuel cell, phosphoric acid fuel cell, molten carbonate fuel cell, Solid Oxide Fuel Cell and polymer fuel cell.
Usually, to use the phosphoric acid fuel cell of phosphoric acid electrolyte to be called first generation fuel cell, wherein use mainly contain by fossil fuel reform and in the hydrogen of the hydrogen of gained and the air contained oxygen act as a fuel, to use fused carbonate to be called second generation fuel cell as electrolyte and at about 650 ℃ of high-temperature molten carbonate fuel cells of working down, the Solid Oxide Fuel Cell (SOFC) that will work and produce peak efficiency electric power under higher relatively temperature be called third generation fuel cell.
Studied third generation fuel cell-Solid Oxide Fuel Cell afterwards at phosphoric acid fuel cell (PAFC) and molten carbonate fuel cell (MCFC), but, because developing rapidly of material technology estimates that Solid Oxide Fuel Cell can rapid commercialization after PAFC and MCFC.In addition, Solid Oxide Fuel Cell is worked under 600-1000 ℃ high temperature, and has the following advantages: it is the most effective in existing fuel cell, discharges pollutants hardly, does not need apparatus for reforming of fuel, can realize mixed power generation.
According to the shape of Solid Oxide Fuel Cell, usually Solid Oxide Fuel Cell is divided into tubular type fuel cell, board-like fuel cell and monomer-type fuel cell.At present, in them, studying maximum is tubular type and board-like fuel cell, and the technology of tubular type fuel cell is considered as state-of-the-art technology, and the research of board-like fuel cell is than the research advanced person of monomer-type fuel cell.For the tubular type fuel cell, the U.S. and Japan after deliberation the air electrode support type fuel cell, for board-like fuel cell, studied and comprised electrolyte as the self-supporting film type fuel cell of supporter and the board-like fuel cell of anode-supported.
Plate type solid oxide fuel cell has the current density higher than disc type fuel cell, but has following shortcoming: because following problem causes using plate type solid oxide fuel cell to be difficult to make large-scale board-like fuel cell, described large-scale board-like fuel cell is that the big volume of fuel cells of manufacturing is necessary, and described problem is the sealing and because the thermal shock that the difference of heat balance coefficient causes between fuel cell module of for example gas.
Compare with plate type solid oxide fuel cell, tubular solid oxide fuel cell has the following advantages: the element cell that constitutes battery pile seals easily, the thermal stress resistance of battery pile and mechanical strength height, thus tubular solid oxide fuel cell is considered as the most easily making the excellent technology of large-scale fuel cell.Yet tubular solid oxide fuel cell has following shortcoming: tubular solid oxide fuel cell has the powerperunitarea density lower than plate type solid oxide fuel cell, and the manufacturing cost of tubular solid oxide fuel cell is than higher.
Yet conventional tubular type fuel cell be to use air electrode to act as a fuel fuel cell that the air electrode of cell support body supports is because the raw material of this air electrode such as La and Mn be very costliness and LSM (LaSrMnO 3) manufacturing very difficult, so the production cost of this fuel cell raises.In addition, because made by pottery as the air electrode of supporter, and anode is to use the cermet of being made up of metal and pottery to make, so the mechanical strength of element cell is low, and can not withstand shocks.
And, according to the high method that applies cost of needs in the process of the tubular solid oxide fuel cell of making conventional air electrode support, dielectric substrate is coated on the surface of air electrode stay pipe, the tubular solid oxide fuel cell that therefore conventional air electrode supports is disadvantageous aspect economic benefit.
In other words, because the air electrode as supporter in the tubular solid oxide fuel cell of conventional air electrode support is made by pottery such as La at high price, so air electrode is frangible, in the ceramic structure that constitutes air electrode, at high temperature, because chemical reaction causes the intensity decreases of air electrode, and because utilize very expensive EVD method on the air electrode surface, to form dielectric substrate, so the fuel cell price raises.
And because the electrolyte and the anode that form on the surface of the air electrode stay pipe of sintering of co-sintering at high temperature, so the activity of air electrode descends, and the efficient of fuel cell reduces.
The above-mentioned shortcoming of the Solid Oxide Fuel Cell that supports for fear of air electrode, after deliberation use the tubular solid oxide fuel cell of anode as the anode-supported of supporter.The anode support tube that uses in the tubular solid oxide fuel cell of anode-supported satisfies the required characteristic of electrode, and as supporter, its advantage is: because reactive low between supporter and dielectric substrate, so co-sintering is feasible, and because the mechanical strength height of anode, so can make stable fuel cell pack.
In addition, anode support tube has enough pores therein; Because in anode support tube, form continuous gas cell distribution, so supply of fuel is unrestricted; Because the conductivity height is so electric current is steady; And the production cost of this fuel cell is low.
When making the tubular solid oxide fuel cell of anode-supported, the greatest factor that influences productivity ratio is that dielectric substrate is coated to the lip-deep method of anode support tube.
In detail, the conductivity that is widely used as electrolytical YSZ in the Solid Oxide Fuel Cell is most descended to be about 10 at 1000 ℃ -1S/cm, this dielectric substrate should have about 30 μ m or littler thickness, and because the working temperature of fuel cell is low more, conductivity is just low more or resistance is just big more, so this dielectric substrate should be very fine and close.
The shortcoming that the tubular solid oxide fuel cell of anode-supported has is: should form extremely thin and fine and close dielectric substrate on the surface of the porous anode stay pipe of high surface area very having.Therefore, many researchs have been started recently to develop the method for the excellent dielectric substrate of effective formation.
When the physics by using vacuum and chemical vapor deposition method such as EVD method or plasma spraying method form dielectric substrate, can form densification and thin dielectric substrate, but it is too huge to be used to form the equipment of dielectric substrate, and the reaction time is long.In addition, because electrolyte once only is deposited on a small amount of element cell, so said method is unsuitable for making fuel cell with economical quantities.
Summary of the invention
Therefore, keep it in mind the problems referred to above that occur in the prior art and created the present invention, one aspect of the present invention provides a kind of flat tube shape solid-oxide fuel cell stack of anode-supported and makes the method for the flat tube shape solid-oxide fuel cell stack of this anode-supported, this battery pile comprises the anode support tube with semicylinder part and plate part, thereby has the advantage of tubular solid oxide fuel cell heap of anode-supported and the tubular solid oxide fuel cell that improves anode-supported is piled low relatively power density.
Aspect that the present invention is other and/or advantage part will state in explanation subsequently that part is become apparent by following description, maybe can understand by implementing the present invention.
Realize above-mentioned and/or others by the flat tube shape solid-oxide fuel cell stack that the anode-supported that is equipped with the anode support tube that comprises semicylinder part and plate part is provided.At this moment, plate part parallel to each other laying in anode support tube.
The accompanying drawing summary
In conjunction with the accompanying drawings, can more be expressly understood above-mentioned and other aspect, feature and other advantage of the present invention by following detailed description, wherein:
Fig. 1 is the perspective view of monoreactant battery that constitutes the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention;
Fig. 2 is the perspective view of last connector board, middle connector board and lower connector plate that constitutes the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention;
Fig. 3 is the front view of last connector board, middle connector board and lower connector plate that constitutes the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention;
Fig. 4 is the end view of last connector board, middle connector board and lower connector plate that constitutes the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention;
Fig. 5 is the cutaway view of the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention;
Fig. 6 A and 6B are the nickel distributed images that constitutes in the Ni/YSZ cermet anode of monoreactant battery of flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention, wherein Fig. 6 A is the SEM figure of Ni/YSZ cermet anode, and Fig. 6 B is the X-ray diagram of Ni/YSZ cermet anode;
Fig. 7 is the graph of pore diameter distribution according to the monoreactant cell support pipe of sintering condition;
Fig. 8 is the sectional structure chart of monoreactant battery of the present invention;
Fig. 9 is the performance map of monoreactant battery of the present invention, and this figure has illustrated for the monoreactant battery, the relation of voltage and power density and current density;
The figure of Figure 10 A and the 10B voltage-current characteristic that to be explanation change according to the working temperature and the fuel of monoreactant battery, wherein Figure 10 A is at 750 ℃ of following graphs of a relation of voltage and current density in the monoreactant batteries of work, and Figure 10 B is the graph of a relation of voltage and current density in 850 ℃ of monoreactant batteries of working down;
Figure 11 is the profile that is coated in the connector on the stay pipe of the present invention; With
Figure 12 is conductivity and time relation figure in the connector board of the present invention.
Detailed Description Of The Invention
Now, will be in detail with reference to the existing preferred embodiment of the present invention, embodiment has been described in the accompanying drawings, in institute's drawings attached, identical label refers to components identical.
The flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention is characterised in that: it is equipped with two or more fuel cells and three or more connector boards to arrange fuel cell on demand and to make fuel cell each other in an electrically conductive.In addition, thus this battery pile has the flat tube fuel cell obtains the board-like and advantage tubular type fuel cell.And, according to wet method such as plasma spraying method or slurry cladding process connector is coated on the outer surface of stay pipe, thereby makes fuel cell and connector board conduction.
The flat tube shape monoreactant battery that constitutes battery pile of the present invention comprises semicylinder part and plate part, and this connector board is used for piling up flat tube shape fuel cell and makes flat tube shape fuel cell each other in an electrically conductive.
With reference to figure 1, the anode support tube 11 of supporter effect that works the monoreactant battery 1 of the flat tube shape solid-oxide fuel cell stack that constitutes anode-supported comprises upper plate 11A and the lower plate 11B that is installed in parallel with each other, with upper plate 11A and the whole semicylinder 11C that combines of lower plate 11B, therefore section shape with the combining structure that is two straight lines and two semicircles.
In addition, by supporting upper plate 11A and the lower plate 11B that constitutes anode support tube 11 with at least two bridges (B) that form the mode at right angle with upper plate 11A and lower plate 11B and combine with upper plate 11A and lower plate 11B integral body.
In other words, the anode support tube 11 that constitutes monoreactant battery 1 comprises upper plate 11A and lower plate 11B and the semicylinder 11C that connects with following method, thereby promptly semicylinder 11C combines the section shape with the combining structure that is two straight lines and two semicircles with the upper plate 11A and the lower plate 11B integral body of anode support tube 11.At this moment, semicylinder 11C plays bridge (B), thereby upper plate 11A and lower plate 11B are connected to each other.
And, bridge (B) is used for reducing the electric current move distance and the interior resistance of monoreactant battery 1, thereby make electric current steadily flow through battery pile, to increase the power density of battery pile, and improved the intensity of the anode of supporter effect, thereby the durability of the flat tube shape solid-oxide fuel cell stack of anode-supported is improved.
Therefore, each monoreactant battery that constitutes the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention all comprises stay pipe 11, to be placed in the mode of upper plate 11A center, vertically be coated in the connector with rectangular section 13 on the upper plate 11A of stay pipe 11, part is coated in the dielectric substrate 12 on the outer surface that removes the stay pipe 11 a part of stay pipe 11 that contacts with connector 13 realizations, be coated in the air electrode 14 on the outer surface of dielectric substrate 12 as follows, promptly its two ends respectively with the both sides of connector 13 preset distance (d) at interval.
Generally speaking, each monoreactant battery of formation battery pile of the present invention all has the combining structure of tubular type and slab anode supporter.
With reference to figure 2-4, the connector board 2 that have rectangular section, is made of metal comprises lower connector plate 21, one or more middle connector board 22 and last connector board 23, and connector board is installed in the flat tube shape solid-oxide fuel cell stack of anode-supported, thereby fuel cell is arranged as two or more rows, and fuel cell pack is stacked as two-layer or more multi-layered.
On the upper surface of lower connector plate 21 and middle connector board 22, form many grooves (G) parallel to each other to hold flat tube shape fuel cell.At this moment, each monoreactant battery 1 highly little 50% of the depth ratio of each groove (G) or still less.And, in the mode that is parallel to groove (G) extruding and contact with the upper surface of the connector 13 of fuel cell 1, with the corresponding position, center of groove (G) on, on the part lower surface of last connector board 23 and middle connector board 22 formation many hexahedron connector ridges (E).The lower surface of the upper surface of last connector board 23 and lower connector plate 21 all is smooth, and is connected with battery pile electrode of the present invention.
And, on the upper surface of lower connector plate 21 and middle connector board 22, to form many gas passages (C) with rectangular section with the rectangular mode of groove (G).In this respect, gas passage (C) is installed in parallel with each other and plays inlet air flow path.
Fuel cell 1 is installed in the groove (G) of lower connector plate 21, and as follows the first intermediate connector plate 22 is covered on the fuel cell 1, the connector ridge (E) of the middle connector board 22 of winning is contacted with the connector 13 of fuel cell 1.
In addition, fuel cell 1 is installed in the groove (G) of connector board 22 in first, then connector board 22 in second is covered on the fuel cell 1.Method above repeating is to pile up many middle connector boards 22 and fuel cell 1, finally, to go up connector board 23 layers as follows on fuel cell 1, make the connector ridge (E) of going up connector board 23 contact, thereby realize the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention with the connector 13 of fuel cell 1.
In other words, as shown in Figure 5, according to lower connector plate 21, fuel cell 1, middle connector board 22, fuel cell 1, middle connector board 22 ..., fuel cell 1, middle connector board 22, fuel cell and last connector board 23 sequence stack connector board 2 and fuel cell 1.At this moment, battery pile electrode 3 and 3 ' be connected with the lower surface of lower connector plate 21 and the upper surface of last connector board 23 respectively.
In this respect, quantity of groove (G), connector ridge (E) and the middle connector board 22 of the connector board 2 of installation fuel cell 1 depends on the wattage that obtains on it from the flat tube shape solid-oxide fuel cell stack of this anode-supported.
As mentioned above, make up the flat tube shape solid-oxide fuel cell stack of anode-supported like this, make hydrogen flow in the stay pipe 11 of fuel cell 1, air is with approximately perpendicular to the flow through gas passage (C) of connector board 2 of the flow direction of hydrogen.In this respect, at the groove (G) of lower connector plate 21 and middle connector board 22 thus in be arranged parallel to each other fuel cell 1 and be collected in the electric current that air electrode forms, anode is connected in series by the flat upper surfaces of last connector board 21 and the flat bottom surface and the air electrode of lower connector plate 23, and the connector ridge (E) of last connector board 21 contacts with the connector of the fuel cell 1 that is installed in the connector board 22 that is arranged in the extreme higher position.
To method that make flat tube shape fuel cell and connector board be described in detail.
The method of making the flat tube shape solid-oxide fuel cell stack of anode-supported comprises pushes the slurry that zirconia (hereinafter referred to as " the YSZ ") powder of stabilized with yttrium oxide was used, contained to also dry stay pipe, thereby makes flat tube shape stay pipe at the slurry of 1200-1400 ℃ of following presintering gained; With band shape organic protection layer be coated in the stay pipe upper plate in the heart, the stay pipe of gained is impregnated in the electrolyte slurry that contains the YSZ powder, thereby this electrolyte slurry is coated on the outer surface of stay pipe, dry this electrolyte slurry is removed band shape organic layer and make this electrolyte slurry degreasing repeatedly under 200-450 ℃; Stay pipe at 1300-1500 ℃ of following co-sintering gained; According to plasma spraying method or slurry cladding process the perovskite powder (is wherein joined LaCrO with Ca, Sr, Mg, Co or Al 3In) apply on the part of the stay pipe of removing organic layer thereon, thereby on this stay pipe, form ceramic connector; Another kind of organic layer is coated on this ceramic connector, wet being impregnated into of the stay pipe of gained contained LaSrMnO 3In the air electrode slurry of powder, thereby the air electrode slurry is coated on the dielectric substrate, removes this organic layer, thereby realize the monoreactant battery at this air electrode slurry of 1150-1250 ℃ of following sintering from ceramic connector.
At this moment, dielectric substrate 12 must be connected with the outer surface of stay pipe 11 tightly with connector 13, to prevent that reacting gas is mixed with each other, and connector 13 must be predetermined at interval with the two ends of air electrode distance (d), with the connector 13 that prevents from the stay pipe that plays anodize, to form with on electricity, form short circuit at the air electrode that forms on the dielectric substrate.
When making fuel cell, 10-50vol%, the carbon dust that plays the pore creating material effect are joined in the YSZ powder that contains 30-60vol% nickel, and will join in the mixture of carbon dust and YSZ powder, thereby make the stay pipe slurry in distilled water, the organic bond of 5-20wt%, the plasticizer of 3-10wt% and the lubricant of 1-7wt% of the 15-30wt% of amount of the mixture.Aging then (seasoned) slurry so that moisture be evenly distributed in the slurry.At this moment, the ceramic-metallic conductivity of Ni/YSZ depends on nickel content.When nickel content is 30vol% or when bigger, because the contact between the nickel particles increases, so conductivity improves.Yet when nickel content was lower than 30vol%, electronic conductivity significantly reduced.
As mentioned above, by increasing the conductivity that nickel content improves anode, but when nickel content during greater than 60vol%, the ceramic-metallic thermal coefficient of expansion of Ni/YSZ raises, therefore aspect thermal coefficient of expansion, other component in the tubular solid oxide fuel cell of Ni/YSZ cermet and anode-supported is different, thereby during in the process of making fuel cell or in the estimating fuel battery performance, occurs the crack usually in fuel cell.Therefore, according to the present invention, the YSZ powder preferably comprises the nickel metal of 30-60vol%, make the coefficient of thermal expansion differences minimum between other component in the tubular solid oxide fuel cell of Ni/YSZ cermet and anode-supported like this, and this anode has enough conductivity.
In addition, in anode support tube presintering step and after being squeezed into the step of anode support tube, the anode stay pipe is inner to add the carbon dust 10-50vol% amount, contained in the effective powder of anode-supported as pore creating material.For example, when the amount of carbon dust was less than 10vol%, anode was inoperative usually, because the porosity in the anode support tube descends.On the other hand, when this measured greater than 50vol%, the intensity decreases of anode support tube was because porosity excessively increases.
And, when the amount of distilled water is less than 15wt%, because the moisture that slurry contains is not enough, so the extrusion performance of slurry descends.On the other hand, when the amount of distilled water during greater than 30wt%, the extrudate easy deformation.And, when the amount of organic adhesive during, in anode support tube, form crackle or this anode support tube has poor intensity less than 5wt%, but when the amount of organic adhesive greater than 20wt%, then be difficult to control the pore of final sintered body.
In addition, when the amount of plasticizer is less than 3wt%, in the process of molded model starting powder and organic bond, be difficult to molded equably starting powder and organic bond, but when the amount of plasticizer during greater than 10wt%, extrudate easy deformation.And, when the amount of lubricant is less than 1wt%, because friction increases in the process of extruding slurry, so the extrusion performance of slurry descends.Yet, when the amount of lubricant surpasses 7wt%, because excessive lubrication causes the briquetting pressure of deficiency is applied on the slurry, so the density of extrudate descends.
Simultaneously, when pre-sintering temperature after extruding and dry stay pipe are with slurry when being lower than 1200 ℃, the undercapacity that this anode support tube has to be bearing the step that forms dielectric substrate, thereby because this slurry not have sintering ideally to obtain the resistance to impact that differs from.And when this temperature was higher than 1400 ℃, anode support tube seriously shrank, therefore in the process of co-sintering slurry and after with slurry coated anode stay pipe, because the difference of component contraction percentage aspect can cause the fuel cell cracking in the fuel cell.
This electrolyte slurry comprises YSZ powder and the additive of the organic solvent of 60-95wt% such as 2-propyl alcohol and toluene, 5-40wt%.For example, when the concentration of YSZ powder during less than 5wt%, it is too thin so that can not form fine and close dielectric substrate when being impregnated into anode support tube in the slurry to be coated in pulp layer on the anode-supported tube outer surface.On the other hand, when the concentration of YSZ powder during greater than 40wt%, it is too thick so that this pulp layer is kept evenly to be coated in pulp layer on the anode support tube.
As mentioned above, this electrolyte slurry comprises YSZ powder and additive.In detail, in 100 gram YSZ powder, this electrolyte slurry comprises 5-12 weight portion adhesive, 5-15cc plasticizer, 1-3cc levelling agent and 1-3cc dispersant as additive.In this respect, if the amount of additive such as adhesive, plasticizer, levelling agent and dispersant departs from above-mentioned scope, then this slurry is of no use to the present invention.
In addition, according to the concentration of YSZ powder in the electrolyte slurry, be impregnated in the electrolyte slurry 2-5 time anode support tube is wet, with the surface of usefulness pulp layer coated anode stay pipe.If the dipping number of times then can not obtain to have the dielectric substrate of suitable thickness beyond above-mentioned scope.And, the pulp layer of dry gained under 200-450 ℃, and at 1300-1500 ℃ of following co-sintering.Under being lower than 200 ℃ temperature during dry pulp layer, because do not remove additive fully, so form fine and close dielectric substrate.On the other hand, when the baking temperature of pulp layer was higher than 450 ℃, the thermal deformation meeting that occurs in pulp layer reduced the quality of dielectric substrate.And, when when being lower than 1300 ℃ of following co-sintering pulp layers, form fine and close dielectric substrate, but when above 1500 ℃ of following co-sintering pulp layers the time, because NiO particle undue growth, so the decreased performance of anode support tube.
The connector that forms on the outer surface of the anode support tube of removing organic layer from it is by the perovskite powder constituent, preferably after the perovskite powder that according to spray drying process with particle diameter is 0.1-2 μ m changes the piece that is of a size of 10-60 μ m into, on anode support tube, form this piece according to plasma spraying method.Perhaps, make powder form piece according to the wet slurry method after, can on anode support tube, form this piece according to infusion process.
Use LaSrMnO 3Powder, LaSrMnO 3The mixed-powder of powder and 20-50wt%YSZ powder and LaSrCoFeO 3Powder forms the air electrode slurry as raw material.Each powder is mixed with the organic solvent of 50-75wt% and the additive of 5-40wt%, thereby make 3 kinds of air electrode slurries.At this moment, the amount of each powder is 10-30wt%.If the amount of above-mentioned material departs from above-mentioned scope, then this air electrode slurry is of no use to the present invention.
To contain LaSrMnO 3The slurry of the mixed-powder of powder and 20-50wt%YSZ powder, contain LaSrMnO 3The slurry of powder and contain LaSrCoFeO 3It is last or repeatedly that the slurry of powder is coated in dielectric substrate separately, 200-450 ℃ dry down, and at 1150-1250 ℃ of following sintering.For example, when baking temperature is lower than 200 ℃, because fully do not remove additive, so do not form fine and close air electrode layer.On the other hand, when baking temperature is higher than 450 ℃ because heat causes pulp layer distortion, thus air electrode layer separate with dielectric substrate, thereby the quality of fuel cell descends.And, when sintering temperature is lower than 1150 ℃, because the air electrode slurry does not have abundant sintering, so the diffusion interlayer reduces, but when sintering temperature is higher than 1250 ℃, because the excessive sintering of air electrode slurry, so the manganese element in the air electrode is destroyed and the structural behaviour variation of air electrode.
Simultaneously, manufacturing is used for the layer fuel cell and the method for fuel cell connector board connected to one another be may further comprise the steps:
On last connector board, middle connector board and lower connector plate, form groove (G), gas passage (C) and connector ridge (E), describedly go up connector board, middle connector board is made by being selected from following metallic plate with the lower connector plate: Fe-Cr base alloy such as ducrolloy, SUS310S or under 600-800 ℃ of operation of fuel cells, have relative little thermal coefficient of expansion and excellent heat resistance SUS 430, contain LaCrO 3, Y 2O 3Or La 2O 3Fe-Cr alloy, evanohm and Ni alloy;
The surface of polishing metal plate;
Mix ceramic powders such as LaSrMnO mutually with electronic conductivity 3Or La 1-XCa XCr 1-YO 3, adhesive (PVB), plasticizer (dibutyl phthalate), dispersant (fish oil), levelling agent (triton-X) and solvent (toluene or 2-propyl alcohol), thereby the mixture of ball milling gained is made the connector board slurry;
Metallic plate is impregnated into connector board with in the slurry, and twice of the metallic plate of dry gained or more times are to be coated in connector board on the metallic plate with slurry;
At 1100-1300 ℃, 10 -10-10 -3Sintering contains LaSrMnO under the atmospheric partial pressure of oxygen 3Slurry, or at 1150-1350 ℃, 10 -3Sintering contains La under atmospheric pressure or the lower partial pressure of oxygen 1-XCa XCr 1-YO 3Thereby slurry on metallic plate, form ceramic coating.
In this respect, connector board comprises the LaSrMnO of 20-50wt% with slurry 3Or La 1-XCa XCr 1-YO 3, 0.5-10wt% adhesive, 0.2-2wt% solvent and 0.2-5wt% additive such as plasticizer, dispersant and levelling agent.
For example, the ceramic powders such as the LaSrMnO that in slurry, have electronic conductivity 3Or La 1-XCa XCr 1-YO 3Content when being lower than 20wt%, the ceramic coating on the metallic plate is very thin, and the oxonium ion in the atmosphere is diffused in the metal group of ceramic powders, thereby makes ceramic coating have low non-oxidizability.On the other hand, the content of this ceramic powders is greater than 50wt%, because the flowability of slurry descends, so the pulp layer between the metallic plate upper channel has uneven thickness.In addition, when binder content is lower than 0.5wt% in the slurry, because the bonding force of ceramic powders and metallic plate significantly reduces after the ceramic powders drying, so the pulp layer on the metallic plate has uneven thickness in the process of sintering pulp layer.And when binder content during greater than 10wt%, the flowability of slurry descends, and is difficult to form fine and close pulp layer behind the pulp layer sintering.
And when the solvent in the slurry was lower than 0.2wt%, adhesive was not dissolved in the slurry fully, and because the flowability of slurry reduces, so the dispersiveness of slurry descends.But,, be difficult on metallic plate, form uniform slurry coating when solvent during greater than 2wt%.
Contain La in use 1-XCa XCr 1-YO 3The situation of slurry under, preferably X is greater than 0 to up to 0.4, Y is 0 to 0.5.When X is 0, because contain La 1-XCa XCr 1-YO 3Slurry sintering at elevated temperatures, so because heat causes the metallic plate easy deformation.On the other hand, when X greater than 0.4 the time, because the thermal coefficient of expansion between metallic plate and slurry coating is variant, so slurry coating peels off from metallic plate easily.
In addition, contain LaSrMnO 3Slurry and contain La 1-XCa XCr 1-YO 3Slurry at aforesaid different partial and sintering temperature.In this respect, when containing LaSrMnO 3Slurry be lower than 10 -10During sintering, because noted phase separation phenomena, the conductivity of slurry descends under the atmospheric partial pressure of oxygen, but when containing LaSrMnO 3Slurry be higher than 10 -3Under the atmospheric partial pressure of oxygen during sintering, because the metal component over oxidation in the slurry, so the conductivity of slurry descends.And, when containing LaSrMnO at the sintering temperature that is lower than 1100 ℃ 3Slurry the time, be difficult to this slurry of abundant sintering, but when containing LaSrMnO at the sintering temperature that is higher than 1300 ℃ 3Slurry the time because because heat causes the metal component distortion in the slurry, so slurry coating can be out of shape.
And, when containing La 1-XCa XCr 1-YO 3Slurry be higher than 10 -3Under the atmospheric partial pressure of oxygen during sintering, because the metal component over oxidation in the slurry, so the conductivity of slurry descends.And, when containing LaSrMnO at the sintering temperature that is lower than 1150 ℃ 3Slurry the time, be difficult to this slurry of abundant sintering, but when containing La at the sintering temperature that is higher than 1350 ℃ 1-XCa XCr 1-YO 3Slurry the time because because heat causes the metal component distortion in the slurry, so slurry coating can be out of shape.
Therefore, after making under these conditions, alternately pile up connector board and fuel cell to make flat tube shape solid-oxide fuel cell stack according to anode-supported of the present invention.
The present invention may be better understood according to following examples, and described embodiment is used for explanation, but is not considered as limiting the present invention.
Fuel cell
According to extrusion, use the NiO-YSZ powder to make anode support, use the zirconia (8YSZ is made by TosohCo.) of the stabilized with yttrium oxide of NiO (by Junsei Chemical Co.) and 8mol%, prepare anode powder in the mode that contains 40vol%Ni/YSZ.
To be used for making this powder porous active carbon (making), extrusion to join this powder, the distilled water of scheduled volume and the powder of gained will also be pushed this powder equably with the viscosity of suitably controlling extrudate with organic bond, plasticizer and lubricant by KURARAYChemical Co. as pore creating material.The powder that contains distilled water of aging then and extruding gained.
Dry repeatedly extrudate several times in the baking oven of low temperature, with prevent its in the process of dry extrudate owing to solvent evaporation is out of shape, or prevent from the process of dry this extrudate, in extrudate, to form crackle, then 120 ℃ dry 24 hours down.Then at the supporter of 1300 ℃ of following presintering dryings.
Use organic additive such as polyvinyl butyral resin, two-positive buthalate, Triton-X and fish oil and organic solvent such as toluene and 2-propyl alcohol to make electrolyte and air electrode slurry.In addition, being coated on the stay pipe repeatedly the 8YSZ slurry and degreasing, is the slurry coating of about 20 μ m to form thickness according to slurry immersion coating method.Then, at 1400 ℃ of these slurry coatings of following co-sintering.
According to the synthetic (La of solid reaction process as air electrode material 0.85Sr 0.15) 0.9MnO 3(LSM) powder and La 0.65Sr 0.4Co 0.2Fe 0.8O 3(LSCF) powder.To contain the slurry of the mixture of 40wt%8YSZ and LSM, the slurry sequential applications that contains the slurry of LSM and contain LSCF on dielectric substrate, realize the monoreactant battery at 1200 ℃ of following sintering then.
Use mercury porosimeter (Autopore IV 9500 V1.00, Micromeritics) porosity and the aperture of measurement anode support, by SEM (scanning electron microscopy), and the distribution of nickel of electron path effect and the connectedness between the Ni particle in the anode support have been determined according to the composition analysis method.
By means of electric loading and power supply, the measuring unit fuel cell voltage changes by changing the current density in the monoreactant battery, thus the evaluation unit fuel cell performance.
At this moment, by the gas manifold that is installed in monoreactant battery two ends, made by aluminium oxide the hydrogen that acts as a fuel is sent in the monoreactant battery, air flows along the outer surface of this monoreactant battery.Use platinum guaze and nickel felt as the electric current collection body of air electrode and the electric current collection body of anode respectively.
The slurry that will contain LSM is coated on SUS 430 alloys, at 1200 ℃, Ar-5%H 2Sintering is piled up many fuel cells with this connector board, thereby is realized the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention to make connector board under the gas.Estimate the conductivity of each connector board according to DC2 terminal method, use SEM and XRD to carry out the fine-structure distribution and the facies analysis of interlayer.
According to the synthetic La of Pechini method 0.75Ca 0.27CrO 3Powder uses SEM and XRD analysis to depend on the La of sintering condition as the ceramic connector powder that is coated on the anode support 0.75Ca 0.27CrO 3The physical property of powder and sintering characteristic.
In addition, predetermined amounts is with La (NO 3) 36H 2O, Cr (NO 3) 36H 2O and Ca (NO 3) 24H 2O mixes with a small amount of distilled water and makes as the nitrate solution of connector with powder raw material.Under low relatively temperature, by 1: 1: 1 mol ratio citric acid and ethylene glycol are mixed with the nitrate solution for preparing like this, be heated to 70 ℃ then, stir the mixture of gained simultaneously and prepare the viscosity intermediate of gel state.Then, this intermediate stayed in 100 ℃ the drying oven 5 hours, thereby make the sponge-type resin.
In addition, in 250 ℃ of following carbonizations after 3 hours, with its pulverizing, 950 ℃ of following sintering 5 hours and carry out spray drying treatment, thereby manufacturing dimension is the particle of 40 μ m at the resin that will make like this.The particle coating that use air plasma spraying equipment (being made by SULZER METCO Co.) will be made like this is on anode support tube, and the fine structure of observing coat on this anode support tube.At this moment, this coat can with compare according to another coat of slurry cladding process manufacturing.
The result
The effect of the predrying technology of anode support is that solvent is evenly separated with organic additive with the pore of anode powder under low relatively temperature, thereby prevents the anode-supported body deformability.After above-mentioned predrying technology, the anode support tube of gained is 1.9 millimeters thick.
Anode must have continuous pore size distribution so that play the fuel gas diffusion layers reposefully, and the Ni and the YSZ that play the anode material effect must be evenly distributed in the anode to reduce the electrochemical polarization resistance of anode.Particularly, the Ni element that plays anode catalyst and conductor effect must be connected each other ideally to reduce the interior resistance of monoreactant battery.With reference to figure 6A, 6B and 7, the connectedness of aperture, pore-size distribution, Ni distribution and the Ni element of anode support has been described.
As can be seen, under 750 ℃, after anode support was reduced in hydrogen, the connectedness of Ni element was excellent as the cylindrical anode stay pipe from Fig. 6 A and 6B.At this moment, the connectedness of nickel element shows that anode support has electronic conductivity.
In addition, as can be seen from Figure 7, when anode support during 1300 ℃ of following presintering, the porosity of anode support is 50.18%, but behind 1400 ℃ of these anode supports of co-sintering, porosity reduces to 42.08%.On the other hand, when reduction in hydrogen during this anode support, it is about 9% that the porosity of this anode support increases, and reaches 50.64%, and the average pore size of this anode support increases to 0.23 μ m from 0.21 μ m.
Fig. 8 has illustrated according to the dielectric substrate of slurry immersion coating method formation and the section of air electrode layer.In this respect, formed the compact YSZ dielectric substrate of thickness for about 20-25 μ m, air electrode layer comprises composite bed, LSM layer of being made up of 40wt%YSZ and LSM and the LSCF layer with excellent electronics and ionic conductivity.At this moment, will be placed in by the composite bed that 40wt%YSZ and LSM form between dielectric substrate and the air electrode layer at the interface.
With reference to figure 9, illustrated that the active electrode area is 24.5cm 2The I-V performance curve of monoreactant battery, this performance depends on the working temperature of monoreactant battery.In this respect, will contain 3%H 2The H of O 2Act as a fuel and deliver in the anode, deliver in the air electrode with the flow velocity of 5l/min with the flow velocity of 1.5l/min.Reduce the interior resistance and the polarization resistance of monoreactant battery by the working temperature that improves the monoreactant battery, thereby improve the performance of monoreactant battery.
And as can be seen from Figure 9, the performance of monoreactant battery is 300mW/cm down at 800 ℃ 2(0.6V, 500mA/cm 2).And, in Figure 10 A and 10B, illustrated with deliver to anode and air electrode in the I-V performance curve of the relevant monoreactant battery of the state of gas.At this moment, in Figure 10 A and 10B, the monoreactant battery is respectively 750 and 850 ℃ of work down.
Turn to Figure 11, this figure has illustrated according to the air plasma spraying method and has been coated in ceramic connector (La on the anode support 0.75Ca 0.27CrO 3) section.As shown in figure 11, forming thickness on anode support is the fine and close connector layer of about 70 μ m, and under 800 ℃, the hydrogen and air of the gas that acts as a fuel, this densification connector layer has 8m Ω cm 2Sheet resistance.Above-mentioned sheet resistance value is corresponding with the condition of work of the flat tube shape solid-oxide fuel cell stack of anode-supported, therefore as can be seen, the connector layer can be coated on the flat tube shape solid-oxide fuel cell stack of anode-supported.
Figure 12 is the conductivity and the time relation figure of explanation connector of the present invention.At this moment, with the LSM wet coating metal double polar plates with commercially available ferrite base SUS 430 alloys on improving the non-oxidizability of ferrite base SUS 430 alloys, and sintering is used to the connector board that makes fuel cell each other in an electrically conductive with manufacturing.In air, estimate the conductivity of this connector board, this result has been described in Figure 12.
After being coated on ferrite base SUS 430 alloys, sintering LSM in oxygen-containing gas therefore suppressed the oxidation of metallic element among the LSM, thereby the LSM coat stably forms the perovskite phase.
In addition, before LSM being coated on ferrite base SUS 430 alloys, blowing (blast) that the surface of ferrite base SUS 430 alloys is lacked or macroscopic view (macro) corrosion, thereby control the surface roughness of this ferrite base SUS 430 alloys ideally, to improve the bonding force between ferrite base SUS 430 alloys and the LSM.
As mentioned above, the advantage of the flat tube shape solid-oxide fuel cell stack of anode-supported of the present invention is, the monoreactant battery that constitutes the flat tube shape solid-oxide fuel cell stack of anode-supported has board-like and the advantage tubular type fuel cell, and comprise anode support tube, like this, the performance of monoreactant battery does not descend because the working temperature of monoreactant battery descends, so connector board can be made by relatively cheap metal.And, having large-area monoreactant battery according to being easy to the method manufacturing, and compare with the tubular type fuel cell than board-like fuel cell, the power density of this monoreactant battery greatly improves.
Other advantage is, because use the cermet of forming by metal and pottery as the raw material that play the anode of supporter effect, and on anode support tube, form fine and close dielectric substrate economically according to immersion-type wet slurry coating processes, so electrolytical conventional method is different with forming, can make the flat tube shape solid-oxide fuel cell stack of anode-supported economically with commercial quantities.
And, because the metallic element in the anode forms wire netting in ceramic masses under the predetermined work temperature of fuel cell, thereby improve the intensity of anode, and this anode has the loose structure that fuel gas is steadily infiltrated, so reduced the production cost of flat tube shape Solid Oxide Fuel Cell, but do not made the decreased performance of flat tube shape Solid Oxide Fuel Cell.
Therefore, in the purpose that can understand according to the narration of front, can realize the purpose of upper surface statement effectively, because state on the implementation can carry out in the method some variation or to the statement structure carry out some change and do not deviate from the spirit and scope of the present invention, so contained all the elements should be interpreted as illustrative but not limited significance in the accompanying drawing.

Claims (9)

1. flat tube shape solid-oxide fuel cell stack that uses the anode-supported of anode support tube, described battery pile comprises:
Many fuel cells, each fuel cell comprises:
Stay pipe comprises the upper plate and the lower plate that are installed in parallel with each other, and it makes the end of upper plate be connected with the end of lower plate with semicylinder, with so that at least two bridges that the upper plate mode vertical with lower plate combines with upper plate and following slab integral;
In the mode that is placed in the upper plate center, vertically be coated in connector on the stay pipe upper plate with rectangular section;
Part is coated in the dielectric substrate on the outer surface of the stay pipe except that a part of stay pipe that contacts with connector; With
Be coated in the air electrode on the dielectric substrate outer surface as follows, promptly its two ends respectively with the both sides of connector preset distance at interval; With
Many connector boards, each connector board comprises:
The lower connector plate, it is connected with the battery pile positive electrode at its downside, has first groove of many formation parallel to each other thereon on the surface, and each first groove all has than each the fuel cell height low 50% or the degree of depth still less;
Connector board in one or more, connector board all has second groove of many formation parallel to each other thereon on the surface in each, the many gas passages that form in the mode that meets at right angles with second channel shaped and be installed in parallel with each other are gone up on the surface thereon, with mode to be parallel to second groove extruding and to contact with the upper surface of the connector of fuel cell, with corresponding position, the center of second groove, the many hexahedron connector ridges that on the predetermined portions of its lower surface, form, each second groove all has than each the fuel cell height low 50% or the degree of depth still less, and each gas passage all has the open rectangular section of a side; With
Last connector board, its thereon side be connected with the battery pile negative electrode, each all have be parallel to groove extruding and the mode that contacts with the upper surface of the connector of fuel cell, with corresponding position, the center of second groove, many hexahedron connector ridges of on the predetermined portions on its lower surface, forming.
2. method of making the flat tube shape solid-oxide fuel cell stack of anode-supported, described method comprises:
Extruding and the dry slurry that contains the NiO-YSZ powder;
Thereby the slurry at 1250-1400 ℃ of following presintering gained is made stay pipe;
With band shape organic layer be coated in the stay pipe upper plate in the heart, electrolyte slurry is coated on the outer surface of stay pipe dry this electrolyte slurry by wet infusion process;
From stay pipe, remove band shape organic layer and under 200-450 ℃, make the electrolyte slurry degreasing repeatedly;
Stay pipe at 1300-1500 ℃ of following co-sintering gained;
By plasma spraying method the perovskite powder coated is removed thereon on the part of stay pipe of organic layer, thereby on this stay pipe, form ceramic connector, in described perovskite powder, Ca, Sr, Mg, Co or Al are joined LaCrO 3In;
Another kind of organic layer is coated on the ceramic connector, with the LaSrMnO of 10-30wt% 3The LaSrMnO of powder, 10-30wt% 3With the mixed-powder of 20-50wt%YSZ and the LaSrCoFeO of 10-30wt% 3Powder mixes with the additive of 50-75wt% organic solvent and 5-40wt% to make three kinds of air electrode slurries;
To contain LaSrMnO 3The slurry of powder, contain LaSrMnO 3With the slurry of the mixed-powder of 20-50wt%YSZ and contain LaSrCoFeO 3The slurry sequential applications of powder on dielectric substrate once or repeatedly;
Remove organic layer from ceramic connector;
Thereby realize the monoreactant battery at 1150-1250 ℃ of following sintering air electrode slurry;
By being selected from ducrolloy, iron-chromium-base alloy, containing LaCrO 3, Y 2O 3Or La 2O 3Fe-cr alloy, evanohm and nickel alloy in metal metallic plate on form many grooves, gas passage and connector ridge;
The surface of polishing metal plate;
Make that connector board is used, contain LaSrMnO 3Or La 1-XCa XCr 1-YO 3Slurry;
Metallic plate is impregnated into connector board with in the slurry, thereby dry repeatedly metallic plate one or many is coated in connector board on the metallic plate with slurry;
At 1100-1350 ℃, 10 -20-10 -3The metallic plate of sintering gained under the atmospheric partial pressure of oxygen, thus ceramic coating layer on metallic plate, formed to realize connector board; With
Stacking connector plate and fuel cell to be making the flat tube shape solid-oxide fuel cell stack of anode-supported, and the battery pile electrode is connected with the flat tube shape solid-oxide fuel cell stack of anode-supported.
3. method as claimed in claim 2, wherein stay pipe comprises with slurry and contains 30-60vol% nickel and the 10-50vol% YSZ powder as the carbon dust of pore creating material, and will join in the mixture of carbon dust and YSZ powder in distilled water, the organic bond of 5-20wt%, the plasticizer of 3-10wt% and the lubricant of 1-7wt% of the 15-30wt% of amount of the mixture.
4. method as claimed in claim 2, wherein electrolyte slurry comprises the organic solvent of 60-95wt% and the YSZ powder of 5-40wt%, and will join in the mixture of organic solvent and YSZ powder in 5-12 weight portion adhesive, 5-15cc plasticizer, 1-3cc levelling agent and the 1-3cc dispersant of 100 gram YSZ powder.
5. method as claimed in claim 2, wherein ceramic connector comprises the perovskite powder, wherein Ca, Sr, Mg, Co or Al is joined LaCrO 3In.
6. method as claimed in claim 2, wherein three kinds of air electrode slurries comprise the LaSrMnO as raw-material 10-30wt% respectively 3The LaSrMnO of powder, 10-30wt% 3With the mixed-powder of 20-50wt%YSZ and the LaSrCoFeO of 10-30wt% 3Powder, and comprise the organic solvent of 50-75wt% and the additive of 5-40wt% in addition.
7. method as claimed in claim 2, wherein connector board comprises the LaSrMnO of 20-50wt% with slurry 3Or La 1-XCa XCr 1-YO 3The additive of the adhesive of powder, 0.5-10wt%, the solvent of 0.2-2wt% and 0.2-5wt%.
8. method as claimed in claim 2 is wherein at 1100-1300 ℃, 10 -10-10 -3Sintering contains LaSrMnO under the atmospheric partial pressure of oxygen 3The connector board slurry.
9. method as claimed in claim 2 is wherein at 1150-1350 ℃, 10 -3Sintering contains La under atmospheric pressure or the lower partial pressure of oxygen 1-XCa XCr 1-YO 3Slurry.
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