CN102881929B - Structure of flat-plate type metal-support solid oxide fuel cell for immersing electrodes - Google Patents

Structure of flat-plate type metal-support solid oxide fuel cell for immersing electrodes Download PDF

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CN102881929B
CN102881929B CN201210419649.8A CN201210419649A CN102881929B CN 102881929 B CN102881929 B CN 102881929B CN 201210419649 A CN201210419649 A CN 201210419649A CN 102881929 B CN102881929 B CN 102881929B
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layer
porous
zirconia
fuel cell
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CN102881929A (en
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周玉存
王绍荣
占忠亮
孟燮
袁春
刘雪娇
钱继勤
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Shanghai Institute of Ceramics of CAS
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    • 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

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Abstract

The invention discloses a structure of a flat-plate type metal-support solid oxide fuel cell for immersing electrodes. The cell is provided with a porous metal support layer, a compact electrolyte layer and a porous cathode precursor layer from inside to outside in sequence; and the porous metal support layer, the compact electrolyte layer and the porous cathode precursor layer are commonly sintered into an integrated structure. The structure disclosed by the invention has the advantages that the cost is low, the operability is strong, the problem that the coarsening of anode particles and diffusion among alloy elements due to high-temperature common sintering can be effectively avoided, simultaneously the contradiction that the combination of the cathode and a electrolyte is bad during low-temperature common sintering and the excessive oxidation of the metal support layer can exists during high-temperature sintering is also solved, so that the application prospect is wide.

Description

The flat metallic support type solid oxide fuel cell structure of a kind of impregnated electrode
Technical field
The present invention relates to the flat metallic support type solid oxide fuel cell structure of a kind of impregnated electrode, belong to Solid Oxide Fuel Cell technical field.
Background technology
Solid Oxide Fuel Cell (SOFC) is the electrochemical appliance that a kind of chemical energy by hydrogen, natural gas and biogas fuel is converted into electric energy, have that fuel rich, efficiency are high, pollution-free, noiseless, can the feature such as cogeneration, large-scale power station, distributed power station, automobile accessory power supply, household cogeneration systems etc. can be widely used in.Although SOFC has many excellent performance, not yet move towards large-scale application at present, its main restricting factor is cost and life problems.Novel metal support structure is for traditional electrolyte-supported or electrode supporting structure, monocell mechanical strength can be improved, increase battery thermal shock resistance, reduce SOFC system cost, and contribute to solving pile sealing and being connected a difficult problem, therefore metallic support SOFC worldwide attracts wide attention in the last few years, and becomes study hotspot new in SOFC research field gradually.
But also there is a lot of problem in the preparation of the preparation of metallic support SOFC, especially electrode:
1, anode problem: traditional metallic support SOFC adopts the structure of metal support/anode/electrolyte/negative electrode, in the preparation of high temperature co-firing knot or During Process of Long-term Operation of battery, can there is alligatoring in anode metal particle Ni, also and between alloying element Fe, Cr, counterdiffusion can occur simultaneously.This not only lowers the catalytic performance of anode, also can cause the problems such as the thermal coefficient of expansion of supporter changes, long-time stability decline, electric conductivity decline, antioxygenic property reduction simultaneously.The counterdiffusion that one deck diffusion impervious layer can prevent between alloying element and anode metal particle is added between anode and metal support, but the complexity of preparation technology and the decline of battery performance can be caused, in addition, diffusion impervious layer can not solve the alligatoring problem of anode Ni particle.
2, negative electrode problem: conventional cathode material such as LSM, LSCF etc. need to sinter to obtain good chemical property under the air atmosphere of 1000 ~ 1200 DEG C, and at such high temperatures, the oxidation of stainless steel supporter will become very serious.Under reducing atmosphere, sintering effectively can avoid the oxidation of metal support, but LSM, LSCF etc. can decompose under high temperature reducing atmospheres, cause the reduction of performance.The methods such as one side plasma spraying or pulsed laser deposition are prepared negative electrode and can be addressed this problem, but these method complex process and cost is high; Also the method for sintering or in-situ sintering negative electrode in Cryogenic air can be used on the other hand, but this method often needs highly active cathode material, this can bring particular/special requirement to the preparation of cathode powder, and highly active cathode material can affect the long-time stability of battery.
It is that the tube type metal of supporter supports the five-layer structure of SOFC with stainless steel that the people such as Michael C.Tucker disclose a kind of, be respectively porous stainless steel support body layer/porous YSZ intermediate layer/dense YSZ electrolyte layer/porous YSZ intermediate layer/porous stainless steel current collector layer from inside to outside, then in internal porous YSZ layer, impregnating metal Ni obtains galvanic anode, floods LSM obtain cell cathode in outside porous ysz layer.The method efficiently avoid Ni in battery high-temperature sintering process alligatoring and and alloying element between counterdiffusion, also solve a difficult problem for LSM negative electrode low-temperature growth simultaneously.But this five-layer structure is not obtained by high temperature co-firing knot, but adopt the methods such as isostatic pressed, aerosol spray deposition, colloidal deposition to experience twice high temperature sintering to obtain, complex structure and technique is loaded down with trivial details.This structure is used for tubular type SOFC simultaneously, and opposing plates formula, tubular type SOFC cost is high, complex process, power density low (see Journal of Power Sources, 171 (2007): 477 – 482).
Chinese patent application 200810129800.8 discloses the structure of a kind of metallic support SOFC, comprise porous metals supporter/cathode functional/electrolyte/porous anode precursor layer, wherein cathode functional is not essential, porous anode precursor layer both can adopt co-sintering, also can be formed on the surface in dense electrolyte after other layer first sinters again.This patent is also described the material of dipping simultaneously.In that patent, the metal support after completing, in cell cathode side, is exposed to high temperature air side, easily oxidized, and this can bring considerable influence to the long-time stability of battery; Anode layer if make after other each layer sintering again simultaneously, then more loaded down with trivial details, brings the problem of poor bonding strength simultaneously.
Summary of the invention
In order to overcome prior art above shortcomings, the object of this invention is to provide a kind of structure simple and be convenient to the flat metallic support type solid oxide fuel cell structure of impregnated electrode that realizes, to solve the preparation difficult problem that conventional metals supports SOFC electrode.
For achieving the above object, the technical solution used in the present invention is as follows:
The flat metallic support type solid oxide fuel cell structure of a kind of impregnated electrode, be followed successively by porous metals supporting layer, dense electrolyte layer, porous cathode precursor layer from the inside to the outside, and described porous metals supporting layer and dense electrolyte layer and porous cathode precursor layer co-sintering into a single integrated structure.
As a kind of preferred version, described porous metals supporting layer is the metal supporting layer with transition structure, that is, be porous metallic layers away from electrolyte side, and near electrolyte side is being the composite bed of porous metals-pottery; And the metal ratio in composite bed is 0-50wt% (comprising zero point), the thickness of composite bed is 20 ~ 100 μm, and porosity is 30 ~ 70%, and aperture is 1 ~ 20 μm.
As further preferred version, described ceramic layer material is selected from the zirconia of YSZ(stabilized with yttrium oxide), the zirconia of SSZ(scandia stabilized), the stable altogether zirconia of ScYSZ(yittrium oxide, scandium oxide), SDC(be oxidized Sm doped CeO_2), the cerium oxide of GDC(gadolinium oxide doping), LSGM(strontium oxide strontia and magnesium oxide distinguishes the lanthanum gallate of doped in lanthanum site and gallium position) in any one or a few.
As a kind of preferred version, the thickness of described porous metals supporting layer is 0.1 ~ 1mm, and porosity is 30 ~ 70%, and aperture is 1 ~ 40 μm.
As further preferred version, described metal is stainless steel.
As further preferred version, described stainless steel is FeCrM alloy, and wherein M is any one or a few in the alloying elements such as Ni, Ti, Mn, N, Nb, Mo, Si, Y, Al, Ce, La.
As further preferred version, doped with metal oxide in described stainless steel powder, described metal oxide includes but not limited to Cr 2o 3, TiO 2, MgO, WO 3, V 2o 3, V 2o 5, Ga 2o 3, CeO 2, ZrO 2in any one or a few; The doping of described metal oxide is 0 ~ 50% of described stainless steel powder gross mass, does not comprise zero point.
As a kind of preferred version, the thickness of described dense electrolyte layer is 10 ~ 40 μm.
As further preferred version, described electrolyte is selected from the zirconia of YSZ(stabilized with yttrium oxide), the zirconia of SSZ(scandia stabilized), the stable altogether zirconia of ScYSZ(yittrium oxide, scandium oxide), SDC(be oxidized Sm doped CeO_2), the cerium oxide of GDC(gadolinium oxide doping), LSGM(strontium oxide strontia and magnesium oxide distinguishes the lanthanum gallate of doped in lanthanum site and gallium position) in any one or a few.
As a kind of preferred version, the thickness of described porous cathode precursor layer is 20 ~ 100 μm, and porosity is 30 ~ 70%, and aperture is 0.3 ~ 5 μm.
As further preferred version, described negative electrode precursor layer material is selected from the zirconia of YSZ(stabilized with yttrium oxide), the zirconia of SSZ(scandia stabilized), the stable altogether zirconia of ScYSZ(yittrium oxide, scandium oxide), SDC(be oxidized Sm doped CeO_2), the cerium oxide of GDC(gadolinium oxide doping), LSGM(strontium oxide strontia and magnesium oxide distinguishes the lanthanum gallate of doped in lanthanum site and gallium position) in any one or a few.
The impregnated electrode of said structure can adopt curtain coating lamination co-sintering method, compound curtain coating co-sintering method, silk screen printing co-sintering method by flat metallic support type solid oxide fuel cell structure, rolls the method preparations such as embrane method, coating process, spraying process, sputtering method and obtain.
Because flooding active material of positive electrode to porous metals supporting layer of the present invention, galvanic anode can be formed and (also can flood reforming catalyst again, realize the interior reformation of hydrocarbon fuel), to porous cathode precursor layer impregnated cathode active material of the present invention, can cell cathode be formed; Therefore, compared with prior art, the present invention has following beneficial effect:
1) relative to traditional metallic support type solid oxide fuel cell, this invention simplifies structure and the preparation technology of metallic support type solid oxide fuel cell, shorten the production cycle, reduce cost;
2) porous metals supporting layer is in anode-side after completing, not easily oxidized;
3) battery-active anode adopts infusion process preparation, and the alligatoring of anode metal particle and the issue of inter-diffusion with alloying element thereof that can effectively avoid high temperature co-firing to tie causing, improve the performance of anode;
4) batteryactive cathode also adopts infusion process to prepare, and when solving low-temperature sintering, negative electrode is combined the contradiction that poor and high temperature sintering can cause metal supporting layer over oxidation with electrolyte;
5) reforming catalyst also can be flooded to realize the inside reforming of the fuel such as ethanol, propane, natural gas in metal supporting layer side on the basis of impregnated activated anode material, thus improves the suitability of fuel of battery, eliminates outer reformation, reduces costs;
6) because porous metals supporting layer and porous electrode are all previously prepared good (experience high-temperature sintering process), so battery is in relative cold operation process, there is good stability;
7) because electrode material is immersed in porous metals supporting layer and porous cathode precursor layer inside, cause the porosity to reduce so reunion can not occur electrode material, thus be conducive to battery and obtain good long-time stability.
In sum, not only cost is low, workable with flat metallic support type solid oxide fuel cell for impregnated electrode of the present invention, and can effectively avoid high temperature co-firing to tie the alligatoring of the anode pellets caused and the issue of inter-diffusion with alloying element thereof, when also solving low-temperature sintering, negative electrode is combined the contradiction that poor and high temperature sintering can cause metal supporting layer over oxidation with electrolyte simultaneously, therefore has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the structural representation of impregnated electrode provided by the invention with flat metallic support type solid oxide fuel cell, in figure: 1, porous metals supporting layer, 2, dense electrolyte layer, 3, porous cathode precursor layer;
The impregnated electrode of Fig. 2 prepared by embodiment 1 ESEM (SEM) photo of flat metallic support type solid oxide fuel cell;
The impregnated electrode of Fig. 3 prepared by embodiment 2 ESEM (SEM) photo of flat metallic support type solid oxide fuel cell.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.
Embodiment 1
Take 430 stainless steel powder 50g, add solvent absolute ethyl alcohol 10g and butanone 5g successively, dispersant triethanolamine 6g, plasticiser dibutyl phthalate 2g, binding agent polyvinyl butyral resin 6g, pore creating material ammonium oxalate 20g; Take electrolyte YSZ powder 30g, add solvent xylene and each 5g of butyl acetate successively, dispersant acrylic resin DM-55 1g, plasticiser benzoic ether B-50 2g and binding agent acrylic resin B-72 4g; Take negative electrode precursor layer YSZ powder 15g, add solvent xylene and each 4g of butyl acetate successively, dispersant acrylic resin DM-55 1g and dispersant acrylic copolymer BYK1g, plasticiser benzoic ether B-50 0.5g, binding agent acrylic resin B-72 1g, pore creating material ammonium oxalate 10g;
The above-mentioned 3 kinds of slurries of ball milling respectively, and the slurry of mixing is sieved and vacuum treatment through screen cloth respectively, remove air in slurry;
Respectively flow casting molding and drying are carried out to above-mentioned 3 kinds of slurries, respectively the biscuit of obtained porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer;
The biscuit of the porous metals supporting layer upper step obtained, dense electrolyte layer and porous cathode precursor layer is stacked from bottom to top successively, then in 75 DEG C, carry out hot pressing 10 minutes under 5Mp condition;
The compound biscuit that upper step hot pressing obtains is cut into the disk of 19mm, then at 4%H 2+ 96%N 2co-sintering is carried out under atmosphere, in 1300 DEG C, obtain the flat metallic support type solid oxide fuel cell of impregnated electrode of the present invention, its structure is as shown in Figure 1: be followed successively by porous metals supporting layer 1, dense electrolyte layer 2, porous cathode precursor layer 3 from the inside to the outside, and described porous metals supporting layer 1 and dense electrolyte layer 2 and porous cathode precursor layer 3 co-sintering into a single integrated structure.
The impregnated electrode of Fig. 2 prepared by the present embodiment ESEM (SEM) photo of flat metallic support type SOFC, as seen from Figure 2: the metal supporting layer of this battery is loose structure, thickness about 270 μm, pore size are about 10 ~ 50 μm, porosity about 40%; Dielectric substrate is fine and close, no significant defect, thickness about 30 μm; Negative electrode precursor layer is loose structure, and thickness about 30 μm, pore size are about 0.5 ~ 8 μm, porosity 30%; Each Coating combination is tight, and interface flawless or lamination occur.
Embodiment 2
Take 430 stainless steel powder 50g, add solvent absolute ethyl alcohol 12g and butanone 6g successively, dispersant triethanolamine 5g, plasticiser dibutyl phthalate 2g and polyethylene glycol 2g, binding agent polyvinyl butyral resin 3g, pore creating material ammonium carbonate 20g; Take electrolyte YSZ powder 30g, add solvent xylene and each 5g of butyl acetate successively, dispersant acrylic resin DM-551g, plasticiser benzoic ether B-50 2g and binding agent acrylic resin B-72 4g; Take negative electrode precursor layer YSZ powder 15g, add solvent xylene and each 4g of butyl acetate successively, dispersant acrylic resin DM-55 1.5g and acrylic copolymer BYK1g, plasticiser benzoic ether B-50 1g, binding agent acrylic resin B-72 2g, pore creating material ammonium oxalate 15g;
The above-mentioned 3 kinds of slurries of ball milling respectively, and the slurry of mixing is sieved and vacuum treatment through screen cloth respectively, remove air in slurry;
Respectively flow casting molding and drying are carried out to above-mentioned 3 kinds of slurries, respectively the biscuit of obtained porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer;
The biscuit of the porous metals supporting layer upper step obtained, dense electrolyte layer and porous cathode precursor layer is stacked from bottom to top successively, then in 60 DEG C, carry out hot pressing 30 minutes under 15Mp condition;
The compound biscuit that upper step hot pressing obtains is cut into the disk of 19mm, then at 4%H 2+ 96%N 2co-sintering is carried out under atmosphere, in 1340 DEG C, obtain the flat metallic support type solid oxide fuel cell of impregnated electrode of the present invention, its structure is as shown in Figure 1: be followed successively by porous metals supporting layer 1, dense electrolyte layer 2, porous cathode precursor layer 3 from the inside to the outside, and described porous metals supporting layer 1 and dense electrolyte layer 2 and porous cathode precursor layer 3 co-sintering into a single integrated structure.
The impregnated electrode of Fig. 3 prepared by the present embodiment ESEM (SEM) photo of flat metallic support type SOFC, as seen from Figure 3: the metal supporting layer of this battery is loose structure, thickness about 230 μm, pore size are about 5 ~ 30 μm, porosity about 35%; Dielectric substrate is fine and close, no significant defect, thickness about 16 μm; Negative electrode precursor layer is loose structure, and thickness about 30 μm, pore size are about 0.5 ~ 3 μm, porosity 50%; Each Coating combination is tight, and interface flawless or lamination occur.
Embodiment 3
Take 430 stainless steel powder 50g, add solvent absolute ethyl alcohol 15g and butanone 7.5g successively, dispersant triethanolamine 5g, plasticiser dibutyl phthalate 2g and polyethylene glycol 2g, binding agent polyvinyl butyral resin 3.5g, pore creating material wheat flour 20g; Take electrolyte YSZ powder 30g, add solvent xylene and each 5g of butyl acetate successively, dispersant acrylic resin DM-551g, plasticiser benzoic ether B-50 2g and binding agent acrylic resin B-72 4g; Take negative electrode precursor layer YSZ powder 15g, add solvent xylene and each 4g of butyl acetate successively, dispersant acrylic resin DM-55 1g and acrylic copolymer BYK 1g, plasticiser benzoic ether B-50 0.5g, binding agent acrylic resin B-72 1g, pore creating material wheat flour 10g;
The above-mentioned 3 kinds of slurries of ball milling respectively, and the slurry of mixing is sieved and vacuum treatment through screen cloth respectively, remove air in slurry;
Respectively flow casting molding and drying are carried out to above-mentioned 3 kinds of slurries, respectively the biscuit of obtained porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer;
The biscuit of the porous metals supporting layer upper step obtained, dense electrolyte layer and porous cathode precursor layer is stacked from bottom to top successively, then in 85 DEG C, carry out hot pressing 5 minutes under 5Mp condition;
The compound biscuit that upper step hot pressing obtains is cut into the disk of 19mm, prior to pre-burning in 500 DEG C of air, then at 4%H 2+ 96%N 2co-sintering is carried out under atmosphere, in 1400 DEG C, obtain the flat metallic support type solid oxide fuel cell of impregnated electrode of the present invention, its structure is as shown in Figure 1: be followed successively by porous metals supporting layer 1, dense electrolyte layer 2, porous cathode precursor layer 3 from the inside to the outside, and described porous metals supporting layer 1 and dense electrolyte layer 2 and porous cathode precursor layer 3 co-sintering into a single integrated structure.
The sem test result of battery prepared by the present embodiment and embodiment 1 are had to the consistency within the scope of theoretical error.
Embodiment 4
The casting slurry formula of porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer, with embodiment 1, wherein adds the YSZ of 3% in stainless steel, electrolyte is ScYSZ, negative electrode precursor layer is ScYSZ, adopt the method for compound curtain coating to prepare the three-decker of compound, do not need hot pressing, 5%H 2+ 95%N 2under atmosphere, 1250 DEG C of co-sinterings obtain porous stainless steel/fine and close ScYSZ/ porous ScYSZ three-decker.
Metallic support layer thickness is about 1mm, pore size is about 1 ~ 40 μm, porosity about 70%; Dielectric substrate thickness about 40 μm; Negative electrode precursor layer is loose structure, and thickness about 100 μm, pore size are about 0.3 ~ 5 μm, porosity 70%.
Embodiment 5
Stainless steel powder, SSZ electrolyte powder and SSZ negative electrode precursor layer powder are deployed into slurry with a certain amount of terpinol-ethyl cellulose solution respectively, wherein in stainless steel powder and negative electrode precursor layer powder the selection of pore creating material and addition with embodiment 1.Adopt the method first screen-printed metal support body layer of silk screen printing, then distinguish silk screen printing SSZ electrolyte, SSZ negative electrode precursor layer thereon, at 5%H after drying 2+ 95%N 2under atmosphere, 1400 DEG C of co-sinterings obtain porous stainless steel/fine and close SSZ/ porous SSZ three-decker.
Metallic support layer thickness about 100 μm, pore size are about 3 ~ 20 μm, porosity about 30%; Dielectric substrate thickness about 10 μm; Negative electrode precursor layer is loose structure, and thickness about 20 μm, pore size are about 0.3 ~ 3 μm, porosity 30%.
Embodiment 6
The preparation of porous metals supporting layer, dense electrolyte layer is with embodiment 4, and adopt compound curtain coating legal system to obtain, porous cathode precursor layer adopts the slurry in embodiment 5, adopts coating process to be coated in the surface of metal supporting layer/dielectric substrate biscuit, at 5%H after drying 2+ 95%N 2under atmosphere, 1300 DEG C of co-sinterings obtain porous stainless steel/fine and close ScYSZ/ porous SSZ three-decker.
Embodiment 7
With embodiment 1, in the middle of porous metals supporting layer and electrolyte layers, just increase the composite bed of one deck porous metals-pottery again, thus form the porous metals supporting layer with transition structure, the casting formulation of composite bed is with the supporter formula in embodiment 1, in this composite bed, ceramic phase is YSZ, and content is 50%, and the thickness of composite bed is 100 μm, porosity is 30%, and aperture is 1 ~ 20 μm.
Embodiment 8
With embodiment 7, just between the composite bed and electrolyte of embodiment 7, add porous ceramic layer again, this ceramic layer is porous YSZ, thickness is 20 μm, porosity is 70%, and aperture is 1 ~ 4 μm, and casting formulation is with the porous cathode precursor layer formula in embodiment 1, the porous metals supporting layer of final formation has transition structure, i.e. porous metals/porous metals-pottery/porous ceramic.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.

Claims (3)

1. the flat metallic support type solid oxide fuel cell structure of impregnated electrode, it is characterized in that: described battery is followed successively by porous metals supporting layer, dense electrolyte layer, porous cathode precursor layer from the inside to the outside, and described porous metals supporting layer and dense electrolyte layer and porous cathode precursor layer co-sintering into a single integrated structure; Described metal is stainless steel; Described electrolyte is selected from the zirconia of stabilized with yttrium oxide, the zirconia of scandia stabilized, the zirconia that yittrium oxide, scandium oxide are stable altogether, oxidation Sm doped CeO_2, the cerium oxide of gadolinium oxide doping, any one in the lanthanum gallate of strontium oxide strontia and magnesium oxide doped in lanthanum site and gallium position respectively; Described negative electrode precursor layer material is selected from the zirconia of stabilized with yttrium oxide, the zirconia of scandia stabilized, the zirconia that yittrium oxide, scandium oxide are stable altogether, oxidation Sm doped CeO_2, the cerium oxide of gadolinium oxide doping, any one in the lanthanum gallate of strontium oxide strontia and magnesium oxide doped in lanthanum site and gallium position respectively; And the thickness of described porous metals supporting layer is 0.1 ~ 1mm, porosity is 30 ~ 70%, and aperture is 1 ~ 40 μm; The thickness of described dense electrolyte layer is 10 ~ 40 μm; The thickness of described porous cathode precursor layer is 20 ~ 100 μm, and porosity is 30 ~ 70%, and aperture is 0.3 ~ 5 μm.
2. the flat metallic support type solid oxide fuel cell structure of impregnated electrode according to claim 1, it is characterized in that: described porous metals supporting layer is the metal supporting layer with transition structure, namely, be porous metallic layers away from electrolyte side, and near electrolyte side be the composite bed of porous metals-pottery; And the metal ratio in composite bed is 0-50wt%, the thickness of composite bed is 20 ~ 100 μm, and porosity is 30 ~ 70%, and aperture is 1 ~ 20 μm; Described ceramic layer material is selected from the zirconia of stabilized with yttrium oxide, the zirconia of scandia stabilized, the zirconia that yittrium oxide, scandium oxide are stable altogether, oxidation Sm doped CeO_2, the cerium oxide of gadolinium oxide doping, any one in the lanthanum gallate of strontium oxide strontia and magnesium oxide doped in lanthanum site and gallium position respectively; Described metal is stainless steel.
3. the flat metallic support type solid oxide fuel cell structure of impregnated electrode according to claim 1 and 2, it is characterized in that: described stainless steel is FeCrM alloy, wherein M is any one or a few in Ni, Ti, Mn, N, Nb, Mo, Si, Y, Al, Ce, La element.
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103326035B (en) * 2013-06-17 2015-05-20 北京科技大学 Automatic impregnating system for solid oxide fuel cell electrode
CN105675690B (en) * 2014-11-17 2018-08-24 中国科学院上海硅酸盐研究所 A kind of nitrogen oxide sensor and preparation method thereof of reference electrode support
CN107658486B (en) * 2017-08-13 2020-07-10 长沙小新新能源科技有限公司 Preparation method of solid oxide fuel cell electrolyte membrane
CN107903668A (en) * 2017-11-17 2018-04-13 广东康荣高科新材料股份有限公司 A kind of fuel-cell electrolyte dip-coating slurry and preparation method thereof
CN108461759B (en) * 2018-01-19 2020-05-22 合肥国轩高科动力能源有限公司 Method for preparing nano composite cathode material of solid oxide fuel cell by impregnation method
CN109904497B (en) * 2019-01-09 2020-07-10 华中科技大学 Anti-carbon-deposition metal-supported solid oxide fuel cell and preparation method thereof
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1672281A (en) * 2002-07-25 2005-09-21 阿尔伯达研究理事会股份公司 Metal-supported tubular fuel cell
CN1985397A (en) * 2004-06-10 2007-06-20 丹麦科技大学 Solid oxide fuel cell

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1021547C2 (en) * 2002-09-27 2004-04-20 Stichting Energie Electrode-supported fuel cell.
DK2031684T3 (en) * 2007-08-31 2016-12-05 Univ Denmark Tech Dtu Metal Supported faststofoxidbrændselscelle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1672281A (en) * 2002-07-25 2005-09-21 阿尔伯达研究理事会股份公司 Metal-supported tubular fuel cell
CN1985397A (en) * 2004-06-10 2007-06-20 丹麦科技大学 Solid oxide fuel cell

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