CN102881930A - Method for preparing flat-plate type metal-support solid oxide fuel cell - Google Patents
Method for preparing flat-plate type metal-support solid oxide fuel cell Download PDFInfo
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Abstract
The invention discloses a method for preparing a flat-plate type metal-support solid oxide fuel cell. The method comprises the following steps of: firstly respectively preparing three layers of biscuits such as a porous metal support layer, a compact electrolyte layer and a porous cathode precursor layer, then superimposing from bottom to top in sequence for carrying out hot pressing, then carrying out high-temperature common sintering, using a surface active agent to carry out surface treatment on the porous metal support layer, finally immersing a salt solution of an active cathode material in the porous cathode precursor layer, and performing heat treatment, so as to obtain a cathode of the cell; and immersing a salt solution of an active anode material in the porous metal support layer, performing the heat treatment, so as to obtain an anode of the cell. The method has the advantages that the cost is low, the operability is strong, the batched and continuous production is convenient; and according to the prepared cell, the combination among all the layers is close, the thickness, the porosity and the like of all the function layers can be controlled, the cathode and the anode of the cell are prepared by immersion, the performance of the cell is high, the stability is good, the service life of an electric pile can be guaranteed, the cost of a system is reduced and the application prospect is very good.
Description
Technical field
The present invention relates to a kind of method for preparing flat metallic support type solid oxide fuel cell, belong to the Solid Oxide Fuel Cell technical field.
Background technology
Solid Oxide Fuel Cell (SOFC) is the electrochemical appliance that a kind of chemical energy with hydrogen, natural gas and biogas fuel is converted into electric energy, but have the characteristics such as fuel rich, efficient are high, pollution-free, noiseless cogeneration, can be widely used in large-scale power station, distributed power station, automobile accessory power supply, family's cogeneration system etc.Although SOFC has many excellent performance, not yet move towards at present large-scale application, its main restricting factor is cost and life problems.The novel metal support structure is for traditional electrolyte-supported or electrode supporting structure, can improve the monocell mechanical strength, increase the battery thermal shock resistance, reduce the SOFC system cost, and help to solve the pile sealing and be connected a difficult problem, therefore metallic support SOFC worldwide attracts wide attention in the last few years, and becomes gradually new study hotspot in the SOFC research field.
But also there are a lot of problems 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, alligatoring can occur in anode metal particle Ni, simultaneously also can and alloying element Fe, Cr between counterdiffusion occurs.This has not only reduced the catalytic performance of anode, also can cause the thermal coefficient of expansion of supporter to change simultaneously, the problem such as long-time stability decline, electric conductivity decline, antioxygenic property reduction.Can prevent counterdiffusion between alloying element and the anode metal particle adding one deck diffusion impervious layer between anode and the metal support, but can cause preparation technology's complexity and the decline of battery performance, 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 be under 1000～1200 ℃ air atmosphere sintering obtaining preferably chemical property, and under high temperature like this, it is very serious that the oxidation of stainless steel supporter will become.Sintering can effectively be avoided the oxidation of metal support under the reducing atmosphere, but LSM, LSCF etc. can decompose under high temperature reduction atmosphere, cause reduction of performance.Preparing negative electrode with methods such as plasma spraying or pulsed laser depositions on the one hand can address this problem, but these method complex process and cost are high; On the other hand also can be with the method for sintering in the Cryogenic air or in-situ sintering negative electrode, but this method often needs highly active cathode material, this can bring specific (special) requirements to the preparation of cathode powder, and highly active cathode material can affect the long-time stability of battery.
The people such as Michael C.Tucker disclose the five-layer structure that a kind of tube type metal take stainless steel as supporter supports SOFC, be respectively from inside to outside porous stainless steel support body layer/porous YSZ intermediate layer/compact YSZ dielectric substrate/porous YSZ intermediate layer/porous stainless steel electric current collection body layer, then impregnating metal Ni obtains galvanic anode in inner porous YSZ layer, externally dipping LSM obtains cell cathode in the porous YSZ layer.The method effectively avoided Ni in the battery high-temperature sintering process alligatoring and and alloying element between counterdiffusion, also solved simultaneously the difficult problem of LSM negative electrode low temperature preparation.But this five-layer structure is not to obtain by a high temperature co-firing knot, obtains but the methods such as the static pressure such as employing, aerosol spray deposition, colloidal deposition experience twice high temperature sintering, and complex structure and technique are loaded down with trivial details.This structure is used for tubular type SOFC simultaneously, and relatively flat, tubular type SOFC cost is high, complex process, power density low (referring to Journal ofPower 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, cell cathode adopts infusion process to form in metal support or metal support and cathode functional, the porous anode precursor layer both can adopt co-sintering, also can form on the dense electrolyte surface after other layer sinters first again.In this patent, the metal support after finishing is exposed to high temperature air one side in the cell cathode side, and is easily oxidized, and this can bring considerable influence to the long-time stability of battery; In addition, do not consider the problem that porous metallic layers is poor to the aqueous solution wetability during impregnated electrode, the while anode layer is if make behind each layer sintering at other again, and is then more loaded down with trivial details, and brings the problem of poor bonding strength.
Summary of the invention
In order to overcome the prior art above shortcomings; the purpose of this invention is to provide a kind of method for preparing the flat metallic support type solid oxide fuel cell with good electrical chemical property, to realize the large-scale production of metallic support type solid oxide fuel cell.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of method for preparing flat metallic support type solid oxide fuel cell comprises the steps:
A) prepare respectively the mixed slurry for preparing porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer;
B) 3 kinds of mixed slurries step a) being prepared carry out respectively flow casting molding and drying, make respectively the biscuit of porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer;
C) with step b) biscuit of the porous metals supporting layer, dense electrolyte layer and the porous cathode precursor layer that make is stacked from bottom to top successively, then carries out hot pressing 5～30 minutes under 60～85 ℃, 4～15Mp condition;
D) with step c) the compound biscuit that obtains of hot pressing cuts into behind the required size under the mixed atmosphere that inert atmosphere or inert atmosphere and reducing atmosphere form, carries out co-sintering in 1250～1400 ℃;
E) with surfactant the porous metals supporting layer is carried out surface treatment;
F) salting liquid of dipping active cathode material in the porous cathode precursor layer obtains cell cathode after the heat treatment; The salting liquid of dipping active anode material obtains galvanic anode after the heat treatment in the porous metals supporting layer.
As a kind of preferred version, the prescription of the mixed slurry of preparation porous metals supporting layer is as follows:
As a kind of preferred version, the prescription of the mixed slurry of preparation dense electrolyte layer is as follows:
As a kind of preferred version, the prescription of the mixed slurry of preparation porous cathode precursor layer is as follows:
As further preferred version, described metal-powder is the stainless steel powder.
As preferred version further, described stainless steel powder is the FeCrM alloy powder, 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 preferred version further, be doped with metal oxide in the 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 further preferred version, described electrolyte powder is selected from the YSZ(yttria stabilized zirconia), the zirconia of SSZ(scandia stabilized), ScYSZ(yittrium oxide, scandium oxide stable zirconia altogether), the cerium oxide that mixes of SDC(samarium oxide), the cerium oxide that mixes of GDC(gadolinium oxide), LSGM(strontium oxide strontia and the magnesium oxide lanthanum gallate of doped in lanthanum site and gallium position respectively) etc. in the powder any one or a few.
As further preferred version, described negative electrode precursor layer powder is selected from the YSZ(yttria stabilized zirconia), the zirconia of SSZ(scandia stabilized), ScYSZ(yittrium oxide, scandium oxide stable zirconia altogether), the cerium oxide that mixes of SDC(samarium oxide), the cerium oxide that mixes of GDC(gadolinium oxide), LSGM(strontium oxide strontia and the magnesium oxide lanthanum gallate of doped in lanthanum site and gallium position respectively) etc. in the powder any one or a few.
As further preferred version, described solvent is selected from any one or a few in dimethylbenzene, absolute ethyl alcohol, acetone, butanone, the butyl acetate.
As further preferred version, described dispersant is selected from any one or a few among triethanolamine, acrylic copolymer BYK, methyl anyl alcohol, the acrylic resin DM-55.
As further preferred version, described plasticiser is selected from any one or a few any one or a few in benzoic ether B-50, polyethylene glycol, the dibutyl phthalate.
As further preferred version, described binding agent is selected from any one or a few in polyvinyl butyral resin, acrylic resin B-72, the epoxy resin.
As further preferred version, described pore creating material is selected from any one or a few in graphite, starch, ammonium oxalate, the ammonium carbonate.
As further preferred version, described surfactant is selected from any one or a few in lauryl mercaptan, dimethyl silicone polymer, the neopelex; Described surface treatment is battery to be immersed contain in the solution of above-mentioned surfactant, stirs under the room temperature 3～5 hours, then with ethanol, washed with de-ionized water and oven dry.
As further preferred version, described active cathode material is selected from LSM(oxidation Strontinum doped lanthanum manganite), LSF (strontium oxide strontia mix ferrous acid lanthanum), LSCF(strontium oxide strontia and the iron oxide cobalt acid lanthanum of doped in lanthanum site and cobalt position respectively), SSC(strontium oxide strontia doping cobalt acid samarium), the strontium molybdate that mixes of SFM(iron oxide), the ferrous acid lanthanum that mixes of LNF(nickel oxide), the cerium oxide that mixes of GDC(gadolinium oxide), the cerium oxide that mixes of SDC(samarium oxide) in any one or a few.
As further preferred version, described active anode material is selected from the cerium oxide that the NiO-GDC(gadolinium oxide mixes), the cerium oxide that mixes of NiO-SDC(samarium oxide), NiO-CeO
2, NiO-LST(strontium oxide strontia doped titanic acid lanthanum), the strontium molybdate that mixes of SFM(iron oxide), Cu-CeO
2In any one or a few.
As further preferred version, step f) described in heat treatment temperature be 350～900 ℃, heat-treating atmosphere is air or inert atmosphere.
As further preferred version, step f) described in the solvent of salting liquid be the mixed solvent that deionized water and ethanol form, wherein the volume content of ethanol is 20～50%.
As further preferred version, described inert atmosphere is blanket of nitrogen or argon atmospher.
As further preferred version, the percent by volume that contains reducing atmosphere in the described mixed atmosphere is 2%～10%.
Battery structure by the method for the invention preparation is followed successively by porous metals supporting layer, dense electrolyte layer, porous cathode precursor layer from the inside to the outside, described porous metals supporting layer and dense electrolyte layer and porous cathode precursor layer co-sintering are into a single integrated structure, and in the porous cathode precursor layer, be impregnated with active cathode material, in the porous metals supporting layer, be impregnated with active anode material; Described porous metals supporting layer can also be the metal supporting layer with transition structure, that is, be porous metallic layers away from electrolyte side, and is being the composite bed of porous metals-pottery near electrolyte side; And the metal ratio in the described composite bed is that 0-50wt%(comprises zero point), the thickness of described composite bed is 20～100 μ m, and porosity is 30～70%, and the aperture is 1～20 μ m.
As a kind of preferred version, the thickness of described porous metals supporting layer is 0.1～1mm, and porosity is 30～70%, and the aperture is 1～40 μ m; The thickness of described dense electrolyte layer is 10～40 μ m; The thickness of described porous cathode precursor layer is 20～100 μ m, and porosity is 30～70%, and the aperture is 0.3～5 μ m.
As a kind of preferred version, described ceramic layer material is selected from the YSZ(yttria stabilized zirconia), the zirconia of SSZ(scandia stabilized), ScYSZ(yittrium oxide, scandium oxide stable zirconia altogether), the cerium oxide that mixes of SDC(samarium oxide), the cerium oxide that mixes of GDC(gadolinium oxide), LSGM(strontium oxide strontia and the magnesium oxide lanthanum gallate of doped in lanthanum site and gallium position respectively) in any one or a few.
Compared with prior art, the present invention has following beneficial effect:
1) with respect to traditional anode supporting type solid oxide fuel cell, preparation method provided by the invention has simplified structure and the preparation technology of metallic support type solid oxide fuel cell, adopt curtain coating, laminate, the technique of co-sintering so that between each layer of battery in conjunction with tight, and the thickness of each layer, porosity all can be regulated, shorten the production cycle, reduced cost; The present invention is low performance and the long-time stability that improve battery that also help of cost not only; Electrode material all adopts the infusion process preparation, has solved the difficult problem of metallic support SOFC electrode preparation; Be in anode-side after metal support is finished, be subject to that reducing atmosphere protection is difficult for oxidation and conductivity is high; Whole battery structure is through once sintered namely plastic, simple and convenient, and cost is low.
2) metallic support type solid oxide battery provided by the invention adopts low-cost stainless steel powder as metal support, has preferably high-temperature oxidation resistance, and its thermal coefficient of expansion is close with traditional electrolyte YSZ, has avoided not mating the defectives such as electrolyte cracking that cause because of thermal coefficient of expansion in the high temperature co-firing knot process; In addition, for the Fe in the stainless steel, Cr element easily with the problem of anode Ni generation counterdiffusion, this patent adopts ceramic phase (such as GDC) and Ni is composited and the content of Ni is tried one's best few galvanic anode active material on the one hand, because the ceramic phase uniform fold is on the metal supporting layer surface, thereby reduced to a great extent the counterdiffusion of its interior stainless steel and Ni and prevented stainless oxidation and anticathode the poisoning of Cr volatilization, simultaneously since the Ni distribution of particles in ceramic phase, be difficult for alligatoring occurs, thereby improved chemical property and the long-time stability of battery; On the other hand, preparation method provided by the invention also can not adopt Ni as anode material, and adopts the ceramic oxide materials such as SFM also can obtain well behaved SOFC fully; For the stainless steel problem poor to the wetability of water, preparation method provided by the invention carries out modification by surfactant to stainless steel surfaces on the one hand, improves its wetability; Adopt on the other hand the mixed solvent of deionized water and ethanol as the solvent of negative electrode and active material of positive electrode in dipping process, reducing the surface tension of dipping solution, thereby pattern and the micro-structural of change impregnate layer obtain the dip coating of stable uniform.
3) negative electrode of SOFC provided by the invention and anode material be all by infusion process preparation, not only effectively avoided high temperature co-firing process Anodic metallic particles alligatoring and with the issue of inter-diffusion of alloying element, improved the chemical property of anode; And negative electrode is combined poor with electrolyte and high temperature sintering can cause the contradiction of metal support over oxidation when having solved low-temperature sintering; In addition, the pickup of electrode material and granular size can be controlled because electrode material is immersed in porous metals supporter and porous cathode precursor layer inside by concentration, character and the dipping number of times of dipping solution, the destruction that causes the porosity to reduce or cause battery structure because of thermal expansion problem so electrode material can not be reunited, thus being conducive to battery obtains preferably long-time stability; Also can on the basis of dipping active material of positive electrode, realize the inside reforming of the fuel such as ethanol, propane, natural gas by impregnated catalyst, thereby improve the suitability of fuel of battery, reduce operating cost.
In sum, the method for preparing metallic support type solid oxide fuel cell provided by the invention, not only cost is low, workable, be convenient to mass and produce continuously, and combination is tight between each layer of prepared SOFC battery, each functional layer thickness, porosity etc. are controlled, and make the anode and cathode of battery by dipping, the battery performance that makes than sintering is higher, stability is better, can ensure the pile life-span, reduce system cost, have good application prospect.
Description of drawings
Fig. 1 is the prepared Cross Section Morphology figure (SEM photo) without the flat metallic support type solid oxide fuel cell of impregnation process of embodiment 1;
Fig. 2 is that the prepared flat metallic support type solid oxide fuel cell of embodiment 1 is at 750 ℃ of chemical property figure that record;
Fig. 3 is the prepared Cross Section Morphology figure (SEM photo) without the flat metallic support type solid oxide fuel cell of dipping of embodiment 2;
Fig. 4 is that the prepared flat metallic support type solid oxide fuel cell of embodiment 2 is at 700 ℃ of chemical property figure that record.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is further elaborated.
Embodiment 1
In 50g 430 stainless steel powders, add successively solvent absolute ethyl alcohol 7g, butanone 5g, dispersant triethanolamine 4g, BYK1g, plasticiser dibutyl phthalate 1g, binding agent polyvinyl butyral resin 6g, pore creating material ammonium oxalate 20g; In 30g electrolyte YSZ powder, add successively solvent xylene, each 5g of butyl acetate, dispersant DM-55 1g, plasticiser B-50 1g, binding agent B-724g; In 15g negative electrode precursor layer YSZ powder, add successively solvent xylene, each 4g of butyl acetate, dispersant DM-55 1g, plasticiser B-500.5g, binding agent B-72 1g, pore creating material ammonium oxalate 10g;
Distinguish the above-mentioned 3 kinds of slurries of ball milling, and the slurry of mixing is sieved and vacuum treatment through screen cloth respectively, remove the slurry Air;
Above-mentioned 3 kinds of slurries are carried out respectively flow casting molding and drying, obtain metal supporting layer, dielectric substrate, negative electrode precursor layer biscuit, and each base substrate is cut into the base substrate that meets dimensional requirement;
Metal supporting layer, dielectric substrate, negative electrode precursor layer biscuit is stacked successively from bottom to top, then carry out hot pressing 10min in 75 ℃, 6Mp, cut into again the disk biscuit of 19mm, at 4%H
2+ 96%N
2Mixed atmosphere under, in 1300 ℃ of co-sinterings, make metal supporting layer/dielectric substrate/negative electrode precursor layer three-decker;
Above-mentioned three-decker is immersed in the lauryl mercaptan solution, stirred 5 hours under the room temperature, then with ethanol, washed with de-ionized water and oven dry;
The nitrate water-ethanol solution of dipping active cathode material SSC in the negative electrode precursor layer, wherein the addition of ethanol is 40% of solvent for use cumulative volume; Then under inert atmosphere, in 850 ℃ of heat treatments, obtain cell cathode; The nitrate water-ethanol solution of dipping active anode material NiO-SDC in metal supporting layer, wherein the addition of ethanol is 40% of solvent for use cumulative volume; Then in air, 500 ℃ of lower heat treatments, obtain galvanic anode; Thereby make described flat metallic support type SOFC.
Fig. 1 is the prepared Cross Section Morphology figure (SEM) that does not carry out the flat metallic support type SOFC of impregnation process of the present embodiment, as seen from Figure 1: from left to right be respectively porous cathode precursor layer, dense electrolyte layer, porous metals supporting layer among the figure, wherein metal supporting layer is loose structure, thickness is 270 μ m approximately, pore size is about 10～50 μ m, porosity approximately 40%, without layering, defects i.e.cracks; Dielectric substrate is fine and close, and no significant defect, thickness be 30 μ m approximately; The negative electrode precursor layer also is loose structure, and thickness is 30 μ m approximately, and pore size is about 0.5～8 μ m, porosity approximately 30%; Each interlayer is in conjunction with tight, and flawless or lamination occur at the interface, and metal support layer and negative electrode forerunner all are loose structures, and metal support layer aperture is large, porosity is high, is beneficial to the transmission of gas.
Fig. 2 for the prepared flat metallic support type SOFC of this enforcement at 750 ℃ of chemical property curves that record, cathode side is that surrounding air, anode-side are 97%H
2+ 3%H
2O is shown by test result shown in Figure 2, and this battery still has preferably electrical property under 750 ℃, and maximum power density is 372mW/cm
2
Embodiment 2
In 50g 430 stainless steel powders, add successively solvent absolute ethyl alcohol 12g, butanone 6g, dispersant triethanolamine 4g, plasticiser dibutyl phthalate 2g and polyethylene glycol 2g, binding agent polyvinyl butyral resin 3g, pore creating material ammonium carbonate 20g; In 30g electrolyte YSZ powder, add successively solvent xylene, each 5g of butyl acetate, dispersant DM-55 1g, plasticiser B-50 2g, binding agent B-72 4g; In 15g negative electrode precursor layer YSZ powder, add successively solvent xylene, each 4g of butyl acetate, dispersant DM-55 1.5g, plasticiser B-50 1g, binding agent B-72 2g, pore creating material ammonium carbonate 15g;
Distinguish the above-mentioned 3 kinds of slurries of ball milling, and the slurry of mixing is sieved and vacuum treatment through screen cloth respectively, remove the slurry Air;
Above-mentioned 3 kinds of slurries are carried out respectively flow casting molding and drying, obtain metal supporting layer, dielectric substrate, negative electrode precursor layer biscuit, and each base substrate is cut into the base substrate that meets dimensional requirement;
Metal supporting layer, dielectric substrate, negative electrode precursor layer biscuit is stacked successively from bottom to top, then carry out hot pressing 30min in 60 ℃, 15Mp, then cut into the disk biscuit of 19mm, at 4%H
2+ 96%N
2Mixed atmosphere under, in 1400 ℃ of co-sinterings, make metal supporting layer/dielectric substrate/negative electrode precursor layer three-decker;
Above-mentioned three-decker is immersed in the lauryl mercaptan solution, stirred 5 hours under the room temperature, then with ethanol, washed with de-ionized water and oven dry;
The nitrate water-ethanol solution of dipping active cathode material LSF in the negative electrode precursor layer, wherein the addition of ethanol is 20% of solvent for use cumulative volume; Then under inert atmosphere, in 900 ℃ of heat treatments, obtain cell cathode; The nitrate water-ethanol solution of dipping active anode material NiO-GDC in metal supporting layer, wherein the addition of ethanol is 40% of solvent for use cumulative volume; Then in air, 350 ℃ of lower heat treatments, obtain galvanic anode; Thereby make described flat metallic support type SOFC.
Fig. 3 is the Cross Section Morphology figure (SEM) of the prepared untreated flat metallic support type SOFC of the present embodiment, as seen from Figure 3: from left to right be respectively porous cathode precursor layer, dense electrolyte layer, porous metals supporting layer among the figure, wherein metal supporting layer is loose structure, thickness is 250 μ m approximately, pore size is about 5～30 μ m, porosity approximately 40%, without layering, defects i.e.cracks; Dielectric substrate is fine and close, and no significant defect, thickness be 16 μ m approximately; The negative electrode precursor layer also is loose structure, and thickness is 30 μ m approximately, and pore size is about 0.5～3 μ m, porosity approximately 50%; Each interlayer is in conjunction with tight, and flawless or lamination occur at the interface, and metal support layer and negative electrode forerunner all are loose structures, and metal support layer aperture is large, porosity is high, is conducive to the transmission of gas.
Fig. 4 for the prepared flat metallic support type SOFC of this enforcement at 700 ℃ of chemical property curves that record, cathode side is that surrounding air, anode-side are 97%H
2+ 3%H
2O is shown by test result shown in Figure 4, and this battery still has preferably electrical property under 700 ℃, and maximum power density is 300mW/cm
2
Embodiment 3
The preparation technology of the SOFC of three-decker is consistent with embodiment 2; The nitrate water-ethanol solution of dipping active cathode material LSCF-GDC in the negative electrode precursor layer, wherein the addition of ethanol is 50% of solvent for use cumulative volume; Then in inert atmosphere, obtain cell cathode after 850 ℃ of lower heat treatments; Dipping active anode material Ni-CeO in metal supporting layer
2Nitrate water-ethanol solution, wherein the addition of ethanol is 40% of solvent for use cumulative volume; Then in air, obtain galvanic anode after 500 ℃ of lower heat treatments; Namely get described flat metallic support type SOFC.
After testing, be that surrounding air, anode-side are 97%H at cathode side
2+ 3%H
2O, 700 ℃ of prepared battery maximum power densities of lower the present embodiment are 350mW/cm
2, still have preferably electrical property.
Embodiment 4
The preparation technology of the SOFC of three-decker is consistent with embodiment 2; The nitrate water-ethanol solution of dipping active cathode material SSC in the negative electrode precursor layer, wherein the addition of ethanol is 40% of solvent for use cumulative volume; Then in inert atmosphere, obtain cell cathode after 850 ℃ of lower heat treatments; Dipping active anode material Cu-CeO in metal supporting layer
2Nitrate water-ethanol solution, wherein the addition of ethanol is 40% of solvent for use cumulative volume; Then in air, obtain galvanic anode after 500 ℃ of lower heat treatments; Namely get described flat metallic support type SOFC.
After testing, be that surrounding air, anode-side are that methane, 750 ℃ of prepared battery maximum power densities of lower the present embodiment are 400mW/cm at cathode side
2, still have preferably electrical property.
Embodiment 5
The preparation technology of the SOFC of three-decker is consistent with embodiment 2; All flood SFM solution in the negative electrode precursor layer, in the anode precursor layer, wherein the addition of ethanol is 40% of solvent for use cumulative volume; Then in inert atmosphere, obtain cell cathode, anode after 850 ℃ of lower heat treatments; Namely get described flat metallic support type SOFC.
After testing, be that air, anode-side are 97%H at cathode side
2+ 3%H
2O, 800,750,700,650 ℃ of prepared battery maximum power densities of lower the present embodiment are respectively 738,560,404,255mW/cm
2
Embodiment 6
The battery preparation is with embodiment 5, but anode-side fuel is isooctane, and battery is 300mW/cm at 800 ℃ maximum power density
2
Embodiment 7
In 50g 430 stainless steel powders, add successively solvent absolute ethyl alcohol 15g, butanone 15g, dispersant B YK 15g, plasticiser dibutyl phthalate 8g, polyethylene glycol 8g, binding agent polyvinyl butyral resin 15g, pore creating material ammonium carbonate 60g; In 30g electrolyte ScYSZ powder, add successively solvent xylene, each 5g of butyl acetate, dispersant B YK 2.5g, plasticiser B-50 5g, binding agent B-72 7.5g; In 20g negative electrode precursor layer ScYSZ powder, add successively solvent xylene, each 5g of butyl acetate, dispersant DM-55 1g, plasticiser B-50 0.5g, binding agent B-72 0.5g, pore creating material ammonium carbonate 10g.
Distinguish the above-mentioned 3 kinds of slurries of ball milling, and the slurry of mixing is sieved and vacuum treatment through screen cloth respectively, remove the slurry Air;
Above-mentioned 3 kinds of slurries are carried out respectively flow casting molding and drying, obtain metal supporting layer, dielectric substrate, negative electrode precursor layer biscuit, and each base substrate is cut into the base substrate that meets dimensional requirement.
Metal supporting layer, dielectric substrate, negative electrode precursor layer biscuit is stacked successively from bottom to top, then carry out hot pressing 5min in 85 ℃, 4Mp, then cut into the disk biscuit of 19mm, at 4%H
2+ 96%N
2Mixed atmosphere under, in 1250 ℃ of co-sinterings, make metal supporting layer/dielectric substrate/negative electrode precursor layer three-decker.
Approximately 1mm, pore size are about 1～40 μ m, porosity approximately 70% to obtain the metallic support layer thickness; Dielectric substrate thickness is 40 μ m approximately; The negative electrode precursor layer is loose structure, and thickness approximately 100 μ m, pore size is about 0.3～5 μ m, porosity 70%.
The preparation method is with embodiment 5 for residue.
Embodiment 8
In 50g 430 stainless steel powders, add successively solvent absolute ethyl alcohol 5g, butanone 5g, dispersant triethanolamine 3g, plasticiser dibutyl phthalate 2g, binding agent polyvinyl butyral resin 3g, pore creating material ammonium carbonate 20g; In 30g electrolyte SSZ powder, add successively solvent xylene, each 10g of butyl acetate, dispersant B YK 0.5g, plasticiser B-50 1g, binding agent B-72 1.5g; In 20g negative electrode precursor layer SSZ powder, add successively solvent xylene, each 7.5g of butyl acetate, dispersant DM-55 2.5g, plasticiser B-50 2.5g, binding agent B-72 2.5g, pore creating material ammonium carbonate 20g.
The preparation method is with embodiment 5 for residue.
Approximately 100 μ m, pore size are about 3～20 μ m, porosity approximately 30% to obtain the metallic support layer thickness; Dielectric substrate thickness is 10 μ m approximately; The negative electrode precursor layer is loose structure, and thickness approximately 20 μ m, pore size is about 0.3～3 μ m, porosity 30%.
Embodiment 9
With embodiment 1, just in the middle of porous metals supporting layer and electrolyte layers, increase again one deck porous metals---the composite bed of pottery, thereby form the porous metals supporting layer with transition structure, the curtain coating prescription of composite bed is with the supporter prescription among the embodiment 1, and ceramic phase is YSZ in this composite bed, and content is 50%, the thickness of composite bed is 100 μ m, porosity is 30%, and the aperture is 1～20 μ m
Embodiment 10
With embodiment 9, just between the composite bed of embodiment 9 and electrolyte, add again porous ceramic layer, this ceramic layer is porous YSZ, thickness is 20 μ m, porosity is 70%, and the aperture is 1～4 μ m, and the curtain coating prescription is filled a prescription with the porous cathode precursor layer among the embodiment 1, the final porous metals supporting layer that forms has transition structure, i.e. porous metals/porous metals-pottery/porous ceramic.
Be necessary at last in this explanation to be: above embodiment only is used for technical scheme of the present invention is described in more detail; 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 (10)
1. a method for preparing flat metallic support type solid oxide fuel cell is characterized in that, comprises the steps:
A) prepare respectively the mixed slurry for preparing porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer;
B) 3 kinds of mixed slurries step a) being prepared carry out respectively flow casting molding and drying, make respectively the biscuit of porous metals supporting layer, dense electrolyte layer and porous cathode precursor layer;
C) with step b) biscuit of the porous metals supporting layer, dense electrolyte layer and the porous cathode precursor layer that make is stacked from bottom to top successively, then carries out hot pressing 5～30 minutes under 60～85 ℃, 4～15Mp condition;
D) with step c) the compound biscuit that obtains of hot pressing cuts into behind the required size under the mixed atmosphere that inert atmosphere or inert atmosphere and reducing atmosphere form, carries out co-sintering in 1250～1400 ℃;
E) with surfactant the porous metals supporting layer is carried out surface treatment;
F) salting liquid of dipping active cathode material in the porous cathode precursor layer obtains cell cathode after the heat treatment; The salting liquid of dipping active anode material obtains galvanic anode after the heat treatment in the porous metals supporting layer.
2. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 1 is characterized in that, the prescription of the mixed slurry of preparation porous metals supporting layer is as follows:
The prescription of the mixed slurry of preparation dense electrolyte layer is as follows:
The prescription of the mixed slurry of preparation porous cathode precursor layer is as follows:
3. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 2, it is characterized in that: described metal-powder is the stainless steel powder; Described electrolyte powder is selected from the YSZ(yttria stabilized zirconia), the zirconia of SSZ(scandia stabilized), ScYSZ(yittrium oxide, scandium oxide stable zirconia altogether), the cerium oxide that mixes of SDC(samarium oxide), the cerium oxide that mixes of GDC(gadolinium oxide), LSGM(strontium oxide strontia and the magnesium oxide lanthanum gallate of doped in lanthanum site and gallium position respectively) in any one or a few; Described negative electrode precursor layer powder is selected from the YSZ(yttria stabilized zirconia), the zirconia of SSZ(scandia stabilized), ScYSZ(yittrium oxide, scandium oxide stable zirconia altogether), the cerium oxide that mixes of SDC(samarium oxide), the cerium oxide that mixes of GDC(gadolinium oxide), LSGM(strontium oxide strontia and the magnesium oxide lanthanum gallate of doped in lanthanum site and gallium position respectively) in any one or a few.
4. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 3, it is characterized in that: described stainless steel powder is FeCrM alloy powder or the FeCrM alloy powder that is doped with metal oxide, and wherein M is any one or a few in Ni, Ti, Mn, N, Nb, Mo, Si, Y, Al, Ce, the La element; The doping of described metal oxide is 0～50% of described stainless steel powder gross mass, but does not comprise zero point.
5. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 2, it is characterized in that: described solvent is selected from any one or a few in dimethylbenzene, absolute ethyl alcohol, acetone, butanone, the butyl acetate; Described dispersant is selected from any one or a few among triethanolamine, acrylic copolymer BYK, methyl anyl alcohol, the acrylic resin DM-55; Described plasticiser is selected from any one or a few in benzoic ether B-50, polyethylene glycol, the dibutyl phthalate; Described binding agent is selected from any one or a few in polyvinyl butyral resin, acrylic resin B-72, the epoxy resin; Described pore creating material is selected from any one or a few in graphite, starch, ammonium oxalate, the ammonium carbonate.
6. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 1, it is characterized in that: the inert atmosphere steps d) is blanket of nitrogen or argon atmospher; The percent by volume that contains reducing atmosphere in the described mixed atmosphere is 2%～10%.
7. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 1, it is characterized in that: the surfactant step e) is selected from any one or a few in lauryl mercaptan, dimethyl silicone polymer, the neopelex; Described surface treatment is battery to be immersed contain in the solution of above-mentioned surfactant, stirs under the room temperature 3～5 hours, then with ethanol, washed with de-ionized water and oven dry.
8. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 1, it is characterized in that: the active cathode material step f) is selected from LSM(oxidation Strontinum doped lanthanum manganite), LSF (the ferrous acid lanthanum that strontium oxide strontia mixes), the cobalt acid lanthanum of LSCF(strontium oxide strontia and iron oxide difference doped in lanthanum site and cobalt position), SSC(strontium oxide strontia doping cobalt acid samarium), the strontium molybdate that the SFM(iron oxide mixes), the ferrous acid lanthanum that the LNF(nickel oxide mixes), the cerium oxide that the GDC(gadolinium oxide mixes), the cerium oxide that the SDC(samarium oxide mixes) any one or a few in; Described active anode material is selected from the cerium oxide that the NiO-GDC(gadolinium oxide mixes), the cerium oxide that mixes of NiO-SDC(samarium oxide), NiO-CeO
2, NiO-LST(strontium oxide strontia doped titanic acid lanthanum), the strontium molybdate that mixes of SFM(iron oxide), Cu-CeO
2In any one or a few.
9. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 1, it is characterized in that: the solvent of salting liquid step f) is the mixed solvent that deionized water and ethanol form, and wherein the volume content of ethanol is 20～50%.
10. the method for the flat metallic support type solid oxide fuel cell of preparation according to claim 1, it is characterized in that: the heat treatment temperature step f) is 350～900 ℃, heat-treating atmosphere is air or inert atmosphere.
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