CN104103838A - Anode protection layer for solid oxide fuel cell, and preparation method and application of anode protection layer - Google Patents

Anode protection layer for solid oxide fuel cell, and preparation method and application of anode protection layer Download PDF

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Publication number
CN104103838A
CN104103838A CN201410321236.5A CN201410321236A CN104103838A CN 104103838 A CN104103838 A CN 104103838A CN 201410321236 A CN201410321236 A CN 201410321236A CN 104103838 A CN104103838 A CN 104103838A
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fuel cell
solid oxide
anode
anodic coating
oxide fuel
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李箭
华斌
李檬
蒲健
池波
颜冬
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • H01M4/8889—Cosintering or cofiring of a catalytic active layer with another type of layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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

Abstract

The invention discloses an anode protection layer for an intermediate-temperature solid oxide fuel cell taking hydrocarbon as fuel. The protection layer is obtained by presintering spinel materials or a composite of spinel and oxide such as Gd0.1Ce0.9O1.95-delta(GDC) or BaZr0.1Ce0.7Y0.1Yb0.1O3-delta(BZCYYB) on the surface of an anode by in-situ reduction. The spinel materials can be MnNi2O4, CuFe2O4, NiFe2O4, Ni0.5Cu0.5Fe2O4 and the like, and the mass fraction of added GDC, BZCYYB and the like is 20-40%. The invention further discloses a method for preparing and using the materials. According to the anode protection layer and the method, the spinel and the composite of the spinel and oxide perform the in-situ reduction and then generate a metal ceramic composite, the product has good catalytic activity for partial methane oxidation and reforming reaction and can avoid carbon deposit of the anode inside, and the materials can well resist the carbon deposit, so that the problem of the carbon deposit of the anode of the solid oxide fuel cell taking hydrocarbon as the fuel is solved.

Description

Anodic coating of Solid Oxide Fuel Cell and its preparation method and application
Technical field
The invention belongs to field of solid oxide fuel, more specifically, relate to a kind of anodic coating for the intermediate temperature solid oxide fuel cell taking hydrocarbon as fuel.
Background technology
Solid Oxide Fuel Cell (solid oxide fuel cell, SOFC) is the electricity generation system that by electrochemical reaction, the chemical energy in fossil fuel (coal, oil, natural gas etc.), biomass fuel or other hydrocarbon fuels is directly converted to electric energy.With taking burning compared with basic traditional thermal power generation mode, SOFC technology has greatly reduced the energy loss of fuel and the impact to biological environment.SOFC has a wide range of applications in fields such as stationary electric power plant, portable power source, communications and transportation and military affairs and oceans, for alleviating energy crisis, meeting electricity needs, conserving natural habitats and safeguarding national security is all significant.
SOFC is using hydrogen as fuel for tradition, still, prepares hydrogen and requires the expenditure of energy and/or produce greenhouse gas emission; And directly adopt carbon-containing fuel, as coal gas, natural gas, carbon monoxide or biogas etc., be conducive to the raising of SOFC energy conversion efficiency and the collection of greenhouse gas.The effect of SOFC anode is oxidized fuel gas, and the quality of its performance directly has influence on the performance of SOFC.Verified, Ni based ceramic metal is the SOFC anode material that catalytic performance is good, has under mesophilic condition enough electro-chemical activities.But taking the compound such as natural gas, carbon monoxide as direct fuel in the situation that, can there is the problem of carbon deposition in Ni based ceramic metal anode.The carbon being deposited on anode surface has covered reactivity position, causes SOFC performance degradation; The generation of carbon fiber also causes the efflorescence of Ni structure simultaneously, causes SOFC to break.Although add enough steam can avoid or alleviate carbon deposition, but, the concentration and the electric transformation efficiency that add membership reduction fuel gas of steam, and form inhomogeneous Temperature Distribution, the stress producing will destroy SOFC structure.Such as the Cu-CeO having reported 2-YSZ composite anode, LaCrO 3and SrTiO 3series anode all has reasonable anti-carbon performance.But the anode that these are novel, can not show a candle to traditional Ni based ceramic metal anode at the aspect such as conductivity, electro-chemical activity, it is long-lasting is not also verified fully.
How solving concentration and electric transformation efficiency that the easy carbon deposition of current Solid Oxide Fuel Cell Anodic improves anti-carbon and do not reduce again fuel gas, and have higher guidance quality and chemical property, is current technical problem urgently to be resolved hurrily.
Summary of the invention
For defect and the Improvement requirement of prior art; the object of the present invention is to provide a kind of anodic coating for Solid Oxide Fuel Cell and its preparation method and application; can this protective layer be set at the anode of fuel cell, can effectively improve anti-carbon performance and the fuel availability of anode.
According to one aspect of the present invention; a kind of anodic coating of Solid Oxide Fuel Cell is provided; its in-situ reducing sintering, at the anode surface of Solid Oxide Fuel Cell, is characterized in that, the precursor material of this anodic coating is spinel or is spinelle and Gd 0.1ce 0.9o 1.95-δ(GDC), BaZr 0.1ce 0.7y 0.1yb 0.1o 3-δ(BZCYYb), BaZr 0.2ce 0.7y 0.1o 3-δor Sm (BZCY) 0.2ce 0.8o 1.95-δ(SDC) a kind of compound in these oxides.
Form anodic coating by in-situ reducing presintering at the above-mentioned compound of anode surface, this protective layer has good catalytic activity for methane portion oxidation and reforming reaction, can avoid the generation of nexine anode carbon deposition.
As improvement of the present invention, described spinel can be MnNi 2o 4, CuFe 2o 4, NiFe 2o 4and Ni 0.5cu 0.5fe 2o 4in one, can be also some other containing Ni or containing the spinel of Fe.
As improvement of the present invention, the mass fraction of GDC or the BZCYYb etc. of interpolation is at 20%-40%.
As improvement of the present invention, described precursor material adopts wet chemistry method preparation, is specially:
Take metal nitrate by stoichiometric proportion, with deionized water dissolving, add glycine or citric acid, then by solution agitating heating, until spontaneous combustion becomes cotton-shaped presoma, finally presoma is ground to after-baking 2 hours, make powder.
As improvement of the present invention, described precursor material is CuFe 2o 4, NiFe 2o 4, Ni 0.5cu 0.5fe 2o 4or while thering is GDC in precursor material, adding glycine, precursor material is MnNi 2o 4time, what add is citric acid.
As improvement of the present invention, the mol ratio of described glycine and metal ion is 1.2:1～2:1.
As improvement of the present invention, when described precursor material includes BZCYYb, add citric acid, also add simultaneously and have ethylenediamine tetra-acetic acid (EDTA) ammonia spirit.
As improvement of the present invention, the precursor material of anodic coating adopts the method for ball milling mill and/or mix.
As improvement of the present invention, when anodic coating precursor material is single spinelle, as CuFe 2o 4, NiFe 2o 4, Ni 0.5cu 0.5fe 2o 4, MnNi 2o 4in one, by powder ball milling 24 hours, using alcohol as solvent, the ball of wherein milling: powder: the mass ratio of alcohol is 2:1:1.5.
As improvement of the present invention; in the time that described anodic coating precursor material is the mixture of spinelle and GDC or BZCYYb etc.; powder ball milling is mixed; the quality of GDC or BZCYYb etc. accounts for the 20%-40% of powder gross mass; using alcohol as solvent, the ball of wherein milling: powder: the mass ratio of alcohol is 2:1:1.5.
According to another aspect of the present invention, a kind of preparation method of anodic coating of Solid Oxide Fuel Cell is provided, comprising:
Powder after ball milling is mixed with binding agent, and wherein said powder is by spinel or be spinelle and Gd 0.1ce 0.9o 1.95-δ(GDC), BaZr 0.1ce 0.7y 0.1yb 0.1o 3-δ(BZCYYb), BaZr 0.2ce 0.7y 0.1o 3-δor Sm (BZCY) 0.2ce 0.8o 1.95-δ(SDC) a kind of compound in these oxides is milled and is formed;
Adopt silk screen printing above-mentioned compound to be printed on the anode of Solid Oxide Fuel Cell and sintering;
Then by anode and anodic coating in-situ reducing, can on anode, obtain described anodic coating.
As improvement of the present invention, described binding agent by by terpinol and ethyl cellulose in mass ratio for 96:4 mix after 80 DEG C of constant temperature stirrings, until ethyl cellulose makes after being dissolved in terpinol completely.
As improvement of the present invention, described powder is 60 to 40 with the mass ratio of binding agent.
According to another aspect of the present invention, a kind of Solid Oxide Fuel Cell is provided, it is characterized in that, its anode surface is coated with above-mentioned anodic coating.
As improvement of the present invention, described Solid Oxide Fuel Cell preferably taking hydrocarbon for example methane as the Solid Oxide Fuel Cell of fuel.
In the present invention, the spinel by in-situ reducing sintering on anode or be spinelle and Gd 0.1ce 0.9o 1.95-δ(GDC), BaZr 0.1ce 0.7y 0.1yb 0.1o 3-δ(BZCYYb), BaZr 0.2ce 0.7y 0.1o 3-δor Sm (BZCY) 0.2ce 0.8o 1.95-δ(SDC) a kind of compound in these oxides obtains, realize to taking methane as fuel and working temperature be the protection of the middle temperature flat solid oxide fuel cell anode of 600 DEG C to 800 DEG C.
In general, the above technical scheme of conceiving by the present invention compared with prior art, has following beneficial effect:
Anodic coating working temperature of the present invention is 600 DEG C to 800 DEG C, prepared catalyst after reduction, such as Ni-MnO catalyst is to methane vapor, CO 2 reforming reaction is having reasonable catalytic activity at each temperature.
Anodic coating of the present invention is operated in the mist of methane and water vapour, can in the case of low steam/hydrocarbons ratio, play the effect that suppresses carbon deposition.
The protective layer that in-situ reducing obtains, except methane portion oxidation and reforming reaction are had catalytic activity, also should have good electron conduction.
Brief description of the drawings
Fig. 1 is the structural representation of the button cell of electrolyte-supported, has wherein shown the position using according to anodic coating of the present invention;
Fig. 2 is the ac impedance spectroscopy test result schematic diagram according to the embodiment of the present invention 1;
Fig. 3 is the galvanostatic polarization test result schematic diagram according to the embodiment of the present invention 1;
Fig. 4 is the ac impedance spectroscopy test result schematic diagram according to the embodiment of the present invention 2;
Fig. 5 is the galvanostatic polarization test result schematic diagram according to the embodiment of the present invention 2;
Fig. 6 is the ac impedance spectroscopy test result schematic diagram according to the embodiment of the present invention 3;
Fig. 7 is the galvanostatic polarization test result schematic diagram according to the embodiment of the present invention 3;
Fig. 8 is the generalized section of the button cell of Ni-YSZ anode-supported, has wherein shown the position view using according to the anodic coating of the embodiment of the present invention;
Fig. 9 is the ac impedance spectroscopy test result schematic diagram according to the embodiment of the present invention 4;
Figure 10 is according to the I-V of the embodiment of the present invention 4 and I-P test result schematic diagram.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Anodic protection layer material for the intermediate temperature solid oxide fuel cell taking hydrocarbon as fuel of the present invention, this protective layer precursor material comprises: spinel or these spinelles and Gd 0.1ce 0.9o 1.95-δ(GDC), BaZr 0.1ce 0.7y 0.1yb 0.1o 3-δ(BZCYYb) compound of oxide such as.These spinels can be: MnNi 2o 4, CuFe 2o 4, NiFe 2o 4, Ni 0.5cu 0.5fe 2o 4deng, the mass fraction of GDC or the BZCYYb etc. of interpolation is at 20%-40%.
Anodic coating of the present invention has good catalytic activity to methane portion oxidation and reforming reaction, and these materials self can suppress the growth of carbon under certain conditions.When using CuFe 2o 4, NiFe 2o 4, Ni 0.5cu 0.5fe 2o 4and composite material, this protective layer has good electronic conductance, can replace the metal of platinum, gold or the costliness such as silver-colored to play the effect of electric current collection.
The precursor material of anodic coating of the present invention adopts wet chemistry method preparation:
When described material is CuFe 2o 4, NiFe 2o 4, Ni 0.5cu 0.5fe 2o 4or when GDC, take metal nitrate by stoichiometric proportion, with deionized water dissolving, add glycine, wherein the mol ratio of glycine and metal ion is preferably 1.2:1, then by solution in for example agitating heating at 200 DEG C, until spontaneous combustion becomes cotton-shaped presoma, after finally presoma being ground, preferably 650 DEG C of heat treatments 2 hours, make powder.
When described precursor material is MnNi 2o 4time, take metal nitrate by stoichiometric proportion, with deionized water dissolving, add citric acid, wherein the mol ratio of citric acid and metal ion is preferably 1.5:1, after stirring, solution is placed in to for example 160 DEG C of heating 12h of baking oven, makes it to become loose porous black xerogel, after finally presoma being ground, 800 DEG C of heat treatment for example 2 hours, make powder.
In the time that described precursor material is BZCYYb, take metal nitrate by stoichiometric proportion, be dissolved in deionized water, add subsequently citric acid and ethylenediamine tetra-acetic acid (EDTA) ammonia spirit as complexing agent, the mol ratio of citric acid, EDTA and metal ion is preferably 1.5:1:1, mixed solution is for example being stirred to sticky gel at 80 DEG C, then be placed in and dry as 300 DEG C of baking ovens, gained black xerogel is preferably placed in 1100 DEG C of air atmospheres after grinding and calcines 5h, makes powder.
The precursor material of anodic coating of the present invention adopts the method for ball milling mill and/or mix:
In the time that described anodic coating precursor material is single spinelle, as CuFe 2o 4, NiFe 2o 4, Ni 0.5cu 0.5fe 2o 4, MnNi 2o 4in one, by powder ball milling for example 24 hours, using alcohol as solvent, the ball of wherein milling: powder: the mass ratio of alcohol is preferably 2:1:1.5, but is not limited to this in the present invention.
In the time that described anodic coating precursor material is the mixture of spinelle and GDC or BZCYYb etc.; powder ball milling is mixed for example 24 hours; the quality optimization of GDC or BZCYYb etc. accounts for the 20%-40% of powder gross mass; but in the present invention, be not limited to aforementioned proportion; using alcohol as solvent; the ball of wherein milling: powder: the mass ratio of alcohol is preferably 2:1:1.5, but is not limited to this in the present invention.
Anodic coating of the present invention is prepared into the anode surface of dull and stereotyped SOFC by the mode of silk screen printing and sintering, battery structure adopts electrode supporting or electrolyte-supported; Anode is electrolyte/nickel composite anode, negative electrode adopts the one of lanthanum strontium ferro-cobalt (LSCF), lanthanum strontium manganese (LSM), palladium injection zirconia (Pd-YSZ), the one in the cerium oxide (SDC) of the zirconia (YSZ) of electrolyte employing stabilized with yttrium oxide, the cerium oxide (GDC) of gadolinium oxide doping, samarium oxide doping.
In the present invention, the concrete steps of preparing anodic coating are: the powder after ball milling is mixed to powder with binding agent: the mass ratio of binding agent is preferably 60:40, can be also other ratios, for example (50-80): (50-20); The collocation method of binding agent used be by terpinol and ethyl cellulose in mass ratio for 96:4 mix after stirring at 80 DEG C of constant temperature, until ethyl cellulose is dissolved in terpinol completely.Wherein, 200 orders are elected in silk screen printing network optimization used as, and area is 0.5cm 2; When printing, the distance between net and sample is preferably 5mm, finish printing rear preferably at 900～1000 DEG C of sintering, then by anode and anodic coating preferably 650 DEG C of in-situ reducing, the anodic coating finally obtaining, its thickness is preferably 20～30 μ m.
In the present invention, the oxide mixing with spinelle is not limited to above several, for example, can also be BaZr 0.2ce 0.7y 0.1o 3-δor Sm (BZCY) 0.2ce 0.8o 1.95-δ(SDC) etc.
Below for prepare and use the embodiment of spinel based anodic coating according to the present invention.
Embodiment 1
In the present embodiment, taking methane+steam as fuel, Ni-YSZ|YSZ half-cell anode applies MnNi 2o 4protective layer:
The first step, preparation MnNi 2o 4spinelle: get manganese nitrate solution (for example: analyze pure, 50wt.%in H 2o) 30.1212g is (approximately containing 0.06mol Mn 2+) be dissolved in 50ml deionized water, in this solution, add for example 34.8961g Ni (NO 3) 26H 2o is (approximately containing 0.12mol Ni 2+) and 56.7378g citric acid (about 0.27mol), for example 80 DEG C stir until solution becomes thick, then in baking oven preferably 160 DEG C heating 12h, make it to become loose porous black xerogel, after finally presoma being ground, preferably 800 DEG C of heat treatment 2 hours, makes MnNi 2o 4spinel powder.
The powder ball milling obtaining 24 hours, using alcohol as solvent, the ball of wherein milling: powder: the mass ratio of alcohol is preferably 2:1:1.5.
Second step, the button half-cell of preparation YSZ electrolyte-supported: take Japanese TOS0H 8mol.%Y 2o 3-ZrO 2(8YSZ) such as 28.5g of powder, adds PVA solution (5wt.%PVA in H 2o) for example 1.5g, mills evenly.Preferably take the electrolyte powder that the above-mentioned granulation of 2.5g obtains, by mould by electrolyte dry-pressing precedent as base substrate, be preferable over 1500 DEG C of sintering 300min, obtain density 99.0%, be of a size of ySZ electrolyte sheet.
In YSZ electrolyte substrate one side, prepare anode, preferably take NiO powder 3g, YSZ powder 2g, adds binding agent to mix, powder in the present embodiment: the mass ratio of binding agent is preferably 70:30; The collocation method of self-control binding agent used is that terpinol and ethyl cellulose are preferably in mass ratio after 96:4 mixes and are stirred at 80 DEG C of constant temperature, until ethyl cellulose is dissolved in terpinol completely; 200 orders are elected in silk screen printing network optimization used as, and area is 0.5cm 2; When printing, the distance between net and sample is preferably 5mm, finishes printing afterwards preferably 1400 DEG C of sintering 2 hours, and the NiO-YSZ anode thickness finally obtaining is 20～30 μ m.
The 3rd step, prepares anodic coating: by the MnNi after ball milling 2o 4spinel powder mixes with binding agent, powder: the quality of binding agent is than being preferably 60:40 in the present embodiment; Binding agent used with prepare the identical of anode; Silk-screen printing technique, with to prepare anode identical, is printed on slurry on the surface of anode, finishes printing afterwards preferably 1000 DEG C of sintering 2 hours, and obtaining thickness is the unreduced protective layer of 20～30 μ m.
Carry out electro-chemical test: adopt three-electrode method to test; as shown in Figure 1; prepare Pt to electrode and reference electrode at YSZ electrolyte substrate another side; identical with anode to the area of electrode, be positioned at anode right opposite, reference electrode is at edge in the form of a ring; and reference electrode and must be greater than 2 times of YSZ electrolyte thickness to the distance between electrode; first battery is used at 650 DEG C to hydrogen in-situ reducing 2 hours, obtained Ni-YSZ anode and Ni-MnO protective layer, then test.As shown in Figures 2 and 3, contrast Ni-YSZ anode and Ni-MnO/Ni-YSZ anode, experimental result shows to introduce Ni-MnO protective layer and makes anode at methane (3%H 2o) polarization impedance in has reduced to exceed 1/3 compared with Ni-YSZ anode, at methane (20%H 2and 0.2Acm O) -2anode current effect under, the stability of introducing the anode of Ni-MnO protective layer is significantly improved, and has avoided carbon deposition completely under this condition.
Embodiment 2
In the present embodiment, preferably taking methane+steam as fuel, Ni-YSZ|YSZ half-cell anode applies Ni 0.5cu 0.5fe 2o 4-GDC protective layer:
The first step, preparation Ni 0.5cu 0.5fe 2o 4spinelle and GDC:Ni 0.5cu 0.5fe 2o 4the preparation of spinelle, gets 32.3198g Fe (NO 3) 39H 2o is (approximately containing 0.08mol Fe 3+), 5.8162g Ni (NO 3) 26H 2o is (approximately containing 0.02mol Ni 2+), 4.8320g Cu (NO 3) 23H 2o is (approximately containing 0.02mol Cu 2+) and 10.8101g glycine (about 0.144mol) be dissolved in 100ml deionized water, after stirring by solution agitating heating at 200 DEG C, until spontaneous combustion becomes cotton-shaped presoma, finally presoma is ground to rear 650 DEG C of heat treatments 2 hours, make powder.The preparation of GDC, gets 39.0708g Ce (NO 3) 36H 2o is (approximately containing 0.09mol Ce 3+), 4.5136g Gd (NO 3) 36H 2o is (approximately containing 0.01mol Gd 3+) and 9.0084g glycine (approximately containing 0.12mol) be dissolved in 100ml deionized water, after stirring by solution agitating heating at 200 DEG C, until the powdered presoma of spontaneous combustion finally grinds presoma rear 650 DEG C of heat treatments 2 hours, make GDC.Powder is pressed Ni 0.5cu 0.5fe 2o 4: GDC mass ratio is that 80:20 ball milling mixes 24 hours, using alcohol as solvent, and the ball of wherein milling: powder: the mass ratio of alcohol is 2:1:1.5, the mixed powder obtaining is abbreviated as NCFO-GDC.
Second step, the button half-cell of preparation YSZ electrolyte-supported: method is with example 1.
The 3rd step, prepares anodic coating: the NCFO-GDC powder after ball milling is mixed to powder with binding agent: the mass ratio of binding agent is 70:30; Binding agent used is with to prepare anode identical; Silk-screen printing technique, with to prepare anode identical, is printed on slurry on the surface of anode, and after finishing printing, 900 DEG C of sintering 2 hours, obtaining thickness was the unreduced protective layer of 20～30 μ m.
The 4th step, carries out electro-chemical test: battery structure is with example 1.Experimental result is (in-situ reducing Ni as shown in Figure 4 0.5cu 0.5fe 2o 4the NiCuFe alloy obtaining, writes a Chinese character in simplified form into NCF), contrast Ni-YSZ anode and NCF-GDC/Ni-YSZ anode, experimental result shows to introduce NCF-GDC protective layer and makes anode at methane (3%H 2o) polarization impedance in has reduced to exceed shown in 1/2, Fig. 5 compared with Ni-YSZ anode, introduces NCF-GDC protective layer and makes anode at low vapour content (3%H 2o) stability under has obtained significantly mentioning.
Embodiment 3
In the present embodiment, preferably taking methane+steam as fuel, Ni-YSZ|YSZ half-cell anode applies Ni 0.5cu 0.5fe 2o 4-BZCYYb protective layer:
The first step, preparation Ni 0.5cu 0.5fe 2o 4the preparation method of spinelle and BZCYYb:NCFO is with example 2.The preparation of BZCYYb, takes metal nitrate by stoichiometric proportion, 5.2270g Ba (NO 3) 3(approximately containing 0.02mol Ba 2+), 6.0774g Ce (NO 3) 36H 2o is (approximately containing 0.014mol Ce 3+), 0.6785g Zr (NO 3) 45H 2o is (approximately containing 0.002mol Zr 4+), 0.7661g Y (NO 3) 36H 2o is (approximately containing 0.002mol Y 3+), 0.8983g Yb (NO 3) 35H 2o is (approximately containing 0.002mol Yb 3+), be dissolved in deionized water, add subsequently ethylenediamine tetra-acetic acid (EDTA) ammonia spirit (EDTA is 0.04mol) as complexing agent, add again 12.6072g citric acid (about 0.06mol), regulate PH to 7 left and right, mixed solution is stirred to sticky gel at 80 DEG C, is then placed in 300 DEG C of baking ovens and dries, gained black xerogel grinds to be placed in 1100 DEG C of air atmospheres calcines 5h, makes powder.Powder is that 80:20 ball milling mixes 24 hours by NCFO:BZCYYb mass ratio, using alcohol as solvent, and the ball of wherein milling: powder: the mass ratio of alcohol is 2:1:1.5, the mixed powder obtaining is abbreviated as NCFO-BZCYYb.
Second step, the button half-cell of preparation YSZ electrolyte-supported: method is with example 1 and example 2.
The 3rd step, prepares anodic coating: method is with example 2.
The 4th step, carries out electro-chemical test: battery structure is with example 1 and example 2.Experimental result as shown in Figure 6 and Figure 7, can find out that applying NCF-BZCYYb protective layer makes anode at methane (3%H 2o) polarization impedance in has reduced 3/4 compared with Ni-YSZ anode, at low vapour content (3%H 2o) operation that can be stable in methane.
Embodiment 4
In the present embodiment preferably taking methane+steam as fuel, Ni-YSZ|YSZ|La 0.8sr 0.2co 0.8fe 0.2the full galvanic anode of-GDC applies NCFO-BZCYYb protective layer:
The first step, preparation Ni 0.5cu 0.5fe 2o 4spinelle and BZCYYb mixed-powder: method is with example 3.
Second step, the full battery of button of preparation Ni-YSZ anode-supported: ball milling 24 hours after getting 171g NiO, 129g YSZ, 135ml solvent (volume ratio is 1:1 alcohol and dimethylbenzene), 15g starch, 6g fish oil and mixing, add again 13.5g butyl benzyl, 10.5gPAG, 24g PVB, 0.3g cyclohexanone to continue ball milling 24 hours, after the mixed slurry flow casting molding obtaining, be cut into disk, then silk screen printing NiO-YSZ anode and YSZ electrolyte slurry successively in the above, entered high temperature sintering and obtained half-cell, finally prepare LSCF-GDC negative electrode by silk screen printing and sintering in the above, obtain full battery.
The 3rd step, prepares anodic coating: method is with example 2 and example 3.
The 4th step, carries out electro-chemical test: shown in Fig. 8, be the section of battery, wherein shown the position using according to anodic coating of the present invention.When test, adopt four point probe structure.Can find out from Fig. 9 and Figure 10, apply after Catalytic Layer, in the time of 800 DEG C, at methane (3%H 2o) the electrochemical activation impedance in has reduced 1/3, and peak power density is also improved.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. an anodic coating for Solid Oxide Fuel Cell, its in-situ reducing sintering, at the anode surface of Solid Oxide Fuel Cell, is characterized in that, is spinelle for the precursor material of in-situ reducing sintering, or is spinelle and Gd 0.1ce 0.9o 1.95-δ(GDC), BaZr 0.1ce 0.7y 0.1yb 0.1o 3-δ(BZCYYb), BaZr 0.2ce 0.7y 0.1o 3-δor Sm (BZCY) 0.2ce 0.8o 1.95-δ(SDC) compound of one or more in these oxides.
2. the anodic coating of a kind of Solid Oxide Fuel Cell according to claim 1, wherein, described spinel is containing Ni or contains one or more in the spinel of Fe, preferably MnNi 2o 4, CuFe 2o 4, NiFe 2o 4and Ni 0.5cu 0.5fe 2o 4in one or more.
3. the anodic coating of a kind of Solid Oxide Fuel Cell according to claim 1 and 2, wherein, the mass fraction of the oxide of interpolation is at 20-40%.
4. according to the anodic coating of a kind of Solid Oxide Fuel Cell described in any one in claim 1-3, wherein, described precursor material adopts wet chemistry method preparation, is specially:
Take metal nitrate by stoichiometric proportion, with deionized water dissolving, add glycine or citric acid, then by solution agitating heating, until spontaneous combustion becomes cotton-shaped presoma, finally presoma is ground to after-baking 2 hours, make powder.
5. the anodic coating of a kind of Solid Oxide Fuel Cell according to claim 4, wherein, described precursor material is CuFe 2o 4, NiFe 2o 4, Ni 0.5cu 0.5fe 2o 4or while thering is GDC in precursor material, adding glycine, precursor material is MnNi 2o 4time, what add is citric acid.
6. the anodic coating of a kind of Solid Oxide Fuel Cell according to claim 5, wherein, the mol ratio of described glycine and metal ion is 1.2:1～2:1.
7. the anodic coating of a kind of Solid Oxide Fuel Cell according to claim 4, wherein, when described precursor material includes BZCYYb, adds citric acid, also adds simultaneously and has ethylenediamine tetra-acetic acid (EDTA) ammonia spirit.
8. according to the anodic coating of a kind of Solid Oxide Fuel Cell described in any one in claim 1-7, wherein, the precursor material of anodic coating adopts the method for ball milling mill and/or be mixed into powder;
Wherein, when described anodic coating precursor material is single spinelle, by its ball milling, and using alcohol as solvent, the ball of wherein milling: powder: the mass ratio of alcohol is 2:1:1.5; When described anodic coating precursor material is the mixture of spinelle and GDC or BZCYYb etc.; powder ball milling is mixed; the quality of GDC or BZCYYb etc. accounts for 20% of powder gross mass, using alcohol as solvent, and the ball of wherein milling: powder: the mass ratio of alcohol is 2:1:1.5.
9. a preparation method for the anodic coating of Solid Oxide Fuel Cell, comprising:
First the powder after ball milling is mixed with binding agent, wherein said powder is by spinelle or be spinelle and Gd 0.1ce 0.9o 1.95-δ(GDC), BaZr 0.1ce 0.7y 0.1yb 0.1o 3-δ(BZCYYb), BaZr 0.2ce 0.7y 0.1o 3-δor Sm (BZCY) 0.2ce 0.8o 1.95-δ(SDC) in this type oxide, a kind of compound being mixed to form is milled and is formed;
Secondly adopt silk screen printing above-mentioned compound to be printed on the anode of Solid Oxide Fuel Cell and sintering;
Then by anode and anodic coating in-situ reducing, can on anode, obtain described anodic coating.
10. a Solid Oxide Fuel Cell, is characterized in that, its anode surface in-situ reducing sintering has the anodic coating described in any one in the claims 1-8.
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CN109964349A (en) * 2016-11-24 2019-07-02 罗伯特·博世有限公司 Method for the anode of fuel cell and for manufacturing anode
CN107200358A (en) * 2017-04-25 2017-09-26 昆明理工大学 A kind of iron system CuFe for sodium-ion battery2O4The preparation method of material
CN111201652A (en) * 2017-10-20 2020-05-26 株式会社Lg化学 Interconnector for solid oxide fuel cell, method for producing same, and solid oxide fuel cell
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CN110247074B (en) * 2019-05-20 2021-11-30 内蒙古科技大学 Composite anode powder using PVP-K30 pore-forming agent and preparation method thereof
CN110247074A (en) * 2019-05-20 2019-09-17 内蒙古科技大学 A kind of composite anode powder and preparation method thereof using PVP-K30 pore creating material
CN110600775A (en) * 2019-09-29 2019-12-20 武汉华科福赛新能源有限责任公司 In-situ reforming type solid oxide fuel cell
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CN113233518A (en) * 2020-12-25 2021-08-10 南京工业大学 Solid oxide fuel cell anode catalytic material with multi-carbon fuel catalytic hydrogen production function and preparation method thereof
CN114361471A (en) * 2022-01-10 2022-04-15 国家能源集团新能源有限责任公司 Integrated independent catalytic layer, preparation method and application
CN115055067A (en) * 2022-05-05 2022-09-16 清华大学 Proton conduction medium-temperature fuel cell electrolyte based on flame synthesis and preparation method thereof
CN115055067B (en) * 2022-05-05 2024-02-02 清华大学 Proton conduction medium-temperature fuel cell electrolyte based on flame synthesis and preparation method thereof
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