CN103682373A - Non-cobalt IT-SOFC (Intermediate-Temperature Solid Oxide Fuel Cell) stable anode material and application thereof - Google Patents

Non-cobalt IT-SOFC (Intermediate-Temperature Solid Oxide Fuel Cell) stable anode material and application thereof Download PDF

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CN103682373A
CN103682373A CN201310717760.XA CN201310717760A CN103682373A CN 103682373 A CN103682373 A CN 103682373A CN 201310717760 A CN201310717760 A CN 201310717760A CN 103682373 A CN103682373 A CN 103682373A
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nsfcu
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CN103682373B (en
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殷洁炜
尹屹梅
卢军
马紫峰
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Shanghai Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
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    • 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

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Abstract

The invention relates to a non-cobalt IT-SOFC (Intermediate-Temperature Solid Oxide Fuel Cell) stable anode material and application thereof and belongs to the technical field of fuel cells. The A site of SrFeO3-delta is doped with Nd, and the B site of the SrFeO3-delta is doped with Cu, so that the prepared (Nd1-xSrx)a (Fe1-yCuy)bO3-detal (NSCFu) anode material has high oxygen reduction catalytic activity, and the electrochemical performance is greatly improved. The anode material has long-term stability, and meanwhile has the advantages of high electronic conductivity, and high chemical compatibility and thermal expansion compatibility with cerium-oxide-based electrolytes. Thus, the SOFC anode material is potential.

Description

Non-cobalt intermediate temperature solid oxide fuel cell is stablized cathode material and application thereof
Technical field
What the present invention relates to is the material in a kind of fuel cell technology field, specifically a kind of non-cobalt-based intermediate temperature solid oxide fuel cell (SOFC) cathode material and as the application of negative electrode and composite cathode.
Background technology
Solid Oxide Fuel Cell (Solid Oxide Fuel Cells, SOFCs) be a kind of device that can fossil fuel is efficient, low row be converted into electric energy, having fuel-flexible, structure of whole solid state and do not use noble metal as advantages such as catalyst, is energy-saving and emission-reduction and a kind of effective alternative energy source of realizing sustainable development.Traditional SOFC is due to working temperature high (800-1000 ℃), the at high temperature poor stability of battery material, the life-span is short, material price cost is high, it is harsh etc. that battery maintenance and other auxiliary devices (as connector) are required, and has seriously hindered its commercialization process.The middle low temperature (600-800 ℃) of SOFC can expand the range of choice of battery material and connecting material etc., effectively reduce preparation and the operating cost of SOFC, and be conducive to its operation steady in a long-term and fast opening and closing, thereby intermediate temperature SOFC (IT-SOFC) has caused people's extensive concern.But along with the reduction of working temperature, it is one of bottleneck hindering the raising of SOFC monocell performance and cost that cathode overpotential increases sharply.Therefore it is extremely important that exploitation has the novel cathode material that more hyperoxia reduction catalysts activity, chemical stability and thermal expansivity are mated with electrolyte.
Perovskite oxide Ln containing cobalt 1-xsr xco 1-yfe yo 3(LnSCF, Ln=rare earth element and alkali earth metal) because having good hybrid ionic-electron conduction and oxygen transport property, and be widely used as intermediate temperature solid oxide fuel cell cathode material.But due to characteristics such as volatile, the easy reduction of cobalt in LnSCF material, make containing cobalt perovskite cathode material exist thermal structure stability and chemical stability poor, thermal coefficient of expansion is larger, its thermal coefficient of expansion with conventional in low-temperature electrolytic material as problems such as doping cerium dioxide do not mate.So it is extremely important to study the non-cobalt cathode material of stable high-performance, therefore caused people's attention.
From document < < International journal of hydrogen energy > > (37,2012,11963-11968; Chinese translation: international Hydrogen Energy journal, open day: 2012-06-22) and Chinese patent 201310158671.6, " a kind of cathode material of intermediate temperature solid oxide fuel cell and preparation thereof " (open day: 2013-7-31), find, people are to SrFeO 3-δperovskite oxide carries out A position and the doping of B position obtains non-cobalt cathode material La xsr 1-xfe 1-ycu yalthough, improved SrFeO 3-δhydrogen reduction catalytic activity, but cathode impedance is still larger, as La 0.6sr 0.4fe 0.8cu 0.2o 3-δ700 ℃ of cathode impedance be 0.306 Ω cm 2, and material is not clear in the stability of (600-800 ℃) of mesophilic range.
Through the retrieval of prior art is found, Chinese patent literature CN103296286A, open day 2013-09-11, discloses " a kind of novel C O 2and H 2the superlattice composite oxygen electrode of O high temperature common-battery solution "; on the dielectric substrate of half electrolytic cell sheet, cover strontium doping cobalt barium ferrite or strontium doping ferro-cobalt acid lanthanum basalis; strontium doping cobalt-based layered perovskites active layer covers on strontium doping cobalt barium ferrite or strontium doping ferro-cobalt acid lanthanum basalis, and strontium doping cobalt-based layered perovskites active layer and strontium doping cobalt barium ferrite or strontium doping ferro-cobalt acid lanthanum basalis form novel C O 2and H 2the superlattice composite oxygen electrode of O high temperature common-battery solution; Wherein, strontium doping cobalt barium ferrite or strontium doping ferro-cobalt acid lanthanum basalis are the basalis of SOEC composite oxygen electrode, and strontium doping cobalt-based layered perovskites active layer is the active layer of SOEC composite oxygen electrode; SOEC is electrolytic tank of solid oxide, and BSCF is strontium doping cobalt barium ferrite, and LSCF is strontium doping ferro-cobalt acid lanthanum, M 2-zSrzCoO 4+ δ is strontium doping cobalt-based layered perovskites, YSZ is the zirconia of stabilized with yttrium oxide, SDC is the ceria of samarium oxide doping, GDC is the cerium oxide of gadolinium oxide doping, Ni-YSZ is the zirconia of nickel-stabilized with yttrium oxide, Ni-SDC is the ceria of nickel-samarium oxide doping, and Ni-GDC is the cerium oxide of nickel-gadolinium oxide doping.But this technology basalis used is the perovskite material containing cobalt, exist thermal structure stability and chemical stability poor, thermal coefficient of expansion is larger, its thermal coefficient of expansion does not mate with dielectric substrate YSZ, SDC and GDC used, the high temperature problems such as easily occurring the hydraulic performance decline that occurs because of structural change and delamination splitting that works long hours.
Summary of the invention
The present invention is directed to prior art above shortcomings, propose a kind of non-cobalt intermediate temperature solid oxide fuel cell and stablize cathode material and application thereof, can solve at present conventional intermediate temperature solid oxide fuel cell containing cobalt and non-cobalt cathode material LnSCF in high-temperature stability, hydrogen reduction catalytic activity, the deficiency that is difficult to simultaneously meet the anticathode requirement of IT-SOFC of the aspect such as conductivity and thermal expansivity, provide a kind of intermediate temperature solid oxide fuel cell non-cobalt cathode material, make it in middle low temperature range, there is higher stability simultaneously, good hydrogen reduction catalytic activity and preferably electronic conductivity.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of non-cobalt intermediate temperature solid oxide fuel cell and stablize cathode material, its molecular formula is (Nd 1-xsr x) a(Fe 1- ycu y) bo 3-δ, wherein: 0.01<x<1,0.01<y<1,0.8<a/b<1.2 ,-0.5< δ <0.5.
The present invention relates to the preparation method of above-mentioned material, by sol-gal process at Sr xfe yo 3a position mix Nd, B mixes Cu in position, prepares (Nd after heat-agglomerating 1-xsr x) a(Fe 1- ycu y) bo 3-δpowder.
Described at Sr xfe yo 3a position mix Nd, B mixes position Cu and refers to:
By Nd (NO 3) 36H 2o, Sr (NO 3) 2, Fe (NO 3) 39H 2o and Cu (NO 3) 23H 2o is dissolved in the mixed solution of ethylenediamine tetra-acetic acid (EDTA) and ammoniacal liquor, then adds citric acid abundant reaction to generating jello.
The mol ratio of described EDTA, citric acid and total metal ion is 1:1.5:1, wherein: total metal ion refers to Nd 3+, Sr 2+, Fe 3+and Cu 2+ion.
Described abundant reaction refers to: by adding ammoniacal liquor to regulate the pH value of reaction system to 5-8, and reaction is to the colloidal sol that forms homogeneous transparent under 50-90 ℃ of heating environment, and then further concentration obtains the jello of thickness.
Described heat-agglomerating refers to: jello is obtained to fluffy presoma 200-500 ℃ of heat treatment, (the Nd that presoma is got final product requiredly 600-1000 ℃ of roasting 1-xsr x) a(Fe 1- ycu y) bo 3-δpowder.
Said method replaces Co to be incorporated into B position by a small amount of Cu, has reduced the material structure causing because of Co vaporization at high temperature and reduction and has changed, and can effectively improve the stability of negative electrode.The common existence of A position Nd makes the crystal structure of material be stable Emission in Cubic, has further increased its stability.And due to Cu variable valency, make material on the basis of stability increase, and still can there is more oxygen vacancies, therefore there is good cathodic oxygen reduction catalytic performance.These features, make NSFCu become potential a kind of SOFC cathode material above.
The present invention relates to the application of above-mentioned cathode material, use it for and prepare composite cathode material, concrete passing through (Nd 1-xsr x) a(Fe 1- ycu y) bo 3-δpowder with as electrolytical Ce 1-xsm xo 2-δor Ce (SDC) 1-xgd xo 2-δ(GDC) obtain after fully mixing according to the ratio ball milling 1-24h of mass ratio 1:0.1～1:4.
The present invention relates to composite cathode material NSFCu-SDC and NSFCu-GDC that said method prepares.
The present invention relates to a kind of application based on above-mentioned composite cathode material, use it for and prepare the symmetrical battery of negative electrode and monocell.
The composite construction of the described symmetrical battery of negative electrode is Nd xsr 1-xfe 0.8cu 0.2o 3-δ(0.3≤x≤0.7)/SDC/Nd xsr 1-xfe 0.8cu 0.2o 3-δ, 0.3≤x≤0.7 wherein.
The symmetrical battery of described negative electrode prepares in the following manner: by the SDC(preparing with dry pressing or GDC) electrolyte sheet high temperature sintering 1-20h at 1300-1500 ℃ obtains fine and close electrolyte sheet, then by arbitrary in NSFCu powder, NSFCu-SDC or NSFCu-GDC, adopts brushing or spraying or silk screen printing to SDC(or GDC after being made into cathode slurry with organic substance) electrolyte sheet both sides obtain.
Described monocell prepares in the following manner: will with common platen press, make anode-supported, take NiO-SDC or NiO-GDC as anode, SDC(or GDC) as electrolytical cell piece, at 1300-1500 ℃, sintering 5-10h is to form fine and close electrolytic thin-membrane; Then after arbitrary in NSFCu powder, NSFCu-SDC or NSFCu-GDC and organic substance being made into cathode slurry, adopt spraying, silk screen printing or brushing to described electrolytic thin-membrane, at 900-1100 ℃ of sintering 1-10h, obtain monocell.
Described anode is by quality, than scope, to be respectively the NiO of (35%, 100%) and the SDC of (0,65%) or the mixing of GDC ball milling to make.
The fuel cell preparing in the present invention is by being used hydrogen to test its I-V curve for fuel gas, and the air of cathode terminal static state is as oxidant, and electric current and voltage data that the digital instrument of controlling by computer is measured battery obtain.Adopt mass flowmenter to control the flow velocity of fuel gas (hydrogen), adopt elargol as encapsulant and collected current.
Technique effect
With comparing containing the perovskite cathode material of cobalt and the non-cobalt cathode material of other cupric of commonly using at present, the advantage of this material is: at high temperature there is good structure and thermal reduction stability, and low with the reactivity of Cr in battery connecting structure; (maximum is greater than 100Scm in 600-800 ℃ of temperature range, to show good conductivity -1); Good hydrogen reduction catalytic performance, the electrochemical impedance during as 700 ℃ is 0.071 Ω cm -2; And between electrolyte, having good chemical compatibility and thermal expansion matching, is a kind of stable, well behaved intermediate temperature solid oxide fuel cell (IT-SOFC) cathode material.
Accompanying drawing explanation
Fig. 1 is the Nd obtaining through 1000 ℃ of roastings 1-xsr xfe 0.8cu 0.2o 3-δthe XRD collection of illustrative plates of powder.
Fig. 2 is Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δthe battery cross section collection of illustrative plates of symmetrical battery.
Fig. 3 is configured as Ni-SDC/SDC/Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δthe curve of output of full battery under different temperatures.
Fig. 4 is Nd 0.4sr 0.6fe 0.8cu 0.2o 3-δconductivity variations collection of illustrative plates in the time of 25-900 ℃.
Fig. 5 Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δ-SDC(1:1) composite cathode powder mixes the XRD collection of illustrative plates of the negative electrode after 1200 ℃ of roasting 3h.
Fig. 6 Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δ-GDC(1:1) composite cathode powder mixes the XRD collection of illustrative plates of the negative electrode after 1200 ℃ of roasting 3h.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
0.1mol Nd xsr 1-xfe 0.8cu 0.2o 3-δsynthetic, the structured testing of (0.3≤x≤0.7) and cathode performance test thereof.
First the EDTA of 58.4484g is dissolved in 100mL ammoniacal liquor to the Nd (NO then taking respectively according to stoichiometric proportion 3) 36H 2o powder (13.152-30.688g), Sr (NO 3) 2powder 10.5815g, Fe (NO 3) 39H 2o powder 32.32g and Cu (NO 3) 23H 2o powder 4.832g, be dissolved in the EDTA solution having prepared, and then add the citric acid of 57.6370g, the mol ratio of EDTA, citric acid and total metal ion is 1:1.5:1, and then the pH value that adds ammoniacal liquor regulator solution is 6-10, be heated to the colloidal sol that forms homogeneous transparent at 50-100 ℃, further extend heating time until moisture evaporation, obtain the jello of thickness, jello is obtained to fluffy presoma 200-400 ℃ of heat treatment, the Nd that presoma is got final product requiredly 900-1200 ℃ of roasting 0.5sr 0.5fe 0.8cu 0.2o 3-δpowder.
As shown in Figure 1, be Nd xsr 1-xfe 0.8cu 0.2o 3-δthe XRD collection of illustrative plates of (0.3≤x≤0.7), it is perovskite structure as seen.
SDC electrolyte sheet high temperature sintering 5h at 1500 ℃ with dry pressing compacting, obtains fine and close electrolyte, then by Nd xsr 1-xfe 0.8cu 0.2o 3-δ(0.3≤x≤0.7) powder and organic substance adopt silk screen printing to SDC electrolyte sheet both sides after being made into cathode slurry, obtain being configured as Nd xsr 1-xfe 0.8cu 0.2o 3-δ(0.3≤x≤0.7)/SDC/Nd xsr 1-xfe 0.8cu 0.2o 3-δthe symmetrical battery of negative electrode of (0.3≤x≤0.7), as shown in Figure 2, the digital instrument of controlling by computer records the ac impedance spectroscopy in the time of 700 ℃, Nd in battery cross section 0.5sr 0.5fe 0.8cu 0.2o 3-δplane of polarization resistance be only 0.071 Ω cm -2, the catalytic capability of oxygen reduction is very strong.
With the preparation of common platen press, take the cell piece that SDC is electrolytical anode-supported, anode is to be mixed and made by 60%NiO and 40%SDC ball milling.The electrolyte of anode-supported at 1400 ℃ sintering 5h to form fine and close electrolytic thin-membrane.Then by Nd xsr 1-xfe 0.8cu 0.2o 3-δ(0.3≤x≤0.7) powder and organic substance adopt silk screen printing to SDC dielectric substrate after being made into cathode slurry, at 1000 ℃ of sintering 2h, obtain the Nd of porous xsr 1-xfe 0.8cu 0.2o 3-δ(0.3≤x≤0.7) cathode layer.
The I-V curve test of fuel cell is with moistening hydrogen (～3%H 2o) be fuel gas, the air of cathode terminal static state is as oxidant, and electric current and voltage data that the digital instrument of controlling by computer is measured battery obtain.The flow velocity that adopts mass flowmenter to control wet hydrogen is 80mLmin-1, adopts elargol as encapsulant and collected current, and the cell I-V recording as shown in Figure 3.In the time of visible 800 ℃, peak power has reached 900mWcm -2, this illustrates Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δit is a kind of very potential SOFC cathode material.
With hydraulic press by Nd xsr 1-xfe 0.8cu 0.2o 3-δ(0.3≤x≤0.7) powder is pressed into bar under 100-300Mpa, is placed in Muffle furnace 1000-1200 ℃ of roasting 5-10h, and the fine and close bar of gained records the conductivity of (25-900 ℃) under different temperatures by four probe method, as shown in Figure 4.
Embodiment 2
The Nd of 0.05mol 0.3sr 0.7fe 0.8cu 0.2o 3-δsynthetic, structured testing.
The EDTA of 29.2242g is dissolved in 80mL ammoniacal liquor to the Nd (NO then taking respectively according to stoichiometric proportion 3) 36H 2o powder 6.576g, Sr (NO 3) 2powder 7.408g, Fe (NO 3) 39H 2o powder 16.16g and Cu (NO 3) 23H 2o powder 2.416g, be dissolved in the EDTA solution having prepared, and then add the citric acid of 28.8185g, the mol ratio of EDTA, citric acid and total metal ion is 1:1.5:1, and then to add the pH value of ammoniacal liquor regulator solution be 7, is heated to the colloidal sol at 80 ℃ of formation homogeneous transparents, further extend heating time until moisture evaporation, obtain the jello of thickness, jello is obtained to fluffy powder presoma, the Nd that presoma is got final product requiredly 1000 ℃ of roastings 250 ℃ of heat treatments 0.3sr 0.7fe 0.8cu 0.2o 3-δpowder.Fig. 5 is Nd 0.3sr 0.7fe 0.8cu 0.2o 3-δxRD collection of illustrative plates, it is perovskite structure as seen.
Embodiment 3
The Nd of 0.05mol 0.7sr 0.3fe 0.8cu 0.2o 3-δsynthetic, structured testing.
The EDTA of 29.2242g is dissolved in 80mL ammoniacal liquor to the Nd (NO then taking respectively according to stoichiometric proportion 3) 36H 2o powder 15.344g, Sr (NO 3) 2powder 3.175g, Fe (NO 3) 39H 2o powder 16.16g and Cu (NO 3) 23H 2o powder 2.416g, be dissolved in the EDTA solution having prepared, and then add the citric acid of 28.8185g, the mol ratio of EDTA, citric acid and total metal ion is 1:1.5:1, and then to add the pH value of ammoniacal liquor regulator solution be 8, is heated to the colloidal sol at 80 ℃ of formation homogeneous transparents, further extend heating time until moisture evaporation, obtain the jello of thickness, jello is obtained to fluffy powder presoma, the Nd that presoma is got final product requiredly 1000 ℃ of roastings 250 ℃ of heat treatments 0.7sr 0.3fe 0.8cu 0.2o 3-δpowder.Fig. 6 is Nd 0.7sr 0.3fe 0.8cu 0.2o 3-δxRD collection of illustrative plates, it is perovskite structure as seen.
Embodiment 4
Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δthe test of the synthetic and chemical compatibility of-SDC composite cathode.
Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δthe preparation process of powder is identical with embodiment mono-.By synthetic Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δpowder obtains composite cathode material after fully mixing according to the ratio ball milling 20h of mass ratio 1:1 with SDC.In order to characterize Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δwith the chemical compatibility of SDC powder, by mixed powder, at 1200 ℃ of roasting 3h and carry out XRD sign, result as shown in Figure 7.Visible powder after baking mixed is still Pr 0.5sr 0.5fe 0.8cu 0.2o 3-δwith SDC powder mixture, the appearance of no third phase impurity peaks, shows Nd 0.5sr 0.5fe 0.8cu 0.2o 3-δthere is good chemical compatibility with SDC electrolyte.
Embodiment 5
Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δthe test of the synthetic and chemical compatibility of-GDC composite cathode.
Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δthe preparation process of powder is identical with embodiment tri-.By synthetic Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δpowder obtains composite cathode material after fully mixing according to the ratio ball milling 10h of mass ratio 1:1 with GDC.In order to characterize Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δwith the chemical compatibility of GDC powder, by mixed powder, at 1200 ℃ of roasting 3h and carry out XRD sign, result as shown in Figure 8.Visible powder after baking mixed is still Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δwith GDC powder mixture, the appearance of no third phase impurity peaks, shows Nd 0.6sr 0.4fe 0.8cu 0.2o 3-δthere is good chemical compatibility with GDC electrolyte.

Claims (13)

1. non-cobalt intermediate temperature solid oxide fuel cell is stablized a cathode material, it is characterized in that, its molecular formula is (Nd 1-xsr x) a(Fe 1- ycu y) bo 3-δ, wherein: 0.01<x<1,0.01<y<1,0.8<a/b<1.2 ,-0.5< δ <0.5.
2. cathode material according to claim 1, is characterized in that, y=0.2.
3. cathode material according to claim 1 and 2, is characterized in that, 0.3<x<0.7, a=b=1 ,-0.3< δ <0.3.
4. according to a preparation method for arbitrary described cathode material in claim 1-3, it is characterized in that, by sol-gal process at Sr xfe yo 3a position mix Nd, B mixes Cu in position, prepares (Nd after heat-agglomerating 1-xsr x) a(Fe 1- ycu y) bo 3-δpowder.
5. method according to claim 4, is characterized in that, described at Sr xfe yo 3a position mix Nd, B mixes position Cu and refers to: by Nd (NO 3) 36H 2o, Sr (NO 3) 2, Fe (NO 3) 39H 2o and Cu (NO 3) 23H 2o is dissolved in ethylenediamine tetra-acetic acid and containing in the mixed solution of tax, then adds citric acid abundant reaction to generating jello.
6. method according to claim 5, is characterized in that, the mol ratio of described EDTA, citric acid and total metal ion is 1:1.5:1.
7. a composite cathode material, is characterized in that, its molecular formula is NSFCu-MDC, M=Sm, Gd; Cerium oxide base electrolyte is wherein the cerium oxide of doping, and its molecular formula is M 1-xsm xo 2-δ, 0.01<x<0.4.
8. a preparation method for composite cathode material according to claim 7, is characterized in that, by by (Nd 1-xsr x) a(Fe 1- ycu y) bo 3-δpowder with as electrolytical Ce 1-xsm xo 2-δor Ce (SDC) 1-xgd xo 2-δ(GDC) obtain after fully mixing according to the ratio ball milling 1-24h of mass ratio 1:0.1～1:4.
9. composite cathode material NSFCu-SDC and the NSFCu-GDC that method prepares according to claim 7.
10. an application for the composite cathode material based in arbitrary in claim 7-9, is characterized in that, uses it for and prepares the symmetrical battery of negative electrode;
The composite construction of the described symmetrical battery of negative electrode is Nd xsr 1-xfe 0.8cu 0.2o 3-δ(0.3≤x≤0.7)/SDC/Nd xsr 1-xfe 0.8cu 0.2o 3-δ, 0.3≤x≤0.7 wherein.
11. application according to claim 10, it is characterized in that, the symmetrical battery of described negative electrode prepares in the following manner: by the SDC preparing with dry pressing or GDC electrolyte sheet, high temperature sintering 1-20h at 1300-1500 ℃ obtains fine and close electrolyte sheet, then arbitrary and organic substance in NSFCu powder, NSFCu-SDC or NSFCu-GDC is made into and adopts after cathode slurry brushing or spraying or silk screen printing to obtain to SDC or GDC electrolyte sheet both sides.
The application of 12. 1 kinds of composite cathode materials based in arbitrary in claim 7-9, is characterized in that, uses it for and prepares monocell; Described monocell prepares in the following manner: by make anode-supported with common platen press, using SDC or GDC as electrolytical cell piece, at 1300-1500 ℃, sintering 5-10h is to form fine and close electrolytic thin-membrane; Then after arbitrary in NSFCu powder, NSFCu-SDC or NSFCu-GDC and organic substance being made into cathode slurry, adopt spraying or silk screen printing to described electrolytic thin-membrane, at 900-1100 ℃ of sintering 1-10h, obtain monocell.
13. application according to claim 12, is characterized in that, described anode is by quality, than scope, to be respectively the NiO of (35%, 100%) and the SDC of (0,65%) or the mixing of GDC ball milling to make.
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Publication number Priority date Publication date Assignee Title
CN105576251A (en) * 2016-02-03 2016-05-11 上海交通大学 SSOFC electrode material and composite electrode material thereof
CN109437882A (en) * 2018-11-26 2019-03-08 北京科技大学 Adulterate the BaFeO of La element and Cu element3-δBase ceramic oxygen-permeable membrane material and preparation method thereof
CN109437882B (en) * 2018-11-26 2020-11-27 北京科技大学 BaFeO doped with La element and Cu element3-Ceramic-based oxygen-permeable membrane material and preparation method thereof
CN111129517A (en) * 2019-12-30 2020-05-08 黑龙江大学 Preparation method of Ruddlesden-Popper layered structure iron-based cathode catalyst
CN113410477A (en) * 2021-06-09 2021-09-17 长春师范大学 Preparation method of cathode material of intermediate-temperature solid oxide fuel cell
CN113809343A (en) * 2021-09-17 2021-12-17 中国科学技术大学 Carbon dioxide resistant solid oxide fuel cell cathode material and preparation method thereof
CN113871637A (en) * 2021-10-12 2021-12-31 国网江苏省电力有限公司常州供电分公司 High-performance solid oxide fuel cell cathode material and preparation method thereof
CN117080468A (en) * 2023-08-11 2023-11-17 渤海大学 Self-assembled two-phase heterostructure solid oxide fuel cell composite cathode material and preparation method and application thereof

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