CN101359739A - Cathode material for solid-oxide fuel cell and method for preparing the same - Google Patents
Cathode material for solid-oxide fuel cell and method for preparing the same Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 32
- 239000000446 fuel Substances 0.000 title claims abstract description 19
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- 239000000463 material Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
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- 238000005507 spraying Methods 0.000 claims abstract description 7
- 238000007650 screen-printing Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 15
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- 238000006555 catalytic reaction Methods 0.000 claims description 12
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- 238000003756 stirring Methods 0.000 claims description 9
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000006257 cathode slurry Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
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- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
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- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
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- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract description 26
- 239000004471 Glycine Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 12
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Images
Classifications
-
- 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 relates to a solid oxide fuel battery cathode material and a preparation method thereof. The chemical formula of the material is MxA(1-x)M`yB(1-y)O(3-Delta). The material is prepared by adopting an EDTA-citrate combination and complexation method or a glycine combustion method. The cathode material can be smeared onto the electrolyte surface by screen printing, spraying, dip coating or flow casting, and then calcined at high temperatures to obtain a cathode catalyst layer. The catalyst layer is in the working state, that is, the negative current passes through the electrode, so that the precious metal oxides can obtain electrons to take the reduction reaction, emerge out of the lattice of the perovskite or perovskite-like ceramic material to enrich on the surface of the material and to form the precious metal-ceramic composite cathode. The precious metals can be re-oxidized and enter the ceramic oxide lattice when the positive current passes through the electrode.
Description
Technical field
The invention belongs to novel energy, materials processing and power domain, be specifically related to a kind of cathode material for solid-oxide fuel cell and preparation method thereof.
Background technology
The energy is the basis of economic development, does not have the development of energy industry just not have modern civilization.Human in order more effectively to utilize the energy carrying out unremitting effort always.Utilize the mode of the energy that revolutionary change was arranged repeatedly in history, from original steam engine to steam turbine, high-pressure turbine, internal combustion engine, gas turbine, the change of energy utilization patterns has each time all greatly advanced the development of modern civilization.Along with the development of modern civilization, people recognize that gradually traditional energy utilization patterns have two big disadvantages.The one, be stored in and just can be transformed into mechanical or electrical energy after chemical energy in the fuel must at first be transformed into heat energy, be subjected to the restriction of Carnot cycle and modern material, have only 33～35% in the efficient that the machine end is obtained, energy over half has lost in vain; The 2nd, traditional energy utilization patterns give today the mankind living environment caused the pollution of waste water,waste gas and industrial residue, used heat and the noise of flood tide.For power industry, though the technology that adopts is in upgrading constantly, as superhigh pressure, overcritical, ultra supercritical unit have been developed, fluid-bed combustion and Integrated gasification combined cycle generation technology have been developed, but the result of this effort is: unit is huge, superhigh pressure long distance power transmission, investment rise, still have only about 35% to user's comprehensive energy efficient, the large-scale pollution still do not solved at all.People are striving to find existing higher efficiency of energy utilization energy utilization patterns free from environmental pollution again always for many years.
1), problems such as no material corrosion and electrolyte corrosion Solid Oxide Fuel Cell adopts soild oxide as electrolyte, and except efficiently, outside the eco-friendly characteristics, it also has the not available advantage of other fuel cell:; 2), battery is discharged under high working temperature high-quality waste heat can make full use of, and its overall efficiency can be brought up to more than 70% by 50%.When operating temperature during greater than 850 ℃, the tail gas of battery can combine with hot machine (Gas Turbine) and waste heat be fully utilized, this moment, the total energy approach rate of fuel cell can be up to more than 80%, so high temperature solid oxide fuel cell is fit to be applied in MW level power large-scale electric generating station; 3), its fuel is applied widely, fuel can not only be used H
2, also can directly use CO, natural gas (methane), coal boil-off gas, hydrocarbon, NH
3, H
2S etc. make fuel.
But the operating temperature of traditional SOFC is up to 1000 ℃.So high operating temperature can guarantee that sufficiently high oxygen ionic conductivity of electrolyte and negative electrode have good catalytic activity to oxygen, yet also introduced a series of problem: the sintering that promotes porous electrode, thereby the interface phase reaction between accelerating electrode and the electrolyte has increased the interfacial polarization resistance of battery greatly, simultaneously the sealing of battery and the auxiliary device of bipolar plate material and battery has been proposed harsh requirement.The operating temperature reduction that generally believes at present fuel cell in the world is that decision SOFC is able to key in application in practice.When the operating temperature of fuel cell is reduced to below 800 ℃, just can adopt metal connector, thereby reduce the material cost of battery greatly, reduced the phase reaction speed between the battery component simultaneously, battery component thermal coefficient of expansion difference also diminishes to the influence of stability test simultaneously, makes sealing become easy.
Yet along with the reduction of temperature, electrolyte Ohmic resistance and the electrode polarization resistance of the SOFC that conventional electrolysis matter supports sharply increase, and cause the power density of battery to descend fast.In order to guarantee also to have at low temperatures high power density, the cathode material that has high activity hypopolarization resistance at low temperatures of development of new necessitates.Because the activation of oxygen is a comparatively process of difficulty, development of new low temperature high activity cathode material has become the focus of research.What research was maximum at present is the perovskite type ceramic material, uses this class not only can reduce cost and also can prolong the useful life of negative electrode.The a spot of noble metal of adding such as Pt, Pd etc. can further improve the catalytic performance of negative electrode to oxygen reduction in this class material.But the high-temperature operation meeting makes the noble metal granule sintering for a long time, causes the polarization resistance of negative electrode to rise rapidly.Therefore the stability that how to improve noble metal catalyst is for key very in the useful life that prolongs fuel cell.
Summary of the invention:
The objective of the invention is in order to improve the oxygen catalytic reduction activity and the stability of negative electrode noble metal catalyst, and provide a kind of cathode material for solid-oxide fuel cell that can " breathe ", another object of the present invention provides the preparation method of above-mentioned material, and the present invention also provides the cathode catalysis layer that contains above-mentioned material.Technical scheme of the present invention is: a kind of cathode material of Solid Oxide Fuel Cell, the chemical formula that it is characterized in that described material is M
xA
1-xM '
yB
1-yO
3-δ
Wherein M and M ' are selected from one or both the combination of arbitrary proportion among Ag, Pt, Pd, Ru and the Rh, and M is different elements with M ';
A is at least a kind of among La, Sm, Gd, Ce, Nd, Pr, Dy, Er, Ba, Sr, Ca, Bi, Y, the Yb;
B is at least a kind of among Mn, Cr, Fe, Co, Ni, Cu, Sc, Nb, Sb, Mo, V, Ti, Zn, Zr, Ce, Y, Pb, the Al;
0≤x≤0.5,0≤y≤0.5,0≤δ≤0.7, x and y are not 0 simultaneously, δ is an oxygen vacancies concentration.
The preferred M of the present invention is Ag or Pd; M ' is one or both the combination of arbitrary proportion among Pt, Pd, Ru and the Rh.
Preferred 0≤x≤0.2,0≤y≤0.2,0≤δ≤0.5, x and y are not 0 simultaneously.
Cathode material of the present invention is by the preparation of EDTA-citric acid associating complexometry.The metering of product chemical formula according to target is dissolved in the deionized water than with metallic salt, the EDTA-ammonia spirit is added in the above-mentioned solution, add citric acid again, be made into precursor aqueous solution, wherein the mol ratio of metal ion, EDTA, citric acid and ammoniacal liquor is 0.01～0.1: 0.01～0.1: 0.02～0.2: 1; The precursor aqueous solution that stirs after clarifying is placed air dry oven, behind 100～250 ℃ of down dry 1～8h, obtaining solid precursor; Solid precursor is put into Muffle furnace, obtain cathode powder at 700～1000 ℃ of following roasting 1～10h.
Cathode material of the present invention also can be by the preparation of glycine firing method.The metering of product chemical formula according to target is dissolved in the deionized water than with the metallic salt of certain mass, be made into mixed solution, the mol ratio that accounts for glycine according to metal ion is an amount of glycine of 25%～50% adding, on 60～150 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to cause spontaneous combustion down then, promptly obtain cathode powder at 150～350 ℃.
Described metallic salt is for containing Ag, Pt, La, Sm, Gd, Ce, Nd, Pr, Dy, Er, Ba, Sr, Ca, Bi, Y, Yb, Fe, Co, Ni, Cu, Zn, Zr, Pb or Al nitrate, the oxalates that contains Mn, Sc or Nb, contain Mn, Sb or Sc acetate, contain the villaumite of Pd, Pt, Ru, Rh, Ti, V or Mo.
The present invention also provides the cathode catalysis layer that contains above-mentioned cathode material, it is characterized in that in cathode powder and organic pore-forming agents adding organic solvent, being uniformly dispersed and make the organic substance suspension that contains cathode powder, make cathode slurry by grinding, wherein milling time is 0.5～3.0 hour; Cathode slurry is applied to bath surface by silk screen printing, spraying, dip coated or curtain coating means, makes cathode catalysis layer again after 900～1150 ℃ of following roastings.
Organic pore-forming agents is preferably selected for use in starch, glycerine, polyvinyl alcohol, polyvinyl butyral resin, ethyl cellulose or various material with carbon elements etc.; Organic solvent is preferably selected for use in ethylene glycol, isopropyl alcohol, acetone, ethanol or methyl alcohol etc.; The mass ratio that organic pore-forming agents is occupied the machine solvent is 5%～50%, and the mass ratio of cathode material and organic solvent is 2～25%.
Above-mentioned negative electrode (cathode catalysis layer) is down that negative current is when passing through electrode in working order, metal oxide containing precious metals will obtain electronics generation reduction reaction, from the lattice of perovskite or perovskite-like ceramic material, come out to be enriched to the surface of material, form noble metal-Ceramic Composite negative electrode.This noble metal granule is owing to discharge from lattice, so grain diameter is very little, between tens nanometer, so the catalytic activity of this noble metal catalyst will be very high several.Through long-time operation, sintering may take place this noble metal catalyst particle descends cathode performance, can find fall by instrument monitoring, when range of decrease degree reaches certain particular range instantly, the method that can take to add positive current makes noble metal be forced to oxidation again and enters catalyst crystal lattice, after the answer by the short time, return to normal operating conditions again, noble metal catalyst will regenerate, and this moment, catalytic activity was also recovered simultaneously.Therefore we are called the reduction and the oxidizing process of the noble metal catalyst in this cathode material " breathing ".
Beneficial effect:
By the method that enters the perovskite negative electrode that precious metal element is mixed noble metal is dispersed in the whole negative electrode uniformly.Force reduction to become metallic particles precious metal ion by negative current subsequently, the metallic particles of this moment only is several between tens nanometer, and is therefore very high to the oxygen reduction catalytic activity.Increase along with the electrode operating time, noble metal catalyst may be grown up by sintering, this moment, we can make that noble metal granule is oxidized again to be entered among the perovskite oxide lattice by the method that adds positive current, and then add negative current nano-noble metal catalyst is lived again, reciprocal like this operation can increase the stability of noble metal catalyst greatly, thereby prolong the useful life of electrode, reduce the use cost of fuel cell.
Description of drawings:
Fig. 1 is La after the different temperatures roasting
0.76Sr
0.19Ag
0.05MnO
3-δThe X ray diffracting spectrum of cathode material.
Fig. 2 is La
0.76Sr
0.19Ag
0.05MnO
3-δCathode catalysis layer is with the variation of negative current utmost point time impedance.
Fig. 3 is La
0.76Sr
0.19Ag
0.05MnO
3-δThe temperature variant curve of the interface resistance of cathode catalysis layer.
Fig. 4 is La
0.76Sr
0.19Ag
0.05MnO
3-δCathode catalysis layer is at the polarization curve of different temperatures.
Fig. 5 is La
0.76Sr
0.19Ag
0.05MnO
3-δThe long-time stability test result of cathode catalysis layer.
Fig. 6 is LaCo
0.38Fe
0.57Pd
0.05O
3-δThe X ray diffracting spectrum of cathode material.
Fig. 7 is LaCo
0.38Fe
0.57Pd
0.05O
3-δCathode catalysis layer is in negative current polarization front and back, the variation of cathode impedance.
Embodiment
Embodiment 1:
La
0.76Sr
0.19Ag
0.05MnO
3-δThe preparation of cathode material and application.
La
0.76Sr
0.19Ag
0.05MnO
3-δSynthetic by EDTA-citric acid associating complexometry, this synthetic method belongs to sol-gel process.With Sr (NO
3)
2, La (NO
3)
3, AgNO
3And Mn (CH
3COO)
2Be dissolved in deionized water in proportion, be made into mixed solution, according to metal ion: EDTA: citric acid: the mol ratio of ammoniacal liquor is 0.1: 0.1: 0.2: 1 adds an amount of EDTA-ammonia spirit and citric acid, on 80 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to obtain solid precursor behind the dry 8h down at 250 ℃ then, solid precursor at high temperature obtains La behind the roasting 5h
0.76Sr
0.19Ag
0.05MnO
3-δCathode powder.Fig. 1 is the X ray diffracting spectrum of this cathode material after the different temperatures roasting.During greater than 800 ℃, this cathode material can form at sintering temperature for result proof.
By high-energy ball milling with 5g La
0.76Sr
0.19Ag
0.05MnO
3-δPowder, 10g ethylene glycol, 40g isopropyl alcohol and 10g starch (organic pore-forming agents) add in the ball grinder, and ball milling 2h makes cathode slurry under the 500rpm rotating speed.The secondary cathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of anode-supported by the excusing from death sprayer, anode dry body body must be placed on the heating station in spraying process, and temperature is 250 ℃, carrier gas is a nitrogen, flow is 30mL/min, and gas pressure is 1.0atm, spray time 10s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1100 ℃, and heating rate is 5 ℃/min, temperature retention time 3h.Obtain monocell after the heat treatment.
Cathode impedance obtains by the Solartron1260+1287 test.Fig. 2 is the variation of cathode impedance after the polarization of different time negative current.Along with the lengthening of polarization time, the cathode interface resistance decreasing only is 0.139 Ω cm after the polarization
2, this explanation Ag comes out from perovskite crystalline lattice, and catalytic performance is improved.Fig. 3 is the temperature variant curve of the interface resistance of this negative electrode.Negative electrode cross section resistance only is 0.237 Ω cm in the time of 750 ℃
2, activation energy also has only 98.4kJ/mol.Fig. 4 is the polarization curve in different temperatures of this negative electrode, at polarization current is-1.33mA/cm
2The time, the negative electrode overpotential only is-0.22V.
Fig. 5 is the long-time stability test result of this negative electrode.At polarization current be-600mA/cm
2, cathodic polarization resistance does not have significant change behind 750 ℃ of following operation 1300min, and the stable operation for a long time of this electrode is described.
Embodiment 2:
LaCo
0.38Fe
0.57Pd
0.05O
3-δThe preparation of cathode material and application.
LaCo
0.38Fe
0.57Pd
0.05O
3-δSynthetic by the glycine firing method, this synthetic method belongs to auto-combustion method.With La (NO
3)
3, Co (NO
3)
2And PdCl
2Be dissolved in deionized water in proportion, be made into mixed solution, according to metal ion: the mol ratio of glycine is to add an amount of glycine at 1: 2, on 80 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to cause spontaneous combustion down then, obtain LaCo at 250 ℃
0.38Fe
0.57Pd
0.05O
3-δCathode powder.Fig. 6 is the X ray diffracting spectrum of this cathode material of making behind 800 ℃ of roasting 5h.Result's proof this cathode material after spontaneous combustion can form.
By high-energy ball milling with 5g LaCo
0.38Fe
0.57Pd
0.05O
3-δPowder, 10g ethylene glycol, 40g isopropyl alcohol and 10g glycerine add in the ball grinder, and ball milling 2h makes cathode slurry under the 500rpm rotating speed.By silk screen printing with LaCo
0.38Fe
0.57Pd
0.05O
3-δCathode slurry is sprayed on the dielectric substrate of electrolyte duplicature of anode-supported, and anode dry body body must be placed on the heating station in spraying process, and temperature is 250 ℃, and carrier gas is a nitrogen, and flow is 30mL/min, and gas pressure is 1.0atm, spray time 10s.The negative electrode that spraying is good | electrolyte | the anode trilamellar membrane places high-temperature electric resistance furnace heat treatment, and treatment temperature is 1000 ℃, and heating rate is 5 ℃/min, temperature retention time 2h.Obtain monocell after the heat treatment.
Cathode impedance obtains by the Solatron1260+1287 test.Fig. 7 is before and after the negative current polarization, the variation of cathode impedance.The preceding negative electrode polarization resistance of polarization is 0.3 Ω cm in the time of 800 ℃
2, only be 0.2 Ω cm after the polarization
2, this explanation Pd comes out from perovskite crystalline lattice, has played good catalytic effect.
Embodiment 3:
La
0.4Ca
0.4Ag
0.15Pd
0.05V
0.3Co
0.7O
3-δThe preparation of cathode material.
La
0.4Ca
0.4Ag
0.15Pd
0.05V
0.3Co
0.7O
3-δSynthetic by EDTA-citric acid associating complexometry, this synthetic method belongs to sol-gel process.With La (NO
3)
3, Ca (NO
3)
2, AgNO
3, Co (NO
3)
2, PdCl
2And VCl
3Be dissolved in deionized water in proportion, be made into mixed solution, according to metal ion: EDTA: citric acid: the mol ratio of ammoniacal liquor is 0.05: 0.05: 0.1: 1 adds an amount of EDTA-ammonia spirit and citric acid, on 100 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to obtain solid precursor behind the dry 5h down at 300 ℃ then, solid precursor at high temperature obtains La behind the roasting 8h
0.4Ca
0.4Ag
0.15Pd
0.05V
0.3Co
0.7O
3-δCathode powder.
Embodiment 4:
Sm
0.5Sr
0.5Fe
0.7Sc
0.1Pd
0.1Pt
0.1O
3-δThe preparation of cathode material
Sm
0.5Sr
0.5Fe
0.7Sc
0.1Pd
0.1Pt
0.1O
3-δSynthetic by EDTA-citric acid associating complexometry, this synthetic method belongs to sol-gel process.With Sm (NO
3)
3, Sr (NO
3)
2, Fe (NO
3)
3, Sc
2(C
2O
4)
3, PdCl
2And PtCl
4Be dissolved in deionized water in proportion, be made into mixed solution, according to metal ion: EDTA: citric acid: the mol ratio of ammoniacal liquor is 0.05: 0.1: 0.05: 1 adds an amount of EDTA-ammonia spirit and citric acid, on 80 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to obtain solid precursor behind the dry 4h down at 350 ℃ then, solid precursor at high temperature obtains Sm behind the roasting 10h
0.5Sr
0.5Fe
0.7Sc
0.1Pd
0.1Pt
0.1O
3-δCathode powder.
Embodiment 5:
La
0.25Sr
0.25Sm
0.3Pr
0.2Fe
0.6Rh
0.1Co
0.3O
3-δSynthesizing of cathode material.
La
0.25Sr
0.25Sm
0.3Pr
0.2Fe
0.6Rh
0.1Co
0.3O
3-δSynthetic by the glycine firing method, this synthetic method belongs to auto-combustion method.With La (NO
3)
3, Sr (NO
3)
2, Sm (NO
3)
3, Pr (NO
3)
3, Co (NO
3)
2, Fe (NO
3)
3And RhCl
3Be dissolved in deionized water in proportion, be made into mixed solution, according to metal ion: the mol ratio of glycine is to add an amount of glycine at 1: 3, on 80 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to cause spontaneous combustion down then, obtain La at 300 ℃
0.25Sr
0.25Sm
0.3Pr
0.2Fe
0.6Rh
0.1Co
0.3O
3-δCathode powder.
Embodiment 6:
La
0.5Sr
0.4Pd
0.1Mn
0.2Al
0.6Nb
0.1Ni
0.1O
3-δSynthesizing of cathode material.
La
0.5Sr
0.4Pd
0.1Mn
0.2Al
0.6Nb
0.1Ni
0.1O
3-δSynthetic by the glycine firing method, this synthetic method belongs to auto-combustion method.With La (NO
3)
3, Sr (NO
3)
2, PdCl
2, Mn (CH
3COO)
2, Al (NO
3)
3, Nb (HC
2O
4)
5And Ni (NO
3)
2Be dissolved in deionized water in proportion, be made into mixed solution, according to metal ion: the mol ratio of glycine is to add an amount of glycine at 1: 4, on 120 ℃ of heating stations, evaporate and remove moisture and make it to become gel stirring precursor aqueous solution after the clarification, place air dry oven to cause spontaneous combustion down then, obtain La at 350 ℃
0.5Sr
0.4Pd
0.1Mn
0.2Al
0.6Nb
0.1Ni
0.1O
3-δCathode powder.
Claims (7)
1, a kind of cathode material of Solid Oxide Fuel Cell, the chemical formula that it is characterized in that described material is M
xA
1-xM '
yB
1-yO
3-δWherein M and M ' are selected from one or both the combination of arbitrary proportion among Ag, Pt, Pd, Ru and the Rh, and M is different elements with M '; A is at least a kind of among La, Sm, Gd, Ce, Nd, Pr, Dy, Er, Ba, Sr, Ca, Bi, Y, the Yb;
B is at least a kind of among Mn, Cr, Fe, Co, Ni, Cu, Sc, Nb, Sb, Mo, V, Ti, Zn, Zr, Ce, Y, Pb, the Al; 0≤x≤0.5,0≤y≤0.5,0≤δ≤0.7, x and y are not 0 simultaneously, δ is an oxygen vacancies concentration.
2,, it is characterized in that M is Ag according to the described cathode material of claim 1; M ' is one or both the combination of arbitrary proportion among Pt, Pd, Ru and the Rh.
3, according to the described cathode material of claim 1, it is characterized in that: 0≤x≤0.2,0≤y≤0.2,0≤δ≤0.5, x and y are not 0 simultaneously.
4, a kind of preparation method of cathode material as claimed in claim 1, its concrete steps are as follows: the metering of product chemical formula according to target is dissolved in the deionized water than with metallic salt, the EDTA-ammonia spirit is added in the above-mentioned solution, add citric acid again, get precursor aqueous solution, wherein the mol ratio of metal ion, EDTA, citric acid and ammoniacal liquor is 0.01～0.1: 0.01～0.1: 0.02～0.2: 1; The precursor aqueous solution that stirs after clarifying is placed air dry oven, behind 100～250 ℃ of down dry 1～8h, obtaining solid precursor; Solid precursor is put into Muffle furnace, obtain cathode powder at 700～1000 ℃ of following roasting 1～10h.
5, preparation method according to claim 4, it is characterized in that described metallic salt is for containing Ag, Pt, La, Sm, Gd, Ce, Nd, Pr, Dy, Er, Ba, Sr, Ca, Bi, Y, Yb, Fe, Co, Ni, Cu, Zn, Zr, Pb or Al nitrate, the oxalates that contains Mn, Sc or Nb, contain Mn, Sb or Sc acetate, contain the villaumite of Pd, Pt, Ru, Rh, Ti, V or Mo.
6, a kind of cathode catalysis layer that contains the described cathode material of claim 1, it is characterized in that making the organic substance suspension that contains cathode powder with being uniformly dispersed in cathode powder and the organic pore-forming agents adding organic solvent, make cathode slurry by grinding, wherein milling time is 0.5～3.0 hour; Cathode slurry is applied to bath surface by silk screen printing, spraying, dip coated or curtain coating means, makes cathode catalysis layer again after 900～1150 ℃ of following roastings.
7, cathode catalysis layer according to claim 6 is characterized in that described organic pore-forming agents is starch, glycerine, polyvinyl alcohol, polyvinyl butyral resin, ethyl cellulose or material with carbon element; Organic solvent is ethylene glycol, isopropyl alcohol, acetone, ethanol or methyl alcohol; Wherein to occupy the mass ratio of machine solvent be 5%～50% to organic pore-forming agents, and the mass ratio of cathode material and organic solvent is 2～25%.
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