CN109382113B - Perovskite type oxide catalyst, preparation method and application thereof - Google Patents

Perovskite type oxide catalyst, preparation method and application thereof Download PDF

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CN109382113B
CN109382113B CN201811432804.3A CN201811432804A CN109382113B CN 109382113 B CN109382113 B CN 109382113B CN 201811432804 A CN201811432804 A CN 201811432804A CN 109382113 B CN109382113 B CN 109382113B
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oxide catalyst
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samarium
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CN109382113A (en
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王洲航
袁金良
苗鹤
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Ningbo University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

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Abstract

The invention discloses a perovskite type oxide catalyst, a preparation method and application thereof. The preparation method of the perovskite type oxide catalyst comprises the following steps: mixing a samarium source, a strontium source, a cobalt source, a complexing agent, a gadolinium source and a cerium source uniformly, adding a binder, and carrying out in-situ compounding on the obtained uniformly mixed reaction system to obtain a dark yellow spongy precursor; and carrying out high-temperature calcination treatment on the dark yellow sponge precursor to obtain the perovskite type oxide catalyst. The preparation method for preparing the perovskite oxide catalyst by the in-situ compounding of the samarium-doped modified strontium cobaltate and the cerium oxide-doped gadolinium oxide has the advantages that the experimental raw materials are low in cost and easy to obtain, two catalytic materials can be well combined and grown together by adopting an in-situ compounding process, the compounding preparation process is simple and feasible, the period is short, the catalytic activity is high, the catalytic performance of the obtained material is good, and the application prospect is wide.

Description

Perovskite type oxide catalyst, preparation method and application thereof
Technical Field
The invention relates to a perovskite type oxide catalyst and a preparation method thereof, in particular to a preparation method of a perovskite type oxide catalyst prepared by in-situ compounding samarium-doped modified strontium cobaltate and cerium oxide-doped gadolinium oxide and application of the catalyst in the field of catalysis, belonging to the technical field of catalyst preparation.
Background
To alleviate the problems of energy crisis, greenhouse gas emission, climate warming, environmental deterioration and the like, China is promoting the development of new energy industry. At present, the development of the new energy automobile industry is changing day by day, and the key three-electricity technology is as follows: the development of batteries, motors and electric control is the struggle of hundreds of flowers and families. However, as a power source of a new energy automobile, the development of a fuel cell is always restricted by a very slow dynamic reaction of oxygen, and at present, the composite preparation process of the fuel cell oxygen electrode catalyst is complex and tedious, has a long period and poor oxygen reduction performance, so that improvement of the composite process is urgently needed.
Disclosure of Invention
The invention mainly aims to provide an in-situ composite perovskite oxide catalyst of samarium-doped modified strontium cobaltate and cerium oxide-doped gadolinium oxide and a preparation method thereof, so as to overcome the defects in the prior art.
It is another object of the present invention to provide the use of said catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method for preparing a perovskite type oxide catalyst by in-situ compounding samarium-doped modified strontium cobaltate and cerium oxide-doped gadolinium oxide, which comprises the following steps:
mixing a samarium source, a strontium source, a cobalt source, a complexing agent, a gadolinium source and a cerium source uniformly, adding a binder, and carrying out in-situ compounding on the obtained uniformly mixed reaction system to obtain a dark yellow spongy precursor;
and carrying out high-temperature calcination treatment on the dark yellow sponge precursor to obtain the perovskite type oxide catalyst.
In some embodiments, the molar ratio of samarium source, strontium source, and cobalt source is X: (1-X): 1, wherein X is more than or equal to 0 and less than or equal to 0.5.
In some embodiments, the method of making further comprises: stirring the obtained uniformly mixed reaction system at 50-90 ℃ for 1-5 h for in-situ compounding, drying at 80-200 ℃, preferably 120-180 ℃ for 10-15 h to obtain a dark yellow spongy precursor, tabletting, and performing the high-temperature calcination treatment.
Further, the pressure used during tabletting is 150 to 250 MPa.
In some embodiments, the high-temperature calcination treatment is performed at a temperature of 800 to 1300 ℃, preferably 900 to 1250 ℃, for 5 to 15 hours.
Embodiments of the present invention also provide perovskite oxide catalysts prepared by the foregoing methods, and having a chemical formula of Sr1-xSmxCoO3GdCe, wherein X is more than or equal to 0 and less than or equal to 0.5.
Further, the perovskite-type oxide catalyst has a perovskite tetragonal structure.
Furthermore, the particles of the perovskite type oxide catalyst are uniformly distributed and are flaky, and the size of the perovskite type oxide catalyst is 30-100 mu m.
Furthermore, a plurality of small holes are distributed on the particle surface of the perovskite type oxide catalyst, and the size of each small hole is 2-10 mu m.
The embodiment of the invention also provides application of the perovskite type oxide catalyst in preparation of a fuel cell catalyst material.
Compared with the prior art, the invention has the advantages that:
the experimental raw materials of the invention have low cost and are easy to obtain, the two catalytic materials can be well combined and grown together by adopting an in-situ composite process, the composite preparation process is simple and feasible, the period is short, the catalytic activity is high, the catalytic performance of the obtained material is good, and the application prospect is wide.
Drawings
FIG. 1 is an XRD diffraction pattern of SSC-GDC catalytic material prepared by the in-situ composite process of example 1 of the present invention.
FIG. 2 is a typical SEM topography of a SSC-GDC composite sample prepared by the in-situ composite process of example 1 of the present invention.
Fig. 3 is a picture of a flat plate type electrolyte supported solid oxide fuel cell obtained by using the SSC-GDC catalytic material prepared by the in-situ composite process of example 1 of the present invention as a cell oxygen electrode.
Fig. 4 is a graph of the I-P-V performance of the solid oxide fuel cell of example 3 using hydrogen as the fuel and air as the oxidant.
Fig. 5 is a graph showing the results of cell performance tests of catalysts obtained in an exemplary embodiment of the present invention and comparative example 1.
Detailed Description
In view of the problems of complex and tedious composite preparation process, long period and the like of the current fuel cell catalyst, the inventor of the present invention provides a technical scheme of the invention through long-term research and a large amount of practices, and the catalyst is prepared by stirring and mixing a strontium source, a samarium source, a cerium source, a gadolinium source and a cobalt source at constant temperature through deionized water and then calcining at high temperature. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for preparing a perovskite oxide catalyst by in-situ compounding samarium-doped modified strontium cobaltate and cerium oxide-doped gadolinium oxide, including:
mixing a samarium source, a strontium source, a cobalt source, a complexing agent, a gadolinium source and a cerium source uniformly, adding a binder, and carrying out in-situ compounding on the obtained uniformly mixed reaction system to obtain a dark yellow spongy precursor;
and carrying out high-temperature calcination treatment on the dark yellow sponge precursor to obtain the perovskite type oxide catalyst.
In some embodiments, the molar ratio of samarium source, strontium source, and cobalt source is X: (1-X): 1, wherein X is more than or equal to 0 and less than or equal to 0.5.
Further, the samarium source includes samarium nitrate, but is not limited thereto.
Further, the strontium source includes strontium nitrate, but is not limited thereto.
Further, the cobalt source includes cobalt nitrate hexahydrate, but is not limited thereto.
In some embodiments, the molar ratio of the source of gadolinium to the source of cerium is 1: 2 to 6.
Further, the source of gadolinium includes, but is not limited to, gadolinium oxide.
Further, the cerium source includes cerium oxide, but is not limited thereto.
In some embodiments, the molar ratio of the complexing agent to the cobalt source is 2 to 7: 1.
further, the complexing agent is an organic compound capable of combining with various metal ions to form a stable complex, and may be any one or a combination of two or more of anhydrous citric acid, EDTA, ammonium citrate, and the like, but is not limited thereto.
Further, the molar ratio of the binder to the cobalt source is 1: 5 to 10.
Further, the binder comprises polyvinyl alcohol, preferably 10-20ml of polyvinyl alcohol with the concentration of 1%.
In some embodiments, the method of making further comprises: stirring the obtained uniformly mixed reaction system at 50-90 ℃ for 1-5 h for in-situ compounding, drying at 80-200 ℃, preferably 120-180 ℃ for 10-15 h to obtain a dark yellow spongy precursor, tabletting, and performing the high-temperature calcination treatment.
Further, the pressure used in tableting is 150 to 250MPa, and the diameter and thickness of the tablet obtained by tableting are 13mm and 1mm, respectively.
Further, the temperature of the high-temperature calcination treatment is 800-1300 ℃, preferably 900-1250 ℃, and the time of the high-temperature calcination treatment is 5-15 hours.
In some more specific embodiments, the preparation method specifically includes the following steps:
weighing samarium nitrate, strontium nitrate, cobalt nitrate hexahydrate, anhydrous citric acid, gadolinium oxide and cerium oxide in a certain ratio, adding a proper amount of deionized water, uniformly stirring, placing in a water bath kettle of a magnetic stirrer, stirring at constant temperature, dripping a proper amount of polyvinyl alcohol until the mixture is viscous, drying for several hours at constant temperature in a blast drying oven to obtain a dark yellow spongy precursor, pressing the precursor into a wafer with a certain thickness and diameter by a tablet press, and calcining at high temperature in a muffle furnace to obtain the product.
Further, the stirring temperature of the water bath kettle is 50-90 ℃.
Furthermore, the muffle furnace sintering temperature is 800-1300 ℃, preferably 900-1250 ℃, and the heat preservation time is 5-15 hours.
In conclusion, the experimental raw materials are low in cost and easy to obtain, the two catalytic materials can be well combined and grown together by adopting the in-situ composite process, and the composite preparation process is simple and feasible and has a short period.
It is also an aspect of an embodiment of the present invention to provide a perovskite-type oxide catalyst having a chemical formula of Sr prepared by the foregoing method1-xSmxCoO3GdCe, wherein X is more than or equal to 0 and less than or equal to 0.5.
Further, the perovskite-type oxide catalyst has a perovskite tetragonal structure.
Furthermore, the particles of the perovskite type oxide catalyst are uniformly distributed and are flaky, and the size of the perovskite type oxide catalyst is 30-100 mu m.
Particularly preferably, the particle surface of the perovskite type oxide catalyst is smooth, a plurality of small holes are distributed on the particle surface, the size of each small hole is 2-10 mu m, the particles are well combined, and the porous structure of the perovskite type oxide catalyst ensures smooth gas diffusion.
In conclusion, the perovskite type oxide catalyst material provided by the invention has good catalytic performance and wide application prospect.
Another aspect of an embodiment of the present invention also provides the use of the aforementioned perovskite-type oxide catalyst in the preparation of fuel cell catalyst materials, in particular, battery oxygen electrode materials.
The technical solution of the present invention is explained in further detail below with reference to several preferred embodiments and the accompanying drawings, but the present invention is not limited to the following embodiments.
Example 1
Taking a clean beaker, pouring 200ml of deionized water into the beaker by using a measuring cylinder, slowly adding 0.23mol of samarium nitrate, 0.92mol of strontium nitrate, 1.05mol of cobalt nitrate hexahydrate, 3mol of anhydrous citric acid, 0.41mol of gadolinium oxide and 1.26mol of cerium oxide into the beaker while stirring until solid is dissolved, then placing the beaker into a water bath kettle of a magnetic stirrer, stirring for 2 hours at 80 ℃, gradually dropping 15ml of 1% polyvinyl alcohol until the solution is viscous, placing the beaker into a blast drying oven, drying for 14 hours at 100 ℃ to obtain a dark yellow spongy precursor, pressing the precursor into a wafer with a certain diameter of 13mm and a height of 1mm under the pressure of 220MPa of a tablet press, wherein the wafer surface has no crack, and then heating the wafer to 1000 ℃ from room temperature at the speed of 100 ℃ per hour by a muffle furnace for 8 hours for high-temperature calcination to obtain the product.
The perovskite-type oxide catalyst obtained in this example was subjected to performance tests, and the results were as follows:
fig. 1 is an XRD diffractogram of the SSC-GDC (SrSmCo-GdCe,) catalytic material prepared by the in-situ composite process of this embodiment, and as can be seen from fig. 1, the material prepared by the in-situ composite process has a perovskite tetragonal structure and no impurity phase.
FIG. 2 shows a typical SEM morphology of an SSC-GDC composite sample, wherein the particle size of the powder prepared by the in-situ composite method is about 30-100 μm, the scale bar is 50 μm, and the powder is uniform in particle distribution and is in a flake shape. The particle surface is smooth, a certain number of small holes are distributed, the size of each hole is about 2-10 mu m, the particles are well combined, and the porous structure ensures smooth gas diffusion.
Fig. 3 is a flat plate type electrolyte supported solid oxide fuel cell, the oxygen electrode of the cell is the SSC-GDC material prepared by the in-situ composite process in this embodiment, the electrolyte is YSZ, the fuel electrode is NiO, and experimental tests show that the oxygen electrode material prepared by the in-situ composite process has high catalytic activity.
FIG. 4 shows the I-P-V performance curve of the solid oxide fuel cell with hydrogen as the fuel and air as the oxidant, with the test temperature of 700 deg.C, the amount of hydrogen of 400sccm, and the amount of air of 1600 sccm. As can be seen, the maximum power density of the SSC-GDC battery prepared by the in-situ composite process is as high as 0.2W/cm2Compared with the traditional LSM, the performance of the oxygen electrode battery is obviously improved.
Example 2
Taking a clean beaker, pouring 200ml of deionized water into the beaker by using a measuring cylinder, slowly adding 0.43mol of samarium nitrate, 1.22mol of strontium nitrate, 1.15mol of cobalt nitrate hexahydrate, 3.16mol of anhydrous citric acid, 0.62mol of gadolinium oxide and 2.28mol of cerium oxide into the beaker while stirring until solids are dissolved, then placing the beaker into a water bath kettle of a magnetic stirrer, stirring for 1 hour at 90 ℃, gradually dripping 1% of polyvinyl alcohol (0.2mol) until the solution is viscous, placing the beaker into an air-blast drying oven, drying for 15 hours at 80 ℃ to obtain a dark yellow sponge precursor, pressing the precursor into a wafer with a certain diameter of 13mm and a height of 2mm under the pressure of 250MPa of a tablet press, wherein the wafer has no crack on the surface, and then heating from room temperature to 1300 ℃ for 5 hours at the speed of 100 ℃ per hour through a muffle furnace to obtain the dark yellow sponge precursor.
The perovskite-type oxide catalyst obtained in this example was subjected to performance tests, and the results were as follows:
the XRD diffraction pattern of the SSC-GDC catalytic material prepared by the in-situ composite process in the embodiment shows that the material prepared by the in-situ composite method is of a perovskite tetragonal structure and has no impurity phase. As can be seen from a typical SEM (scanning electron microscope) topography of an SSC-GDC composite sample, the particle size of the powder prepared by the in-situ composite method is about 50-120 mu m, the scale bar is 50 mu m, and the particles are uniformly distributed and are in a flake shape. The particle surface is smooth, a certain number of small holes are distributed, the size of each hole is about 5-20 mu m, the particles are well combined, and the porous structure ensures smooth gas diffusion.
Meanwhile, the prepared catalyst material is applied to an oxygen electrode of a solid oxide fuel cell, an I-P-V performance curve with hydrogen as fuel and air as oxidant is tested at the temperature of 800 ℃, the amount of hydrogen is 400sccm, and the amount of air is 1600 sccm. Therefore, the maximum power density of the SSC-GDC battery prepared by the in-situ composite process is as high as 0.27W/cm2Compared with the test result of the embodiment 1, the test result shows that the battery performance is obviously improved.
Example 3
Taking a clean beaker, pouring 200ml of deionized water into the beaker by using a measuring cylinder, slowly adding 0.55mol of samarium nitrate, 0.86mol of strontium nitrate, 2.11mol of cobalt nitrate hexahydrate, 14.7mol of anhydrous citric acid, 1.22mol of gadolinium oxide and 7.32mol of cerium oxide into the beaker while stirring until solids are dissolved, then placing the beaker into a water bath kettle of a magnetic stirrer, stirring for 5 hours at 50 ℃, gradually dripping 1% of polyvinyl alcohol (0.211mol) until the solution is viscous, placing the beaker into an air-blast drying oven, drying for 10 hours at 200 ℃ to obtain a dark yellow sponge precursor, pressing the precursor into a wafer with a certain diameter of 13mm and a height of 2mm under the pressure of 150MPa of a tablet press, wherein the wafer has no crack on the surface, and then heating from room temperature to 1250 ℃ for 8 hours at the speed of 100 ℃ per hour by using a muffle furnace to perform high-temperature calcination.
The perovskite-type oxide catalyst obtained in this example was subjected to performance tests, and the results were as follows:
the XRD diffraction pattern of the SSC-GDC catalytic material prepared by the in-situ composite process in the embodiment shows that the material prepared by the in-situ composite method is of a perovskite tetragonal structure and has no impurity phase. As can be seen from a typical SEM (scanning electron microscope) topography of an SSC-GDC composite sample, the particle size of the powder prepared by the in-situ composite method is about 50-120 mu m, the scale bar is 50 mu m, and the particles are uniformly distributed and are in a flake shape. The particle surface is smooth, a certain number of small holes are distributed, the size of each hole is about 8-25 mu m, the particles are well combined, and the porous structure ensures smooth gas diffusion.
Meanwhile, the prepared catalyst material is applied to an oxygen electrode of a solid oxide fuel cell, an I-P-V performance curve with hydrogen as fuel and air as oxidant is tested at 850 ℃, the hydrogen gas amount is 400sccm, and the air gas amount is 1600 sccm. Therefore, the maximum power density of the SSC-GDC battery prepared by the in-situ composite process is as high as 0.39W/cm2And the performance is effectively improved.
Example 4
Taking a clean beaker, pouring 200ml of deionized water into the beaker by using a measuring cylinder, slowly adding 2.41mol of strontium nitrate, 2.41mol of cobalt nitrate hexahydrate, 5.12mol of anhydrous citric acid, 2.15mol of gadolinium oxide and 4.3mol of cerium oxide into the beaker while stirring until the solid is dissolved, then placing the beaker into a water bath kettle of a magnetic stirrer, stirring for 4 hours at 80 ℃, gradually dropping 1% of polyvinyl alcohol (0.48mol) until the solution is viscous, placing the beaker into an air-blast drying oven, drying for 14 hours at 120 ℃ to obtain a dark yellow sponge precursor, pressing the precursor into a wafer with a certain diameter of 13mm and a height of 2mm under the pressure of 200MPa of a tablet press, wherein the surface of the wafer has no crack, and then heating to 800 ℃ from room temperature at the speed of 100 ℃ per hour by a muffle furnace for 15 hours at high temperature to obtain the product.
Example 5
Taking a clean beaker, pouring 200ml of deionized water into the beaker by using a measuring cylinder, slowly adding 1.41mol of samarium nitrate, 1.41mol of strontium nitrate, 2.82mol of cobalt nitrate hexahydrate, 10.6mol of anhydrous citric acid, 1.42mol of gadolinium oxide and 4.21mol of cerium oxide into the beaker while stirring until solids are dissolved, then placing the beaker into a water bath kettle of a magnetic stirrer, stirring for 6 hours at 60 ℃, gradually dripping 1% of polyvinyl alcohol (0.282mol) until the solution is viscous, placing the beaker into an air-blast drying oven, drying for 12 hours at 180 ℃ to obtain a dark yellow sponge precursor, pressing the precursor into a wafer with a certain diameter of 13mm and a height of 2mm under the pressure of 220MPa of a tablet press, wherein the wafer has no crack on the surface, and then heating from room temperature to 900 ℃ at the speed of 100 ℃ per hour by using a muffle furnace for continuous high-temperature calcination for 15 hours.
Comparative example 1
The comparison example is prepared by performing ball milling, drying, tabletting, sintering, ball milling again, drying, tabletting, sintering and other processes on a single perovskite samarium strontium cobaltate material to prepare doping, and then performing constant-temperature stirring, drying, sintering and other processes. The method has the advantages of complex preparation process and long preparation period, and the battery performance parameters are shown in figure 5.
As can be seen from FIG. 5, the discharge performance of the battery at 800 ℃ shows that the power density of the composite catalyst battery prepared by the invention is obviously improved, which shows that the technical scheme of the invention not only has simple process flow and easy preparation, but also has obviously improved material performance.
Further, the present inventors have also conducted experiments with other raw materials and conditions and the like listed in the present specification with reference to the manner of examples 1 to 5, and have also produced perovskite-type oxide catalysts having high catalytic activity.
In conclusion, the experimental raw materials are low in cost and easy to obtain, the two catalytic materials can be well combined and grown together by adopting the in-situ composite process, the composite preparation process is simple and feasible, the period is short, the catalytic activity is high, the catalytic performance of the obtained material is good, and the application prospect is wide.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (13)

1. A method for producing a perovskite-type oxide catalyst, characterized by comprising:
uniformly mixing a samarium source, a strontium source, a cobalt source, a complexing agent, a gadolinium source and a cerium source, adding a binder, stirring the obtained uniformly mixed reaction system at 50-90 ℃ for 1-5 h to perform in-situ compounding, and drying at 80-200 ℃ for 10-15 h to obtain a dark yellow spongy precursor, wherein the molar ratio of the samarium source to the strontium source to the cobalt source is X: (1-X): 1, wherein X is more than 0 and less than or equal to 0.5, and the molar ratio of the gadolinium source to the cerium source is 1: 2-6;
tabletting the dark yellow spongy precursor, and then carrying out high-temperature calcination treatment to obtain a perovskite oxide catalyst, wherein the pressure adopted during tabletting is 150-250 MPa, the temperature of the high-temperature calcination treatment is 800-1300 ℃, and the time of the high-temperature calcination treatment is 5-15 h;
the chemical formula of the perovskite type oxide catalyst is Sr1-xSmxCoO3-GdCe, wherein 0 < X.ltoreq.0.5; the perovskite type oxide catalyst has a perovskite square structure, particles of the perovskite type oxide catalyst are uniformly distributed and are in a sheet shape, the size is 30-100 mu m, a plurality of small holes are distributed on the surface of the particles of the perovskite type oxide catalyst, and the size of the small holes is 2-10 mu m.
2. The method of claim 1, wherein: the samarium source is samarium nitrate.
3. The method of claim 1, wherein: the strontium source is strontium nitrate.
4. The method of claim 1, wherein: the cobalt source is cobalt nitrate hexahydrate.
5. The method of claim 1, wherein: the gadolinium source is gadolinium oxide.
6. The method of claim 1, wherein: the cerium source is cerium oxide.
7. The method of claim 1, wherein: the mol ratio of the complexing agent to the cobalt source is 2-7: 1.
8. the method of claim 1, wherein: the complexing agent is selected from one or the combination of more than two of anhydrous citric acid, EDTA and ammonium citrate.
9. The method of claim 1, wherein: the molar ratio of the binder to the cobalt source is 1: 5 to 10.
10. The method of claim 1, wherein: the binder is polyvinyl alcohol.
11. The method of claim 1, further comprising: stirring the obtained uniformly mixed reaction system at 50-90 ℃ for 1-5 h for in-situ compounding, drying at 120-180 ℃ for 10-15 h to obtain a dark yellow spongy precursor, tabletting, and performing the high-temperature calcination treatment.
12. The production method according to claim 1 or 11, characterized in that: the temperature of the high-temperature calcination treatment is 900-1250 ℃.
13. Use of a perovskite-type oxide catalyst prepared by the method of any one of claims 1 to 12 for the preparation of a fuel cell catalyst material.
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