CN113381033A - Electro-catalyst and electro-catalyst slurry of perovskite type oxide and preparation method thereof - Google Patents
Electro-catalyst and electro-catalyst slurry of perovskite type oxide and preparation method thereof Download PDFInfo
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- 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 electrocatalyst and an electrocatalyst slurry of perovskite type oxide and a preparation method thereof, wherein the electrocatalyst with unique electronic structure and chemical and physical properties can be obtained by simple ball milling and heat treatment process and by controlling and optimizing process parameters. And the material does not contain noble metal elements, and the material reserves are large, so the cost of the electrocatalyst is greatly reduced. The catalyst preparation method and the slurry preparation method are economical and suitable for large-scale production. The catalyst can be used as a double-function oxygen electrode catalyst of a renewable alkaline fuel cell, an oxygen reduction catalyst of an alkaline anion exchange membrane fuel cell and an oxygen reduction or oxygen precipitation reaction catalyst under other alkaline conditions.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to an electrocatalyst of a perovskite type oxide, electrocatalyst slurry and preparation methods thereof.
Background
With the increasing energy crisis and environmental pollution problems, the demand of human beings for new generation sustainable clean energy technologies, such as fuel cells, metal-air batteries, solar fuel synthesis, etc., is increasing dramatically. Electrochemical processes of Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) are the core of the above energy conversion devices, but because of their slow reaction kinetics, efficient catalysts are required to drive the reaction to proceed rapidly.
Currently, OER and ORR reactions rely primarily on noble metals or noble metal oxides. Wherein the Pt-based material and the Pd-based material have the best catalytic effect on the oxygen reduction reaction; the Ru/Ir-based metal oxide has the lowest driving initiation potential for oxygen evolution reaction. However, these materials are expensive, have poor stability, and cannot promote both OER and ORR reactions using only one noble metal electrocatalyst.
The perovskite oxide is rich in the earth crust, wherein Bi isxSr1-xCoyFe1-yO3(x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1), the perovskite type oxide has a flexible electronic structure and good conductivity. Thus, the development of BixSr1-xCoyFe1-yO3As a novel practical and efficient non-noble metal bifunctional electrocatalyst, the method has important significance for promoting the development of clean energy technology.
Disclosure of Invention
An object of the present invention is to provide an electrocatalyst and an electrocatalyst paste of perovskite type oxides and a method for preparing the same, which can solve the above problems.
In order to achieve the purpose, the invention provides an electrocatalyst of perovskite type oxide, which comprises the following raw materials in percentage by mass: bi2O3：Fe2O3/Fe3O4：CoO/Co2O3/Co3O4：SrCO30.075:0.85:0.075-0.267:0.1-0.15, the purity is above 99%.
Preferably, the following stoichiometric proportions of raw materials are included:
Bi2O3：Fe2O3/Fe3O4：CoO/Co2O3/Co3O4：SrCO3＝0.075:0.85:0.267:0.1。
a method of preparing a perovskite oxide electrocatalyst, comprising the steps of:
(1) ball mill
Weighing raw materials according to a stoichiometric ratio, soaking the raw materials in a liquid medium, and performing ball milling;
(2) thermal treatment
Carrying out heat treatment on the ball-milled material obtained in the step (1) for 1-5 times, wherein during the interval period of the heat treatment, the material is subjected to ball milling for 1 time and is dried by distillation at the temperature of 80-90 ℃;
(3) ball milling is carried out again
Adding the heat-treated sample into a liquid medium, performing ball milling again, and evaporating to dryness to obtain powder;
(4) heat treatment again
And (4) carrying out heat treatment again on the powder obtained after evaporation to dryness, keeping the temperature, and cooling to room temperature to obtain the electrocatalyst powder.
Preferably, the liquid medium is at least one of isopropanol, alcohol and ultrapure water.
Preferably, the ball milling process comprises the following steps: adding the material soaked in the liquid medium into ball milling beads with the mass 3 times that of the material, and performing ball milling through mechanical rotation; wherein the ball milling beads are at least one of glass beads, steel beads, silicon carbonate beads and zirconium oxide beads
Preferably, the heat treatment process comprises the following steps: under the conditions of heat treatment atmosphere and room temperature, heating to 700-1400 ℃ at the heating rate of 1-5 ℃, preserving heat for 1-6h, and then cooling to room temperature at the cooling rate of 1-5 ℃; wherein the heat treatment atmosphere is at least one of air, nitrogen, argon, oxygen and hydrogen.
An electrocatalyst ink of a perovskite type oxide comprising the following components: the catalyst comprises an electrocatalyst, conductive carbon powder, a binder and a dispersing agent, wherein the electrocatalyst is a perovskite type oxide electrocatalyst.
An electrocatalyst paste of perovskite type oxides, prepared by the following process: the electrocatalyst, the conductive carbon powder, the binder and the dispersant are weighed according to the mass ratio of 1:0.05-10:1-10:10-500, and then dispersed for 0.5-2h to obtain the conductive carbon powder.
Preferably, the conductive carbon powder is at least one of conductive carbon black EC-600JD/EC-300, carbon nano-tubes and acetylene black; the binder is perfluorinated sulfonic acid ion resin solution and/or polytetrafluoroethylene solution; the dispersant is at least one of deionized water, alcohols and alkane compounds.
Preferably, the method of dispersion is ultrasonic dispersion, mechanical agitation dispersion or ball milling dispersion.
In summary, the invention has the following advantages:
1. for the first time, develop BixSr1-xCoyFe1-yO3The perovskite type oxide is used as a novel electrocatalyst, the application of the perovskite type oxide in the electrochemical field is expanded, for example, the perovskite type oxide is used as an oxygen electrocatalyst in a fuel cell, and the electrocatalyst of a zinc-air cell can greatly reduce the energy barrier of electrochemical reaction through special components and electronic structures of the perovskite type oxide, and the energy conversion rate of a device is improved;
2、BixSr1-xCoyFe1-yO3the perovskite type oxide material has larger reserve and lower cost compared with noble metal and noble metal oxide;
3. the catalyst preparation method and the slurry preparation method are economical and suitable for large-scale production.
Drawings
FIG. 1 shows Bi in example 1xSr1-xCoyFe1-yO3A Scanning Electron Microscope (SEM) image of the electrocatalyst;
FIG. 2 shows Bi in example 1xSr1-xCoyFe1-yO3A Scanning Electron Microscope (SEM) image of the electrocatalyst ink;
FIG. 3 shows Bi in example 1xSr1-xCoyFe1-yO3Scanning analysis results of the element energy distribution surface of the electrocatalyst;
FIG. 4 is an X-ray diffraction pattern of the BixSr1-xCoyFe1-yO3 electrocatalyst prepared in example 1;
FIG. 5 is a graph of voltage versus current density (oxygen evolution reaction) obtained from the RDE test of examples 1, 2, and 3 and comparative example 1;
FIG. 6 is a graph showing voltage-current density (oxygen reduction reaction) relationships obtained in the RDE test of examples 1, 2 and 3 and comparative example 1.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
This example provides a Bi-based solution0.15Sr0.85Co0.8Fe0.2O3An electrocatalyst for perovskite type oxides and a method for preparing the same comprising the steps of:
(1) ball mill
Bi with the purity of 99 percent2O3、SrCO3、Co3O4And Fe2O3Weighing according to the stoichiometric ratio of 0.075:0.85:0.267:0.1, soaking by using isopropanol as a liquid medium, selecting zirconia with 3 times of the mass of the raw materials as ball milling beads, performing ball milling for 6 hours, and evaporating to dryness at 85 ℃ to obtain powder;
(2) thermal treatment
Carrying out heat treatment on the dried powder for 3 times in an air atmosphere, firstly heating to 800 ℃ at the speed of 1 ℃/min, keeping the temperature for 6 hours, then cooling to room temperature at the speed of 5 ℃/min, carrying out ball milling for 1 hour in the ball milling mode of the step (1), and evaporating to dryness; then heat treatment is carried out at 950 ℃ and 1000 ℃ under the same conditions of temperature rise, heat preservation and temperature reduction, and ball milling is carried out for 1 time in interval periods;
(3) ball milling is carried out again
Taking isopropanol as a liquid medium, selecting 3 times of zirconium oxide as ball milling beads, performing ball milling for 2 hours, and evaporating to dryness at 85 ℃ to obtain powder;
(4) heat treatment again
And (4) heating the powder evaporated in the step (3) from room temperature to 1050 ℃ at a heating rate of 5 ℃/min, preserving the heat for 6h, and then cooling to room temperature at a cooling rate of 2 ℃/min to obtain the electrocatalyst powder.
The electrocatalyst powder obtained in example 1, for the preparation of a catalyst based on BixSr1-xCoyFe1-yO3An electrocatalyst slurry of a perovskite-type oxide comprising the steps of: preparing electrocatalyst powder, EC-600JD, perfluorinated sulfonic acid ion resin solution and ethanol according to the mass ratio of 1:0.2:1:500, and dispersing in an ultrasonic mode to prepare slurry.
Bi prepared in example 10.15Sr0.85Co0.8Fe0.2O3Scanning electron microscope analysis is carried out on the electrocatalyst and the slurry prepared by using the electrocatalyst, and the obtained SEM topography is respectively shown in figures 1-2. In addition, the scanning result of the element energy distribution surface of the material is shown in fig. 3, the five elements are uniformly distributed, and the atomic ratio accords with the chemical formula Bi0.15Sr0.85Co0.8Fe0.2O3. Fig. 4 is an X-ray diffraction (XRD) spectrum of the material, and the result shows that the material has a perovskite structure. The obtained electro-catalyst slurry is added with the catalyst loading amount of 0.25g/cm2Test electrodes were prepared and mounted to an RDE test apparatus and tested for electrochemical performance, with the results of the catalytic oxygen evolution reaction shown in fig. 5: when the potential reached 1.57V, the current density measured reached 10mA/cm2. Example 1 the results of the catalytic oxygen reduction reaction are shown in fig. 6: the limiting current density can reach 5.3mA/cm2. The results show that Bi in the present invention0.15Sr0.85Co0.8Fe0.2O3The electrocatalyst has excellent bifunctional electrocatalysis effects.
Example 2
This example provides a Bi-based solution0.15Sr0.85Co0.8Fe0.2O3An electrocatalyst for perovskite type oxides and a method for preparing the same comprising the steps of:
(1) ball mill
Bi with the purity of 99.5 percent2O3、SrCO3、Co3O4And Fe2O3Weighing according to the stoichiometric ratio of 0.075:0.85:0.267:0.1, soaking by using isopropanol as a liquid medium, selecting zirconia with 3 times of the mass of the raw materials as ball milling beads, performing ball milling for 6 hours, and evaporating to dryness at 85 ℃ to obtain powder;
(2) thermal treatment
Carrying out heat treatment on the dried powder for 1 time in an air atmosphere, firstly heating to 800 ℃ at the speed of 1 ℃/min, preserving heat for 6 hours, then cooling to room temperature at the speed of 5 ℃/min, ball-milling for 1 hour in the ball-milling mode of the step (1), and evaporating to dryness;
(3) ball milling is carried out again
Taking isopropanol as a liquid medium, selecting 3 times of zirconium oxide as ball milling beads, performing ball milling for 2 hours, and evaporating to dryness at 85 ℃ to obtain powder;
(4) heat treatment again
And (4) heating the powder evaporated in the step (3) from room temperature to 1050 ℃ at a heating rate of 5 ℃/min, preserving the heat for 6h, and then cooling to room temperature at a cooling rate of 2 ℃/min to obtain the electrocatalyst powder.
The electrocatalyst powder prepared in example 2, for the preparation of Bi-based catalystxSr1-xCoyFe1-yO3An electrocatalyst slurry of a perovskite-type oxide comprising the steps of: preparing electrocatalyst powder, EC-600JD, perfluorinated sulfonic acid ion resin solution and ethanol according to the mass ratio of 1:0.3:1:500, and dispersing in an ultrasonic mode to prepare slurry.
Bi prepared in example 20.15Sr0.85Co0.8Fe0.2O3Electrocatalyst ink at catalyst loading of 0.25g/cm2Preparing a test electrode, installing the test electrode to an RDE testing device, and carrying out electrochemical performance detection, wherein the results of the RDE electrochemical performance test and the catalytic oxygen evolution reaction are shown in FIG. 5: when the potential reached 1.65V, the current density measured reached 10mA/cm2. Example 2 the results of the catalytic oxygen reduction reaction are shown in fig. 6: the limiting current density can reach 4.76mA/cm2。
Example 3
This example provides a Bi-based solution0.15Sr0.85Co0.8Fe0.2O3An electrocatalyst for perovskite type oxides and a method for preparing the same comprising the steps of:
(1) ball mill
Adding Bi2O3(purity of 99.9%), SrCO3(purity of 99.95%), Co3O4(purity 99.9%) and Fe2O3(purity is 99.5%) weighing according to a stoichiometric ratio of 0.075:0.85:0.267:0.1, soaking by using isopropanol as a liquid medium, selecting zirconia with 3 times of the mass of the raw materials as ball milling beads, performing ball milling for 6 hours, and evaporating to dryness at 85 ℃ to obtain powder;
(2) thermal treatment
Carrying out heat treatment on the dried powder for 2 times in an air atmosphere, firstly heating to 800 ℃ at the speed of 1 ℃/min, preserving heat for 6 hours, then cooling to room temperature at the speed of 5 ℃/min, carrying out ball milling for 1 hour in the ball milling mode of the step (1), and evaporating to dryness; heating the evaporated powder to 1050 ℃ at the speed of 1 ℃/min, preserving the heat for 6 hours, and cooling to room temperature at the speed of 5 ℃/min;
(3) ball milling is carried out again
Taking isopropanol as a liquid medium, selecting zirconium oxide with the mass being 3 times that of the sample as ball milling beads, performing ball milling for 2 hours, and evaporating to dryness at 85 ℃ to obtain powder;
(4) heat treatment again
And (4) heating the powder evaporated in the step (3) from room temperature to 1050 ℃ at a heating rate of 5 ℃/min, preserving the heat for 6h, and then cooling to room temperature at a cooling rate of 2 ℃/min to obtain the electrocatalyst powder.
The electrocatalyst powder prepared in example 3, for the preparation of Bi-based catalystxSr1-xCoyFe1-yO3An electrocatalyst slurry of a perovskite-type oxide comprising the steps of: preparing electrocatalyst powder, EC-600JD, perfluorinated sulfonic acid ion resin solution and ethanol according to the mass ratio of 1:0.2:1:500, and dispersing in an ultrasonic mode to prepare slurryAnd (5) feeding.
Bi prepared in example 30.15Sr0.85Co0.8Fe0.2O3Electrocatalyst ink at catalyst loading of 0.25g/cm2Preparing a test electrode, installing the test electrode to an RDE testing device, and carrying out electrochemical performance detection, wherein the results of the RDE electrochemical performance test and the catalytic oxygen evolution reaction are shown in FIG. 5: when the potential reached 1.62V, the current density measured reached 10mA/cm2. Example 3 the results of the catalytic oxygen reduction reaction are shown in fig. 6: the limiting current density can reach 5.34mA/cm2。
Comparative example 1
Preparing EC-600JD, perfluorinated sulfonic acid ion resin solution and ethanol according to the mass ratio of 0.2:1:500, and dispersing in an ultrasonic mode to obtain the Bi-free resin0.15Sr0.85Co0.8Fe0.2O3Catalyst slurries, electrodes prepared according to the procedures and parameters of examples 1-3 and mounted to an RDE testing apparatus and tested for electrochemical performance, with the RDE electrochemical performance test results shown in figure 5: as the voltage was increased to 1.69V, the current density was still very low, only 1.76mA/cm2(ii) a Comparative example 1 results of catalytic oxygen reduction reaction as shown in FIG. 6, the limiting current density was only 4.2mA/cm2In clear contrast to examples 1, 2 and 3. The results show that the perovskite type electrocatalyst of the present invention has excellent electrocatalytic effects.
In conclusion, by comparing and analyzing examples 1 to 3 and comparative example 1, Bi can be foundxSr1-xCoyFe1-yO3The perovskite type oxide as the oxygen electrocatalyst can obviously promote the charge transfer on the interfaces of the electrode and the electrolyte and accelerate the reaction. The concrete embodiment is as follows: in the oxygen precipitation reaction, the electrode can reach higher current density only by lower potential through the catalytic reaction of the electrocatalyst in the invention; in contrast to comparative example 1, examples 1 to 3 had higher limiting diffusion current densities in the oxygen reduction reaction, indicating that the catalyst of the present invention had good electrocatalytic effects on oxygen reduction. All the above characteristics can effectively prove that Bi in the inventionxSr1-xCoyFe1-yO3The perovskite type oxygen electrocatalyst can efficiently promote the rates of oxygen precipitation and oxygen reduction reaction, and has great application potential in the field of electrocatalysis.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (10)
1. An electrocatalyst for a perovskite oxide, comprising the following raw materials in stoichiometric proportions: bi2O3：SrCO3：CoO/Co2O3/Co3O4：Fe2O3/Fe3O40.075:0.85:0.075-0.267:0.1-0.15, the purity is above 99%.
2. An electrocatalyst of a perovskite oxide according to claim 1 comprising the following stoichiometric proportions of starting materials:
Bi2O3：Fe2O3/Fe3O4：CoO/Co2O3/Co3O4：SrCO3＝0.075:0.85:0.267:0.1。
3. a process for preparing an electrocatalyst for a perovskite oxide as claimed in claim 1 or 2, comprising the steps of:
(1) ball mill
Weighing raw materials according to a stoichiometric ratio, soaking the raw materials in a liquid medium, and performing ball milling;
(2) thermal treatment
Carrying out heat treatment on the ball-milled material obtained in the step (1) for 1-5 times, wherein during the interval period of the heat treatment, the material is subjected to ball milling for 1 time and is dried by distillation at the temperature of 80-90 ℃;
(3) ball milling is carried out again
Adding the heat-treated sample into a liquid medium, performing ball milling again, and evaporating to dryness to obtain powder;
(4) heat treatment again
And (4) carrying out heat treatment again on the powder obtained after evaporation to dryness, keeping the temperature, and cooling to room temperature to obtain the electrocatalyst powder.
4. A process for preparing an electrocatalyst for a perovskite oxide as claimed in claim 3, wherein: the liquid medium is at least one of isopropanol, alcohol and ultrapure water.
5. The method of preparing an electrocatalyst for perovskite oxides according to claim 3, wherein the ball milling is performed by the steps of: adding the material soaked in the liquid medium into ball milling beads with the mass 3 times that of the material, and performing ball milling through mechanical rotation; wherein the ball milling beads are at least one of glass beads, steel beads, silicon carbonate beads and zirconium oxide beads.
6. A process for preparing an electrocatalyst for a perovskite oxide as claimed in claim 3, wherein: the heat treatment process comprises the following steps: under the conditions of heat treatment atmosphere and room temperature, heating to 700-1400 ℃ at the heating rate of 1-5 ℃, preserving heat for 1-6h, and then cooling to room temperature at the cooling rate of 1-5 ℃; wherein the heat treatment atmosphere is at least one of air, nitrogen, argon, oxygen and hydrogen.
7. An electrocatalyst paste of a perovskite oxide comprising the following components: conductive carbon powder, a binder, a dispersant and an electrocatalyst according to claim 1 or 2.
8. An electrocatalyst paste of a perovskite oxide as claimed in claim 7, prepared by a process comprising: the electrocatalyst, the conductive carbon powder, the binder and the dispersant are weighed according to the mass ratio of 1:0.05-10:1-10:10-500, and then dispersed for 0.5-2h to obtain the conductive carbon powder.
9. The electrocatalyst paste for perovskite-type oxide according to claim 7, wherein the conductive carbon powder is at least one of conductive carbon black EC-600JD/EC-300, carbon nanotubes and acetylene black; the binder is a perfluorinated sulfonic acid ion resin solution and/or a polytetrafluoroethylene solution; the dispersing agent is at least one of deionized water, alcohols and alkane compounds.
10. The electrocatalyst ink for perovskite-type oxide according to claim 7, wherein the method of dispersion is ultrasonic dispersion, mechanical agitation dispersion or ball milling dispersion.
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Application publication date: 20210910 |