CN107978763B - Silver-iron-nitrogen-carbon-oxygen reduction catalyst for fuel cell and preparation method and application thereof - Google Patents
Silver-iron-nitrogen-carbon-oxygen reduction catalyst for fuel cell and preparation method and application thereof Download PDFInfo
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- CN107978763B CN107978763B CN201711181701.XA CN201711181701A CN107978763B CN 107978763 B CN107978763 B CN 107978763B CN 201711181701 A CN201711181701 A CN 201711181701A CN 107978763 B CN107978763 B CN 107978763B
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
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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
- H01M4/9041—Metals or alloys
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- 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 a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell and a preparation method and application thereof. The method comprises the following steps: and simultaneously dropwise adding a silver nitrate aqueous solution and a polyvinylpyrrolidone aqueous solution into a reaction bottle filled with a pyrrole monomer, stirring for a certain time, filtering and drying, uniformly dispersing the dried sample in an iron salt solution, standing for a certain time, filtering and drying again to obtain a pyrolysis precursor, and calcining the obtained pyrolysis precursor at constant temperature under the protection of inert gas to obtain the silver-iron-nitrogen-carbon oxygen reduction catalyst. The method has the advantages of low cost of raw materials, easy control of the synthesis process, simple operation and easy large-scale industrial production. The prepared silver-iron-nitrogen-carbon oxygen reduction catalyst has good oxygen reduction catalytic performance and can be used as a fuel cell cathode catalyst.
Description
Technical Field
The invention relates to the technical field of fuel cell science, in particular to a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell and a preparation method thereof.
Background
Fuel cells have been a hot area of research over the last decade because they are considered as a clean and efficient alternative to traditional fossil energy sources. The cathode oxygen reduction reaction is the primary factor determining the performance of the fuel cell. Platinum-based materials are considered to be the best oxygen reduction catalysts due to their excellent catalytic activity, and are widely used in commercial fuel cells. However, the disadvantages of high cost, low reserves, carbon monoxide poisoning and poor stability of Pt-based catalysts have been major obstacles hindering large-scale application of fuel cells. In order to overcome these problems, researchers have been working on developing an oxygen reduction catalyst that does not contain platinum. Among them, iron-nitrogen-carbon catalysts have become the key research objects of scientists due to their advantages of low cost, good catalytic activity and stability, etc. Silver is also considered as a good alternative to platinum in oxygen reduction reactions, having acceptable catalytic activity for oxygen reduction in alkaline media and better stability. In addition, due to high abundance and low cost, the silver-based catalyst can be applied to large-scale industrial production of fuel cells. However, the catalytic activity of the silver-based catalyst is still weaker than that of the platinum-based catalyst. Therefore, the silver-iron-nitrogen-carbon catalyst with higher oxygen reduction catalytic activity and stability is prepared by combining silver and iron-nitrogen-carbon, and has very important significance for large-scale industrial application of fuel cells.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and aims to provide a preparation method of a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell. The invention takes pyrrole, silver nitrate, polyvinylpyrrolidone and ferric salt as raw materials, and prepares the silver-iron-nitrogen-carbon oxygen reduction catalyst by a chemical polymerization and pyrolysis method. The method is simple and easy to implement, has low cost and is suitable for industrial production. Meanwhile, the prepared catalyst has good oxygen reduction catalytic performance and can be used as a cathode catalyst of a fuel cell.
The purpose of the invention is realized by the following technical scheme.
A method of preparing a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell, comprising the steps of:
(1) simultaneously dripping a silver nitrate aqueous solution and a polyvinylpyrrolidone aqueous solution into a reaction bottle filled with a pyrrole monomer, stirring, filtering and drying to obtain a solid sample;
(2) uniformly dispersing the solid sample obtained in the step (1) in an iron salt solution, standing, and filtering and drying again to obtain a pyrolysis precursor;
(3) and (3) placing the pyrolysis precursor obtained in the step (2) in a tubular furnace for constant-temperature calcination under the protection of inert gas to obtain the silver-iron-nitrogen-carbon oxygen reduction catalyst.
Preferably, in the step (1), the viscosity grade of the polyvinylpyrrolidone ranges from K23 to K30.
Preferably, in the step (1), the dosage ratio of the silver nitrate to the pyrrole monomer is 1 g: 1 mL to 1 g: 3 mL.
Preferably, in the step (1), the stirring time is 30 to 60 hours.
Preferably, in the step (1), the drying temperature is 50-100 ℃ and the drying time is 10-24 hours.
Preferably, in the step (2), the iron salt is any one or more of ferric nitrate, ferric sulfate, ferric chloride, ferrous nitrate, ferrous sulfate and ferrous chloride.
Preferably, in the step (2), the standing time is 24 to 48 hours.
Preferably, in the step (3), the inert gas is one or a mixture of two of nitrogen and argon, and the flow rate of the inert gas is 20-80 mL/min.
Preferably, in the step (3), the tube furnace is heated to 700 ℃ and 900 ℃ at the speed of 2-6 ℃/min under the protection of inert gas, and is calcined at constant temperature for 1-3 hours.
A silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell prepared by the above preparation method, and the use of the silver-iron-nitrogen-carbon oxygen reduction catalyst in a fuel cell.
Compared with the prior art, the invention has the following technical effects:
1. the invention adopts pyrrole, silver nitrate, polyvinylpyrrolidone and ferric salt as raw materials, and has lower cost.
2. The silver-iron-nitrogen-carbon oxygen reduction catalyst is prepared by combining silver and iron-nitrogen-carbon and adopting a chemical polymerization and pyrolysis method, and the method is simple and easy to implement, low in production cost and suitable for industrial production.
3. The silver-iron-nitrogen-carbon oxygen reduction catalyst obtained by the invention has good oxygen reduction catalytic activity and can be used as a fuel cell cathode catalyst.
Drawings
FIG. 1 is a scanning electron microscope image of a silver-iron-nitrogen-carbon-oxygen reduction catalyst (Ag @ Fe-N-C-700) prepared in example 1 of the present invention.
FIG. 2 is a graph showing nitrogen adsorption and desorption of a silver-iron-nitrogen-carbon-oxygen reduction catalyst (Ag @ Fe-N-C-700) prepared in example 1 of the present invention.
FIG. 3 is a graph showing oxygen reduction polarization curves of the silver-iron-nitrogen-carbon oxygen reduction catalyst (Ag @ Fe-N-C-700) prepared in example 1 of the present invention and a commercial platinum carbon catalyst.
FIG. 4 is an X-ray diffraction pattern of a silver-iron-nitrogen-carbon oxygen reduction catalyst (Ag @ Fe-N-C-800) prepared in example 2 of the present invention.
FIGS. 5a and 5b are X-ray photoelectron spectra of the silver-iron-nitrogen-carbon-oxygen reduction catalyst (Ag @ Fe-N-C-800) prepared in example 2 of the present invention.
FIG. 6 is a graph showing oxygen reduction polarization curves of the silver-iron-nitrogen-carbon oxygen reduction catalyst (Ag @ Fe-N-C-800) prepared in example 2 of the present invention and a commercial platinum carbon catalyst.
FIG. 7 is a graph showing oxygen reduction polarization curves of the silver-iron-nitrogen-carbon oxygen reduction catalyst (Ag @ Fe-N-C-900) prepared in example 3 of the present invention and a commercial platinum carbon catalyst.
Detailed Description
The embodiments of the present invention will be further described with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell specifically comprises the following steps:
(1) simultaneously dropping 100 mL of an aqueous solution containing 4 g of silver nitrate and 100 mL of an aqueous solution containing 4 g of polyvinylpyrrolidone (K23) into a reaction flask containing 8 mL of pyrrole monomer, stirring for 30 hours, filtering, and drying at 50 ℃ for 24 hours to obtain a solid sample;
(2) uniformly dispersing 1 g of the solid sample obtained in the step (1) in 100 mL of 0.5M ferrous sulfate solution, standing for 24 hours, and filtering and drying again to obtain a pyrolysis precursor;
(3) and (3) placing the precursor obtained in the step (2) into a tube furnace, heating to 700 ℃ at the speed of 2 ℃/min under the protection of nitrogen at the flow rate of 20 mL/min, calcining at constant temperature for 1 hour, cooling to room temperature to obtain the silver-iron-nitrogen-carbon oxygen reduction catalyst, and naming the silver-iron-nitrogen-carbon oxygen reduction catalyst as Ag @ Fe-N-C-700 catalyst.
The prepared catalyst was characterized by scanning electron microscopy (see FIG. 1)As can be seen from fig. 1, the silver-iron-nitrogen-carbon-oxygen reduction catalyst has a rod-like structure. FIG. 2 is a nitrogen adsorption and desorption graph of a silver-iron-nitrogen-carbon oxygen reduction catalyst, and the specific surface area of the catalyst is 122.3 m2(ii) in terms of/g. Fig. 3 is a graph showing oxygen reduction polarization curves of the silver-iron-nitrogen-carbon oxygen reduction catalyst and the commercial platinum carbon catalyst, and it can be seen by comparison that the initial potential and the limiting current density of the prepared catalyst are almost the same as those of the commercial platinum carbon catalyst, indicating that the silver-iron-nitrogen-carbon oxygen reduction catalyst has good oxygen reduction catalytic activity.
Example 2
A preparation method of a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell specifically comprises the following steps:
(1) simultaneously dropping 100 mL of an aqueous solution containing 4 g of silver nitrate and 100 mL of an aqueous solution containing 4 g of polyvinylpyrrolidone (K30) into a reaction flask containing 4 mL of pyrrole monomer, stirring for 60 hours, filtering, and drying at 100 ℃ for 10 hours to obtain a solid sample;
(2) uniformly dispersing 1 g of the solid sample obtained in the step (1) in 200 mL of 0.2M ferrous chloride solution, standing for 48 hours, and filtering and drying again to obtain a pyrolysis precursor;
(3) and (3) placing the precursor obtained in the step (2) into a tube furnace, heating to 800 ℃ at the speed of 6 ℃/min under the protection of argon at the flow rate of 80 mL/min, calcining at constant temperature for 3 hours, cooling to room temperature to obtain the silver-iron-nitrogen-carbon oxygen reduction catalyst, and naming the silver-iron-nitrogen-carbon oxygen reduction catalyst as Ag @ Fe-N-C-800 catalyst.
The prepared catalyst was characterized by X-ray diffraction technique (see fig. 4), and from fig. 4, it can be seen that the catalyst showed characteristic peaks of metallic silver at 38.1 °, 44.3 ° and 64.4 °, which are respectively assigned to the (111), (200) and (220)) crystal planes of silver, indicating the presence of elemental Ag in the catalyst. Meanwhile, the catalyst has characteristic peaks of elementary iron at 44.5 degrees and 64.6 degrees and has characteristic peaks of ferroferric oxide at 35.5 degrees, which indicates that the elementary iron and the ferroferric oxide exist in the catalyst. FIGS. 5a and 5b are X-ray photoelectron spectra of a silver-iron-nitrogen-carbon oxygen reduction catalyst, wherein the catalyst shows a peak of C1 s at 284.8 eV, a peak of N1 s at 396.8 eV, a peak of O1 s at 529.2 eV, a peak of Fe 2p at 706.7 eV, and a peak of Ag 3d at 368.3eV, and the prepared catalyst contains five elements of C, N, O, Fe and Ag. Fig. 6 is a graph showing the oxygen reduction polarization curves of the silver-iron-nitrogen-carbon oxygen reduction catalyst and the commercial platinum carbon catalyst, from which it can be seen that the initial potential of the prepared catalyst is almost the same as that of the platinum carbon catalyst, indicating that the silver-iron-nitrogen-carbon oxygen reduction catalyst has acceptable oxygen reduction catalytic activity.
Example 3
A preparation method of a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell specifically comprises the following steps:
(1) simultaneously dropping 100 mL of an aqueous solution containing 4 g of silver nitrate and 100 mL of an aqueous solution containing 4 g of polyvinylpyrrolidone (K29) into a reaction flask containing 12 mL of pyrrole monomer, stirring for 45 hours, filtering, and drying at 75 ℃ for 17 hours to obtain a solid sample;
(2) uniformly dispersing 1 g of the solid sample obtained in the step (1) in 200 mL of 0.2M ferrous nitrate solution, standing for 36 hours, and filtering and drying again to obtain a pyrolysis precursor;
(3) and (3) placing the precursor obtained in the step (2) into a tube furnace, heating to 900 ℃ at a speed of 4 ℃/min under the protection of argon at a flow rate of 50 mL/min, calcining at constant temperature for 2 hours, cooling to room temperature to obtain the silver-iron-nitrogen-carbon oxygen reduction catalyst, and naming the silver-iron-nitrogen-carbon oxygen reduction catalyst as the Ag @ Fe-N-C-900 catalyst.
FIG. 7 is a graph showing the oxygen reduction polarization curves of the Ag @ Fe-N-C-900 catalyst and a commercial platinum-carbon catalyst, and it can be seen that the initial potential of the Ag @ Fe-N-C-900 catalyst is almost the same as that of the platinum-carbon catalyst, indicating that the silver-iron-nitrogen-carbon oxygen reduction catalyst has better oxygen reduction catalytic activity.
Claims (10)
1. A method of preparing a silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell, comprising the steps of:
(1) simultaneously dripping a silver nitrate aqueous solution and a polyvinylpyrrolidone aqueous solution into a reaction bottle filled with a pyrrole monomer, stirring, filtering and drying to obtain a solid sample;
(2) uniformly dispersing the solid sample obtained in the step (1) in an iron salt solution, standing, and filtering and drying again to obtain a pyrolysis precursor;
(3) and (3) placing the pyrolysis precursor obtained in the step (2) in a tubular furnace for constant-temperature calcination under the protection of inert gas to obtain the silver-iron-nitrogen-carbon oxygen reduction catalyst.
2. The method according to claim 1, wherein the polyvinylpyrrolidone in step (1) has a viscosity grade in the range of K23-K30.
3. The preparation method according to claim 1, wherein in the step (1), the mass-to-volume ratio of the silver nitrate to the pyrrole monomer is 1 g: 1 mL-1 g: 3 mL.
4. The production method according to claim 1, wherein in the step (1), the stirring time is 30 to 60 hours.
5. The preparation method according to claim 1, wherein in the step (2), the iron salt is any one or more of ferric nitrate, ferric sulfate, ferric chloride, ferrous nitrate, ferrous sulfate and ferrous chloride.
6. The production method according to claim 1, wherein in the step (2), the standing time is 24 to 48 hours.
7. The method according to claim 1, wherein in the step (3), the inert gas is one or a mixture of two of nitrogen and argon, and the flow rate of the inert gas is 20-80 mL/min.
8. The preparation method as claimed in claim 1, wherein in the step (3), the tube furnace is heated to 700 ℃ and 900 ℃ at a rate of 2-6 ℃/min under the protection of inert gas, and is calcined at constant temperature for 1-3 hours.
9. A silver-iron-nitrogen-carbon oxygen reduction catalyst for a fuel cell prepared by the production method according to any one of claims 1 to 8.
10. Use of the silver-iron-nitrogen-carbon oxygen reduction catalyst of claim 9 in a fuel cell.
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