CN113707894A - Fuel cell catalyst and preparation method and application thereof - Google Patents
Fuel cell catalyst and preparation method and application thereof Download PDFInfo
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- CN113707894A CN113707894A CN202110958759.0A CN202110958759A CN113707894A CN 113707894 A CN113707894 A CN 113707894A CN 202110958759 A CN202110958759 A CN 202110958759A CN 113707894 A CN113707894 A CN 113707894A
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- 239000000446 fuel Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 15
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
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- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
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- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 9
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- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
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- 238000000967 suction filtration Methods 0.000 claims description 3
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- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
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- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910000510 noble metal Inorganic materials 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
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- 238000006555 catalytic reaction Methods 0.000 description 2
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
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- 238000001816 cooling Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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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
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- 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
-
- 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 provides a fuel cell catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing a cobalt source, a nitrogen source and an additive with a solvent, heating and stirring uniformly, then freeze-drying, and carrying out one-step sintering treatment to obtain a precursor; (2) mixing the precursor obtained in the step (1) with a carbon source, carrying out hydrothermal reaction, and carrying out two-step sintering treatment to obtain a carbon-coated precursor; (3) and (3) mixing the carbon-coated precursor obtained in the step (2) with a phosphorus source, and carrying out three-step sintering treatment to obtain the fuel cell catalyst. The invention further phosphorizes the prepared nitrogen-doped cobalt-carbon material to realize the multi-atom doping synergistic effect in the carbon material so as to improve the catalytic performance of the material, and the introduction of P element enhances the synergistic effect among elements in Co-N-C after phosphorization, thereby creating more catalytic active sites.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and relates to a fuel cell catalyst, and a preparation method and application thereof.
Background
Fuel Cells (Fuel Cells) are new energy conversion devices that convert chemical energy directly into electrical energy. Because the energy conversion efficiency is not limited by Carnot cycle because of not going through the process of burning, can reach 60% -80%, the actual use efficiency can reach 2-3 times of the ordinary internal-combustion engine, is praised as the fourth generation power generation technology after water power, firepower and nuclear power, the energy star of the '21 st century'.
Today, research on fuel cells has made a great breakthrough, but its large-scale application still faces many challenges at the present stage. One of the biggest problems is high cost. The most effective cathode catalyst at present is Pt which is scarce and expensive, the cost of the Pt accounts for 38% -56% of the cost of the whole fuel cell, and higher catalyst loading is often needed in practical application, which further increases the cost of the cell. How to prepare the ORR catalyst with good stability, high activity and low cost is the main direction of the current fuel cell research. It is worth noting that the synthesis method of the novel catalyst with the special alloy nano structure with high activity is generally complicated, particles are easy to gather, meanwhile, most of metals doped in the binary alloy catalyst in an acid system are easy to dissolve by acid, so that the framework of Pt is exposed, oxygen is difficult to adsorb, and the catalytic activity and efficiency of the catalyst are not high.
Electrocatalysis is a heterogeneous catalytic process during a charge transfer reaction that takes place at the electrode/electrolyte interface. A large number of experiments show that the main product of the cathode ORR in an acidic system is water, however, when anions, H, inert metal atoms and the like are adsorbed on the surface of the electrode, various intermediate products (O) can be generated due to the processes of multi-step electron gain and loss, proton coupling transfer and the like2 2-、O2 -、HO2 -) Finally incompletely reduced to form H2O2. A large number of intermediates generated by the reaction of two electron processes can be harmful to catalysts, proton exchange membranes and other components, H2O2The strong corrosiveness of the free radicals can destroy the active sites of the oxygen reduction catalyst, cause catalyst deactivation, reduce energy conversion efficiency, and the like. It is therefore desirable for the fuel cell that a purely four electron process occurs at the oxygen electrode.
CN111146460A discloses a fuel cell alloy catalyst, its preparation method and application in fuel cells. The fuel cell alloy catalyst comprises a carbon material and a Pt-containing alloy distributed on the surface of the carbon material. In the fuel cell catalyst, Pt alloy particles are only distributed on the surface of a carbon material, (in the preparation process of the invention, solidified high polymer is filled in the inner pore canal of a carbon carrier, the probability of loading catalyst nano particles on the inner pore canal of the carbon carrier is reduced in the catalyst synthesis process, so that the catalyst nano particles are loaded on the outer surface of the carbon carrier, and then the high polymer is removed in the synthesis process of the catalyst), thereby effectively preventing precious metal particles from entering the inner pore canal of the carbon material and entering the inner pore canal of the carbon material, reducing the probability of loading the catalyst nano particles on the inner pore canal of the carbon carrier in the catalyst synthesis process, loading the catalyst nano particles on the outer surface of the carbon carrier, and then removing the high polymer in the synthesis process) and effectively preventing the precious metal particles from entering the inner pore canal of the carbon material, the noble metal particles entering the pore canal in the carbon material are difficult to form an effective three-phase reaction interface, so that the utilization rate of the noble metal particles can be effectively improved.
CN100399612C discloses a fuel cell catalyst with proton-conducting function and a preparation method thereof, wherein nano noble metal particles in the catalyst are modified by proton-conducting high polymer, and the introduced proton-conducting high polymer can increase the steric hindrance of the noble metal particles, so that the noble metal particles of the catalyst are anchored on the surface of a carrier, and the utilization rate of the catalyst is improved. In addition, the proton conducting polymer is also a better adhesive, and the nano noble metal particles modified by the proton conducting polymer have better bonding force with the carrier; meanwhile, the synthesized catalyst has a proton conducting function. The preparation method of the catalyst comprises the following steps: preparing proton conducting polymer modified nanometer noble metal colloid in advance, and depositing the colloid onto carbon carrier. The average particle size of the noble metal of the catalyst is 2-5 nanometers, and the noble metal is uniformly distributed; the prepared catalyst was fabricated into a fuel cell chip CCM and assembled into a single cell.
CN110890551A discloses an encapsulated catalyst, its preparation method and application in fuel cells. The inner layer of the coated catalyst is transition metal oxide nano-particles, and the outer layer is a carbon coating layer doped with sulfur and nitrogen. The sulfur, nitrogen and carbon doped and coated in the coated catalyst have the function of fixing the active sites of the catalyst while increasing the catalytic active sites, and cooperate with the transition metal oxide nanoparticles to promote the oxygen reduction catalytic reaction, so that the coated catalyst has a good catalytic effect, and meanwhile, a compact oxide film is easily formed on the surface of the transition metal oxide nanoparticles after high temperature, and the surface of the coated catalyst is also provided with a coating layer, so that the coated catalyst has good corrosion resistance. The coated catalyst has good catalytic effect, high corrosion resistance and performance superior to that of commercial catalysts; and the preparation process is safe and environment-friendly, the flow is simple, the cost of the used raw materials is low, and the method has wide application prospect in the field of fuel cell catalysts.
The preparation processes of the three catalysts respectively have the following defects: the main catalytic element is still noble metal such as Pt and the like, and the problem of high cost is not completely solved because the loading capacity is not controlled below a certain value; adding a polymer in the synthesis process, wherein the noble metal takes a carbon carrier and the polymer as crystal nuclei to grow crystals, the reduced noble metal does not completely grow on the carbon carrier, and the electron conductivity of the polymer is lower than that of the carbon carrier, so that the electrocatalytic capacity of the catalyst is reduced; the transition metal oxide has poor conductivity, the utilization rate of metal particles is low, the metal particles are easily distributed in the carbon carrier pore channel, the conveying path of reaction gas reaching the catalyst metal particles is prolonged, the gas transmission resistance is increased, and generated water is not easy to discharge so as to further block a gas channel.
Therefore, the non-noble metal catalyst for the fuel cell, which can reduce the synthesis cost of the existing catalyst, is safe and environment-friendly in preparation process and simple in flow, is developed, has wide application prospect in the field of fuel cell catalysts, and has higher practical application value.
Disclosure of Invention
The invention aims to provide a fuel cell catalyst, a preparation method and application thereof, and mainly aims to develop a non-noble metal catalyst with low design cost, high catalytic activity and good stability. Nitrogen doped carbon supported transition metal materials (M-N-C) are considered to be the most likely non-noble metal catalysts to replace commercial Pt/C due to their irreplaceable cost advantages and excellent selectivity. In addition, the heteroatom-doped carbon material has various types, is economic and environment-friendly, has high catalytic activity, and can change the physical and chemical properties of the surface of the carbon material. P and N are taken as same-group elements, the electronic valence states are the same, and the chemical properties are similar, so the prepared Co-N-C catalyst is further subjected to phosphating treatment, and the multi-atom doping synergistic effect in the carbon material is realized to improve the catalytic performance of the material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect the present invention provides a method of preparing a fuel cell catalyst, the method comprising the steps of:
(1) mixing a cobalt source, a nitrogen source and an additive (used for adjusting the pH value of the solution) with a solvent, heating and stirring uniformly, then freeze-drying, and carrying out one-step sintering treatment to obtain a precursor;
(2) mixing the precursor obtained in the step (1) with a carbon source, carrying out hydrothermal reaction, and carrying out two-step sintering treatment to obtain a carbon-coated precursor;
(3) and (3) mixing the carbon-coated precursor obtained in the step (2) with a phosphorus source, and carrying out three-step sintering treatment to obtain the fuel cell catalyst.
The invention uses nitrogen-doped cobalt carbon material to replace non-noble metal catalyst of commercial Pt/C, and phosphorus element is doped in the nitrogen-doped cobalt carbon material to change the physical and chemical properties of the surface of the carbon material, P and N are taken as homologous elements, the electronic valence is the same, the chemical properties are similar, the invention further performs phosphorization treatment on the prepared nitrogen-doped cobalt carbon material, realizes the multi-atom doping synergistic effect in the carbon material to improve the catalytic performance of the material, and the introduction of P element enhances the synergistic effect among elements in the Co-N-C after phosphorization, thereby forming a CoP compound and creating more catalytic active sites.
Preferably, the cobalt source in step (1) comprises any one of cobalt chloride hexahydrate, cobalt sulfate heptahydrate or cobalt nitrate hexahydrate.
Preferably, the nitrogen source comprises any one of dicyandiamide, polyaniline, polypyrrole or melamine.
Preferably, the additive comprises any one of ammonium chloride, ammonium sulfate or ammonium nitrate.
Preferably, the molar ratio of the cobalt source, nitrogen source and additive is 1: (55-60): (450-500), for example: 1:55:450, 1:56:480, 1:57:475, 1:58:490, or 1:60:500, etc.
Preferably, the heating and stirring temperature in the step (1) is 50-70 ℃, for example: 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃ and the like.
Preferably, the heating and stirring time is 5-8 h, for example: 5h, 5.5h, 6h, 6.5h, 7h or 8h and the like.
Preferably, the grinding treatment is performed before the one-step sintering.
Preferably, the temperature of the one-step sintering is 500-600 ℃, for example: 500 deg.C, 520 deg.C, 550 deg.C, 580 deg.C or 600 deg.C.
Preferably, the time of the one-step sintering is 1-3 h, for example: 1h, 1.5h, 2h, 2.5h or 3h and the like.
Preferably, the carbon source of step (2) comprises any one of glucose, citric acid or fructose.
Preferably, the mass ratio of the carbon source to the precursor is (0.8-1): 1, such as: 0.8:1, 0.85:1, 0.9:1, 0.95:1 or 1:1, etc.
Preferably, the temperature of the hydrothermal reaction is 150-200 ℃, for example: 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃ and the like.
Preferably, the hydrothermal reaction time is 8-12 h, for example: 8h, 9h, 10h, 11h or 12h and the like.
Preferably, the suspension obtained from the hydrothermal reaction is filtered, dried and ground before the two-step sintering treatment in step (2).
Preferably, the two-step sintering process is performed under an inert atmosphere.
Preferably, the temperature of the two-step sintering treatment is 700-900 ℃, for example: 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C or 900 deg.C.
Preferably, the time of the two-step sintering treatment is 0.5-2 h, for example: 0.5h, 1h, 1.5h or 2h and the like.
Preferably, the mass ratio of the carbon-coated precursor to the phosphorus source in the step (3) is (0.8-1.2): (0.8-1.2), for example: 0.8:0.9, 0.8:1, 0.8:1.1, 0.9:0.8, 1:0.8 or 1:1, etc., preferably 1: 1.
Preferably, the means of mixing comprises milling.
Preferably, the grinding time is 10-20 min, such as: 10min, 12min, 15min, 18min or 20min and the like.
Preferably, the three-step sintering treatment in step (3) is performed under an inert atmosphere.
Preferably, the temperature of the three-step sintering treatment is 300-400 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃ or 400 ℃ and the like.
Preferably, the time of the three-step sintering treatment is 1-3 h, for example: 1h, 1.2h, 1.5h, 2h, 2.5h or 3h and the like.
In a second aspect, the present invention provides a fuel cell catalyst made by the method of the first aspect.
Preferably, the fuel cell catalyst comprises a cobalt-carbon backbone and nitrogen and phosphorus elements doped therein.
In a third aspect, the present invention provides a fuel cell comprising a fuel cell catalyst as described in the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention is formed by sintering dicyanodiamine and ammonium chlorideg-C3N4As a template, cobalt chloride is used as a metal source, and carbonized glucose is coated on g-C through continuous dehydration and crosslinking processes at high temperature3N4Obtaining a porous sheet product on the template. The prepared nitrogen-doped cobalt-carbon material is further phosphorized, the multi-atom doping synergistic effect in the carbon material is realized to improve the catalytic performance of the material, and through phosphorization and introduction of the P element, the synergistic effect among elements in the Co-N-C is enhanced, a CoP compound is formed, and more catalytic active sites are created.
(2) The prepared cobalt/phosphorus-nitrogen-carbon catalyst has effective electrocatalytic oxygen reduction effect on the ORR process, has lower cost and has popularization and application potentials.
Drawings
FIG. 1 is a CV diagram of a fuel cell catalyst according to example 1 of the present invention.
Fig. 2 is a plot of the LSV of the fuel cell catalyst described in example 1 of the present invention.
FIG. 3 is an i-t plot of a fuel cell catalyst according to example 1 of the present invention.
FIG. 4 is a K-L plot of a fuel cell catalyst according to example 1 of the present invention.
Figure 5 is a plot of the double layer current versus scan rate fitted to a fuel cell catalyst as described in example 1 of the present invention.
FIG. 6 is a graph comparing the linear sweep voltammograms of the catalysts obtained in example 1 of the present invention and comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a fuel cell catalyst, which is prepared as follows:
(1) 2g (23.8mmol) of dicyanodiamide, 95.17mg (0.4mmol) of cobalt chloride hexahydrate and 10g (187mmol) of ammonium chloride are weighed into a 50ml beaker, 30ml of deionized water is added, the beaker is placed on a magnetic stirrer and stirred in a water bath at 60 ℃ for 6h, and then the clear solution is poured into a clean and dry culture dish and freeze-dried for 24 h. Taking out the materials, grinding, levigating, pouring into a crucible, placing into a muffle furnace, and sintering at 550 ℃ for 2h to obtain a precursor;
(2) weighing 0.5g of precursor and 0.432g of glucose, adding 30ml of deionized water, placing the mixture on a magnetic stirrer, stirring for 6 hours, pouring the stirred suspension into a crucible, placing the crucible into a hydrothermal reaction kettle, placing the kettle in an electrothermal blowing drying box, reacting at a constant temperature of 180 ℃ for 10 hours, carrying out suction filtration on the brown suspension after reaction, placing a filter membrane attached with the material in a clean and dry culture dish, placing the culture dish in the electrothermal blowing drying box, drying at a constant temperature of 70 ℃, grinding the dry material, pouring the ground material into the crucible, placing the crucible in a tubular furnace, sintering at a temperature of 900 ℃ for 1 hour under a high-purity argon atmosphere (introducing high-purity argon for 40min in advance to remove air in the tube), and naturally cooling to room temperature under the argon atmosphere to obtain a carbon-coated precursor;
(3) weighing 28mg of carbon-coated precursor, adding 28mg of sodium hypophosphite, uniformly mixing and grinding for 15min, pouring into a crucible, placing into a tube furnace, sintering for 2h (the temperature rise speed is 2 ℃/min) at 350 ℃ under the atmosphere of high-purity argon (high-purity argon is introduced for 40min in advance to remove air in the tube), and absorbing tail gas by using a copper sulfate solution to obtain the fuel cell catalyst.
Example 2
(1) 1.95g (23.2mmol) dicyanodiamide, 95.17mg (0.4mmol) cobalt chloride hexahydrate and 9.5g (177.6mmol) ammonium chloride are weighed out in a 50ml beaker, 30ml deionized water is added, the beaker is placed on a magnetic stirrer and stirred in a water bath at 60 ℃ for 6h, and the clear solution is poured into a clean and dry culture dish and freeze-dried for 24 h. Taking out the materials, grinding, levigating, pouring into a crucible, placing into a muffle furnace, and sintering at 580 ℃ for 2h to obtain a precursor;
(2) weighing 0.5g of precursor and 0.45g of glucose, adding 30ml of deionized water, placing the mixture on a magnetic stirrer, stirring for 6 hours, pouring the stirred suspension into a crucible, placing the crucible into a hydrothermal reaction kettle, placing the kettle in an electrothermal blowing drying oven, reacting at the constant temperature of 190 ℃ for 10 hours, carrying out suction filtration on the brown suspension after reaction, placing a filter membrane attached with the material in a clean and dry culture dish, placing the culture dish in the electrothermal blowing drying oven, drying at the constant temperature of 70 ℃, grinding the dry material, pouring the ground material into the crucible, placing the crucible in a tubular furnace, sintering at the temperature of 950 ℃ for 1 hour under the atmosphere of high-purity argon (introducing high-purity argon in advance for 40min to remove air in the tube), and naturally cooling to the room temperature under the atmosphere of argon to obtain a carbon-coated precursor;
(3) weighing 28mg of carbon-coated precursor, adding 28mg of sodium hypophosphite, uniformly mixing and grinding for 15min, pouring into a crucible, placing into a tube furnace, sintering for 2h (the temperature rise speed is 2 ℃/min) at 380 ℃ under the atmosphere of high-purity argon (high-purity argon is introduced for 40min in advance to remove air in the tube), and absorbing tail gas by using a copper sulfate solution to obtain the fuel cell catalyst.
Example 3
This example is different from example 1 only in that the dicyanodiamide (1) has a mass of 1.8g (molar ratio of cobalt source to nitrogen source is 1:53), and the other conditions and parameters are exactly the same as those of example 1.
Example 4
This example is different from example 1 only in that (1) the dicyanodiamide has a mass of 2.1g (the molar ratio of the cobalt source to the nitrogen source is 1:62), and the other conditions and parameters are exactly the same as those in example 1.
Example 5
This example differs from example 1 only in that, in (3), the mass ratio of the phosphorus source to the carbon-coated precursor is 0.7:1, and the other conditions and parameters are exactly the same as those in example 1.
Example 6
This example differs from example 1 only in that, in (3), the mass ratio of the phosphorus source to the carbon-coated precursor is 1:0.7, and the other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that the treatment with the addition of a phosphorus source in step (3) is not carried out, and the other conditions and parameters are exactly the same as those in example 1.
And (3) performance testing:
the fuel cell catalyst prepared in example 1 was subjected to electrochemical tests on a three-electrode cell (rotating disk electrode), i.e. a Working Electrode (WE), a Counter Electrode (CE) and a Reference Electrode (RE), at room temperature. In the invention, the used electrochemical workstation is a multi-channel electrochemical comprehensive tester, a counter electrode adopts a platinum electrode, a reference electrode adopts a saturated Ag/AgCl electrode, a working electrode adopts a glassy carbon electrode (the diameter is 5mm) to load a catalytic material, an electrolyte adopts 0.1M KOH solution, and high-purity oxygen is introduced for 30min before testing to reach oxygen saturation.
Preparation of a working electrode: 5mg of electrocatalyst sample is weighed and dispersed in 800. mu.L of absolute ethanol and 150. mu.L of deionized water, 50. mu.L of 0.5 mass percent Nafion solution is added, and then ultrasonic dispersion is carried out for about 1 hour to form an ink-like homogeneous solution. Then, 15 μ L of the prepared catalyst dispersion was slowly dropped onto the center of the pretreated round glassy carbon electrode by a microsyringe, and the dispersion was uniformly spread over the electrode, and naturally left to stand at room temperature and dried to obtain a working electrode.
The test method mainly comprises the following steps: cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), chronoamperometry (i-t).
CV: before testing, high-purity oxygen is introduced into the electrolyte for 30min to reach an oxygen saturation state. The scanning voltage range is set to be 0.327-0.397V (vs. Ag/AgCl), the scanning speeds are respectively 10mV/s, 20mV/s, 30mV/s, 40mV/s, 50mV/s, 60mV/s and 70mV/s, the test result is shown in figure 1, as can be seen from figure 1, in the KOH solution saturated by nitrogen, the CV curve shows the capacitance characteristic of quasi-quadrilateral rows, and the reduction peak is not obvious. In contrast, a significant ORR reduction peak at 0.671V (vs RHE) appears on the CV curve at oxygen saturation, indicating that the Co-N-C catalyst has oxygen-reducing electrocatalytic activity.
LSV: linear potential scanning is applied between the working electrode and the reference electrode, and the current flowing between the working electrode and the auxiliary electrode is measured to obtain a polarization curve. Before testing, high-purity oxygen needs to be introduced into the electrolyte for 30min to maintain oxygen saturation of the electrolyte, and a certain oxygen flow is also kept in the testing process. Linear voltammetric scanning at-1 to 0.2 rpm at electrode rotation speeds of 400rpm, 625rpm, 900rpm, 1225rpm, 1600rpm, and 2025rpm, respectivelyThe test was carried out in a potential range of V (vs. Ag/AgCl) with a scanning rate set at 10mV/s, and the test results are shown in FIG. 2. from FIG. 2, it can be seen that the LSV curve shows that the limiting current density is significantly increased during the increase of the rotation rate of the rotating disk electrode from 400rpm to 2025rpm, and the limiting diffusion current density of the Co-N-C catalyst can reach-5.14 mA/cm2Near the limiting diffusion current density of 20 wt% commercial Pt/C (-5.47 mA/cm)2) (ii) a Initial potential 1.09V (vs RHE); the half-wave potential was 0.778V (vs RHE).
i-t: high-purity oxygen is introduced into the electrolyte in advance to achieve and maintain an oxygen saturation state, the change condition of the current density of the ORR along with time is measured under the fixed voltage of 0.6V (vs. Ag/AgCl) and the electrode rotating speed of 1600rpm, the test result is shown in figure 3, and as can be seen from figure 3, under the alkaline condition, the fuel cell catalyst disclosed by the invention still keeps more than 98% of current after being tested for 3500 s. The fuel cell catalyst provided by the invention is proved to have good stability.
The K-L diagram of the fuel cell prepared in example 1 is shown in fig. 4, and it can be seen from fig. 4 that the number of electron transfers in the oxygen reduction process of the fuel cell catalyst is about 4, which is very close to the theoretical number of electron transfers of 4.0, calculated from the slope of each K-L line, indicating that the oxygen reduction electrocatalytic process of the catalyst of the present invention is almost performed according to the four electron process.
The graph of the fitted line of the electric double layer current versus the scanning rate of the fuel cell catalyst obtained in example 1 is shown in fig. 5, and the electric double layer capacitance (C) of the fuel cell catalyst is shown from the slope of the fitted line of the electric double layer current versus the scanning ratedl) Is 22.7mF/cm2The catalyst has large active specific surface area and good catalytic activity.
The catalysts obtained in example 1 and comparative example 1 were compared by linear sweep voltammograms in 0.1M KOH solution saturated with oxygen, and as shown in FIG. 6, it can be seen from FIG. 6 that the ultimate diffusion current density of the Co-N-C catalyst under the same conditions was-5.14 mA/cm2The limiting diffusion current density of the fuel cell catalyst (Co/P-N-C catalyst) prepared by the invention is-5.39 mA/cm2It is clear that the latter is closer to 20 wt.%Limiting diffusion Current Density of commercial Pt/C (-5.47 mA/cm)2) (ii) a The initial potential of the Co/P-N-C catalyst is 1.11V (vs RHE), which is higher than the initial potential of the Co-N-C catalyst by 1.09V (vs RHE); the half-wave potential of the Co/P-N-C catalyst is 0.803V (vs RHE), which is higher than the half-wave potential of Co-N-C, which is 0.778V (vs RHE). Therefore, the catalytic performance of the Co-N-C catalyst after phosphorization is obviously enhanced. Through phosphorization, the introduction of P element enhances the synergistic effect among elements in Co-N-C, and creates more catalytic active sites.
The fuel cell catalysts obtained in examples 1 to 6 and comparative example 1 were used, and the kinetic current densities at 0.2V and 0.6V potentials were measured in an oxygen-saturated 0.1M KOH solution, and the current holding ratio was measured at 0.6V in an oxygen-saturated 0.1M KOH solution under a constant voltage test, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, from examples 1-6, the fuel cell catalyst of the present invention has 31.2mA/cm in 0.2V potential in 0.1M KOH solution saturated with oxygen2The dynamic current density can reach 35.6mA/cm under the potential of 0.6V2Above, all higher than commercial Pt/C13.5 mA/cm2The fuel cell catalyst provided by the invention has excellent oxygen reduction activity, and can still maintain more than 91% of current after 3500s of test.
From the comparison of example 1 with examples 3 to 4, the molar ratio of cobalt source and nitrogen source affects the performance of the catalyst obtained, and the molar ratio of cobalt source and nitrogen source is controlled to be 1: (55-60) the fuel cell catalyst with excellent performance can be prepared, if the cobalt loading is too small, the catalyst does not have enough cobalt atoms and nitrogen atoms to form a cobalt-nitrogen structure, the cobalt-nitrogen structure is an active site of oxygen reduction catalytic reaction, and the catalytic activity is reduced due to the fact that the number of the cobalt-nitrogen structure is reduced; if the cobalt loading is too large, the cobalt content exceeds the saturation adsorption amount of nitrogen atoms, metal cobalt or cobalt oxide particles are generated on the surface of the catalyst and cover the active sites of the catalyst, and the metal cobalt and the cobalt oxide have no oxygen reduction activity, so that the activity of the catalyst is reduced.
Comparing the embodiment 1 with the embodiment 5-6, the quality ratio of the phosphorus source and the carbon-coated precursor can affect the performance of the prepared catalyst, the quality ratio of the phosphorus source and the carbon-coated precursor is controlled to be (0.8-1.2), and (0.8-1.2), the fuel cell catalyst with excellent performance can be prepared, if the phosphorus source is too little, enough CoP compound is difficult to form; if the phosphorus source is too much, there are not enough cobalt atoms to bond with the phosphorus atoms, the phosphorus particles will cover the active sites of the catalyst, and the phosphorus particles will not have oxygen reduction activity, resulting in a decrease in catalyst activity.
The catalytic performance of the phosphated Co-N-C catalyst is significantly enhanced as compared to example 1 and comparative example 1. Through phosphorization, the introduction of P element enhances the synergistic effect among elements in Co-N-C, a CoP compound is formed, and more catalytic active sites are created.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing a fuel cell catalyst, comprising the steps of:
(1) mixing a cobalt source, a nitrogen source and an additive with a solvent, heating and stirring uniformly, then freeze-drying, and carrying out one-step sintering treatment to obtain a precursor;
(2) mixing the precursor obtained in the step (1) with a carbon source, carrying out hydrothermal reaction, and carrying out two-step sintering treatment to obtain a carbon-coated precursor;
(3) and (3) mixing the carbon-coated precursor obtained in the step (2) with a phosphorus source, and carrying out three-step sintering treatment to obtain the fuel cell catalyst.
2. The method of claim 1, wherein the cobalt source of step (1) comprises any one of cobalt chloride hexahydrate, cobalt sulfate heptahydrate, or cobalt nitrate hexahydrate;
preferably, the nitrogen source comprises any one of dicyandiamide, polyaniline, polypyrrole or melamine;
preferably, the additive comprises any one of ammonium chloride, ammonium sulfate or ammonium nitrate;
preferably, the molar ratio of the cobalt source, nitrogen source and additive is 1: (55-60) and (450-500).
3. The method according to claim 1 or 2, wherein the temperature of the heating and stirring in the step (1) is 50 to 70 ℃;
preferably, the heating and stirring time is 5-8 h;
preferably, grinding treatment is carried out before the one-step sintering;
preferably, the temperature of the one-step sintering is 500-600 ℃;
preferably, the time of the one-step sintering is 1-3 h.
4. The method according to any one of claims 1 to 3, wherein the carbon source of step (2) comprises any one of glucose, citric acid or fructose;
preferably, the mass ratio of the carbon source to the precursor is (0.8-1): 1;
preferably, the temperature of the hydrothermal reaction is 150-200 ℃;
preferably, the hydrothermal reaction time is 8-12 h.
5. The method according to any one of claims 1 to 4, wherein the suspension obtained by the hydrothermal reaction is subjected to suction filtration, drying and grinding before the two-step sintering treatment in step (2);
preferably, the two-step sintering treatment is carried out under an inert atmosphere;
preferably, the temperature of the two-step sintering treatment is 700-900 ℃;
preferably, the time of the two-step sintering treatment is 0.5-2 h.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the carbon-coated precursor to the phosphorus source in step (3) is (0.8-1.2): (0.8-1.2), preferably 1: 1;
preferably, the means of mixing comprises milling;
preferably, the grinding time is 10-20 min.
7. The production method according to any one of claims 1 to 6, wherein the three-step sintering treatment in step (3) is performed under an inert atmosphere;
preferably, the temperature of the three-step sintering treatment is 300-400 ℃;
preferably, the time of the three-step sintering treatment is 1-3 h.
8. A fuel cell catalyst, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. The fuel cell catalyst according to claim 8, wherein the fuel cell catalyst comprises a cobalt-carbon backbone and nitrogen and phosphorus elements doped therein.
10. A fuel cell comprising the fuel cell catalyst according to claim 8 or 9.
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