CN114864972A - High-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to fuel cell and preparation method and application thereof - Google Patents

High-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to fuel cell and preparation method and application thereof Download PDF

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CN114864972A
CN114864972A CN202210422310.7A CN202210422310A CN114864972A CN 114864972 A CN114864972 A CN 114864972A CN 202210422310 A CN202210422310 A CN 202210422310A CN 114864972 A CN114864972 A CN 114864972A
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ethanol
nitrogen
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崔志明
卢明佳
黄志宏
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South China University of Technology SCUT
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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
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Abstract

The invention discloses a high-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to a fuel cell, and a preparation method and application thereof. Adding ammonia water and tetraethoxysilane into a mixed solution of water and ethanol, reacting, and centrifugally drying to obtain silicon dioxide pellets; placing the silicon dioxide pellets in an ethanol water solution, performing ultrasonic dispersion, then adding ethylenediamine, resorcinol and formaldehyde solution, stirring, adding tetraethoxysilane, aging, centrifugally washing and drying; calcining and etching to obtain the hollow bowl-shaped nitrogen-carbon-containing carrier. The nitrogen-containing bowl-shaped carbon carrier prepared by the invention has large specific surface area, rich mesopores are beneficial to regulating and controlling the small-particle-size growth of metal particles, the interaction between metal and the carrier can be enhanced by doped nitrogen, and the bowl-shaped carbon has the advantages of large volume density, high stacking density and the like relative to a hollow carbon sphere.

Description

High-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to fuel cell and preparation method and application thereof
Technical Field
The invention relates to the technical field of new energy materials, in particular to a high-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to a fuel cell, and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are one of the important new energy technologies in the 21 st century because of their excellent characteristics such as high energy conversion efficiency, zero pollution emission of water as a product, and the like. However, commercial application of fuel cells has required long search lines due to the cost and performance of the catalyst and stability issues among others. The non-noble metal is used for replacing part of noble metal elements to form alloy, so that the use amount of the noble metal platinum can be reduced, and the adsorption of the platinum on a reaction intermediate can be reduced through a stress effect and an electronic effect, thereby improving the performance of the catalyst. The carbon carrier is a commonly used carrier in the PEMFC, can prevent the agglomeration of the catalyst, and simultaneously, the doping of the heteroatom can increase the interaction between the metal and the carrier and enhance the performance of the catalyst. Common carbon carriers such as XC-72, graphene, carbon nanotubes and the like have small specific surface area, undeveloped pore structure and lack of heteroatom doping, and noble metals are easy to agglomerate on the surface to generate large particles. Therefore, the synthesis of carbon carriers with high specific surface area and doped with heteroatoms is urgently needed.
At present, bowl-shaped carbon synthesis methods are various, wherein a hard template is most widely used due to simple and convenient operation and easy control. For example, the prepared hollow bowl-shaped polystyrene microsphere is sulfonated by concentrated sulfuric acid, then metal salt, hexamethylene amine and citrate are added, precipitation is carried out, and then the bowl-shaped carbon-supported metal oxide is obtained by calcining under an inert atmosphere (Chinese patent 201410406726.5). The aperture of the bowl-shaped carbon of the method can not be adjusted, a surfactant is needed, bowl-shaped polystyrene is difficult to synthesize, and the steps are complicated. Taking silicon dioxide as a hard template, polymerizing phenolic resin on the silicon dioxide, carbonizing the obtained compound, sulfonating the compound by concentrated sulfuric acid, adding metal salt and citrate, etching the silicon dioxide to obtain hollow carbon spheres doped with metal oxide, adding the hollow carbon spheres into the hollow carbon spheres, and performing ball milling and calcination on the hollow carbon spheres to obtain the bowl-shaped hollow carbon composite material. However, the preparation process of the method is complex, the use of concentrated sulfuric acid is dangerous, bowl-shaped carbon cannot be obtained in one step, and the size of metal particles cannot be controlled. Therefore, there is a need to search for a simple and versatile method for precisely synthesizing bowl-shaped carbon in one step.
Disclosure of Invention
The invention aims to provide a hollow bowl-shaped nitrogen-containing carbon-based carrier with a high specific surface area, which is applied to a fuel cell, and a preparation method and application thereof. The raw material for preparing the carbon carrier is low in price, the method is simple and easy to operate, and pollution is less. The carbon carrier has large specific surface area, and the mesoporous structure and the heteroatom doping can prevent the agglomeration growth of metal particles.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a hollow bowl-shaped nitrogen-containing carbon-based carrier with high specific surface area applied to a fuel cell comprises the following steps:
(1) adding ammonia water and tetraethoxysilane into a mixed solution of water and ethanol, reacting, and centrifugally drying to obtain silicon dioxide pellets;
(2) placing the silicon dioxide pellets in the step (1) in an ethanol water solution, performing ultrasonic dispersion, then adding ethylenediamine, resorcinol and formaldehyde solution, stirring, adding tetraethoxysilane, aging, centrifugally washing and drying; calcining and etching to obtain the hollow bowl-shaped nitrogen-containing carbon-based carrier with the high specific surface.
Preferably, in the step (1), the volume ratio of water to ethanol in the mixed solution of water and ethanol is 1 (0.1-10); the reaction time is 0.1-5 h.
Preferably, in the step (1), the volume ratio of the ammonia water, the tetraethoxysilane, the water and the ethanol is (1-8) to (1-10) to (2-10) to (10-90); the volume concentration of the ammonia water is 10-25%.
Preferably, in the step (2), the stirring time is 10-30 minutes; the aging time is 1-4 days, and the temperature is 20-60 ℃; the calcining temperature is 600-1100 ℃, and the time is 1-6 h; the etching solution used for etching is an HF solution, the concentration is 5% -40%, and the etching time is 1-48 h.
Preferably, in the step (2), the mass-to-volume ratio of the silica spheres to the ethanol aqueous solution is 3-60 mg/ml; the volume ratio of ethanol to water in the ethanol water solution is (1-10): 2;
the dosage ratio of the silicon dioxide pellets to the ethylenediamine to the resorcinol to the formaldehyde solution to the ethyl orthosilicate is 0.5-5g to 0.1-3ml to 0.2-2g to 0.3-3ml to 0.5-4 ml; the mass concentration of the formaldehyde solution is 30-40%.
The nitrogen-containing carbon-based carrier with high specific surface area and hollow bowl shape, which is applied to the fuel cell and is prepared by the preparation method.
The application of the high-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to the fuel cell in preparing the electrode material of the fuel cell comprises the following steps:
(a) adding the hollow bowl-shaped nitrogen-containing carbon-based carrier into a chloroplatinic acid and non-noble metal salt solution, ultrasonically dispersing uniformly, and then freeze-drying;
(b) and (b) carrying out high-temperature annealing on the intermediate obtained by freeze drying in the step (a) in a hydrogen-argon mixed gas to obtain the fuel cell electrode material.
Preferably, in the step (a), the concentrations of the chloroplatinic acid and the non-noble metal salt are respectively 0.1-20 mol/L; the non-noble metal salt is one of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, cobalt acetylacetonate, nickel nitrate, ferric nitrate, zinc chloride, ferric chloride, manganese chloride and chromium chloride; the ultrasonic time is 0.5-24 h; the freeze drying time is 2-48h, and the temperature is-60 to-40 ℃.
Preferably, in the step (a), the mass ratio of the hollow nitrogen-doped bowl-shaped carbon carrier to the total amount of platinum and non-noble metal is 1: (2-5).
Preferably, in the step (b), the temperature of the high-temperature annealing is 500-900 ℃, and the time is 2-12 h; the volume fraction of the hydrogen in the hydrogen-argon mixed gas is 5-20%.
The preparation process of the invention is simple and convenient to operate, the prepared nitrogen-containing bowl-shaped carbon carrier has large specific surface area, rich mesopores are beneficial to regulating and controlling the small particle size growth of metal particles, the doped nitrogen can enhance the interaction between metal and the carrier, and the bowl-shaped carbon has the advantages of large volume density, high stacking density and the like relative to the hollow carbon spheres.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, nitrogen-doped bowl-shaped carbon can be directly prepared by a simple method and used as a carrier, a metal precursor is soaked on the bowl-shaped carbon, the metal precursor is confined in the hollow carbon by a freeze drying method, and then high-temperature annealing is carried out to obtain the catalyst with high volume density. The preparation method is simple to operate, does not need to use a surfactant, can directly prepare the hollow bowl-shaped carbon, can easily prepare the small-particle-size load compound, and is simple and convenient and strong in repeatability.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a material prepared according to the present invention.
Fig. 2 is an SEM image of the nitrogen-containing hollow bowl-shaped carbon prepared in example 1.
Fig. 3 is an SEM image of the hollow carbon spheres prepared in example 2.
Fig. 4 is a nitrogen adsorption and desorption curve and a pore size distribution diagram of the nitrogen-containing hollow bowl-shaped carbon prepared in example 1.
FIG. 5 is the ordered Pt prepared in example 3 3 TEM image of Co/N-BC.
FIG. 6 is the ordered Pt prepared in example 3 3 Mapping of the middle N of Co/N-BC.
FIG. 7 is the ordered Pt prepared in example 3 3 Graph of oxygen reduction performance of Co/N-BC.
FIG. 8 is the ordered Pt prepared in example 3 3 Co/N-BC and Pt 3 Mass Activity histogram of Co/HPCS.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
The preparation method of the hollow bowl-shaped nitrogen-containing carbon-based carrier with high specific surface area comprises the following steps:
the preparation method of the high specific surface area hollow nitrogen-doped bowl-shaped carbon refers to figure 1.
(1) Adding 6ml tetraethyl orthosilicate into 50ml ethanol, 5ml water and 3ml ammonia water solution (volume concentration is 25%), stirring for 50 minutes at room temperature, centrifugally drying to obtain silicon dioxide pellets, and then adding 0.5g SiO 2 Adding 160mL of mixed solution of water and ethanol (volume ratio is 6: 10) into the pellets, performing ultrasonic dispersion, then adding 1mL of ethylenediamine, 0.4g of resorcinol and 0.5mL of formaldehyde solution (mass concentration is 37%), stirring for 20 minutes, then adding 1mL of ethyl orthosilicate, then stirring at room temperature for 24 hours, performing centrifugal washing by deionized water and ethanol, collecting samples, drying in an oven at 80 ℃ for 12 hours, then placing in a tube furnace, raising the temperature to 900 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, and preserving the heat for 2 hours.
(2) Grinding the sample obtained in the step (1), washing silicon dioxide with 20% HF solution, washing with water and ethanol to neutrality, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain the hollow nitrogen-doped bowl-shaped carbon with high specific surface area; FIGS. 2 and 4 are SEM image and nitrogen adsorption/desorption curve and pore size distribution diagram, and the specific surface area is 1226m 2 The mesopores are mainly distributed around 3 nm.
Example 2
The preparation method of the hollow carbon sphere comprises the following steps:
(1) adding 6ml tetraethyl orthosilicate into 50ml ethanol, 5ml water and 3ml ammonia water solution (volume concentration is 25%), stirring for 50 minutes at room temperature, centrifugally drying to obtain silicon dioxide pellets, and then adding 0.5g SiO 2 Adding 160mL of mixed solution of water and ethanol (volume ratio is 6: 10) into the pellets, ultrasonically dispersing, adding 0.4g of resorcinol and 0.5mL of formaldehyde solution (mass concentration is 37%), stirring for 20 minutes, adding 0.3mL of ethyl orthosilicate, stirring at room temperature for 24 hours, and addingAnd centrifugally washing the sample by using deionized water and ethanol, collecting the sample, drying the sample in an oven at 80 ℃ for 12 hours, then putting the sample into a tubular furnace, raising the temperature to 900 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and keeping the temperature for 2 hours.
(2) And (2) grinding the sample obtained in the step (1), washing away silicon dioxide with 20% HF solution, washing with water and ethanol to neutrality, drying in a vacuum drying oven at 80 ℃ for 24h to obtain hollow carbon spheres, wherein an SEM image is shown in FIG. 3.
Example 3
The preparation method of the high-specific surface area hollow bowl-shaped nitrogen-containing carbon-based carrier and the electrode material comprises the following steps:
(1) adding 6ml tetraethyl orthosilicate into 50ml ethanol, 5ml water and 3ml ammonia water solution (volume concentration is 25%), stirring for 50 minutes at room temperature, centrifugally drying to obtain silicon dioxide pellets, and then adding 0.5g SiO 2 Adding 160mL of mixed solution of water and ethanol (volume ratio is 6: 10) into the pellets, performing ultrasonic dispersion, then adding 1mL of ethylenediamine, 0.4g of resorcinol and 0.5mL of formaldehyde solution (mass concentration is 37%), stirring for 20 minutes, then adding 1mL of ethyl orthosilicate, then stirring at room temperature for 24 hours, performing centrifugal washing by deionized water and ethanol, collecting samples, drying in an oven at 80 ℃ for 12 hours, then placing in a tube furnace, raising the temperature to 900 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, and preserving the heat for 2 hours.
(2) And (2) grinding the sample obtained in the step (1), washing away silicon dioxide by using a 20% HF solution, washing the silicon dioxide to be neutral by using water and ethanol, and drying the silicon dioxide in a vacuum drying oven at 80 ℃ for 24 hours to obtain the hollow nitrogen-doped bowl-shaped carbon with the high specific surface area.
(3) Taking 20mg of the carbon carrier obtained in the step (2), and adding 129uL of 0.2M H 2 PtCl 6 Solution and 1M Co (NO) 3 ) 2 And (3) after the mixed solution of the solution is uniformly dispersed by ultrasonic wave, freezing and drying, pre-freezing for 5 hours at the temperature of minus 50 ℃, and then vacuumizing and drying for 24 hours. The intermediate obtained was at 8% H 2 And (2) carrying out high-temperature annealing treatment in an/Ar environment at the temperature of 750 ℃ for 2 h. Then obtaining the electrode material Pt of the cathode catalyst layer of the fuel cell 3 The TEM and nitrogen distribution of Co/N-BC are shown in FIGS. 5 and 6. Oxygen reductionThe performance and immunogenicity curve is shown in FIG. 7; the mass activity histogram is shown in fig. 8.
Hollow carbon sphere loaded Pt 3 Co/HPCS was prepared in the same manner except that the selected carbon was the hollow carbon sphere prepared in example 2.
Example 4
The preparation method of the high-specific surface area hollow bowl-shaped nitrogen-containing carbon-based carrier and the electrode material comprises the following steps:
(1) adding 6ml tetraethyl orthosilicate into 50ml ethanol, 5ml water and 3ml ammonia water solution (volume concentration is 25%), stirring for 50 minutes at room temperature, centrifugally drying to obtain silicon dioxide pellets, and then adding 0.5g SiO 2 Adding 160mL of mixed solution of water and ethanol (volume ratio is 6: 10) into the pellets, performing ultrasonic dispersion, then adding 1mL of ethylenediamine, 0.4g of resorcinol and 0.5mL of formaldehyde solution (mass concentration is 37%), stirring for 20 minutes, then adding 1mL of ethyl orthosilicate, then stirring at room temperature for 24 hours, performing centrifugal washing by deionized water and ethanol, collecting samples, drying in an oven at 80 ℃ for 12 hours, then placing in a tube furnace, raising the temperature to 900 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, and preserving the heat for 2 hours.
(2) And (2) grinding the sample obtained in the step (1), washing away silicon dioxide by using a 20% HF solution, washing the silicon dioxide to be neutral by using water and ethanol, and drying the silicon dioxide in a vacuum drying oven at 80 ℃ for 24 hours to obtain the hollow nitrogen-doped bowl-shaped carbon with the high specific surface area.
(3) Taking 20mg of the carbon carrier obtained in the step (2), and then adding 0.2M H 2 PtCl 6 Solution and 1M FeCl 3 The solution is frozen and dried after being dispersed evenly by ultrasonic, and is pre-frozen for 5 hours at the temperature of minus 50 ℃ and then is vacuumized and dried for 24 hours. The intermediate obtained was at 8% H 2 And (2) carrying out high-temperature annealing treatment in an/Ar environment at the temperature of 750 ℃ for 2 h. Then obtaining the electrode material Pt of the cathode catalyst layer of the fuel cell 3 Fe/N-BC。
Example 5
The preparation method of the high-specific surface area hollow bowl-shaped nitrogen-containing carbon-based carrier and the electrode material comprises the following steps:
(1)6ml tetraethyl orthosilicate was added to 50ml ethanol, 5ml water and 3ml aqueous ammonia solution(volume concentration: 25%) at room temperature for 50 minutes, and then dried by centrifugation to obtain silica pellets, and then 0.5g of SiO was added 2 Adding 160mL of mixed solution of water and ethanol (volume ratio is 6: 10) into the pellets, performing ultrasonic dispersion, then adding 1mL of ethylenediamine, 0.4g of resorcinol and 0.5mL of formaldehyde solution (mass concentration is 37%), stirring for 20 minutes, then adding 1mL of tetraethoxysilane, then stirring for 24 hours at room temperature, centrifugally washing with deionized water and ethanol, collecting samples, drying for 12 hours at 80 ℃ in an oven, then placing in a tube furnace, raising the temperature to 900 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, and preserving the heat for 2 hours.
(2) And (2) grinding the sample obtained in the step (1), washing away silicon dioxide by using a 20% HF solution, washing the silicon dioxide to be neutral by using water and ethanol, and drying the silicon dioxide in a vacuum drying oven at 80 ℃ for 24 hours to obtain the hollow nitrogen-doped bowl-shaped carbon with the high specific surface area.
(3) Taking 20mg of the carbon carrier obtained in the step (2), and adding 129uL of 0.2M H 2 PtCl 6 And 1M MnCl 2 The mixed solution is frozen and dried after being evenly dispersed by ultrasonic wave, and is pre-frozen for 5 hours at the temperature of minus 50 ℃ and then is vacuumized and dried for 24 hours. The intermediate obtained was at 8% H 2 And (2) carrying out high-temperature annealing treatment in an/Ar environment at the temperature of 750 ℃ for 2 h. Then obtaining the electrode material Pt of the cathode catalyst layer of the fuel cell 3 Mn/N-BC
Example 6
The preparation method of the high-specific surface area hollow bowl-shaped nitrogen-containing carbon-based carrier and the electrode material comprises the following steps:
(1) adding 6ml tetraethyl orthosilicate into 50ml ethanol, 5ml water and 3ml ammonia water solution (volume concentration is 25%), stirring for 50 minutes at room temperature, centrifugally drying to obtain silicon dioxide pellets, and then adding 0.5g SiO 2 Adding 160mL of mixed solution of water and ethanol (volume ratio is 6: 10) into the pellets, ultrasonically dispersing, then adding 1mL of ethylenediamine, 0.4g of resorcinol and 0.5mL of formaldehyde solution (mass concentration is 37%), stirring for 20 minutes, then adding 1mL of ethyl orthosilicate, then stirring at room temperature for 24 hours, centrifugally washing by deionized water and ethanol, collecting samples, drying in an oven at 80 ℃ for 12 hours, then placing in a tube furnace, and placing in a nitrogen atmosphereAnd then, raising the temperature to 900 ℃ at the temperature rise rate of 10 ℃/min, and preserving the temperature for 2 h.
(2) And (2) grinding the sample obtained in the step (1), washing away silicon dioxide by using a 20% HF solution, washing the silicon dioxide to be neutral by using water and ethanol, and drying the silicon dioxide in a vacuum drying oven at 80 ℃ for 24 hours to obtain the hollow nitrogen-doped bowl-shaped carbon with the high specific surface area.
(3) Taking 20mg of the carbon carrier obtained in the step (2), and adding 129uL of 0.2M H 2 PtCl 6 And 1M CrCl 2 The mixed solution is frozen and dried after being evenly dispersed by ultrasonic wave, and is pre-frozen for 5 hours at the temperature of minus 50 ℃ and then is vacuumized and dried for 24 hours. The intermediate obtained was at 8% H 2 And (2) carrying out high-temperature annealing treatment in an/Ar environment at the temperature of 750 ℃ for 2 h. Then obtaining the electrode material Pt of the cathode catalyst layer of the fuel cell 3 Cr/N-BC
Example 7
Respectively weighing 5mg of the electrode active materials prepared in examples 3-6, dispersing the electrode active materials into a mixed solution of 50uL Nafion (5%) solution and 950uL ethanol, transferring 4uL of the electrode active materials to the surface of a platinum-carbon electrode by using a liquid transfer gun after uniform dispersion, naturally drying the electrode active materials in 0.1M HClO 4 The oxygen reduction catalytic activity was tested in solution.
Pt prepared in example 3 3 The mass activity of Co/N-BC is shown in FIG. 8, showing superiority over hollow carbon sphere-supported ordered Pt 3 Co。
The oxygen reduction performance curves of the catalysts prepared in other examples are similar to those of FIG. 7, and all show excellent oxygen reduction performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a hollow bowl-shaped nitrogen-containing carbon-based carrier with high specific surface area applied to a fuel cell is characterized by comprising the following steps:
(1) adding ammonia water and tetraethoxysilane into a mixed solution of water and ethanol, reacting, and centrifugally drying to obtain silicon dioxide pellets;
(2) placing the silicon dioxide pellets in the step (1) in an ethanol water solution, performing ultrasonic dispersion, then adding ethylenediamine, resorcinol and formaldehyde solution, stirring, adding tetraethoxysilane, aging, centrifugally washing and drying; calcining and etching to obtain the hollow bowl-shaped nitrogen-containing carbon-based carrier with the high specific surface.
2. The preparation method according to claim 1, wherein in the step (1), the volume ratio of water to ethanol in the mixed solution of water and ethanol is 1 (0.1-10); the reaction time is 0.1-5 h.
3. The method according to claim 1, wherein in the step (1), the volume ratio of the ammonia water, the tetraethoxysilane, the water and the ethanol is (1-8): 1-10): 2-10: (10-90); the volume concentration of the ammonia water is 10-25%.
4. The production method according to claim 1, wherein in the step (2), the stirring time is 10 to 30 minutes; the aging time is 1-4 days, and the temperature is 20-60 ℃; the calcining temperature is 600-1100 ℃, and the time is 1-6 h; the etching solution used for etching is an HF solution, the concentration is 5% -40%, and the etching time is 1-48 h.
5. The preparation method according to claim 1, wherein in the step (2), the mass-to-volume ratio of the silica spheres to the ethanol aqueous solution is 3 to 60 mg/ml; the volume ratio of ethanol to water in the ethanol aqueous solution is (1-10) to 2;
the dosage ratio of the silicon dioxide pellets to the ethylenediamine to the resorcinol to the formaldehyde solution to the ethyl orthosilicate is 0.5-5g to 0.1-3ml to 0.2-2g to 0.3-3ml to 0.5-4 ml; the mass concentration of the formaldehyde solution is 30-40%.
6. The nitrogen-containing carbon-based support having a hollow bowl shape with a high specific surface area and used for a fuel cell, which is prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the high specific surface area hollow bowl-shaped nitrogen-containing carbon-based support for fuel cells according to claim 6 for the preparation of fuel cell electrode materials, comprising the steps of:
(a) adding chloroplatinic acid and a non-noble metal salt solution into the hollow bowl-shaped nitrogen-containing carbon-based carrier, uniformly dispersing by ultrasonic, and then freeze-drying;
(b) and (b) carrying out high-temperature annealing on the intermediate obtained by freeze drying in the step (a) in a hydrogen-argon mixed gas to obtain the fuel cell electrode material.
8. The use according to claim 7, wherein in step (a), the concentrations of the chloroplatinic acid and the non-noble metal salt are respectively 0.1 to 20 mol/L; the non-noble metal salt is one of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, cobalt acetylacetonate, nickel nitrate, ferric nitrate, zinc chloride, ferric chloride, manganese chloride and chromium chloride; the ultrasonic time is 0.5-24 h; the freeze drying time is 2-48h, and the temperature is-60 to-40 ℃.
9. The use according to claim 7, wherein in step (a), the mass ratio of the hollow nitrogen-doped bowl-shaped carbon support to the total amount of platinum and non-noble metal is 1: (2-5).
10. The use as claimed in claim 7, wherein in the step (b), the temperature of the high temperature annealing is 500-900 ℃ and the time is 2-12 h; the volume fraction of the hydrogen in the hydrogen-argon mixed gas is 5-20%.
CN202210422310.7A 2022-04-21 2022-04-21 High-specific-surface-area hollow bowl-shaped nitrogen-containing carbon-based carrier applied to fuel cell and preparation method and application thereof Pending CN114864972A (en)

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