CN114300693B - Method for improving stability of fuel cell carbon-supported platinum-based catalyst by activating carbon carrier - Google Patents

Method for improving stability of fuel cell carbon-supported platinum-based catalyst by activating carbon carrier Download PDF

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CN114300693B
CN114300693B CN202111638263.1A CN202111638263A CN114300693B CN 114300693 B CN114300693 B CN 114300693B CN 202111638263 A CN202111638263 A CN 202111638263A CN 114300693 B CN114300693 B CN 114300693B
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carbon carrier
platinum
fuel cell
carbon
stability
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CN114300693A (en
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程年才
王子辰
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Fuzhou University
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Fuzhou University
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    • 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 a method for improving the stability of a fuel cell carbon-supported platinum-based catalyst by activating a carbon carrier, which comprises the following steps: firstly, activating the surface of a carbon carrier by using strong alkali in an inert atmosphere at a high temperature to obtain an activated carbon carrier with a concave pore structure on the surface; and loading the platinum-based nano particles into pores on the surface of the activated carbon carrier to obtain the high-stability fuel cell carbon-loaded platinum-based catalyst. The high-temperature treatment can improve the conductivity and corrosion resistance of the carbon carrier; the unique concave structure on the surface of the activated carbon carrier can generate a limiting effect on the nano particles, so that the stability of the catalyst is improved and the activity is not reduced. The method solves the problem of activity reduction caused by migration and agglomeration of platinum-based metal nano particles in the working environment of the prior fuel cell carbon-supported platinum-based catalyst, has simple operation, and is suitable for large-scale preparation of the fuel cell carbon-supported platinum-based catalyst with high stability.

Description

Method for improving stability of fuel cell carbon-supported platinum-based catalyst by activating carbon carrier
Technical Field
The invention belongs to the technical field of new energy fuel cells, and particularly relates to a method for improving the stability of a carbon-supported platinum-based catalyst of a fuel cell by activating a carbon carrier.
Background
The hydrogen energy is used as a clean, efficient, safe and sustainable secondary energy, and becomes the most promising substitute of fossil energy when the human society faces serious energy crisis and environmental pollution problems. The fuel cell takes hydrogen as fuel, can directly convert chemical energy into electric energy, has a series of advantages of environmental friendliness, high energy density, high energy conversion efficiency and the like, and is one of the most developed energy conversion devices at present. But durability issues and slow cathodic oxygen reduction kinetics greatly limit further development of fuel cells.
The fuel cell durability deficiency results mainly from the performance decay of the catalyst in the membrane electrode catalytic layer. The fuel cell catalysts that are currently the most performing and most widely used are carbon supported platinum catalysts. However, under the working potential of the fuel cell, the carbon carrier of the carbon-supported platinum catalyst is easy to corrode, and the platinum nano particles supported on the surface of the carbon carrier are easy to fall off and undergo migration agglomeration, so that the platinum nano particles continuously grow up, and the performance of the catalyst is quickly attenuated. Therefore, enhancing the corrosion resistance of the carbon support and inhibiting migration agglomeration of the nanoparticles under the operating environment is of great significance to further development of the fuel cell.
Chinese patent 202011605526.4 discloses a method for preparing a fuel cell catalyst having high durability, which mainly comprises modifying the surface of a carbon-supported platinum-based catalyst by forming an ultra-thin coating layer from a mixture of an oxide and a carbon-based compound. The method can effectively inhibit migration and growth of platinum-based nano particles on the surface of the carbon-based carrier, and remarkably improve the stability of the catalyst. However, part of active sites are inevitably covered, so that certain catalytic activity is lost, and the utilization rate of noble metal platinum is reduced.
Chinese patent 201911405226.9 discloses a fuel cell catalyst, a method of preparing the same and use in a fuel cell. The method is mainly used for modifying the carbon carrier by filling the internal pore canal of the carbon carrier with the high polymer and then calcining and solidifying the high polymer, so that the purpose of improving the durability of the catalyst is achieved. However, the polymers and surfactants used in the technical proposal are difficult to remove, and the electrochemical performance of the catalyst is inevitably reduced.
Chinese patent 202110014101.4 discloses a fuel cell catalyst and a preparation method and application thereof, wherein the method protects nano particles by precisely attaching and packaging special structures of Pt-M alloy nano particles through nitrogen-doped carbon nano tubes, and prevents migration and agglomeration of the nano particles and erosion of the nano particles from the outside under the working condition of the fuel cell. However, the encapsulation and protection of the nanoparticles by the carbon-based carrier may result in a portion of the active sites being covered by the carrier and gas diffusion being hindered. In addition, the nano particles prepared by the method have larger particle size, and the utilization rate of noble metal platinum is reduced.
Disclosure of Invention
The invention provides a method for improving the stability of a fuel cell carbon-supported platinum-based catalyst by activating a carbon carrier.
In order to achieve the above purpose, the invention adopts the following technical scheme:
firstly, activating the surface of a carbon carrier by using strong alkali in an inert atmosphere at a high temperature to obtain an activated carbon carrier with a concave pore structure on the surface; and preparing platinum-based nano particles to be loaded on the surface of an activated carbon carrier, so as to obtain the high-stability fuel cell carbon-loaded platinum-based electrocatalyst. The high-temperature treatment can improve the graphitization degree of the carbon carrier, thereby improving the conductivity and corrosion resistance of the carbon carrier; the concave pore structure on the surface of the activated carbon carrier can generate a limiting effect on the nano particles, so that the platinum-based nano particles can be stably limited on the surface of the carbon carrier, and the purpose of improving the durability of the catalyst is achieved.
A method for improving the stability of a fuel cell carbon supported platinum-based catalyst by carbon support activation, specific embodiments comprising the steps of:
1) Preparing a strong alkali solution, adding a carbon carrier, fully stirring and dispersing to obtain a suspension, filtering and collecting the carbon carrier, and carrying out vacuum drying treatment;
2) The carbon carrier obtained through the treatment is treated at high temperature in nitrogen atmosphere, cooled to room temperature, washed and dried to obtain the activated carbon carrier with the pore diameter of 1-3 nm pore structure on the surface;
3) And loading the platinum-based nano particles on the surface of an activated carbon carrier to obtain the high-stability fuel cell carbon-loaded platinum-based catalyst.
Preferably, the platinum-based nanoparticles comprise platinum nanoparticles, alloys formed by platinum and transition metals or core-shell structured nanoparticles; preferably, the transition metal is at least one of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, molybdenum, ruthenium, rhodium, palladium, silver, gold, iridium.
Preferably, the carbon support comprises graphite, graphene, carbon black, porous carbon, nitrogen-doped porous carbon, carbon nanotubes, and carbon nanofibers.
Preferably, the strong alkali solution in the step 1) comprises an aqueous solution, an alcohol solution and an alcohol-water mixed solution of potassium hydroxide and sodium hydroxide, and the concentration is 0.5-3mol/L; the concentration of the carbon carrier in the suspension is 2-12mg/mL, and when the strong alkali is potassium hydroxide, the mass ratio of the potassium hydroxide to the carbon carrier is 5-15:1. when the concentration of strong alkali in the suspension is too high, the surface of the carbon carrier is adsorbed and supersaturated, and a large amount of strong alkali remains in the filtrate, so that the cost is increased additionally; when the concentration of the carbon carrier is too high, the viscosity is too high, and the carbon carrier is not easy to disperse uniformly. Preferably, the concentration of the strong base solution is 0.5 mol/L and the concentration of the carbon carrier is 2 mg/mL.
Preferably, the high temperature treatment in step 2) is 500-1500 ℃ high temperature treatment 5-15 h. When the heat treatment time is shorter, the activation effect is weaker, the surface concave pore structure is smaller, and the effective domain limiting effect cannot be generated; when the heat treatment time is too long, the carbon carrier structure is easily damaged or the pore diameter of the surface pore structure is too large, so that the platinum-based nano particles are sunk into the pores. Preferably, the heat treatment temperature is 750 ℃, the time is 5-15 and h, and the pore diameter distribution of the surface pores is controlled to be 1-3 nm.
Preferably, the method for supporting the platinum-based nanoparticles on the surface of the activated carbon carrier in the step 3) comprises a liquid phase preparation method and an impregnation reduction method, and the platinum loading is 5-80 wt%.
The method for improving the stability of the fuel cell carbon-supported platinum-based catalyst by activating the carbon carrier has the following benefits:
1) According to the technical scheme, a pore structure with a proper pore diameter is constructed on the surface of a carbon carrier through activation treatment of the carbon carrier. The unique pore structure can generate a limiting effect, stabilize the nano particles on the surface of the carbon carrier, inhibit the falling off and migration of the nano particles under the working condition of the fuel cell, and achieve the purpose of improving the stability of the catalyst.
2) According to the technical scheme, a method of high-temperature heat treatment is adopted for activation of the carbon carrier, and graphitization degree of the carbon carrier is improved while a concave hole structure is formed on the surface of the carbon carrier. The improvement of graphitization degree can obviously improve the conductivity and stability of the carbon carrier, and effectively relieve the corrosion of the harsh working environment of the fuel cell to the carbon carrier.
3) According to the technical scheme, the durability of the catalyst is improved, and meanwhile, the activity loss caused by covering the active center of the nano particles by the coating layer in the existing method is avoided. The method is simple to operate, can be expanded to the preparation of other metal catalysts supported by materials such as ruthenium, rhodium, palladium, silver, osmium, iridium and Jin Jitan, is easy to produce in a large scale, and has very important significance for solving the problem of insufficient durability of the fuel cell at present.
Drawings
FIG. 1 is a comparative schematic diagram of pore size distribution of porous carbon carriers in example 1, comparative example 2, comparative example 3, and comparative example 4 according to the present invention;
FIG. 2 is a comparison graph of cyclic voltammograms of the present invention before and after 30000 acceleration durability tests for example 2 and comparative example 5, comparative example 6;
FIG. 3 is a graph showing the polarization curve and the energy density curve before and after 10000 times of 30000 times of accelerated durability test in comparison with comparative example 6.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the invention is not limited thereto.
Example 1
Weighing 2 g potassium hydroxide, dissolving in 100 mL water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g nitrogen-doped porous carbon, fully stirring and dispersing for 20 h to obtain suspension, standing until the suspension is fully precipitated, and performing suction filtration. The residue was dried in vacuo at 40 ℃ for 12 h, and the dried residue was ground to give fine black powder. The black powder was charged into a molybdenum crucible and treated at a high temperature of 750 ℃ under nitrogen atmosphere for 10 h. After cooling to room temperature, the carbon support powder was washed three times with water and dried to obtain an activated porous carbon support I.
Example 2
Platinum nano-particles with the average size of 2 nm of 25 mg are prepared by adopting an ethylene glycol reduction method and uniformly supported on the surface of the porous carbon carrier I obtained in the example 1 of 100 mg, so as to obtain the high-stability fuel cell carbon-supported platinum catalyst I.
Comparative example 1
Weighing 2 g potassium hydroxide, dissolving in 100 mL water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g nitrogen-doped porous carbon, fully stirring and dispersing for 20 h to obtain suspension, standing until the suspension is fully precipitated, and performing suction filtration. The residue was dried in vacuo at 40 ℃ for 12 h, and the dried residue was ground to give fine black powder. The black powder was charged into a molybdenum crucible and treated at a high temperature of 750 ℃ under nitrogen atmosphere for 4 h. After cooling to room temperature, the carbon support powder is washed with water three times and dried to obtain an activated porous carbon support II.
Comparative example 2
Weighing 2 g potassium hydroxide, dissolving in 100 mL water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g nitrogen-doped porous carbon, fully stirring and dispersing for 20 h to obtain suspension, standing until the suspension is fully precipitated, and performing suction filtration. The residue was dried in vacuo at 40 ℃ for 12 h, and the dried residue was ground to give fine black powder. The black powder was charged into a molybdenum crucible and treated at a high temperature of 750 ℃ under nitrogen atmosphere for 16 h. After cooling to room temperature, the carbon support powder was washed three times with water and dried to obtain an activated porous carbon support III.
Comparative example 3
Weighing 2 g potassium hydroxide, dissolving in 100 mL water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g nitrogen-doped porous carbon, fully stirring and dispersing for 20 h to obtain suspension, standing until the suspension is fully precipitated, and performing suction filtration. The residue was dried in vacuo at 40 ℃ for 12 h, and the dried residue was ground to give fine black powder. The black powder was charged into a molybdenum crucible and treated at a high temperature of 400 ℃ under nitrogen atmosphere for 16 h. After cooling to room temperature, the carbon support powder is washed with water for three times and dried to obtain the activated porous carbon support IV.
Comparative example 4
Weighing 2 g potassium hydroxide, dissolving in 100 mL water to prepare 0.5 mol/L potassium hydroxide solution, adding 0.2 g nitrogen-doped porous carbon, fully stirring and dispersing for 20 h to obtain suspension, standing until the suspension is fully precipitated, and performing suction filtration. The residue was dried in vacuo at 40 ℃ for 12 h, and the dried residue was ground to give fine black powder. The black powder was charged into a molybdenum crucible and treated at a high temperature of 1600 ℃ under nitrogen atmosphere for 5 h. After cooling to room temperature, the carbon support powder was washed three times with water and dried to obtain an activated porous carbon support v.
As can be seen from the comparison of the pore size distribution in FIG. 1, the proportion of pores with the pore size of 1-3 nm of the porous carbon carrier I in the activation of 10h in example 1 is obviously increased, and the larger pore size can provide effective limiting effect to inhibit the falling off and migration of particles; whereas in comparative example 1 the activation treatment time was too short, the pore size distribution of the resulting carbon support was mainly concentrated in the range of 0.5-1 nm, and too small pore size did not provide an effective confinement effect; in comparative example 2, the activation treatment time was prolonged, and the pore size distribution of the carbon support was instead concentrated below 1 nm, because the carbon support structure collapsed due to the excessively long activation time. The activation temperatures were reduced and increased in comparative examples 3 and 4, respectively, and when the temperatures were too low, the reaction proceeded too slowly, and treatment 16 h still failed to concentrate the pore diameters mainly in the range of 1 to 3 nm, and when the temperatures were too high, the reaction was too severe, and the porous carbon support structure was liable to collapse.
Comparative example 5
Platinum nano-particles with the average size of 2 nm of 25 and mg are prepared by adopting an ethylene glycol reduction method and uniformly supported on the surface of the porous carbon carrier II obtained in the comparative example 1 of 100 mg, so as to obtain the fuel cell carbon-supported platinum catalyst II.
Comparative example 6
Commercial platinum carbon catalysts.
Electrochemical performance test
The fuel cell catalysts of each example and comparative example were each prepared by adding 590. Mu.L of water, 1.39. 1.39 mL isopropyl alcohol, and 20. Mu.L of nafion solution (DuPont, U.S.) to each of 4 mg, and performing ultrasonic dispersion for 5 minutes to prepare a catalyst slurry, and 10. Mu.L of the catalyst slurry was coated on the surface of a rotating disk electrode having a diameter of 5 mm to form a working electrode.
The platinum sheet electrode is used as a counter electrode, the saturated silver chloride electrode is used as a reference electrode, the accelerated durability test is carried out in 0.1 mol/L perchloric acid electrolyte, the test potential interval is 0.6-0.95V (vs. RHE), and the sweeping speed is 50 mV/s.
FIG. 2 is a graph showing the cyclic voltammograms and the mass activity of example 2, comparative example 5 and comparative example 6 of the present invention before and after the accelerated durability test. Example 2 showed significantly improved attenuation of the electrochemically active area before and after 30000 cycles compared to the comparative example, and was able to maintain a higher proportion of the mass activity. The activated carbon carrier has obvious effects of inhibiting the migration of metal nano particles and improving the stability of the catalyst.
The battery cell was assembled and tested for example 2 and comparative example 6. Catalyst films with an area of 5 x 5 cm were prepared from the catalyst obtained in example 2 of the present invention and comparative examples, and single cells were assembled. The accelerated durability test was performed according to the test method established by the U.S. department of energy, the catalyst was accelerated aged between 0.6 and 0.95. 0.95V, and the polarization curve and the energy density curve were tested at 10000 cycles and 30000 cycles of accelerated aging. Fig. 3 shows polarization curves versus energy density curves for example 2 and comparative example 6 before and after 10000 cycles and 30000 cycles. The 30000 cycles resulted in significant loss of fuel cell activity, but the decay of current density and maximum energy density after cycling of the fuel cell assembled in example 2 was significantly improved over comparative example 6, indicating that the invention is of great significance in solving the durability problem of the fuel cell.
The above examples are only for clarity of illustration of the present invention, and the embodiments of the present invention are not limited thereto. Any modification, replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. A method for improving the stability of a platinum-based catalyst for a cathode oxygen reduction reaction of a hydrogen fuel cell by activating a carbon carrier is characterized by comprising the following steps of: firstly, activating and pore-forming a carbon carrier to obtain an activated carbon carrier with a concave pore structure on the surface; loading platinum-based nano particles into pores on the surface of an activated carbon carrier to obtain a high-stability hydrogen fuel cell cathode oxygen reduction reaction platinum-based catalyst;
the method specifically comprises the following steps:
1) Preparing a strong alkali solution, adding a carbon carrier, fully stirring and dispersing to obtain a suspension, filtering and collecting the carbon carrier, and carrying out vacuum drying treatment;
2) Treating the carbon carrier obtained in the step 1) at a high temperature in a nitrogen atmosphere, cooling to room temperature, washing with water, and drying to obtain an activated carbon carrier with a pore structure with a pore diameter of 1-3 nm on the surface;
3) Carrying platinum-based nano particles on the surface of an activated carbon carrier to obtain a high-stability hydrogen fuel cell cathode oxygen reduction reaction platinum-based catalyst;
the strong alkali solution in the step 1) comprises an aqueous solution, an alcohol solution and an alcohol-water mixed solution of potassium hydroxide and sodium hydroxide, wherein the concentration of the solution is 0.5-3mol/L; the concentration of the carbon carrier in the suspension is 2-12mg/mL;
the high temperature treatment in the step 2) is 750 ℃ high temperature treatment for 10 hours;
the platinum-based nanoparticles in the step 3) are platinum nanoparticles with an average particle diameter of 2 nm; the activated carbon carrier is nitrogen doped porous carbon; the method for loading the platinum-based nano particles on the surface of the activated carbon carrier comprises an impregnation reduction method, and the platinum loading is 5-80 wt%.
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CN115212905A (en) * 2022-06-29 2022-10-21 浙江新和成股份有限公司 Selective hydrogenation catalyst for alkynol and preparation method and application thereof

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