Hydrogen fuel cell catalyst and preparation method thereof
By employing a composite preparation method of precious metals and transition metals, combined with ultrasonic dispersion and optimized processes, the problems of precious metal scarcity and insufficient stability in hydrogen fuel cell catalysts have been solved, achieving efficient and simple catalyst preparation and improving catalytic performance and lifespan.
Patent Information
- Application Number
- CN202511132741.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-13
- Publication Date
- 2025-11-11
AI Technical Summary
Platinum-based materials are scarce and expensive in existing hydrogen fuel cell catalysts, and their preparation methods suffer from problems such as uneven metal particle dispersion, insufficient catalyst stability, and complex processes.
A catalyst is prepared by combining precious metals and transition metals in a specific ratio, combined with ultrasonic dispersion technology and optimized dropping method, through liquid-phase reaction. This includes the preparation of metal precursor solution, formation of carrier dispersion, mixing reaction, reduction treatment and post-treatment. The reduction process and heat treatment are optimized to achieve uniform dispersion of metal particles on the surface of carbon carrier and enhance interaction.
The amount of precious metals used was reduced, the active specific surface area and stability of the catalyst were increased, the preparation process was simplified, and the electrocatalytic performance and service life of the catalyst were improved.
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Figure CN120933386A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the technical field of hydrogen fuel cell catalysts, and in particular to a hydrogen fuel cell catalyst and its preparation method. Background Technology
[0002] Hydrogen fuel cells, as devices that directly convert hydrogen energy into electrical energy, have significant advantages such as high energy conversion efficiency and zero emissions, showing great application potential in fields such as new energy vehicles and distributed power generation. Catalysts are the core materials of hydrogen fuel cells, directly determining the battery's performance and cost.
[0003] Currently, commercially available hydrogen fuel cell catalysts mainly use platinum-based materials. However, platinum resources are scarce and expensive, severely restricting the large-scale application of hydrogen fuel cells. Furthermore, existing preparation methods suffer from problems such as uneven metal particle dispersion, insufficient catalyst stability, and complex preparation processes. Therefore, developing a preparation method that can reduce the amount of precious metals used, improve catalyst performance, and simplify the process is of significant practical importance. Those skilled in the art provide a hydrogen fuel cell catalyst and its preparation method to address the problems mentioned in the background. Summary of the Invention
[0004] To address the problems mentioned in the background art, this application provides a hydrogen fuel cell catalyst and its preparation method.
[0005] This application provides a hydrogen fuel cell catalyst and its preparation method, which adopts the following technical solution:
[0006] A hydrogen fuel cell catalyst and its preparation method, comprising the following steps:
[0007] a) Preparation of metal precursor solution: Dissolve at least one noble metal salt and at least one transition metal salt in a solvent at a molar ratio of 1:0.5-1:5, and stir at 20-40℃ for 20-60 minutes until completely dissolved to obtain a mixed solution;
[0008] b) Preparation of carrier dispersion: Add carbon carrier to the dispersant at a ratio of 0.5-5 g / 100 mL, and treat with ultrasonic power of 100-500 W for 30-180 minutes to form a uniformly dispersed carrier dispersion.
[0009] c) Mixing reaction: The metal precursor solution obtained in step a) is slowly added dropwise to the carrier dispersion in step b) at a rate of 1-5 mL / min, and the mixture is stirred at 300-800 rpm for 1-6 hours at 20-80℃.
[0010] d) Reduction treatment: Add a reducing agent to the mixture obtained in step c), wherein the total molar ratio of the reducing agent to the metal ions is 1:1-5:1, and carry out the reduction reaction at 40-100℃ and 200-600 rpm for 2-8 hours.
[0011] e) Post-processing: Filter the product after the reaction in step d), wash it alternately with deionized water and ethanol 3-5 times, and then dry it at 60-120℃ for 6-24 hours to obtain the hydrogen fuel cell catalyst.
[0012] Preferably, the noble metal salt in step a) is at least one of chloroplatinic acid, platinum nitrate, platinum sulfate, palladium chloride, palladium nitrate, ruthenium chloride, and ruthenium nitrate; the transition metal salt is at least one of ferric nitrate, ferric chloride, ferric sulfate, cobalt nitrate, cobalt chloride, cobalt sulfate, nickel nitrate, nickel chloride, nickel sulfate, copper nitrate, copper chloride, and copper sulfate; the molar ratio of the noble metal to the transition metal in step a) is 1:1 to 1:3; the solvent is at least one of deionized water, ethanol, and ethylene glycol; when it is a mixed solvent, the volume ratio of deionized water to the organic solvent is 1:1 to 3:1.
[0013] Preferably, the carbon support in step b) is at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, activated carbon, carbon black, and mesoporous carbon, the specific surface area of the carbon support is 50-2000 m² / g, the particle size is 10-100 nm, the dispersant in step b) is deionized water or ethanol, the concentration of the carbon support in the dispersant is 1-3 g / 100 mL, the ultrasonic treatment power is 200-400 W, and the treatment time is 60-120 minutes.
[0014] Preferably, in step c), the dropping rate of the metal precursor solution is 2-3 mL / min, the reaction temperature is 40-60℃, the stirring speed is 400-600 rpm, and the reaction time is 2-4 hours.
[0015] Preferably, the reducing agent in step d) is at least one of sodium borohydride, formaldehyde, hydrazine hydrate, ascorbic acid, and sodium citrate. When a mixed reducing agent is used, the molar ratio of sodium borohydride to ascorbic acid is 1:1 to 2:1.
[0016] Preferably, the washing process in step e) is as follows: first wash with deionized water 2-3 times, then wash with ethanol 1-2 times, with a solid-liquid ratio of 1:10-1:20 each time; the drying method is vacuum drying, with a vacuum degree of 0.05-0.1MPa, a drying temperature of 80-100℃, and a drying time of 10-18 hours.
[0017] Preferably, the method further includes step f): the dried product obtained in step e) is heat-treated under an inert gas protection environment, wherein the inert gas is nitrogen or argon, the gas flow rate is 50-200 mL / min, the heat treatment temperature is 200-500℃, the heating rate is 1-5℃ / min, the holding time is 1-4 hours, and then the product is cooled to room temperature at a rate of 1-3℃ / min.
[0018] Preferably, in step f), the inert gas flow rate is 100-150 mL / min, the heat treatment temperature is 300-400℃, the heating rate is 2-3℃ / min, the holding time is 2-3 hours, and the cooling rate is 2℃ / min.
[0019] Preferably, the catalyst has a metal active component loading of 5-30 wt%, an average particle size of 1-10 nm, and a specific surface area of 200-1500 m² / g.
[0020] Preferably, the loading of the metal active component is 10-20 wt%, the average particle size of the metal particles is 2-5 nm, and the specific surface area is 500-1000 m² / g.
[0021] In summary, this application has the following beneficial technical effects: by combining precious metals and transition metals in a specific ratio, this invention reduces the amount of precious metals used and lowers the cost of the catalyst while ensuring high catalytic activity.
[0022] By employing ultrasonic dispersion technology and an optimized dropping method, uniform dispersion of the metal active component on the carbon support surface was achieved, resulting in small-sized (1-10 nm) metal particles and improving the active specific surface area of the catalyst.
[0023] The optimized reduction process and optional heat treatment steps enhance the interaction between the metal particles and the support, thereby improving the stability and durability of the catalyst.
[0024] The entire preparation process uses liquid-phase reaction, which is simple, easy to operate, and has mild conditions, making it easy to scale up for industrial production.
[0025] The prepared catalyst exhibits excellent electrocatalytic performance, demonstrating high catalytic activity and long service life in hydrogen fuel cells. Attached Figure Description
[0026] Figure 1 This is an overall structural block diagram of a hydrogen fuel cell catalyst and its preparation method in the embodiments of this application. Detailed Implementation
[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.
[0028] The illustrative embodiments and descriptions of the present invention are provided herein to explain the invention, but are not intended to limit the invention.
[0029] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.
[0030] It should be understood that the terms "comprising / including," "consisting of," or any other variations are intended to cover non-exclusive inclusion, such that a product, apparatus, process, or method that comprises a list of elements includes not only those elements but may also include, where necessary, other elements not expressly listed, or elements inherent to such a product, apparatus, process, or method. Without further limitation, an element defined by the phrases "comprising / including," "consisting of," does not exclude the presence of additional identical elements in the product, apparatus, process, or method that includes said element.
[0031] It should also be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device, component or structure referred to must have a specific orientation, be constructed or operated in a specific orientation, and should not be construed as a limitation of the present invention.
[0032] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.
[0033] like Figure 1As shown, a hydrogen fuel cell catalyst and its preparation method are described, a) preparing a metal precursor solution: dissolving at least one noble metal salt and at least one transition metal salt in a solvent at a molar ratio of 1:0.5-1:5, stirring at 20-40℃ for 20-60 minutes until completely dissolved to obtain a mixed solution;
[0034] b) Preparation of carrier dispersion: Add carbon carrier to the dispersant at a ratio of 0.5-5 g / 100 mL, and treat with ultrasonic power of 100-500 W for 30-180 minutes to form a uniformly dispersed carrier dispersion.
[0035] c) Mixing reaction: The metal precursor solution obtained in step a) is slowly added dropwise to the carrier dispersion in step b) at a rate of 1-5 mL / min, and the mixture is stirred at 300-800 rpm for 1-6 hours at 20-80℃.
[0036] d) Reduction treatment: Add a reducing agent to the mixture obtained in step c), wherein the total molar ratio of the reducing agent to the metal ions is 1:1-5:1, and carry out the reduction reaction at 40-100℃ and 200-600 rpm for 2-8 hours.
[0037] e) Post-processing: Filter the product after the reaction in step d), wash it alternately with deionized water and ethanol 3-5 times, and then dry it at 60-120℃ for 6-24 hours to obtain the hydrogen fuel cell catalyst.
[0038] Preferably, the noble metal salt in step a) is at least one of chloroplatinic acid, platinum nitrate, platinum sulfate, palladium chloride, palladium nitrate, ruthenium chloride, and ruthenium nitrate; the transition metal salt is at least one of ferric nitrate, ferric chloride, ferric sulfate, cobalt nitrate, cobalt chloride, cobalt sulfate, nickel nitrate, nickel chloride, nickel sulfate, copper nitrate, copper chloride, and copper sulfate; the molar ratio of the noble metal to the transition metal in step a) is 1:1 to 1:3; the solvent is at least one of deionized water, ethanol, and ethylene glycol; when it is a mixed solvent, the volume ratio of deionized water to the organic solvent is 1:1 to 3:1.
[0039] In this embodiment, the carbon support mentioned in step b) is at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, activated carbon, carbon black, and mesoporous carbon. The specific surface area of the carbon support is 50-2000 m² / g, and the particle size is 10-100 nm. The dispersant mentioned in step b) is deionized water or ethanol. The concentration of the carbon support in the dispersant is 1-3 g / 100 mL. The ultrasonic treatment power is 200-400 W, and the treatment time is 60-120 minutes.
[0040] In this embodiment, the dropping rate of the metal precursor solution in step c) is 2-3 mL / min, the reaction temperature is 40-60℃, the stirring speed is 400-600 rpm, and the reaction time is 2-4 hours.
[0041] In this embodiment, the reducing agent mentioned in step d) is at least one of sodium borohydride, formaldehyde, hydrazine hydrate, ascorbic acid, and sodium citrate. When a mixed reducing agent is used, the molar ratio of sodium borohydride to ascorbic acid is 1:1 to 2:1.
[0042] In this embodiment, the washing process in step e) is as follows: first wash with deionized water 2-3 times, then wash with ethanol 1-2 times, with a solid-liquid ratio of 1:10-1:20 each time; the drying method is vacuum drying, with a vacuum degree of 0.05-0.1MPa, a drying temperature of 80-100℃, and a drying time of 10-18 hours.
[0043] In this embodiment, step f) is also included: the dried product obtained in step e) is heat-treated under an inert gas protection, wherein the inert gas is nitrogen or argon, the gas flow rate is 50-200 mL / min, the heat treatment temperature is 200-500℃, the heating rate is 1-5℃ / min, the holding time is 1-4 hours, and then the product is cooled to room temperature at a rate of 1-3℃ / min.
[0044] In this embodiment, in step f), the inert gas flow rate is 100-150 mL / min, the heat treatment temperature is 300-400℃, the heating rate is 2-3℃ / min, the holding time is 2-3 hours, and the cooling rate is 2℃ / min.
[0045] In this embodiment, the loading of the metal active component in the catalyst is 5-30 wt%, the average particle size of the metal particles is 1-10 nm, and the specific surface area is 200-1500 m² / g.
[0046] In this embodiment, the loading of the metal active component is 10-20 wt%, the average particle size of the metal particles is 2-5 nm, and the specific surface area is 500-1000 m² / g.
[0047] Example 1
[0048] Preparation of metal precursor solution: Dissolve 0.5 mmol chloroplatinic acid and 1.0 mmol cobalt nitrate in a mixed solvent of 60 mL deionized water and 30 mL ethanol, and stir at 400 rpm for 30 minutes at 30 °C until completely dissolved to obtain a mixed solution.
[0049] Preparation of carrier dispersion: 2g of multi-walled carbon nanotubes were added to 200mL of deionized water and ultrasonically treated at 300W for 90 minutes to form a uniformly dispersed carrier dispersion.
[0050] Mixed reaction: The metal precursor solution obtained in step 1) was slowly added dropwise to the carrier dispersion in step 2) at a rate of 2 mL / min, and the mixture was stirred at 500 rpm for 3 hours at 50 °C.
[0051] Reduction treatment: Add 3 mmol of sodium borohydride to the above mixture and stir at 400 rpm for 4 hours at 70°C.
[0052] Post-processing: The reaction product was filtered, washed three times with deionized water, and then washed twice with ethanol, with a solid-liquid ratio of 1:15 each time. It was then dried at 90°C and 0.08 MPa vacuum for 12 hours to obtain the hydrogen fuel cell catalyst.
[0053] The catalyst has a metal active component loading of 15 wt%, an average particle size of 3.2 nm, and a specific surface area of 850 m² / g.
[0054] Example 2
[0055] Preparation of metal precursor solution: Dissolve 0.3 mmol platinum nitrate, 0.2 mmol palladium chloride and 1.5 mmol nickel nitrate in a mixed solvent of 80 mL deionized water and 40 mL ethylene glycol, and stir at 500 rpm for 40 minutes at 35 °C until completely dissolved to obtain a mixed solution.
[0056] Preparation of carrier dispersion: Add 1g graphene and 1g carbon black to 200mL deionized water and sonicate at 400W for 120 minutes to form a uniformly dispersed carrier dispersion.
[0057] Mixed reaction: The metal precursor solution obtained in step 1) was slowly added dropwise to the carrier dispersion in step 2) at a rate of 3 mL / min, and the mixture was stirred at 600 rpm for 2.5 hours at 60 °C.
[0058] Reduction treatment: Add 2 mmol sodium borohydride and 2 mmol ascorbic acid to the above mixture, and stir at 500 rpm for 3 hours at 80°C.
[0059] Post-processing: The reaction product was filtered, washed twice with deionized water, and then washed once with ethanol, with a solid-liquid ratio of 1:20 each time; then dried at 100℃ and 0.09MPa vacuum for 10 hours.
[0060] Heat treatment: The dried product was heated to 350°C at a heating rate of 2°C / min under nitrogen protection (gas flow rate 120 mL / min), held at that temperature for 2.5 hours, and then cooled to room temperature at a rate of 2°C / min to obtain the hydrogen fuel cell catalyst.
[0061] The catalyst has a metal active component loading of 18 wt%, an average particle size of 2.8 nm, and a specific surface area of 920 m² / g.
[0062] Example 3
[0063] Preparation of metal precursor solution: Dissolve 0.4 mmol ruthenium chloride and 0.8 mmol cobalt chloride in 100 mL deionized water and stir at 300 rpm for 25 minutes at 25 °C until completely dissolved to obtain a mixed solution.
[0064] Preparation of carrier dispersion: 1.5g of mesoporous carbon was added to 150mL of deionized water and ultrasonically treated at 250W for 80 minutes to form a uniformly dispersed carrier dispersion.
[0065] Mixed reaction: The metal precursor solution obtained in step 1) was slowly added dropwise to the carrier dispersion in step 2) at a rate of 2.5 mL / min, and the mixture was stirred at 450 rpm for 3.5 hours at 45 °C.
[0066] Reduction treatment: Add 4 mmol of ascorbic acid to the above mixture and stir at 350 rpm for 4.5 hours at 65°C.
[0067] Post-processing: The reaction product was filtered, washed three times with deionized water, and then washed once with ethanol, with a solid-liquid ratio of 1:15 each time. It was then dried at 85°C and 0.07 MPa vacuum for 15 hours to obtain the hydrogen fuel cell catalyst.
[0068] The catalyst has a metal active component loading of 12 wt%, an average particle size of 3.5 nm, and a specific surface area of 780 m² / g.
[0069] Finally, the following points should be noted: First, in the description of this application, it should be noted that, unless otherwise specified and limited, the terms "installation", "connection", and "linkage" should be interpreted broadly, and can be mechanical or electrical connections, or internal connections between two components, or direct connections. "Up", "down", "left", "right", etc. are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may change.
[0070] Secondly: The accompanying drawings of the embodiments disclosed in this invention only involve the structures involved in the embodiments disclosed in this invention. Other structures can refer to the general design. In the absence of conflict, the same embodiment and different embodiments of this invention can be combined with each other.
[0071] In conclusion, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing a hydrogen fuel cell catalyst, characterized in that: Includes the following steps: a) Preparation of metal precursor solution: Dissolve at least one noble metal salt and at least one transition metal salt in a solvent at a molar ratio of 1:0.5-1:5, and stir at 20-40℃ for 20-60 minutes until completely dissolved to obtain a mixed solution; b) Preparation of carrier dispersion: Add carbon carrier to the dispersant at a ratio of 0.5-5 g / 100 mL, and treat with ultrasonic power of 100-500 W for 30-180 minutes to form a uniformly dispersed carrier dispersion; c) Mixing reaction: The metal precursor solution obtained in step a) is slowly added dropwise to the carrier dispersion in step b) at a rate of 1-5 mL / min, and the mixture is stirred at 300-800 rpm for 1-6 hours at 20-80℃. d) Reduction treatment: Add a reducing agent to the mixture obtained in step c), wherein the total molar ratio of the reducing agent to the metal ions is 1:1-5:1, and carry out the reduction reaction at 40-100℃ and 200-600 rpm for 2-8 hours. e) Post-processing: Filter the product after the reaction in step d), wash it alternately with deionized water and ethanol 3-5 times, and then dry it at 60-120℃ for 6-24 hours to obtain the hydrogen fuel cell catalyst.
2. The method for preparing a hydrogen fuel cell catalyst according to claim 1, characterized in that: The noble metal salt mentioned in step a) is at least one of chloroplatinic acid, platinum nitrate, platinum sulfate, palladium chloride, palladium nitrate, ruthenium chloride, and ruthenium nitrate; the transition metal salt is at least one of ferric nitrate, ferric chloride, ferric sulfate, cobalt nitrate, cobalt chloride, cobalt sulfate, nickel nitrate, nickel chloride, nickel sulfate, copper nitrate, copper chloride, and copper sulfate; the molar ratio of the noble metal to the transition metal in step a) is 1:1 to 1:3; the solvent is at least one of deionized water, ethanol, and ethylene glycol; when it is a mixed solvent, the volume ratio of deionized water to the organic solvent is 1:1 to 3:
1.
3. The hydrogen fuel cell catalyst and its preparation method according to claim 1, characterized in that: The carbon support mentioned in step b) is at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene, activated carbon, carbon black, and mesoporous carbon. The specific surface area of the carbon support is 50-2000 m² / g, and the particle size is 10-100 nm. The dispersant mentioned in step b) is deionized water or ethanol. The concentration of the carbon support in the dispersant is 1-3 g / 100 mL. The ultrasonic treatment power is 200-400 W, and the treatment time is 60-120 minutes.
4. The hydrogen fuel cell catalyst and its preparation method according to claim 1, characterized in that: In step c), the dropping rate of the metal precursor solution is 2-3 mL / min, the reaction temperature is 40-60℃, the stirring speed is 400-600 rpm, and the reaction time is 2-4 hours.
5. The hydrogen fuel cell catalyst and its preparation method according to claim 1, characterized in that: The reducing agent mentioned in step d) is at least one of sodium borohydride, formaldehyde, hydrazine hydrate, ascorbic acid, and sodium citrate. When a mixed reducing agent is used, the molar ratio of sodium borohydride to ascorbic acid is 1:1 to 2:
1.
6. The hydrogen fuel cell catalyst and its preparation method according to claim 1, characterized in that: The washing process in step e) is as follows: first wash with deionized water 2-3 times, then wash with ethanol 1-2 times, with a solid-liquid ratio of 1:10-1:20 each time; the drying method is vacuum drying, with a vacuum degree of 0.05-0.1MPa, a drying temperature of 80-100℃, and a drying time of 10-18 hours.
7. The hydrogen fuel cell catalyst and its preparation method according to claim 1, characterized in that: It also includes step f): the dried product obtained in step e) is heat-treated under an inert gas protection, wherein the inert gas is nitrogen or argon, the gas flow rate is 50-200 mL / min, the heat treatment temperature is 200-500℃, the heating rate is 1-5℃ / min, the holding time is 1-4 hours, and then cooled to room temperature at a rate of 1-3℃ / min.
8. The hydrogen fuel cell catalyst and its preparation method according to claim 1, characterized in that: In step f), the inert gas flow rate is 100-150 mL / min, the heat treatment temperature is 300-400℃, the heating rate is 2-3℃ / min, the holding time is 2-3 hours, and the cooling rate is 2℃ / min.
9. A hydrogen fuel cell catalyst and its preparation method according to any one of claims 1-7, characterized in that: The catalyst has a metal active component loading of 5-30 wt%, an average particle size of 1-10 nm, and a specific surface area of 200-1500 m² / g.
10. A hydrogen fuel cell catalyst and its preparation method according to claim 9, characterized in that: The loading of the metal active component is 10-20 wt%, the average particle size of the metal particles is 2-5 nm, and the specific surface area is 500-1000 m² / g.