High activity catalyst for proton exchange membrane fuel cell and method for preparing the same
By constructing a core-shell structure and a multi-metal synergistic catalytic system on Ti3C2TxMXene, the problems of insufficient exposure of catalyst active sites and easy corrosion of precious metals were solved, achieving efficient operation and long life of proton exchange membrane fuel cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- XIAMEN JINGBI IND CO LTD
- Filing Date
- 2025-11-04
- Publication Date
- 2026-06-16
AI Technical Summary
Existing proton exchange membrane fuel cell catalysts suffer from insufficient exposure of active sites, poor matching between the conductivity and stability of the support, and the scarcity and high cost of precious metal platinum, which is prone to agglomeration and corrosion leading to a decrease in activity, thus limiting their large-scale application.
Using Ti3C2TxMXene as a support, a core-shell structure was constructed and a platinum-iron alloy and iridium oxide protective layer were introduced to form a multi-metal synergistic catalytic system. The physicochemical properties of the catalyst were improved through surface modification, thereby enhancing the catalyst's stability and activity.
It significantly improves the electrocatalytic activity and stability of the catalyst, extends the service life of the fuel cell, increases the power density and performance of the battery, and reduces dependence on precious metals.
Abstract
Description
Technical Field
[0001] This invention relates to the field of battery catalyst technology, specifically to a highly active catalyst for proton exchange membrane fuel cells and its preparation method. Background Technology
[0002] Proton exchange membrane fuel cells (PEMFCs) are considered an important development direction in the field of clean energy due to their advantages such as high energy conversion efficiency and environmental friendliness. As the core component of PEMFCs, the catalyst's activity, stability, and cost directly affect the cell's performance. Currently, commercial catalysts mostly use platinum as the main active ingredient; however, Pt resources are scarce and expensive, and its activity is easily reduced during the reaction process due to aggregation and corrosion, limiting the large-scale application of PEMFCs.
[0003] In existing technologies, catalyst dispersibility is improved by introducing transition metals to form alloys or composite structures, or by using carbon-based supports (such as carbon nanotubes and graphene). However, problems such as insufficient exposure of active sites and poor matching between the conductivity and stability of the support still exist. MXene, as a novel two-dimensional nanomaterial, possesses high conductivity, good mechanical strength, and abundant surface functional groups, making it an ideal candidate material for catalyst supports. However, the interlayer stacking of MXene can easily lead to the masking of active sites, and its interaction with metal nanoparticles needs further optimization to improve catalytic stability.
[0004] Based on the above, the present invention provides a highly active catalyst for proton exchange membrane fuel cells and its preparation method thereon to solve the technical problems mentioned above. Summary of the Invention
[0005] This invention utilizes Ti3C2T x The optimization of MXene support, synergistic effects of multi-metal components, and surface modification significantly enhance the electrocatalytic activity and stability of the catalyst, reduce dependence on precious metals, and make it suitable for the efficient operation of proton exchange membrane fuel cells.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] In a first aspect, the present invention provides a method for preparing a highly active catalyst for a proton exchange membrane fuel cell, comprising the following steps:
[0008] Step 1: Add Ti3C2T at a dosage ratio of 0.05-0.1 g / mL. x MXene powder was added to a 10wt% tetrabutylammonium hydroxide aqueous solution, ultrasonically dispersed, and the dispersion was centrifuged and washed until the washing solution was neutral. The resulting precipitate was then dispersed in ethanol at a dosage ratio of 0.05-0.1 g / mL to obtain an MXene dispersion.
[0009] Step 2: Add ferric nitrate in an equal molar amount to chloroplatinic acid in a 10-30 g / L ethylene glycol chloroplatinic acid solution, mix well, and then add MXenes dispersion in a volume of 2-3 times that volume to the resulting mixed solution. After magnetic stirring until homogeneous, slowly add ascorbic acid aqueous solution in a volume of 10-20% of the MXenes dispersion and a concentration of 0.1-0.2 mol / L. Keep the reaction at 80-85℃ for 3-5 h, and then add dicyandiamide in a mass of 1.5-2.5 times that of chloroplatinic acid. Mix and stir for 2-3 h. The reaction product is then centrifuged, washed with alcohol, and dried to obtain a solid powder.
[0010] Step 3: Add 0.2-0.3 times the volume of the 10-30 g / L solid powder aqueous dispersion to a chloroiridic acid ethanol solution with a concentration of 0.6-1 mmol / L. After ultrasonic dispersion, add 0.2-0.3 times the volume of the chloroiridic acid ethanol solution to a sodium nitrate aqueous solution with a concentration of 0.1-0.2 mol / L. React at 120-130℃ for 5-8 hours, then cool to room temperature. After centrifugation and vacuum drying, store the resulting composite powder for later use.
[0011] Step 4: Add 5-8 times the mass of ruthenium trichloride and 10-20 times the mass of phenanthroline to an ethanol solution of 10-15 g / L ruthenium trichloride. After magnetic stirring until homogeneous, heat to 630-680℃ under an argon atmosphere and keep at that temperature for 2-3 hours. Then cool to room temperature. Soak the reaction product in 0.4-0.6 mol / L sulfuric acid, centrifuge and wash until neutral, and then vacuum dry, activate and modify the surface in sequence.
[0012] Furthermore, in step one, the ultrasonic dispersion power is 600-800W, the ultrasonic frequency is 35-40kHz, and the ultrasonic dispersion time is 2-3h.
[0013] Furthermore, in step one, the centrifugal washing speed is set to 3000-5000 r / min, and the centrifugal washing time is 10-20 min.
[0014] Furthermore, in step two, the rotation speed of the magnetic stirring is set to 300-500 r / min, and the magnetic stirring time is set to 30-40 min.
[0015] Furthermore, in step three, the ultrasonic dispersion power is 300-500W, and the ultrasonic time is 1-1.5h.
[0016] Furthermore, in step three, the centrifugation speed is set to 4000-6000 r / min, and the centrifugation time is set to 5-10 min.
[0017] Furthermore, the vacuum drying temperature in steps three and four is 60-80℃, and the vacuum drying time is 10-15h.
[0018] Furthermore, the specific steps of the activation treatment in step four are as follows: the reaction product after vacuum drying is treated in a H2 / Ar mixed gas with a volume fraction of 5% at 300-350°C for 2-3 hours, and finally ground through a 400-500 mesh sieve.
[0019] Furthermore, the specific steps of the surface modification are as follows: the activated solid product is immersed in a 0.1-0.12 mol / L 4-aminophenylboronic acid ethanol solution at a dosage ratio of 20-50 g / L, reacted at 55-65℃ for 4-6 h, filtered out, and then vacuum dried.
[0020] Secondly, the present invention provides a highly active catalyst for proton exchange membrane fuel cells, which is prepared by the preparation method described above.
[0021] Compared with the prior art, the beneficial effects of the present invention are:
[0022] 1. This invention utilizes Ti3C2T, which possesses excellent mechanical strength and electrical conductivity. x Using MXene as a substrate, a core-shell structure of "nitrogen-doped carbon layer coating platinum-iron alloy particles" was first constructed on its surface. This core-shell structure physically isolates the erosion of acidic electrolytes and effectively inhibits the dissolution, migration, and aggregation of platinum and iron elements. Then, an "iridium oxide protective layer" was introduced, forming a dual protection mechanism. Iridium oxide not only fills potential defects in the carbon layer, but it is also extremely stable at high potentials, protecting the internal active components and significantly enhancing the oxidation and corrosion resistance of the support material itself. The resulting synergistic protection system allows the catalyst to maintain extremely high electrochemical active area and microstructural integrity even after long-term operation and accelerated stress testing, thereby significantly extending the service life of the fuel cell.
[0023] 2. The platinum-iron alloy in this invention optimizes the adsorption energy of reaction intermediates through intermetallic electronic effects, resulting in significantly better catalytic activity than a single platinum component. Furthermore, the introduction of iridium oxide preferentially induces oxygen evolution under high potentials caused by abnormal operating conditions such as reverse polarity, thereby promptly removing active oxygen species from the reaction interface and effectively mitigating carbon support corrosion and platinum component oxidation and dissolution, thus playing a crucial protective role in the overall catalyst structure. Additionally, the ruthenium-nitrogen coordination structure formed through pyrolysis provides stable and efficient auxiliary catalytic active sites for the system. These three components, coupled through chemical bonding and interfacial effects, constitute an organic synergistic catalytic system. Their synergistic interaction ensures that the catalyst exhibits high activity, high stability, and excellent environmental adaptability under all operating conditions, including normal operation of the proton exchange membrane fuel cell, frequent start-stop cycles, and instantaneous overload.
[0024] 3. This invention uses 4-aminophenylboronic acid to modify the surface of the activated solid product, effectively improving the physicochemical properties of the prepared catalyst surface, transforming it from a completely hydrophilic state to a moderately hydrophobic state. This helps to eliminate excess liquid water generated during the reaction, effectively preventing pore blockage caused by water flooding, thus constructing a smooth "transport channel" for the reaction gas (oxygen), ensuring that oxygen can diffuse more efficiently to each active site, significantly improving battery performance, especially under high current density conditions, resulting in lower voltage loss, higher power density output, and superior performance. Detailed Implementation
[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0026] Example 1
[0027] A method for preparing a highly active catalyst for a proton exchange membrane fuel cell includes the following steps:
[0028] Step 1: Add Ti3C2T at a dosage ratio of 0.05 g / mL. x MXene powder was added to a 10wt% tetrabutylammonium hydroxide aqueous solution, ultrasonically dispersed, and the dispersion was centrifuged and washed until the washing solution was neutral. The resulting precipitate was then dispersed in ethanol at a dosage ratio of 0.05 g / mL to obtain an MXene dispersion.
[0029] The ultrasonic dispersion power was 600W, the ultrasonic frequency was 35kHz, and the ultrasonic dispersion time was 2h; the centrifugal washing speed was set to 3000r / min, and the centrifugal washing time was 20min.
[0030] Among them, Ti3C2T x The specific preparation method of MXene powder is as follows: LiF and HCl solution are mixed and reacted to obtain a reaction solution; then the reaction solution is mixed and reacted with Ti3AlC2 to obtain a reaction product; then the reaction product is dissolved and centrifuged, and the supernatant is dried to obtain the product (for detailed preparation method, please refer to the invention patent with patent application number CN202211156499.6 entitled "A composite film with electromagnetic shielding and thermal conductivity and its preparation method").
[0031] Step 2: Add ferric nitrate in an equal molar amount to chloroplatinic acid in a 10 g / L ethylene glycol chloroplatinic acid solution, mix well, and then add MXenes dispersion in a volume twice that of chloroplatinic acid to the resulting mixed solution. After magnetic stirring until homogeneous, slowly add ascorbic acid aqueous solution with a concentration of 0.2 mol / L and a volume of 10% of the MXenes dispersion. After reacting at 80°C for 5 h, add dicyandiamide in a mass equal to 1.5 times that of chloroplatinic acid, mix and stir for 2 h, and then centrifuge, wash with alcohol and dry the reaction product to obtain a solid powder.
[0032] The stirring speed was set to 300 r / min and the stirring time was set to 40 min.
[0033] Step 3: Add 0.2 times the volume of chloroiridium ethanol solution with a concentration of 0.6 mmol / L to the 10 g / L solid powder aqueous dispersion. After ultrasonic dispersion, add 0.2 times the volume of chloroiridium ethanol solution with a concentration of 0.1 mol / L sodium nitrate aqueous solution. React at 120℃ for 8 h, then cool to room temperature. After centrifugation and vacuum drying, store the resulting composite powder for later use.
[0034] The ultrasonic dispersion power was 300W, and the ultrasonic time was 1.5h; the centrifugation speed was set to 4000r / min, and the centrifugation time was set to 10min; the vacuum drying temperature was 60℃, and the vacuum drying time was 15h.
[0035] Step 4: Add 5 times the mass of ruthenium trichloride and 10 times the mass of o-phenanthroline and composite powder respectively to a 10 g / L ruthenium trichloride ethanol solution. After magnetic stirring until homogeneous, heat to 630℃ under argon atmosphere, keep at this temperature for 3 hours, and then cool to room temperature. Soak the reaction product in 0.4 mol / L sulfuric acid, centrifuge and wash until neutral, and then vacuum dry, activate and modify the surface in sequence.
[0036] The vacuum drying temperature was 60℃ and the vacuum drying time was 15h.
[0037] The specific steps of the activation treatment are as follows: the reaction product after vacuum drying is treated in a H2 / Ar mixed gas with a volume fraction of 5% at 300°C for 3 hours, and finally ground through a 400-mesh sieve.
[0038] The specific steps for surface modification are as follows: the activated solid product is immersed in a 0.1 mol / L 4-aminophenylboronic acid ethanol solution at a dosage ratio of 20 g / L, reacted at 55℃ for 6 h, filtered out, and then vacuum dried.
[0039] Example 2
[0040] A method for preparing a highly active catalyst for a proton exchange membrane fuel cell includes the following steps:
[0041] Step 1: Add Ti3C2T at a dosage ratio of 0.05 g / mL. x MXene powder was added to a 10wt% tetrabutylammonium hydroxide aqueous solution, ultrasonically dispersed, and the dispersion was centrifuged and washed until the washing solution was neutral. The resulting precipitate was then dispersed in ethanol at a dosage ratio of 0.05 g / mL to obtain an MXene dispersion.
[0042] The ultrasonic dispersion power was 700W, the ultrasonic frequency was 35kHz, and the ultrasonic dispersion time was 3h; the centrifugal washing speed was set to 4000r / min, and the centrifugal washing time was 15min.
[0043] Step 2: Add ferric nitrate in an equal molar amount to chloroplatinic acid in a 20 g / L ethylene glycol chloroplatinic acid solution, mix well, and then add MXenes dispersion in a volume of 3 times that amount to the resulting mixed solution. After magnetic stirring until homogeneous, slowly add ascorbic acid aqueous solution with a concentration of 0.15 mol / L and a volume of 15% of the MXenes dispersion. After reacting at 80°C for 4 hours, add dicyandiamide in a mass of 2 times that of chloroplatinic acid, mix and stir for 3 hours, and then centrifuge, wash with alcohol and dry the reaction product to obtain a solid powder.
[0044] The stirring speed was set to 400 r / min and the stirring time was set to 35 min.
[0045] Step 3: Add 0.2 times the volume of chloroiridium acid ethanol solution with a concentration of 0.8 mmol / L to the 20 g / L solid powder aqueous dispersion. After ultrasonic dispersion, add 0.2 times the volume of chloroiridium acid ethanol solution with a concentration of 0.1 mol / L sodium nitrate aqueous solution. React at 125℃ for 6 h, then cool to room temperature. After centrifugation and vacuum drying, store the obtained composite powder for later use.
[0046] The ultrasonic dispersion power was 400W, and the ultrasonic time was 1.5h; the centrifugation speed was set to 5000r / min, and the centrifugation time was set to 10min; the vacuum drying temperature was 70℃, and the vacuum drying time was 15h.
[0047] Step 4: Add o-phenanthroline and 15 times the mass of the composite powder to a 10 g / L ruthenium trichloride ethanol solution. After magnetic stirring until homogeneous, heat to 650℃ under an argon atmosphere, keep at this temperature for 3 hours, and then cool to room temperature. Soak the reaction product in 0.5 mol / L sulfuric acid, centrifuge and wash until neutral, and then vacuum dry, activate and modify the surface in sequence.
[0048] The vacuum drying temperature was 70℃ and the vacuum drying time was 15h.
[0049] The specific steps of the activation treatment are as follows: the reaction product after vacuum drying is treated in a H2 / Ar mixed gas with a volume fraction of 5% at 320°C for 3 hours, and finally ground through a 450-mesh sieve.
[0050] The specific steps for surface modification are as follows: the activated solid product is immersed in a 0.1 mol / L 4-aminophenylboronic acid ethanol solution at a dosage ratio of 30 g / L, reacted at 60℃ for 5 h, filtered out, and then vacuum dried.
[0051] Example 3
[0052] A method for preparing a highly active catalyst for a proton exchange membrane fuel cell includes the following steps:
[0053] Step 1: Add Ti3C2T at a dosage ratio of 0.1 g / mL. x MXene powder was added to a 10wt% tetrabutylammonium hydroxide aqueous solution, ultrasonically dispersed, and the dispersion was centrifuged and washed until the washing solution was neutral. The resulting precipitate was then dispersed in ethanol at a dosage ratio of 0.1g / mL to obtain an MXene dispersion.
[0054] The ultrasonic dispersion power was 800W, the ultrasonic frequency was 40kHz, and the ultrasonic dispersion time was 2h; the centrifugal washing speed was set to 5000r / min, and the centrifugal washing time was 10min.
[0055] Step 2: Add ferric nitrate in an equal molar amount to chloroplatinic acid in a 30 g / L ethylene glycol chloroplatinic acid solution, mix well, and then add MXenes dispersion in a volume of 3 times that amount to the resulting mixed solution. After magnetic stirring until homogeneous, slowly add ascorbic acid aqueous solution with a concentration of 0.2 mol / L and a volume of 20% of the MXenes dispersion. After reacting at 85°C for 3 hours, add dicyandiamide in a mass of 2.5 times that of chloroplatinic acid, mix and stir for 3 hours, and then centrifuge, wash with alcohol and dry the reaction product to obtain a solid powder.
[0056] The stirring speed was set to 500 r / min, and the stirring time was set to 30 min.
[0057] Step 3: Add 0.3 times the volume of the chloroiridium acid ethanol solution with a concentration of 1 mmol / L to the 30 g / L solid powder aqueous dispersion. After ultrasonic dispersion, add 0.3 times the volume of the chloroiridium acid ethanol solution with a concentration of 0.2 mol / L sodium nitrate aqueous solution. React at 130℃ for 5 h, then cool to room temperature. After centrifugation and vacuum drying, store the resulting composite powder for later use.
[0058] The ultrasonic dispersion power was 500W and the ultrasonic time was 1h; the centrifugation speed was set to 6000r / min and the centrifugation time was set to 5min; the vacuum drying temperature was 80℃ and the vacuum drying time was 10h.
[0059] Step 4: Add o-phenanthroline and 20 times the mass of the composite powder to a 15 g / L ruthenium trichloride ethanol solution. After magnetic stirring until homogeneous, heat to 680℃ under an argon atmosphere, keep at this temperature for 3 hours, and then cool to room temperature. Soak the reaction product in 0.6 mol / L sulfuric acid, centrifuge and wash until neutral, and then vacuum dry, activate and modify the surface in sequence.
[0060] The vacuum drying temperature was 80℃ and the vacuum drying time was 10h.
[0061] The specific steps of the activation treatment are as follows: the reaction product after vacuum drying is treated in a H2 / Ar mixed gas with a volume fraction of 5% at 350°C for 2 hours, and finally ground through a 500-mesh sieve.
[0062] The specific steps for surface modification are as follows: the activated solid product is immersed in a 0.12 mol / L 4-aminophenylboronic acid ethanol solution at a dosage ratio of 50 g / L, reacted at 65℃ for 4 h, filtered out, and then vacuum dried.
[0063] Comparative example: Pt / C catalyst (Pt loading 50 wt%) produced by Tanaka Precious Metals Co., Ltd., Japan.
[0064] Performance testing: The catalytic performance of the catalyst samples provided in Examples 1-3 and the comparative examples was tested, and the test data are recorded in the table below:
[0065] Test Project Comparative Example Example 1 Example 2 Example 3 Electrochemical active area (m² / g) 68.5 84.3 88.6 86.7 Mass-specific activity (A / mg) 0.18 0.28 0.30 0.32 Initial mass-specific activity (mA / mg) 232 287 302 297 Reverse polarity test, 1.5V maintained Complete failure (5 minutes) 9.8 12.3 10.6 Activity retention rate (1.0-1.5V) after 30,000 cycles / % 74.3 91.3 94.3 93.6
[0066] By comparing and analyzing the data in the table, it can be seen that the present invention significantly improves the electrocatalytic activity and stability of the catalyst and reduces its dependence on precious metals through MXene support optimization, multi-metal component synergy, and surface modification, making it suitable for the efficient operation of proton exchange membrane fuel cells. This indicates that the highly active catalyst for proton exchange membrane fuel cells and its preparation method provided by the present invention have broader market prospects and are more suitable for widespread application.
[0067] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0068] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims
1. A method for preparing a highly active catalyst for a proton exchange membrane fuel cell, characterized in that, Includes the following steps: Step 1: Add Ti3C2T at a dosage ratio of 0.05-0.1 g / mL. x MXene powder was added to a 10wt% tetrabutylammonium hydroxide aqueous solution, ultrasonically dispersed, and the dispersion was centrifuged and washed until the washing solution was neutral. The resulting precipitate was then dispersed in ethanol at a dosage ratio of 0.05-0.1 g / mL to obtain an MXene dispersion. Step 2: Add ferric nitrate in an equal molar amount to chloroplatinic acid in a 10-30 g / L ethylene glycol chloroplatinic acid solution, mix well, and then add MXenes dispersion in a volume of 2-3 times that volume to the resulting mixed solution. After magnetic stirring until homogeneous, slowly add ascorbic acid aqueous solution in a volume of 10-20% of the MXenes dispersion and a concentration of 0.1-0.2 mol / L. Keep the reaction at 80-85℃ for 3-5 h, and then add dicyandiamide in a mass of 1.5-2.5 times that of chloroplatinic acid. Mix and stir for 2-3 h. The reaction product is then centrifuged, washed with alcohol, and dried to obtain a solid powder. Step 3: Add 0.2-0.3 times the volume of the 10-30 g / L solid powder aqueous dispersion to a chloroiridic acid ethanol solution with a concentration of 0.6-1 mmol / L. After ultrasonic dispersion, add 0.2-0.3 times the volume of the chloroiridic acid ethanol solution to a sodium nitrate aqueous solution with a concentration of 0.1-0.2 mol / L. React at 120-130℃ for 5-8 hours, then cool to room temperature. After centrifugation and vacuum drying, store the resulting composite powder for later use. Step 4: Add 5-8 times the mass of ruthenium trichloride and 10-20 times the mass of phenanthroline to an ethanol solution of 10-15 g / L ruthenium trichloride. After magnetic stirring until homogeneous, heat to 630-680℃ under an argon atmosphere and keep at that temperature for 2-3 hours. Then cool to room temperature. Soak the reaction product in 0.4-0.6 mol / L sulfuric acid, centrifuge and wash until neutral, and then vacuum dry, activate and modify the surface in sequence.
2. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: In step one, the ultrasonic dispersion power is 600-800W, the ultrasonic frequency is 35-40kHz, and the ultrasonic dispersion time is 2-3h.
3. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: In step one, the centrifugal washing speed is set to 3000-5000 r / min, and the centrifugal washing time is 10-20 min.
4. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: In step two, the rotation speed of the magnetic stirring is set to 300-500 r / min, and the magnetic stirring time is set to 30-40 min.
5. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: In step three, the ultrasonic dispersion power is 300-500W, and the ultrasonic time is 1-1.5h.
6. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: In step three, the centrifugation speed is set to 4000-6000 r / min, and the centrifugation time is set to 5-10 min.
7. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: The vacuum drying temperature in steps three and four is 60-80℃, and the vacuum drying time is 10-15h.
8. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: The specific steps of the activation treatment in step four are as follows: the reaction product after vacuum drying is treated in a H2 / Ar mixed gas with a volume fraction of 5% at 300-350℃ for 2-3 hours, and finally ground through a 400-500 mesh sieve.
9. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that, The specific steps of the surface modification are as follows: the activated solid product is immersed in a 0.1-0.12 mol / L 4-aminophenylboronic acid ethanol solution at a dosage ratio of 20-50 g / L, reacted at 55-65℃ for 4-6 h, filtered out, and then vacuum dried.
10. A highly active catalyst for proton exchange membrane fuel cells, characterized in that: It is prepared by the preparation method described in any one of claims 1-9.