High-activity catalyst for proton exchange membrane fuel cell and preparation method thereof

Abstract

The invention relates to the technical field of cell catalysts, in particular to a high-activity catalyst for a proton exchange membrane fuel cell and a preparation method of the high-activity catalyst. The preparation method comprises the following steps: firstly, carrying out pretreatment on Ti < 3 > C < 2 > T < x > MXene powder to obtain dispersion liquid; then reducing chloroplatinic acid and ferric nitrate through ascorbic acid by taking the nitrogen-doped carbon-coated platinum-iron alloy as a carrier, and carrying out high-temperature cracking in combination with dicyandiamide to generate a nitrogen-doped carbon-coated platinum-iron alloy in situ; loading iridium oxide on the surface through a hydrothermal method; and finally introducing ruthenium trichloride and phenanthroline, performing high-temperature pyrolysis to form a ruthenium-nitrogen coordination structure, and performing acid pickling, activation and 4-aminophenylboronic acid surface modification to obtain the final catalyst. Through MXene carrier optimization, multi-metal component collaboration and surface modification, the electrocatalytic activity and stability of the catalyst are remarkably improved, dependence on precious metal is reduced, and the catalyst is suitable for efficient operation of the proton exchange membrane fuel cell.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of battery catalysts, in particular to a high-activity catalyst for a proton exchange membrane fuel cell and a preparation method thereof. BACKGROUND

[0002] The proton exchange membrane fuel cell is regarded as an important development direction in the clean energy field due to high energy conversion efficiency and environmental friendliness. The activity, stability and cost of a catalyst as a core component of the proton exchange membrane fuel cell directly affect the performance of the cell. At present, a commercial catalyst mainly uses platinum as a main active component, but the Pt resource is scarce and the cost is high, and the activity is easily reduced due to agglomeration and corrosion in the reaction process, which limits the large-scale application of the proton exchange membrane fuel cell.

[0003] In the prior art, an alloy or a composite structure is formed by introducing a transition metal, or the dispersibility of the catalyst is improved by using a carbon-based carrier (such as a carbon nanotube or graphene), but there are still problems such as insufficient exposure of active sites and poor matching of the conductivity and stability of the carrier. As a new type of two-dimensional nanomaterial, MXene has high conductivity, good mechanical strength and rich surface functional groups, and is an ideal candidate material for a catalyst carrier. However, the stacking between layers of MXene easily leads to shielding of the active sites, and the interaction between the MXene and metal nanoparticles needs to be further optimized to improve the catalytic stability.

[0004] Based on the above, the application provides a high-activity catalyst for a proton exchange membrane fuel cell and a preparation method thereof to solve the technical problems mentioned above. SUMMARY

[0005] The application significantly improves the electrocatalytic activity and stability of the catalyst, reduces the dependence on noble metals, and is suitable for efficient operation of the proton exchange membrane fuel cell by optimizing the MXene carrier, synergizing the multiple metal components and surface modification. x MXene carrier, synergizing the multiple metal components and surface modification.

[0006] To achieve the above purpose, the application provides the following technical scheme:

[0007] In a first aspect, the application provides a preparation method of a high-activity catalyst for a proton exchange membrane fuel cell, including the following steps:

[0008] Step one, 0.05-0.1 g / mL of Ti3C2T x The MXene powder is put into a 10wt% tetrabutylammonium hydroxide aqueous solution, and after ultrasonic dispersion, the dispersion liquid is centrifuged and washed until the washing liquid is neutral, and then the obtained precipitate is dispersed in ethanol to obtain an MXene dispersion liquid;

[0009] Step two, add iron nitrate with the same molar amount of chloroplatinic acid to 10-30 g / L chloroplatinic acid ethylene glycol solution, mix well, then add 2-3 times the volume of MXenes dispersion liquid to the obtained mixed solution, uniformly stir by magnetic force, then slowly add 10-20% of the volume of the MXenes dispersion liquid and 0.1-0.2 mol / L ascorbic acid aqueous solution, incubate at 80-85°C for 3-5 h, then add 1.5-2.5 times the mass of chloroplatinic acid dicyandiamide, mix and stir for 2-3 h, then sequentially perform centrifugal separation, alcohol washing and drying treatment on the reaction product to obtain a solid powder;

[0010] Step three, add 0.2-0.3 times the volume of 0.6-1 mmol / L chloroiridic acid ethanol solution to 10-30 g / L solid powder aqueous dispersion liquid, ultrasonic dispersion, then add 0.2-0.3 times the volume of 0.1-0.2 mol / L sodium nitrate aqueous solution to the chloroiridic acid ethanol solution, react at 120-130°C for 5-8 h, then cool to room temperature, perform centrifugal separation and vacuum drying, and then store the obtained composite powder for later use;

[0011] Step four, add 5-8 times the mass of o-phenanthroline and 10-20 times the mass of the composite powder to 10-15 g / L ruthenium trichloride ethanol solution, uniformly stir by magnetic force, then heat to 630-680°C under argon atmosphere, incubate for 2-3 h, then cool to room temperature, soak the reaction product in 0.4-0.6 mol / L sulfuric acid, then centrifugally wash until neutral, and then sequentially perform vacuum drying, activation treatment and surface modification.

[0012] Further, the ultrasonic dispersion power in step one is 600-800 W, the ultrasonic frequency is 35-40 kHz, and the ultrasonic dispersion time is 2-3 h.

[0013] Further, the centrifugal washing speed in step one is set to 3000-5000 r / min, and the centrifugal washing time is 10-20 min.

[0014] Further, the magnetic stirring speed in step two is set to 300-500 r / min, and the magnetic stirring time is set to 30-40 min.

[0015] Further, the ultrasonic dispersion power in step three is 300-500 W, and the ultrasonic time is 1-1.5 h.

[0016] Further, the centrifugal separation speed in step three is set to 4000-6000 r / min, and the centrifugal separation time is set to 5-10 min.

[0017] Further, the temperature of vacuum drying in the step three and the step four is 60-80 DEG C, and the vacuum drying time is 10-15h.

[0018] Further, the specific step of the activation treatment in the step four is: the reaction product after vacuum drying is treated in H2 / Ar mixed gas with H2 volume fraction of 5% at 300-350 DEG C for 2-3h, and finally grinded through 400-500 mesh sieve.

[0019] Further, the specific step of the surface modification is: the solid product after activation treatment is soaked in 0.1-0.12mol / L 4-aminobenzoic acid ethanol solution at 20-50g / L of the use ratio, and after reaction at 55-65 DEG C for 4-6h, it is filtered out, and then vacuum dried.

[0020] The second aspect, the present application provides a kind of high activity catalyst for proton exchange membrane fuel cell, which is prepared by the preparation method described above.

[0021] Compared with prior art, the beneficial effects of the present application are:

[0022] 1、The Ti3C2T x MXene is used as the base material, and a core-shell structure of "nitrogen-doped carbon layer coated platinum-iron alloy particles" is first constructed on the surface of the base material. The core-shell structure can physically isolate the erosion of acidic electrolyte, effectively inhibiting the dissolution, migration and agglomeration of platinum and iron elements. Then, an iridium oxide protective layer is introduced, forming a double protection mechanism. The iridium oxide not only can fill the possible defects of the carbon layer, but also is extremely stable at high potential. It can not only protect the active components inside, but also significantly enhance the anti-oxidation corrosion ability of the carrier material itself. The synergistic protection system formed can maintain a very high electrochemical active area and microstructure integrity after long-term operation and accelerated stress testing, thereby greatly prolonging the service life of the fuel cell.

[0023] 2、The platinum-iron alloy in the application optimizes the adsorption energy of the reaction intermediate through the intermetallic electronic effect, and the catalytic activity is obviously better than that of a single platinum component. Furthermore, the introduction of iridium oxide can preferentially occur oxygen evolution reaction at high potential formed by abnormal working conditions such as reverse polarity of the battery, so as to timely remove active oxygen species on the reaction interface, effectively alleviate the corrosion of the carbon carrier and the oxidation and dissolution of the platinum component, and play an important protective role on the overall structure of the catalyst. In addition, the ruthenium-nitrogen coordination structure formed by pyrolysis provides stable and efficient auxiliary catalytic active sites for the system. The above three components are coupled with each other through chemical bonding and interface effect to form an organic synergistic catalytic system, and the mutual synergy of the three ensures that the catalyst can exhibit high activity, high stability and excellent environmental adaptability under the whole working condition of the normal operation, frequent start-stop and transient overload of the proton exchange membrane fuel cell.

[0024] 3、The surface of the solid product after activation treatment is modified by 4-aminobenzene boronic acid, which effectively improves the physical and chemical properties of the surface of the prepared catalyst, changes it from completely hydrophilic to moderately hydrophobic state. It helps to remove excess liquid water generated during the reaction, effectively prevents the problem of pore blockage caused by waterlogging, thereby building a smooth "transport channel" for the reaction gas (oxygen), ensuring that oxygen can diffuse more efficiently to each active site, significantly improving the performance of the battery, especially under high current density working conditions, the voltage loss of the battery is smaller, and the battery can output higher power density, and the performance is more excellent. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, not all embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the application.

[0026] Embodiment 1

[0027] A preparation method of a high-activity catalyst for a proton exchange membrane fuel cell, comprising the following steps:

[0028] Step one, according to the dosage ratio of 0.05g / mL, Ti3C2T x The MXene powder is put into a 10wt% tetrabutylammonium hydroxide aqueous solution, and after ultrasonic dispersion, the dispersion liquid is centrifuged and washed until the washing liquid is neutral, and then the obtained precipitate is dispersed in ethanol according to the dosage ratio of 0.05g / mL to obtain a MXene dispersion liquid;

[0029] The ultrasonic dispersion power is 600 W, the ultrasonic frequency is 35 kHz, and the ultrasonic dispersion time is 2 h; the centrifugal washing speed is set to 3000 r / min, and the centrifugal washing time is 20 min;

[0030] Ti3C2T x The specific preparation method of the MXene powder is: mixing and reacting LiF and HCl solution to obtain a reaction solution; then mixing and reacting the reaction solution with Ti3AlC2 to obtain a reaction product; and then dissolving and centrifuging the reaction product, and the supernatant is dried to obtain (for details, see the invention patent with the patent application number CN202211156499.6 and the name of a composite film with electromagnetic shielding and heat conduction properties and its preparation method);

[0031] Step two, add iron nitrate with the same molar amount of chloroplatinic acid to 10 g / L chloroplatinic acid ethylene glycol solution, mix uniformly, then add MXenes dispersion liquid with a volume of 2 times to the obtained mixed solution, uniformly stir with a magnetic stirrer, then slowly add ascorbic acid aqueous solution with a volume of 10% of the MXenes dispersion liquid and a concentration of 0.2 mol / L, and after reaction at 80℃ for 5 h, add dicyandiamide with a mass of 1.5 times of chloroplatinic acid, mix and stir for 2 h, and then sequentially perform centrifugal separation, alcohol washing and drying treatment on the reaction product to obtain a solid powder;

[0032] The speed of the magnetic stirring is set to 300 r / min, and the time of the magnetic stirring is set to 40 min;

[0033] Step three, add 0.2 times in volume and 0.6 mmol / L in concentration of chloroiridic acid ethanol solution to 10 g / L solid powder aqueous dispersion liquid, ultrasonic disperse, then add 0.2 times in volume and 0.1 mol / L in concentration of sodium nitrate aqueous solution to the chloroiridic acid ethanol solution, and after reaction at 120℃ for 8 h, cool to room temperature, and then perform centrifugal separation and vacuum drying, and the obtained composite powder is stored and used;

[0034] The ultrasonic dispersion power is 300 W, and the ultrasonic time is 1.5 h; the centrifugal separation speed is set to 4000 r / min, and the centrifugal separation time is set to 10 min; the vacuum drying temperature is 60℃, and the vacuum drying time is 15 h;

[0035] Step four, add 5 times in mass of o-phenanthroline and 10 times in mass of the composite powder to 10 g / L ruthenium trichloride ethanol solution, uniformly mix with a magnetic stirrer, then heat to 630℃ under an argon atmosphere, and after heat preservation treatment for 3 h, cool to room temperature, and then perform soaking in 0.4 mol / L sulfuric acid, centrifugal washing until neutral, and then sequentially perform vacuum drying, activation treatment and surface modification;

[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 power of ultrasonic dispersion is 400 W, the ultrasonic time is 1.5 h, the speed of centrifugal separation is set to 5000 r / min, and the centrifugal separation time is set to 10 min; the temperature of vacuum drying is 70 DEG C, and the vacuum drying time is 15 h;

[0047] Step four, 10 g / L of ruthenium trichloride is added to the ethanol solution, the mass of the complex powder is 6 times of the ruthenium trichloride, and the mass of the o-phenanthroline is 15 times of the ruthenium trichloride, the mixture is uniformly stirred by magnetic stirring, and then heated to 650 DEG C under an argon atmosphere, and then cooled to room temperature after heat preservation for 3 h, and then the reaction product is soaked in 0.5 mol / L sulfuric acid, and then washed by centrifugation until neutral, and then vacuum dried, activated and surface modified in sequence, and then obtained;

[0048] The temperature of vacuum drying is 70 DEG C, and the vacuum drying time is 15 h;

[0049] The specific steps of the activation treatment are as follows: the vacuum dried reaction product is treated in a H2 / Ar mixed gas with a H2 volume fraction of 5% at 320 DEG C for 3 h, and then ground through a 450 mesh sieve;

[0050] The specific steps of the surface modification are as follows: the solid product after the activation treatment is soaked in a 0.1 mol / L 4-aminobenzene boronic acid ethanol solution at a dosage ratio of 30 g / L, and then filtered after reaction at 60 DEG C for 5 h, and then vacuum dried.

[0051] Example 3

[0052] A preparation method of a high-activity catalyst for a proton exchange membrane fuel cell, comprising the following steps:

[0053] Step one, 0.1 g / mL of Ti3C2T x The MXene powder is put into a 10 wt% tetrabutylammonium hydroxide aqueous solution, ultrasonic dispersion is carried out, the dispersion liquid is washed by centrifugation until the washing liquid is neutral, and then the obtained precipitate is dispersed in ethanol at a dosage ratio of 0.1 g / mL to obtain a MXene dispersion liquid;

[0054] The power of ultrasonic dispersion is 800 W, the ultrasonic frequency is 40 kHz, and the ultrasonic dispersion time is 2 h; the speed of centrifugal washing is set to 5000 r / min, and the centrifugal washing time is 10 min;

[0055] Step two, add iron nitrate with the same molar amount of chloroplatinic acid to the 30 g / L chloroplatinic acid ethylene glycol solution, mix evenly, then add 3 times the volume of the MXene dispersion solution to the obtained mixed solution, stir uniformly under magnetic force, then slowly add 20% of the volume of the MXene dispersion solution and 0.2 mol / L ascorbic acid aqueous solution, react at 85℃ for 3h, then add 2.5 times the mass of chloroplatinic acid dicyandiamide, mix and stir for 3h, then centrifuge, alcohol wash and dry the reaction product in sequence to obtain a solid powder;

[0056] The rotation speed during magnetic stirring is set to 500 r / min, and the magnetic stirring time is set to 30 min.

[0057] Step three, add 0.3 times the volume of 1 mmol / L chloroiridic acid ethanol solution to the 30 g / L solid powder aqueous dispersion, ultrasonic dispersion, then add 0.3 times the volume of 0.2 mol / L sodium nitrate aqueous solution to the chloroiridic acid ethanol solution, react at 130℃ for 5h, then cool to room temperature, centrifuge and vacuum dry the obtained composite powder for storage and standby use.

[0058] The ultrasonic dispersion power is 500 W, the ultrasonic time is 1h, the centrifugal speed is set to 6000 r / min, and the centrifugal time is set to 5 min; the vacuum drying temperature is 80℃, and the vacuum drying time is 10h.

[0059] Step four, add 8 times the mass of o-phenanthroline and 20 times the mass of the composite powder to the 15 g / L ruthenium trichloride ethanol solution, mix uniformly under magnetic stirring, then heat to 680℃ under argon atmosphere, keep the temperature for 3h, then cool to room temperature, soak the reaction product in 0.6 mol / L sulfuric acid, then centrifuge and wash until neutral, then vacuum dry, activate and modify the surface in sequence.

[0060] The vacuum drying temperature is 80℃, and the vacuum drying time is 10h.

[0061] The specific steps of the activation treatment are as follows: the vacuum dried reaction product is treated in a H2 / Ar mixed gas with a H2 volume fraction of 5% at 350℃ for 2h, and finally ground through a 500 mesh sieve.

[0062] The specific steps of the surface modification are as follows: the solid product after activation treatment is soaked in a 0.12 mol / L 4-aminobenzene boronic acid ethanol solution at a dosage of 50 g / L, reacted at 65℃ for 4h, then filtered out, and vacuum dried to obtain the product.

[0063] Comparative example: Pt / C catalyst produced by Japan Tanaka Precious Metals Co., Ltd. (Pt loading is 50wt%).

[0064] Performance test: the catalytic performance of the catalyst samples provided by examples 1-3 and comparative examples was tested respectively, and the obtained test data were recorded in the following table:

[0065] Test item Comparative example Example 1 Example 2 Example 3 Electrochemically 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, 1.5 V hold Complete failure (5 min) 9.8 12.3 10.6 Activity retention after 30000 cycles (1.0-1.5 V) / % 74.3 91.3 94.3 93.6

[0066] By comparing and analyzing the data in the table, it can be seen that the catalytic activity and stability of the catalyst are significantly improved by optimizing the MXene carrier, synergizing the multi-metal components and surface modification, and reducing the dependence on noble metals, which is suitable for efficient operation of the proton exchange membrane fuel cell. Therefore, the high-activity catalyst for the proton exchange membrane fuel cell and the preparation method thereof provided by the application have a wider market prospect and are more suitable for promotion.

[0067] In the description of the present specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0068] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and limit the application to the specific embodiments described. Obviously, many modifications and changes can be made according to the content of the present specification. The present specification selects and describes these embodiments in order to better explain the principles and practical applications of the application, so that those skilled in the art can well understand and utilize the application. The application is limited only by the claims and their full scope and equivalents.

Claims

1. A method for producing a high-activity catalyst for a proton exchange membrane fuel cell, characterized by, Comprising the following steps: Step one, according to the dosage ratio of 0.05-0.1 g / mL, Ti3C2T x MXene powder was put into 10 wt% tetrabutylammonium hydroxide aqueous solution, and after ultrasonic dispersion, the dispersion was centrifuged and washed until the washing liquid was neutral, and then the obtained precipitate was dispersed in ethanol according to the dosage ratio of 0.05-0.1 g / mL to obtain MXene dispersion liquid; Step two, add the same molar amount of ferric nitrate to the 10-30 g / L chloroplatinic acid ethylene glycol solution, mix well, then add 2-3 times the volume of MXenes dispersion liquid to the obtained mixed solution, magnetically stir uniformly, then slowly add 10-20% of the volume of the MXenes dispersion liquid, and 0.1-0.2 mol / L of the concentration of ascorbic acid aqueous solution, after 3-5 h of incubation at 80-85℃, add 1.5-2.5 times the mass of chloroplatinic acid of dicyandiamide, mix and stir for 2-3 h, then sequentially centrifuge, alcohol wash and dry the reaction product to obtain a solid powder; Step three, add 0.2-0.3 times the volume of 0.6-1 mmol / L chloroiridic acid ethanol solution to the 10-30 g / L solid powder aqueous dispersion liquid, ultrasonic dispersion, then add 0.2-0.3 times the volume of 0.1-0.2 mol / L sodium nitrate aqueous solution to the chloroiridic acid ethanol solution, after 5-8 h of reaction at 120-130℃, cool to room temperature, centrifuge and vacuum dry the obtained composite powder for storage and use; Step four, add 5-8 times the mass of o-phenanthroline and 10-20 times the mass of the composite powder to the 10-15 g / L ruthenium trichloride ethanol solution, magnetically stir uniformly, then heat to 630-680℃ under argon atmosphere, incubate for 2-3 h, then cool to room temperature, soak the reaction product in 0.4-0.6 mol / L sulfuric acid, centrifuge and wash until neutral, then sequentially vacuum dry, activate and modify the surface.

2. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: The ultrasonic dispersion power in step one is 600-800 W, the ultrasonic frequency is 35-40 kHz, and the ultrasonic dispersion time is 2-3 h.

3. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: The centrifugal washing speed in step one 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: The magnetic stirring speed in step two 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: The ultrasonic dispersion power in step three is 300-500 W, and the ultrasonic time is 1-1.5 h.

6. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: The centrifugal separation speed in step three is set to 4000-6000 r / min, and the centrifugal separation 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 10-15 h.

8. The method for preparing a highly active catalyst for a proton exchange membrane fuel cell according to claim 1, characterized in that: The activation treatment in step four is as follows: after vacuum drying, the reaction product is treated in a H2 / Ar mixed gas with a H2 volume fraction of 5% at 300-350℃ for 2-3 h, 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 surface modification is as follows: the solid product after activation treatment is soaked in 0.1-0.12 mol / L 4-aminobenzene boronic acid ethanol solution at a dosage of 20-50 g / L, reacted at 55-65℃ for 4-6 h, then filtered out, vacuum dried, and then obtained.

10. A high activity catalyst for proton exchange membrane fuel cells, characterized by: Prepared by the preparation method of any one of claims 1-9.