Anti-antipolar catalyst for proton exchange membrane fuel cell and preparation method of anti-antipolar catalyst
By embedding transition metal on the carbon support, an anti-reverse catalyst was prepared, which solved the problem of performance degradation of fuel cells under reversed conditions, and significantly improved the anti-reverse performance and service life of the catalyst.
Patent Information
- Application Number
- CN202510221621.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-27
- Publication Date
- 2025-05-06
AI Technical Summary
Proton exchange membrane fuel cells (PEMFCs) are prone to occur when the anode potential exceeds the cathode potential under frequent start-up and rapid change-load conditions, causing the battery to reverse, thereby damaging the anode catalyst and reducing the performance of the fuel cell.
Anti-reverse catalyst is prepared by embedding transition metals such as Co, Ta, Ru, Ir on a carbon support, combining the reaction of chloroplatinic acid, ethylene glycol and sodium hydroxide to improve the anti-reverse ability of the catalyst.
It effectively improves the anti-reverse performance of the catalyst, extends the service life of the catalyst, and significantly improves the performance of the fuel cell.
Smart Images
Figure CN119943980A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a proton exchange membrane fuel cell anti-reverse polarity catalyst and a preparation method thereof, belonging to the technical field of proton exchange membrane fuel cell catalyst preparation. Background Art
[0002] During the operation of PEMFCs, sudden changes in reactant demand caused by frequent startup, rapid load changes, etc. can lead to hydrogen starvation at the anode. When the anode potential exceeds the cathode potential, the battery voltage becomes negative, which is called battery reversal.
[0003] Under the conditions of battery reversal, the anode catalyst (Pt / C) undergoes carbon oxidation reaction, and the anode will be severely damaged; the Pt catalyst will fall off and agglomerate from the carbon carrier; and the thinning of the carbon support layer and the collapse of the pore structure will cause mass transfer problems. Ultimately, the performance of PEMFCs will be catastrophically reduced. Carbon materials as fuel cell catalyst carriers face some problems, such as the agglomeration of precious metal platinum particles due to the corrosion of the carbon carrier, which reduces the oxygen reduction catalytic activity and thus leads to a decrease in catalyst durability. Summary of the invention
[0004] In view of the deficiencies in the prior art, the present invention provides a proton exchange membrane fuel cell anti-reverse polarity catalyst and a preparation method thereof, which solves the reverse polarity phenomenon of the anode cell of the fuel cell.
[0005] The technical solution provided by the present invention is as follows:
[0006] The present invention provides a method for preparing a proton exchange membrane fuel cell anti-reverse polarity catalyst, characterized in that the preparation method comprises the following steps: The transition metal salt and the carbon-containing matrix material are ultrasonically dispersed in a polar solvent, subjected to a high-temperature oil bath reaction after degassing, and then separated and purified to obtain a primary composite; The primary composite is subjected to primary calcination under an inert atmosphere to obtain a primary calcined product; the primary calcined product is then ball-milled and acid-washed, filtered, dried, subjected to secondary calcination, and then ground to obtain a composite carrier after pyrolysis treatment; After the composite carrier is uniformly mixed with chloroplatinic acid, ethylene glycol and sodium hydroxide aqueous solution, the reaction liquid is heated to react so as to generate a target proton exchange membrane fuel cell anti-reverse polarity catalyst.
[0007] Furthermore, the transition metal salt is selected from any one of Co, Ta, Ru, and Ir, a chloride or a hydrate thereof, a sulfate or a hydrate thereof, a phosphate or a hydrate thereof, and a nitrate or a hydrate thereof.
[0008] Furthermore, the carbon-containing matrix material includes a mixture of activated carbon and glucose, and the mass ratio of the transition metal salt, activated carbon and glucose is 1:(4~5):(6~8).
[0009] Furthermore, the ultrasonic dispersion is carried out in a low temperature environment, the temperature is controlled at 0-5°C, and the treatment time is 50-70 minutes; the degassing treatment is degassing under vacuum conditions for at least 1 hour, and the temperature is 25°C±10°C.
[0010] Furthermore, the polar solvent is formamide; the reaction temperature of the high-temperature oil bath is 150-160° C., the stirring rate is 500-600 rpm, and the duration is 6-8 hours.
[0011] Furthermore, in the heating reaction, the molar ratio of the composite carrier, chloroplatinic acid, ethylene glycol and sodium hydroxide is (1-2.5): 0.08-0.09: 20-22: 0.4-0.6.
[0012] Furthermore, the reaction solution was heated using an oil bath, and the temperature was controlled at 150-160°C.
[0013] Furthermore, the temperature range of the primary calcination is 800°C-900°C, and the time is no more than 4 hours; the temperature range of the secondary calcination is 900°C-1200°C, and the time is 1 hour.
[0014] Furthermore, after generating the target proton exchange membrane fuel cell anti-reverse polarity catalyst, the method further comprises: Concentrated hydrochloric acid is added to the reaction solution, and the reaction solution is allowed to stand for 12 to 24 hours in an ice-water bath, and then filtered, washed, and dried in sequence to obtain a purified proton exchange membrane fuel cell anti-reverse polarity catalyst.
[0015] The present invention also provides a proton exchange membrane fuel cell anti-reverse polarity catalyst, which is prepared by the above-mentioned method.
[0016] Beneficial Effects
[0017] The present invention embeds metal on a carbon carrier, and the metal used includes any one of Co, Ta, Ru, and Ir, so as to effectively improve the anti-reverse polarity ability of the catalyst, thereby improving the performance and life of the catalyst.
[0018] The present invention improves the activity of the catalyst through the interaction between the metal and the supported platinum, improves the stability of the catalyst by embedding, and effectively improves the anti-reverse polarity ability of the catalyst. The anti-reverse polarity time of the present invention can reach 2 hours. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 is a transmission electron microscope image of a PtCoC anti-reversal catalyst provided in an embodiment of the present invention;
[0020] Figure 2 is an X-ray diffraction diagram of the PtCoC anti-reversal catalyst provided in an embodiment of the present invention;
[0021] Figure 3 1 is a single cell performance diagram of a PtCoC anti-reversal catalyst provided by an embodiment of the present invention;
[0022] Figure 4 1 is a graph showing the anti-reverse polarity performance of the PtCoC anti-reverse polarity catalyst provided in an embodiment of the present invention;
[0023] Figure 5 The single cell anti-reverse polarity performance diagram of PtTaC and PtRuC catalysts prepared from the cobalt-embedded carbon carriers prepared in Examples 2 and 3;
[0024] Figure 6 This is a diagram showing the anti-reverse polarity performance of the comparative PtC catalyst. DETAILED DESCRIPTION
[0025] The present invention will be further described below in conjunction with the accompanying drawings. The following examples are only used to more clearly illustrate the technical solution of the present invention, and are not intended to limit the scope of protection of the present invention. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.
[0026] Embodiment 1
[0027] This embodiment provides a proton exchange membrane fuel cell anti-reverse polarity catalyst and a preparation method thereof, and the specific process is as follows:
[0028] (1) Preparation of primary composites of metal-embedded carbon carriers: 0.6 g of glucose and 0.375 g of cobalt chloride hexahydrate were dissolved in 250 g of formamide to form a solution, 3 g of EC300J was weighed and added to the solution to form a mixed solution, and the mixed solution was ultrasonically crushed in an ice-water bath (0-5°C) for 50 min to allow the carbon powder EC300J to be fully dispersed in the solution to obtain a slurry; the slurry was stored in a vacuum drying oven at room temperature for 1 h to degas, and then placed in an oil bath at 150°C for 6 h, with the stirring rate set at 500 rpm to allow it to react fully. After the reaction was completed, the slurry was taken out and allowed to stand and cool naturally, then filtered, washed with deionized water 6 times, and the conductivity of the filtrate was detected to be less than 20. The filtered carbon powder was placed in a vacuum drying oven at 50°C for vacuum drying for 24 h to obtain a primary composite.
[0029] (2) Gradient pyrolysis treatment: The primary composite obtained in step (1) was calcined at 800°C for 4 h under an argon atmosphere, and ground into fine powder after calcination. 13.585 mL of 98% concentrated sulfuric acid was weighed to prepare 250 mL of 1 M sulfuric acid solution. The ground fine powder was placed in the sulfuric acid solution for acid washing for 4 h, then filtered and washed with deionized water for 6 times. The conductivity of the filtrate was detected to be less than 20. The filtered fine powder was placed in a vacuum drying oven at 50°C and vacuum dried for 24 h to obtain a primary calcined product. The primary calcined product was calcined at 1100°C for 1 h under an argon atmosphere, and ground into fine powder after calcination to obtain a composite carrier after pyrolysis treatment.
[0030] (3) Precious metal loading: 3 g of chloroplatinic acid hexahydrate, 90 g of ethylene glycol, 50 g of pure water, and 15 g of a 9% aqueous sodium hydroxide solution were uniformly mixed with the composite carrier obtained in step (2) (0.8 g), sheared, emulsified, and homogenized. The molar ratio of the composite carrier, chloroplatinic acid hexahydrate, ethylene glycol, and sodium hydroxide was 2.25:0.087:21.75:0.0375. The obtained slurry was transferred to a reactor, the stirring rate was set to 500 rpm, and the mixture was placed in an oil bath at 155° C. for 4 h to allow it to react fully.
[0031] (4) Post-treatment: After the slurry reaction in step (3) is completed, the slurry is taken out and 4.5 g of 37% concentrated hydrochloric acid is added in an ice-water bath, stirred for 2 h, and allowed to stand for 12 h; the slurry after standing is filtered and washed with deionized water until the filtrate conductivity is less than 20 S / m; the obtained filter cake is placed in a vacuum drying oven at 60°C and dried for 24 h. After drying, it is ground to obtain the anti-reversal catalyst PtCoC.
[0032] Embodiment 2
[0033] This embodiment provides a proton exchange membrane fuel cell anti-reverse polarity catalyst and a preparation method thereof, and the specific process is as follows:
[0034] (1) Preparation of primary composites of metal-embedded carbon carriers: 0.75 g glucose and 0.375 g tantalum chloride were dissolved in 250 g formamide to form a solution, 3 g EC300J was weighed and added to the solution to form a mixed solution, and the mixed solution was ultrasonically crushed in an ice-water bath (0-5°C) for 50 min to fully disperse the carbon powder EC300J in the solution to obtain a slurry; the slurry was stored in a vacuum drying oven at room temperature for 1 h to degas, and then placed in an oil bath at 150°C for 6 h, with the stirring rate set at 500 rpm to allow it to fully react. After the reaction was completed, the slurry was taken out and allowed to stand and cool naturally. Then it was filtered and washed with deionized water 6 times. The conductivity of the filtrate was detected to be less than 20. The filtered carbon powder was placed in a vacuum drying oven at 50°C for vacuum drying for 24 h to obtain a primary composite.
[0035] (2) Gradient pyrolysis treatment: The primary composite obtained in step (1) was calcined at 800°C for 4 h in an argon atmosphere, and ground into fine powder after calcination; 13.585 mL of 98% concentrated sulfuric acid was weighed to prepare 250 mL of 1 M sulfuric acid solution; the ground fine powder was placed in the sulfuric acid solution for acid washing for 4 h, then filtered, washed with deionized water 6 times, and the conductivity of the filtrate was detected to be less than 20. The filtered fine powder was placed in a vacuum drying oven at 50°C and vacuum dried for 24 h to obtain a primary calcined product; the primary calcined product was calcined at 1100°C for 1 h in an argon atmosphere, and ground into fine powder after calcination to obtain a composite carrier after pyrolysis treatment.
[0036] (3) Precious metal loading: 3 g of chloroplatinic acid hexahydrate, 90 g of ethylene glycol, 50 g of pure water, and 15 g of a 9% aqueous sodium hydroxide solution were uniformly mixed with the composite carrier obtained in step (2) (0.8 g), sheared, emulsified, and homogenized. The molar ratio of the composite carrier, chloroplatinic acid hexahydrate, ethylene glycol, and sodium hydroxide was 2.25:0.087:21.75:0.0375. The obtained slurry was transferred to a reactor, the stirring rate was set to 500 rpm, and the mixture was placed in an oil bath at 155° C. for 4 h to allow it to react fully.
[0037] (4) Post-treatment: After the slurry reaction in step (3) is completed, the slurry is taken out and 4.5 g of 37% concentrated hydrochloric acid is added in an ice-water bath, stirred for 2 h, and allowed to stand for 12 h; the slurry after standing is filtered and washed with deionized water until the filtrate conductivity is less than 20 S / m; the obtained filter cake is placed in a vacuum drying oven at 60°C and dried for 24 h. After drying, it is ground to obtain the anti-reverse polarity catalyst PtTaC.
[0038] Embodiment 3
[0039] This embodiment provides a proton exchange membrane fuel cell anti-reverse polarity catalyst and a preparation method thereof, and performs preparation of a cobalt-embedded carbon carrier. The specific process is as follows:
[0040] (1) Preparation of primary composites of metal-embedded carbon carriers: 0.6 g glucose and 0.375 g ruthenium chloride were dissolved in 250 g formamide to form a solution, 3 g EC300J was weighed and added to the solution to form a mixed solution, and the mixed solution was ultrasonically crushed in an ice-water bath (0-5°C) for 50 min to fully disperse the carbon powder EC300J in the solution to obtain a slurry; the slurry was stored in a vacuum drying oven at room temperature for 1 h to degas, and then placed in an oil bath at 150°C for 6 h, with the stirring rate set at 500 rpm to allow it to fully react. After the reaction was completed, the slurry was taken out and allowed to stand and cool naturally. Then it was filtered and washed with deionized water 6 times. The conductivity of the filtrate was detected to be less than 20. The filtered carbon powder was placed in a vacuum drying oven at 50°C for vacuum drying for 24 h to obtain a primary composite.
[0041] (2) Gradient pyrolysis treatment: The primary composite obtained in step (1) was calcined at 800 °C for 4 h in an argon atmosphere, and ground into fine powder after calcination; 13.585 mL of 98% concentrated sulfuric acid was weighed to prepare 250 mL of 1 M sulfuric acid solution. The ground carbon powder was acid-washed in the sulfuric acid solution for 4 h, then filtered and washed with deionized water 6 times, and the conductivity of the filtrate was detected to be less than 20. The filtered carbon powder was placed in a vacuum drying oven at 50 °C and vacuum dried for 24 h to obtain a primary calcined product; the primary calcined product was calcined at 1100 °C for 1 h in an argon atmosphere, and ground into fine powder after calcination to obtain a composite carrier after pyrolysis treatment.
[0042] (3) Precious metal loading: 3 g of chloroplatinic acid hexahydrate, 90 g of ethylene glycol, 50 g of pure water, and 15 g of a 9% aqueous sodium hydroxide solution were uniformly mixed with the composite carrier obtained in step (2) (0.8 g), sheared, emulsified, and homogenized. The molar ratio of the composite carrier, chloroplatinic acid hexahydrate, ethylene glycol, and sodium hydroxide was 2.25:0.087:21.75:0.0375. The obtained slurry was transferred to a reactor, the stirring rate was set to 500 rpm, and the mixture was placed in an oil bath at 155° C. for 4 h to allow it to react fully.
[0043] (4) Post-treatment: After the slurry reaction in step (3) is completed, the slurry is taken out and 4.5 g of 37% concentrated hydrochloric acid is added in an ice-water bath, stirred for 2 h, and allowed to stand for 12 h. The slurry after standing is filtered and washed with deionized water until the filtrate conductivity is less than 20 S / m; the obtained filter cake is placed in a vacuum drying oven and dried at 60°C for 24 h. After drying, it is ground to obtain the anti-reverse polarity catalyst PtRuC.
[0044] Comparative Example 1
[0045] PtC catalyst (purchased from Suzhou Shengernuo Technology Co., Ltd., product number TEC10VE50E).
[0046] Figure 1 The transmission electron microscope image of the PtCoC catalyst prepared by the cobalt-embedded carbon carrier prepared in Example 1 is shown in FIG. Figure 1 It can be seen that platinum does not agglomerate and can be evenly dispersed on the carbon particles.
[0047] Figure 2 The X-ray diffraction pattern of the PtCoC catalyst prepared from the cobalt-embedded carbon carrier prepared in Example 1 is shown in FIG. Figure 2 It can be seen that the PtCoC catalyst prepared by cobalt-embedded carbon support has good crystallinity.
[0048] Figure 3This is a single cell performance diagram of the PtCoC catalyst prepared using the cobalt-embedded carbon support prepared in Example 1. It can be seen from the figure that the single cell performance is good.
[0049] Figure 4 This is a graph showing the single cell anti-reverse polarity performance of the PtCoC catalyst prepared using the cobalt-embedded carbon carrier obtained in Example 1. It can be seen from the graph that it has very good anti-reverse polarity performance.
[0050] Figure 5 The single cell anti-reverse polarity performance diagram of PtTaC and PtRuC catalysts prepared from the cobalt-embedded carbon carriers prepared in Examples 2 and 3 shows that they also have anti-reverse polarity performance.
[0051] Figure 6 This is a comparative example PtC catalyst. It can be seen from the figure that it has no anti-reverse polarity performance.
[0052] The present invention will embed metal on a carbon carrier, and the metal precursor used includes any one of Co, Ta, Ru, and Ir. The activity of the catalyst is improved by the interaction between the metal and the supported platinum, and the stability of the catalyst is improved by embedding, and the anti-reverse polarity ability of the catalyst is effectively improved, wherein the anti-reverse polarity time of Example 1 can reach two hours. Relative to Comparative Example 1, due to the presence of metal Co in Example 1, the anti-reverse polarity effect of the catalyst is significantly better than that of Comparative Example 1, indicating that the method of metal embedding can obtain better technical effects. Examples 2 and 3 respectively add metals Ta and Ru, and their anti-reverse polarity performance is also slightly improved compared to Comparative Example 1. Among the three embodiments, the anti-reverse polarity performance of Example 1 is improved the most.
[0053] The above embodiments are only some of the embodiments of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention.
Claims
1. A method for preparing a proton exchange membrane fuel cell anti-reverse polarity catalyst, characterized in that: The preparation method comprises the following steps: The transition metal salt and the carbon-containing matrix material are ultrasonically dispersed in a polar solvent, subjected to a high-temperature oil bath reaction after degassing, and then separated and purified to obtain a primary composite; The primary composite is subjected to primary calcination under an inert atmosphere to obtain a primary calcined product; the primary calcined product is then ground and pulverized, acid washed, filtered, dried, subjected to secondary calcination, and then ground to obtain a composite carrier after pyrolysis treatment; After the composite carrier is uniformly mixed with chloroplatinic acid, ethylene glycol and sodium hydroxide aqueous solution, the reaction liquid is heated to react so as to generate a target proton exchange membrane fuel cell anti-reverse polarity catalyst.
2. The preparation method according to claim 1, characterized in that: The transition metal salt is selected from any one of Co, Ta, Ru, and Ir, a chloride or a hydrate thereof, a sulfate or a hydrate thereof, a phosphate or a hydrate thereof, and a nitrate or a hydrate thereof.
3. The preparation method according to claim 2, characterized in that: The carbon-containing matrix material includes a mixture of activated carbon and glucose, and the mass ratio of the transition metal salt, the activated carbon and the glucose is 1:(4-5):(6-8).
4. The preparation method according to claim 1, characterized in that: The ultrasonic dispersion is carried out in a low temperature environment, the temperature is controlled at 0-5°C, and the treatment time is 50-70 minutes; the degassing treatment is carried out under vacuum conditions for at least 1 hour, and the temperature is 25°C±10°C.
5. The preparation method according to claim 1, characterized in that: The polar solvent is formamide; the reaction temperature of the high-temperature oil bath is 150-160° C., the stirring rate is 500-600 rpm, and the duration is 6-8 hours.
6. The preparation method according to claim 1, characterized in that: The molar ratio of the composite carrier, chloroplatinic acid, ethylene glycol and sodium hydroxide in the heating reaction is (1-2.5): 0.08-0.09: 20-22: 0.4-0.
6.
7. The preparation method according to claim 1, characterized in that: The reaction solution was heated in an oil bath and the temperature was controlled at 150-160°C.
8. The preparation method according to claim 1, characterized in that: The temperature range of the primary calcination is 800°C-900°C, and the time is no more than 4 hours; the temperature range of the secondary calcination is 900°C-1200°C, and the time is 1 hour.
9. The preparation method according to claim 1, characterized in that: After the target proton exchange membrane fuel cell anti-reverse polarity catalyst is generated, the method further includes: Concentrated hydrochloric acid is added to the reaction solution, and the reaction solution is allowed to stand for 12 to 24 hours in an ice-water bath, and then filtered, washed, and dried in sequence to obtain a purified proton exchange membrane fuel cell anti-reverse polarity catalyst.
10. A proton exchange membrane fuel cell anti-reverse polarity catalyst, characterized in that: The method is prepared by any one of claims 1 to 9.