Hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, preparation method of hydrogen production electrode and water electrolysis hydrogen production device

Abstract

The invention provides a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, a preparation method of the hydrogen production electrode and a water electrolysis hydrogen production device, and relates to the field of water electrolysis hydrogen production. The preparation method of the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium comprises the following steps: coating the surface of a conductive substrate with mixed powder; the conductive base material coated with the mixed powder is subjected to thermal oxidation treatment, the mixed powder comprises first metal powder, second metal powder and a pore forming agent, the first metal powder comprises Ni powder, and the second metal powder comprises Pt powder, Ru powder, Sn powder and Pr powder; and putting the structure subjected to thermal oxidation treatment into an alkaline solution, and activating to obtain the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium. The platinum, the ruthenium, the tin and the praseodymium are introduced into the hydrogen production electrode, so that the hydrogen evolution overpotential can be reduced. The hydrogen production electrode prepared by the method disclosed by the invention has relatively high catalytic activity, relatively high stability and a uniformly distributed porous structure, the electrolytic efficiency can be remarkably improved, and the service life of equipment is prolonged.

Description

Technical Field

[0001] The present application relates to the field of hydrogen production by water electrolysis, and in particular to a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, a preparation method thereof, and a hydrogen production device by water electrolysis. Background Art

[0002] In the field of hydrogen production by alkaline water electrolysis, the performance of the electrode is a key factor that directly affects the electrolysis efficiency and the service life of the equipment. However, the existing hydrogen production electrodes have significant technical bottlenecks in many aspects, which are specifically manifested in the following aspects: First, insufficient catalytic activity: The catalytic activity of the existing hydrogen production electrodes in the hydrogen evolution reaction is relatively low, resulting in a high hydrogen evolution overpotential, which not only increases the energy consumption in the electrolysis process, but also limits the improvement of the electrolysis efficiency. Second, poor stability: During long-term operation, the catalytic layer of the existing hydrogen production electrode is susceptible to mechanical damage, oxidation, and the by-products of the hydrogen evolution reaction, which leads to the degradation of the catalytic layer and a significant decrease in electrode performance, which not only shortens the service life of the equipment, but also increases the cost of maintenance and replacement. Third, the pore distribution is difficult to accurately control: The pore distribution of the catalyst layer of the existing hydrogen production electrode is often difficult to accurately control, which may lead to an increase in the local concentration polarization phenomenon and further reduce the catalytic efficiency. Summary of the invention

[0003] The purpose of the present application is to provide a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, a preparation method thereof and a hydrogen production device by electrolyzing water to solve the above problems.

[0004] To achieve the above objectives, this application adopts the following technical solutions:

[0005] A method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, comprising:

[0006] Providing a mixed powder, wherein the mixed powder comprises a first metal powder, a second metal powder and a pore-forming agent, the first metal powder comprises Ni powder, and the second metal powder comprises Pt powder, Ru powder, Sn powder and Pr powder;

[0007] Applying the mixed powder to the surface of a conductive substrate;

[0008] The conductive substrate coated with the mixed powder is subjected to thermal oxidation treatment, wherein the coating amount of the mixed powder on the conductive substrate is greater than 2 mg / cm 2 ;

[0009] The structure that has undergone the thermal oxidation treatment is placed in an alkaline solution for activation treatment to obtain the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium.

[0010] According to an embodiment of the present application, the mixed powder includes 70-85wt% of a first metal powder, 10-25wt% of a second metal powder, and 5-15wt% of a pore-forming agent.

[0011] According to an embodiment of the present application, the mass ratio of Pt powder to Ru powder, Sn powder and Pr powder in the second metal powder is 1:(0.7-1.3):(0.7-1.3):(0.7-1.3).

[0012] According to an embodiment of the present application, the pore-forming agent includes any one of Al powder, zinc powder, magnesium powder, and carbonate;

[0013] And / or, the conductive substrate includes any one of nickel mesh, nickel felt, and nickel foam.

[0014] According to an embodiment of the present application, the coating amount of the mixed powder on the conductive substrate is 5 to 15 mg / cm 2 .

[0015] According to an embodiment of the present application, the thermal oxidation treatment is carried out in an atmosphere of oxygen or air or a mixture of nitrogen and oxygen;

[0016] And / or, the heating rate of the thermal oxidation treatment is 5-10° C. / min.

[0017] According to an embodiment of the present application, the temperature of the thermal oxidation treatment is 450-600°C;

[0018] And / or, the thermal oxidation treatment time is 2 to 6 hours.

[0019] According to an embodiment of the present application, the alkaline solution includes a KOH solution;

[0020] And / or, the concentration of the alkaline solution is 6-10 mol / L;

[0021] And / or, the activation treatment time is 2-36 hours.

[0022] The present application also provides a hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium, wherein the hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium is prepared by the preparation method of the hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium described above.

[0023] The present application also provides a hydrogen production device by electrolysis of water, including a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium prepared by the preparation method of the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium as described above, or including the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium as described above.

[0024] Compared with the prior art, the beneficial effects of this application include:

[0025] This application introduces platinum, ruthenium, tin, and praseodymium into the hydrogen production electrode, which can significantly reduce the hydrogen evolution overpotential. Moreover, the method of this application can form a multi-metal oxide layer on a conductive substrate, significantly enhancing the corrosion resistance and mechanical stability of the electrode, further extending the service life of the electrode, and ensuring its long-term stable operation. In addition, this application combines thermal oxidation with activation treatment technology to form a uniformly distributed porous structure on the surface of the catalyst layer, which not only increases the specific surface area, but also significantly increases the density of catalytic active sites, providing strong support for performance improvement.

[0026] In addition, since the present application introduces praseodymium into the hydrogen production electrode, thanks to the unique hydrogen storage properties of the praseodymium element, the electrode can have excellent reverse current resistance, and the catalytic layer can remain stable when encountering reverse current, effectively avoiding the failure of the electrode caused by oxidation and ensuring the reliable operation of the electrode under various conditions.

[0027] The hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium of the present application has both lower hydrogen evolution overpotential and higher stability. DETAILED DESCRIPTION

[0028] As used herein:

[0029] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0030] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0031] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0032] In these examples, parts and percentages are by mass unless otherwise indicated.

[0033] "Parts by mass" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.

[0034] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0035] In order to better explain the technical solution provided by this application, before the embodiments, the technical solution is first described as a whole, as follows:

[0036] A method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, comprising:

[0037] Providing a mixed powder, wherein the mixed powder comprises a first metal powder, a second metal powder and a pore-forming agent, the first metal powder comprises Ni powder, and the second metal powder comprises Pt powder, Ru powder, Sn powder and Pr powder;

[0038] Applying the mixed powder to the surface of a conductive substrate;

[0039] The conductive substrate coated with the mixed powder is subjected to thermal oxidation treatment, wherein the coating amount of the mixed powder on the conductive substrate is greater than 2 mg / cm 2 ;

[0040] The structure that has undergone the thermal oxidation treatment is placed in an alkaline solution for activation treatment to obtain the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium.

[0041] The hydrogen production electrode prepared by the present application has high catalytic activity, high stability and uniformly distributed porous structure, which can significantly improve the electrolysis efficiency, extend the service life of the equipment, and reduce production costs. Specifically, the present application adopts the multi-metal thermal oxidation technology of platinum, ruthenium, tin and praseodymium, which significantly optimizes the electronic structure and stability of the catalyst layer. Moreover, the present application adopts thermal oxidation combined with activation treatment to form a uniform porous structure on the surface of the catalyst layer, which can effectively improve the catalytic activity. In addition, the present application also introduces praseodymium as a hydrogen storage material, which can improve the electrode's ability to resist reverse current.

[0042] The present application provides a first metal powder for matrix strength and conductivity, Pt and Ru can improve the electron transfer ability in the hydrogen evolution reaction and reduce the hydrogen evolution overpotential, Sn can adjust the intermediate binding energy and improve the chemical stability of the catalyst layer, Pr can enhance the hydrogen storage capacity and give the electrode better anti-reverse current ability, Pt, Ru, Sn and Pr cooperate with each other, so that the second metal powder can improve the catalytic performance of the electrode, and the pore-forming agent is used to form a porous structure of the electrode. The first metal powder, the second metal powder and the pore-forming agent cooperate with each other, so that the hydrogen-producing electrode has a higher structural strength, a higher overall conductivity and a higher catalytic activity.

[0043] According to an embodiment of the present application, the mixed powder includes 70-85wt% of the first metal powder, 10-25wt% of the second metal powder, and 5-15wt% of the pore former. When the composition of the mixed powder is within the above range, the first metal powder, the second metal powder and the pore former support and cooperate with each other in function, so that the hydrogen production electrode has a higher structural strength, a higher overall conductivity and a higher catalytic activity. If the content of the first metal powder is too low, the overall conductivity of the electrode will be reduced; if the content of the first metal powder is too high, the content of the second metal powder will be relatively reduced, resulting in a decrease in catalytic activity. If the content of the second metal powder is too low, the catalytic activity will be insufficient; if the content of the second metal powder is too high, the stability of the catalyst layer will be affected and the production cost will be increased. If the content of the pore former is too low, the porosity will be insufficient and the density of the catalyst active sites will be low; if the content of the pore former is too high, the strength of the electrode structure may be reduced.

[0044] For example, the content of the first metal powder in the mixed powder may be 70 wt%, 75 wt%, 80 wt%, 85 wt% or any value between 70 and 85 wt%.

[0045] The content of the second metal powder in the mixed powder may be 10wt%, 15wt%, 20wt%, 25wt% or any value between 10 and 25wt%.

[0046] The content of the pore former in the mixed powder can be 5wt%, 10wt%, 15wt% or any value between 5 and 15wt%.

[0047] According to an embodiment of the present application, the mass ratio of Pt powder to Ru powder, Sn powder, and Pr powder in the second metal powder is 1: (0.7-1.3): (0.7-1.3): (0.7-1.3). As a result, the catalytic performance of the electrode can be effectively improved. If the content of each component in the second metal powder is too low, the improvement in catalytic performance will be small; if the content of each component in the second metal powder is too high, it will still be unfavorable to improve the catalytic performance. Specifically, if the content of Pt and / or Ru is too high, it may cause surface instability and increase costs; if the content of Sn is too high, it will affect the conductivity of the electrode; if the content of Pr is too high, it may reduce the mechanical stability of the catalyst layer.

[0048] For example, the mass ratio of Pt powder to Ru powder, Sn powder and Pr powder in the second metal powder can be any value between 1:0.7:0.7:0.7, 1:0.8:0.8:0.8, 1:0.9:0.9:0.9, 1:1:1:1, 1:1.1:1.1:1.1, 1:1.2:1.2:1.2, 1:1.3:1.3:1.3 or 1:(0.7~1.3):(0.7~1.3).

[0049] According to some embodiments of the present application, the second metal powder may further include at least one of iridium (Ir) and palladium (Pd).

[0050] According to an embodiment of the present application, the pore-forming agent includes any one of Al powder, zinc powder, magnesium powder, and carbonate;

[0051] And / or, the conductive substrate includes any one of nickel mesh, nickel felt, and nickel foam.

[0052] According to some embodiments of the present application, the method further comprises: pre-treating the conductive substrate, and coating the mixed powder on the surface of the pre-treated conductive substrate, thereby enhancing the adhesion of the mixed powder.

[0053] Furthermore, pre-treating the conductive substrate includes: sandblasting or pickling the conductive substrate, thereby removing the surface oxide layer of the conductive substrate and increasing the surface roughness, which is beneficial to the adhesion of the mixed powder.

[0054] Furthermore, the coating method of the mixed powder on the conductive substrate includes spraying or screen printing.

[0055] According to an embodiment of the present application, the coating amount of the mixed powder on the conductive substrate is 5 to 15 mg / cm 2When the coating amount is within the above range, it is beneficial to obtain a uniform catalytic layer and improve the catalytic activity of the electrode. If the coating amount is too large, the thickness of the catalytic layer will be uneven and the conductivity may be affected. If the coating amount is too small, the catalytic sites will be insufficient and the electrolysis efficiency will be reduced.

[0056] For example, the coating amount of the mixed powder on the conductive substrate can be 5 mg / cm 2 , 6mg / cm 2 , 7mg / cm 2 , 8mg / cm 2 , 9mg / cm 2 、10mg / cm 2 、11mg / cm 2 , 12mg / cm 2 、13mg / cm 2 、14mg / cm 2 、15mg / cm 2 Or 5-15 mg / cm 2 Any value in between.

[0057] According to an embodiment of the present application, the thermal oxidation treatment is carried out in an atmosphere of oxygen or air or a mixture of nitrogen and oxygen;

[0058] Furthermore, the thermal oxidation treatment is performed in a high temperature oxidation furnace.

[0059] And / or, the heating rate of the thermal oxidation treatment is 5-10°C / min. This can quickly increase the temperature to the thermal oxidation treatment temperature, and can also avoid the occurrence of adverse problems such as excessive internal stress of the material caused by rapid heating. If the heating rate of the thermal oxidation treatment is too fast, it will also cause cracks on the surface of the catalyst layer.

[0060] For example, the heating rate of the thermal oxidation treatment can be 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min or any value between 5 and 10°C / min.

[0061] According to an embodiment of the present application, the temperature of the thermal oxidation treatment is 450-600°C; when the temperature of the thermal oxidation treatment is within the above range, it is conducive to forming a stable oxide catalytic layer. If the temperature of the thermal oxidation treatment is too low, the oxide layer will not be fully formed.

[0062] For example, the temperature of the thermal oxidation treatment may be 450°C, 500°C, 550°C, 600°C, or any value between 450°C and 600°C.

[0063] And / or, the thermal oxidation treatment time is 2 to 6 hours. When the thermal oxidation treatment time is within the above range, the thermal oxidation reaction can be fully carried out, and the abnormal growth of grains can be prevented, so as to obtain the ideal oxidation effect and material properties. If the thermal oxidation treatment time is too short, the problem of incomplete thermal oxidation will occur. If the thermal oxidation treatment time is too long, it may cause grain growth, affect the microstructure and performance of the material, and lead to a decrease in catalytic activity.

[0064] For example, the time of the thermal oxidation treatment may be 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or any value between 2 and 6 hours.

[0065] Furthermore, after the thermal oxidation treatment is completed, the method further comprises: naturally cooling to room temperature to obtain a structure that has undergone the thermal oxidation treatment.

[0066] According to an embodiment of the present application, the alkaline solution includes a KOH solution; by adding the alkaline solution, the pore-forming agent can be dissolved to form a porous structure, while the metal oxides weakly bound to the surface can be removed, thereby improving the electrochemical activity of the catalytic layer.

[0067] And / or, the concentration of the alkaline solution is 6-10 mol / L; for example, the concentration of the alkaline solution can be 6 mol / L, 7 mol / L, 8 mol / L, 9 mol / L, 10 mol / L or any value between 6-10 mol / L.

[0068] And / or, the time of the activation treatment is 2-36 hours. For example, the time of the activation treatment can be 2 hours, 5 hours, 7 hours, 10 hours, 12 hours, 15 hours, 17 hours, 20 hours, 22 hours, 24 hours, 25 hours, 27 hours, 30 hours, 32 hours, 35 hours, 36 hours or any value between 2-36 hours.

[0069] The present application also provides a hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium, wherein the hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium is prepared by the preparation method of the hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium described above.

[0070] The present application also provides a hydrogen production device by electrolysis of water, including a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium prepared by the preparation method of the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium as described above, or including the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium as described above.

[0071] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0072] 1. Preparation of hydrogen production electrode

[0073] Example 1

[0074] Embodiment 1 provides a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, and the preparation method thereof comprises:

[0075] (1) A mixed powder is provided, wherein the mixed powder includes a first metal powder, a second metal powder and a pore-forming agent.

[0076] The composition and content of the first metal powder, the second metal powder and the pore-forming agent are specifically as follows:

[0077] The first metal powder is Ni powder, and the Ni powder accounts for 70wt% in the mixed powder;

[0078] The second metal powder is Pt powder, Ru powder, Sn powder and Pr powder, and the proportions of Pt powder, Ru powder, Sn powder and Pr powder in the mixed powder are 5wt%, 5wt%, 5wt% and 5wt% respectively;

[0079] The pore-forming agent is Al powder, and the proportion of Al powder in the mixed powder is 10wt%.

[0080] (2) Applying the mixed powder to the surface of a conductive substrate.

[0081] The conductive substrate is nickel mesh, and the coating amount of the mixed powder on the conductive substrate is 10 mg / cm 2 .

[0082] (3) The conductive substrate coated with the mixed powder is subjected to thermal oxidation treatment.

[0083] The thermal oxidation treatment was carried out in an air atmosphere, the heating rate of the thermal oxidation treatment was 5° C. / min, the temperature of the thermal oxidation treatment was 550° C., and the time of the thermal oxidation treatment was 4 hours.

[0084] (4) The structure after thermal oxidation treatment is placed in an alkaline solution for activation treatment to obtain a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium.

[0085] The alkaline solution is a KOH solution with a concentration of 8 mol / L, and the activation treatment time is 24 hours.

[0086] Example 2

[0087] A hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium was prepared by referring to the method of Example 1. The other steps were the same as those of Example 1, except that:

[0088] The composition and content of the first metal powder, the second metal powder and the pore-forming agent in step (1) of Example 2 are specifically as follows:

[0089] The first metal powder is Ni powder, and the proportion of Ni powder in the mixed powder is 80wt%;

[0090] The second metal powder is Pt powder, Ru powder, Sn powder and Pr powder, and the proportions of Pt powder, Ru powder, Sn powder and Pr powder in the mixed powder are 3wt%, 3wt%, 3wt% and 3wt% respectively;

[0091] The pore-forming agent is magnesium powder, and the proportion of magnesium powder in the mixed powder is 8wt%.

[0092] The temperature of the thermal oxidation treatment in step (3) of Example 2 is 520°C.

[0093] Comparative Example 1

[0094] A hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium was prepared by referring to the method of Example 1. The other steps and parameters were the same as those of Example 1, except that: in step (1) of Comparative Example 1, no second metal powder was added.

[0095] Comparative Example 2

[0096] A hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium was prepared by referring to the method of Example 1. The other steps and parameters were the same as those of Example 1, except that the coating amount of the mixed powder on the conductive substrate in step (2) of Comparative Example 2 was 2 mg / cm 2 .

[0097] 2. Performance Test

[0098] The performance of the hydrogen production electrodes prepared in the embodiment and the comparative example was tested under the same test conditions, and the specific test conditions are as follows.

[0099] Electrolyte: 800 mL of 0.1 M KOH aqueous solution. Electrolysis temperature: 60°C. Electrolysis area: 25 mm × 25 mm. Three-electrode system, with calomel electrode as reference electrode. Current density: 10,000 A / m 2 .

[0100] The test results of Examples 1-2 and Comparative Examples 1-2 are shown in Table 1.

[0101] Table 1 Test results of Examples 1-2 and Comparative Examples 1-2

[0102] Hydrogen evolution overpotential (mV) Potential decay rate after 48h operation Example 1 80 1％ Example 2 82 1％ Comparative Example 1 110 6％ Comparative Example 2 95 9％

[0103] The potential decay rate after 48 hours of operation refers to the ratio of the difference in voltage change between the electrode at the beginning of operation and after 48 hours of operation to the voltage at the beginning of operation.

[0104] It can be seen from Table 1 that the hydrogen evolution overpotential of Example 1-2 is lower than that of Comparative Example 1-2, and the potential decay rate of Example 1-2 after running for 48 hours is lower than that of Comparative Example 1-2, indicating that compared with Comparative Example 1-2, the hydrogen production electrode of Example 1-2 has better catalytic activity and higher stability. It can also be shown that when the mixed powder includes the second metal powder and the coating amount of the mixed powder on the conductive substrate is greater than 2 mg / cm 2 When the catalytic activity is better, the prepared hydrogen production electrode has higher stability.

[0105] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

[0106] In addition, those skilled in the art will appreciate that, although some embodiments herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments may be used in any combination. The information disclosed in this background technology section is intended only to deepen the understanding of the overall background technology of the present application and should not be regarded as an admission or in any form of implication that the information constitutes prior art known to those skilled in the art.

Claims

1. A method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, characterized in that: include: Providing a mixed powder, wherein the mixed powder comprises a first metal powder, a second metal powder and a pore-forming agent, the first metal powder comprises Ni powder, and the second metal powder comprises Pt powder, Ru powder, Sn powder and Pr powder; Applying the mixed powder to the surface of a conductive substrate; The conductive substrate coated with the mixed powder is subjected to thermal oxidation treatment, wherein the coating amount of the mixed powder on the conductive substrate is greater than 2 mg / cm 2 ; The structure that has undergone the thermal oxidation treatment is placed in an alkaline solution for activation treatment to obtain the hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium.

2. The method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium according to claim 1, characterized in that: The mixed powder includes 70-85wt% of first metal powder, 10-25wt% of second metal powder, and 5-15wt% of pore-forming agent.

3. The method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium according to claim 2, characterized in that: The mass ratio of Pt powder to Ru powder, Sn powder and Pr powder in the second metal powder is 1:(0.7-1.3):(0.7-1.3):(0.7-1.3).

4. The method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium according to claim 1, characterized in that: The pore-forming agent includes any one of Al powder, zinc powder, magnesium powder and carbonate; And / or, the conductive substrate includes any one of nickel mesh, nickel felt, and nickel foam.

5. The method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium according to claim 1, characterized in that: The coating amount of the mixed powder on the conductive substrate is 5 to 15 mg / cm 2 .

6. The method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium according to claim 1, characterized in that: The thermal oxidation treatment is carried out in an atmosphere of oxygen, air, or a mixture of nitrogen and oxygen; And / or, the heating rate of the thermal oxidation treatment is 5-10° C. / min.

7. The method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium according to claim 6, characterized in that: The temperature of the thermal oxidation treatment is 450-600°C; And / or, the thermal oxidation treatment time is 2 to 6 hours.

8. The method for preparing a hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium according to any one of claims 1 to 7, characterized in that: The alkaline solution includes a KOH solution; And / or, the concentration of the alkaline solution is 6 to 10 mol / L; And / or, the activation treatment time is 2-36 hours.

9. A hydrogen production electrode doped with platinum, ruthenium, tin and praseodymium, characterized in that: The hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium is prepared by the method for preparing the hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium according to any one of claims 1 to 8.

10. A hydrogen production device by electrolysis of water, characterized in that: A hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium prepared by the method for preparing a hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium as described in any one of claims 1 to 8, or a hydrogen-producing electrode doped with platinum, ruthenium, tin and praseodymium as described in claim 9.