Multilayer alloy electrode, preparation method thereof and hydrogen evolution device

Abstract

The invention provides a multilayer alloy electrode, a preparation method thereof and a hydrogen evolution device, and relates to the field of hydrogen evolution electrodes. The multi-layer alloy electrode comprises a metal base body, a first coating and a second coating, wherein the first coating and the second coating are sequentially arranged on the surface of the metal base body in a stacked mode. The first coating is a porous coating; the first coating comprises one or more of nickel-molybdenum alloy, nickel-iron alloy and nickel-molybdenum-iron alloy; and the second coating comprises one or more of nickel-platinum alloy, nickel-ruthenium alloy and nickel-platinum-ruthenium alloy. Due to the fact that the second coating has proper hydrogen adsorption and desorption capacity and excellent intrinsic catalytic activity, the second coating is arranged on the first coating, the hydrogen evolution performance of electrolyzed water can be further improved, the hydrogen evolution overpotential is reduced, meanwhile, the second coating is a compact coating, and therefore dissolution of non-nickel transition metal of the first coating is remarkably inhibited, and the stability of the electrode is greatly improved.

Description

Technical Field

[0001] The present application relates to the field of hydrogen evolution electrodes, and in particular to a multilayer alloy electrode and a preparation method thereof, and a hydrogen evolution device. Background Art

[0002] Multi-element alloy electrodes have excellent catalytic activity, but due to the problem of metal dissolution, their stability is insufficient and their attenuation is accelerated. During the electrolysis of water, especially under high temperature and concentrated alkali conditions, the surface of the multi-element alloy electrode will corrode.

[0003] Certain metals (such as Mo and Cr) in multi-element alloys will gradually dissolve in alkaline solution, causing changes in the composition and structure of the electrode material, thereby affecting the catalytic performance of the electrode. During the electrolysis of water, the start and stop operation of the electrolytic cell will generate reverse current, which may lead to the dissolution of metals, thereby affecting the stability and overall performance of the catalytic electrode. Under the action of reverse current, certain metal elements in the electrode material may dissolve into the electrolyte in the form of ions, causing changes in the composition and structure of the electrode material. Dissolved metals will not only reduce the effective catalytic area, but may also change the electrochemical properties of the electrode and reduce its catalytic activity. As the metal dissolves, the structural integrity of the electrode may be damaged, and the number and quality of catalytic active centers will decrease.

[0004] Therefore, there is an urgent need to provide a new electrode to overcome the above problems. Summary of the invention

[0005] The purpose of the present application is to provide a multilayer alloy electrode and a preparation method thereof and a hydrogen evolution device to solve the above problems.

[0006] To achieve the above objectives, the present application provides a multilayer alloy electrode in a first aspect, comprising a metal substrate and a first coating layer and a second coating layer sequentially stacked on the surface of the metal substrate;

[0007] The first coating is a porous coating;

[0008] The first coating comprises one or more of a nickel-molybdenum alloy, a nickel-iron alloy, and a nickel-molybdenum-iron alloy;

[0009] The second coating layer includes one or more of nickel-platinum alloy, nickel-ruthenium alloy, and nickel-platinum-ruthenium alloy.

[0010] Optionally, the multilayer alloy electrode satisfies at least one of the following conditions:

[0011] A. The thickness of the first coating is 20 μm-100 μm;

[0012] B. The thickness of the second coating is 0.005 μm-5 μm;

[0013] C. The second coating is a dense coating.

[0014] The second aspect of the present application provides a method for preparing the multilayer alloy electrode, comprising:

[0015] Spraying alloy powder onto the surface of a metal substrate to obtain a sprayed substrate;

[0016] The sprayed substrate and alkali solution are mixed and activated to obtain a porous coating substrate;

[0017] Depositing an alloy target material onto the surface of the porous coating substrate to obtain a multilayer alloy electrode;

[0018] The alloy powder includes one or more of nickel-molybdenum-aluminum alloy powder, nickel-iron-aluminum alloy powder, and nickel-molybdenum-iron-aluminum alloy powder;

[0019] The alloy target includes one or more of a nickel-platinum alloy target, a nickel-ruthenium alloy target, and a nickel-platinum-ruthenium alloy target.

[0020] Optionally, the alkali solution includes potassium hydroxide solution and / or sodium hydroxide solution.

[0021] Optionally, the method for preparing the multilayer alloy electrode satisfies at least one of the following conditions:

[0022] A. The alloy powder, calculated by mass as 100%, comprises:

[0023] Aluminum 5%-30%, nickel 40%-90%, iron and / or molybdenum 5%-30%;

[0024] B. The particle size of aluminum in the alloy powder is 5 μm-150 μm;

[0025] C. The alloy target material, calculated by mass as 100%, comprises:

[0026] Nickel 50%-90%, platinum and / or ruthenium 10%-50%.

[0027] Optionally, the method for preparing the multilayer alloy electrode satisfies at least one of the following conditions:

[0028] A. The spraying includes a plasma spraying process;

[0029] B. The deposition includes one or more of magnetron sputtering, atomic layer deposition, and pulsed laser deposition.

[0030] Optionally, the argon flow rate of the plasma spraying process is 50L / min-70L / min, the hydrogen flow rate is 0.5L / min-5L / min, the current is 500A-1000A, the gun distance is 120mm-180mm, and the powder feeding speed is 50g / min-200g / min.

[0031] Optionally, the working pressure of the magnetron sputtering is 0.5Pa-1Pa, the deposition time is 10min-10h, the flow rate of argon gas is 30sccm-100sccm, and the power is 50W-100W.

[0032] Optionally, the activation temperature is 20°C-80°C, and the activation time is 1h-24h.

[0033] A third aspect of the present application provides a hydrogen production device, comprising the multi-layer alloy electrode or the multi-layer alloy electrode prepared by the multi-layer alloy electrode preparation method.

[0034] Compared with the prior art, the beneficial effects of this application include:

[0035] The multilayer alloy electrode provided in the present application has a first coating layer made of a transition metal multi-element alloy, which not only has a large specific surface area but also can improve the intrinsic catalytic activity of the first coating layer compared to the traditional Raney nickel alloy; the second coating layer has suitable hydrogen adsorption and desorption capabilities and excellent intrinsic catalytic activity, which can further improve the hydrogen evolution performance of water electrolysis and reduce the hydrogen evolution overpotential; the second coating layer is deposited on the first coating layer, and since the second coating layer is very dense, it can significantly inhibit the dissolution of non-nickel transition metals, thereby greatly improving the electrode stability.

[0036] The method for preparing a multilayer alloy electrode provided in the present application adopts a spraying technology to prepare a first coating layer, which has high production efficiency, strong coating bonding strength, and is not easy to fall off; and adopts a deposition technology to prepare a second coating layer, which has a dense coating layer.

[0037] The hydrogen evolution device provided in the present application has low power consumption and long service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0039] Figure 1 This is a flow chart of the method for preparing the multilayer alloy electrode provided in Example 1. DETAILED DESCRIPTION

[0040] As used herein:

[0041] "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.

[0042] 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.

[0043] 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.

[0044] In these examples, parts and percentages are by mass unless otherwise indicated.

[0045] "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.

[0046] "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).

[0047] In a first aspect, the present application provides a multilayer alloy electrode, comprising a metal substrate and a first coating layer and a second coating layer sequentially stacked on the surface of the metal substrate;

[0048] The first coating is a porous coating;

[0049] The first coating comprises one or more of a nickel-molybdenum alloy, a nickel-iron alloy, and a nickel-molybdenum-iron alloy;

[0050] The second coating layer includes one or more of nickel-platinum alloy, nickel-ruthenium alloy, and nickel-platinum-ruthenium alloy.

[0051] In some embodiments, the multilayer alloy electrode satisfies at least one of the following conditions:

[0052] A. The thickness of the first coating is 20 μm-100 μm;

[0053] Optionally, the thickness of the first coating layer may be 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or any value between 20 μm and 100 μm;

[0054] B. The thickness of the second coating is 0.005 μm-5 μm;

[0055] Optionally, the thickness of the second coating layer may be 0.005 μm, 0.05 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, or any value between 0.05 μm and 5 μm;

[0056] It should be noted that the first coating is relatively thick, mainly because the catalytic activity of the first coating is positively correlated with the coating thickness. A thicker coating has better catalytic activity, but a coating that is too thick will significantly increase the preparation cost and the coating is more prone to cracks. The second coating is thin because it is a dense coating, and a thinner thickness can protect the first coating. At the same time, because it contains precious metals, a thinner coating thickness can play a good catalytic role. Too thick a coating will significantly increase the preparation cost.

[0057] C. The second coating is a dense coating.

[0058] It should be noted that, compared with the porous coating in the first coating, the dense coating does not have the porous structure in the first coating.

[0059] The second aspect of the present application provides a method for preparing the multilayer alloy electrode, comprising:

[0060] Spraying alloy powder onto the surface of a metal substrate to obtain a sprayed substrate;

[0061] The sprayed substrate and alkali solution are mixed and activated to obtain a porous coating substrate;

[0062] Depositing an alloy target material onto the surface of the porous coating substrate to obtain a multilayer alloy electrode;

[0063] The alloy powder includes one or more of nickel-molybdenum-aluminum alloy powder, nickel-iron-aluminum alloy powder, and nickel-molybdenum-iron-aluminum alloy powder;

[0064] The alloy target includes one or more of a nickel-platinum alloy target, a nickel-ruthenium alloy target, and a nickel-platinum-ruthenium alloy target.

[0065] In some embodiments, the alkaline solution includes potassium hydroxide solution and / or sodium hydroxide solution.

[0066] In some embodiments, the method for preparing the multilayer alloy electrode satisfies at least one of the following conditions:

[0067] A. The alloy powder, calculated by mass as 100%, comprises:

[0068] Aluminum 5%-30%, nickel 40%-90%, iron and / or molybdenum 5%-30%;

[0069] Optionally, the alloy powder is calculated by taking the mass of 100%, aluminum can be 5%, 10%, 15%, 20%, 25%, 30% or any value between 5% and 30%, nickel can be 40%, 50%, 60%, 70%, 80%, 90% or any value between 40% and 90%, iron can be 5%, 10%, 15%, 20%, 25%, 30% or any value between 5% and 30%, molybdenum can be 5%, 10%, 15%, 20%, 25%, 30% or any value between 5% and 30%, and in some optional embodiments, the sum of the mass of iron and molybdenum can be 5%, 10%, 15%, 20%, 25%, 30% or any value between 5% and 30%;

[0070] It should be noted that transition metal multi-element alloys have better intrinsic catalytic activity than single nickel, and the appropriate amount can ensure both the catalytic performance and the bonding strength of the coating;

[0071] Preferably, the alloy powder includes nickel, molybdenum, iron, and aluminum, which has the best catalytic activity;

[0072] B. The particle size of aluminum in the alloy powder is 5 μm-150 μm;

[0073] Optionally, the particle size of aluminum in the alloy powder may be 5 μm, 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 150 μm or any value between 5 μm and 150 μm;

[0074] It should be noted that when the particle size of aluminum in the alloy powder is 5μm-150μm, the particle size is limited to ensure that the spray powder can be stably transported and the first coating has a suitable pore size after activation; if the aluminum powder particle size is too small, it will affect the powder fluidity and cause powder blockage during the spraying process, which is not conducive to continuous production; if the aluminum powder particle size is too large, the pores of the first coating will be too large, which will increase the probability of coating shedding;

[0075] C. The alloy target material, calculated by mass as 100%, comprises:

[0076] Nickel 50%-90%, platinum and / or ruthenium 10%-50%.

[0077] Optionally, the alloy target material is calculated as 100% by mass, and nickel can be 50%, 60%, 70%, 80%, 90% or any value between 50% and 90%, platinum can be 10%, 20%, 30%, 40%, 50% or any value between 10% and 50%, and ruthenium can be 10%, 20%, 30%, 40%, 50% or any value between 10% and 50%; in some optional embodiments, the sum of the mass of platinum and ruthenium can be 10%, 20%, 30%, 40%, 50% or any value between 10% and 50%.

[0078] It should be noted that nickel is a metal that is resistant to alkali corrosion. Combining it with precious metals can further improve the catalytic performance. The appropriate amount can not only ensure excellent catalytic performance, but also control costs. Nickel platinum is the preferred alloy target material. Under frequent start-stop conditions, the nickel platinum coating is more resistant to reverse current shock and the coating is more stable.

[0079] In some embodiments, the method for preparing the multilayer alloy electrode satisfies at least one of the following conditions:

[0080] A. The spraying includes a plasma spraying process;

[0081] It should be noted that due to the thick thickness of the first coating and the alloy material, the spraying process needs to be selected to set the alloy powder on the substrate surface, while the deposition process is not suitable for the setting of the first coating because the deposition efficiency of the deposition process is relatively low and it is not suitable for thick coatings;

[0082] B. The deposition includes one or more of magnetron sputtering, atomic layer deposition, and pulsed laser deposition.

[0083] It should be noted that due to the thin thickness of the second coating, a deposition process needs to be selected to set the alloy target on the surface of the first coating, while the spraying process is not suitable for the setting of the second coating.

[0084] In some embodiments, the argon flow rate of the plasma spraying process is 50L / min-70L / min, the hydrogen flow rate is 0.5L / min-5L / min, the current is 500A-1000A, the gun distance is 120mm-180mm, and the powder feeding speed is 50g / min-200g / min.

[0085] Optionally, the argon flow rate of the plasma spraying process can be 50L / min, 60L / min, 70L / min or any value between 50L / min-70L / min, the hydrogen flow rate can be 0.5L / min, 1L / min, 2L / min, 5L / min or any value between 0.5L / min-5L / min, the current can be 500A, 700A, 900A, 1000A or any value between 500A-1000A, the gun distance can be 120mm, 140mm, 160mm, 180mm or any value between 120mm-180mm, and the powder feeding speed can be 50g / min, 100g / min, 150g / min, 200g / min or any value between 50g / min-200g / min.

[0086] In some embodiments, the working pressure of the magnetron sputtering is 0.5Pa-1Pa, the deposition time is 10min-10h, the flow rate of argon gas is 30sccm-100sccm, and the power is 50W-100W.

[0087] Optionally, the working pressure of magnetron sputtering can be 0.5Pa, 0.6Pa, 0.7Pa, 0.7Pa, 0.9Pa, 1Pa or any value between 0.5Pa-1Pa, the deposition time can be 10min, 30min, 1h, 5h, 10h or any value between 10min-10h, the flow rate of argon gas can be 30sccm, 60sccm, 90sccm, 100sccm or any value between 30sccm-100sccm, and the power can be 50W, 60W, 70W, 80W, 90W, 100W or any value between 50W-100W.

[0088] In some embodiments, the activation temperature is 20°C-80°C, and the activation time is 1h-24h.

[0089] Optionally, the activation temperature can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C or any value between 20°C and 80°C, and the activation time can be 1h, 8h, 16h, 24h or any value between 1h and 24h.

[0090] A third aspect of the present application provides a hydrogen production device, comprising the multi-layer alloy electrode or the multi-layer alloy electrode prepared by the multi-layer alloy electrode preparation method.

[0091] 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 in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0092] Example 1

[0093] A first aspect of the present embodiment provides a multilayer alloy electrode, comprising a nickel braided mesh and a first coating layer and a second coating layer sequentially stacked on the surface of the nickel braided mesh;

[0094] The first coating is a porous nickel-molybdenum-iron alloy with a thickness of 40 μm;

[0095] The second coating is a dense nickel-platinum alloy with a thickness of 2 μm;

[0096] A second aspect of this embodiment provides a method for preparing a multilayer alloy electrode, the specific steps comprising:

[0097] S1: A nickel woven mesh with a wire diameter of 0.19 mm and a mesh size of 40 was roughened by sandblasting with white corundum sand, the sandblasting angle was 70°, the air pressure was 0.3 MPa, and the sandblasting distance was 120 mm to obtain a pretreated nickel mesh;

[0098] S2: spraying NiMoFeAl alloy powder onto a pretreated nickel mesh by plasma spraying process to obtain a NiMoFeAl alloy coated electrode; wherein the NiMoFeAl alloy powder, calculated by mass, comprises: 20% aluminum, 65% nickel, 10% molybdenum, 5% iron, and the particle size of aluminum is 50 μm; the specific conditions of plasma spraying are: argon flow rate 65 L / min, hydrogen flow rate 3 L / min, current 600 A, gun distance 120 mm, and powder feeding speed 80 g / min;

[0099] S3: immersing the NiMoFeAl alloy coating electrode in an activation solution for activation and pore formation treatment, wherein the activation solution component is 30wt% KOH, the activation time is 12h, and the activation temperature is 30°C, and then washing with deionized water and drying to obtain a porous NiMoFe alloy electrode;

[0100] S4: Place the porous NiMoFe alloy electrode in a magnetron sputtering composite ion beam thin film deposition device and evacuate the vacuum to 10 -5Pa, open the argon valve, use argon as the working gas, use nickel-platinum alloy as the target material, apply bias to the substrate, the working pressure is 0.8Pa, and use magnetron sputtering technology to deposit on the electrode surface for 30 minutes to form a nickel-platinum alloy layer; wherein, the nickel-platinum alloy is 100% by mass, including: 80% nickel and 20% platinum, the flow rate of argon is 50sccm, the power is 60W, after the sputtering is completed, close the gas valve, power supply, etc., the electrode is naturally cooled in the vacuum chamber of the equipment to obtain a multi-layer alloy electrode.

[0101] The preparation method process is as follows Figure 1 shown.

[0102] Example 2

[0103] The difference from Example 1 is that the first coating layer is a nickel-iron alloy, and the alloy powder, calculated by mass as 100%, includes: 20% aluminum, 70% nickel, and 10% iron.

[0104] Example 3

[0105] The difference from Example 1 is that the second coating is a nickel-ruthenium alloy, and the alloy target material, calculated by mass as 100%, includes: 80% nickel and 20% ruthenium.

[0106] Comparative Example 1

[0107] The difference from Example 1 is that the first coating layer is not provided.

[0108] Comparative Example 2

[0109] The difference from Example 1 is that no second coating layer is provided.

[0110] Comparative Example 3

[0111] The difference from Example 1 is that the positions of the first coating layer and the second coating layer are replaced.

[0112] Comparative Example 4

[0113] The difference from Example 1 is that the first coating is not activated and is not a porous coating.

[0114] Comparative Example 5

[0115] The difference from Example 1 is that the first coating layer is provided with only nickel, and the alloy powder, calculated by mass as 100%, includes: 20% aluminum and 80% nickel.

[0116] Comparative Example 6

[0117] The difference from Example 1 is that the second coating layer is only provided with nickel, and the alloy target material is only nickel.

[0118] The electrodes prepared in the above examples and comparative examples were subjected to performance tests (including ultrasonic weight loss, electrode performance, and Mo dissolution rate). The specific test results are shown in Table 1.

[0119] Among them, bonding strength: the coating bonding strength is determined by ultrasonic weight loss method. The ultrasonic weight loss conditions are: ultrasonic power 300W, ultrasonic time 2h, and the weight of the electrode test piece before and after ultrasonic treatment is weighed with a balance, and the difference between the two is the ultrasonic weight loss.

[0120] Potential test method: The catalytic electrode activity was measured by linear sweep voltammetry in a standard three-electrode configuration using an electrochemical workstation. The prepared coating electrode was directly used as the working electrode, mercury / mercuric oxide as the reference electrode, platinum sheet as the counter electrode, 30wt% potassium hydroxide solution as the electrolyte, the test temperature was 80°C, and the scan rate was 5mV / s to test the hydrogen evolution reaction potential.

[0121] Mo dissolution rate: The electrode is placed at 5 kA / m 2 Under electrical density, a 30wt% potassium hydroxide solution was used as the electrolyte, and the test temperature was 80°C. After 48 hours, the amount of molybdenum ions dissolved in the electrolyte was tested, and the Mo dissolution rate was obtained by comparing it with the initial amount.

[0122] Table 1 Performance test

[0123]

[0124] analyze:

[0125] As can be seen from Table 1 above, Example 1 has the least ultrasonic weight loss, the lowest overpotential and an extremely low Mo dissolution rate by combining the NiMoFe first coating and the NiPt second coating. Example 2 replaces Mo with Fe, and the catalytic activity of NiFe is not as good as that of NiMoFe, but the difference in coating bonding strength is not large. Example 3 replaces the NiPt coating with NiRu, and the bonding strength and Mo dissolution rate are relatively close, but the hydrogen evolution potential is relatively higher. Comparative Example 1 has only NiPt coating, the coating has good bonding strength and is thin, the ultrasonic weight loss is small, and the hydrogen evolution potential is relatively high. Comparative Example 2 has only NiMoFe coating, the ultrasonic weight loss and hydrogen evolution potential are relatively higher, and the Mo dissolution rate is fast. Comparative Example 3 has a fast Mo dissolution rate because there is no protective layer. Comparative Example 4 has a significant increase in the hydrogen evolution potential because the first coating is not activated. Comparative Example 5 uses a traditional Raney nickel electrode, which also leads to a high hydrogen evolution potential. The second coating of Comparative Example 6 is replaced by Ni, and the hydrogen evolution potential is relatively higher.

[0126] 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.

[0127] 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 multilayer alloy electrode, characterized in that: It comprises a metal substrate and a first coating layer and a second coating layer which are sequentially stacked on the surface of the metal substrate; The first coating is a porous coating; The first coating comprises one or more of a nickel-molybdenum alloy, a nickel-iron alloy, and a nickel-molybdenum-iron alloy; The second coating layer includes one or more of nickel-platinum alloy, nickel-ruthenium alloy, and nickel-platinum-ruthenium alloy.

2. The multilayer alloy electrode according to claim 1, characterized in that: At least one of the following conditions is met: A. The thickness of the first coating is 20 μm-100 μm; B. The thickness of the second coating is 0.005 μm-5 μm; C. The second coating is a dense coating.

3. A method for preparing a multilayer alloy electrode according to claim 1 or 2, characterized in that: include: Spraying alloy powder onto the surface of a metal substrate to obtain a sprayed substrate; The sprayed substrate and alkali solution are mixed and activated to obtain a porous coating substrate; Depositing an alloy target material onto the surface of the porous coating substrate to obtain a multilayer alloy electrode; The alloy powder includes one or more of nickel-molybdenum-aluminum alloy powder, nickel-iron-aluminum alloy powder, and nickel-molybdenum-iron-aluminum alloy powder; The alloy target includes one or more of a nickel-platinum alloy target, a nickel-ruthenium alloy target, and a nickel-platinum-ruthenium alloy target.

4. The method for preparing a multilayer alloy electrode according to claim 3, characterized in that: The alkali solution includes potassium hydroxide solution and / or sodium hydroxide solution.

5. The method for preparing a multilayer alloy electrode according to claim 3, characterized in that: At least one of the following conditions is met: A. The alloy powder, calculated by mass as 100%, comprises: Aluminum 5%-30%, nickel 40%-90%, iron and / or molybdenum 5%-30%; B. The particle size of aluminum in the alloy powder is 5 μm-150 μm; C. The alloy target material, calculated by mass as 100%, comprises: Nickel 50%-90%, platinum and / or ruthenium 10%-50%.

6. The method for preparing a multilayer alloy electrode according to claim 3, characterized in that: At least one of the following conditions is met: A. The spraying includes a plasma spraying process; B. The deposition includes one or more of magnetron sputtering, atomic layer deposition, and pulsed laser deposition.

7. The method for preparing a multilayer alloy electrode according to claim 6, characterized in that: The plasma spraying process has an argon flow rate of 50 L / min-70 L / min, a hydrogen flow rate of 0.5 L / min-5 L / min, a current of 500 A-1000 A, a gun distance of 120 mm-180 mm, and a powder feeding speed of 50 g / min-200 g / min.

8. The method for preparing a multilayer alloy electrode according to claim 6, characterized in that: The working pressure of the magnetron sputtering is 0.5Pa-1Pa, the deposition time is 10min-10h, the flow rate of argon gas is 30sccm-100sccm, and the power is 50W-100W.

9. The method for preparing a multilayer alloy electrode according to any one of claims 3 to 8, characterized in that: The activation temperature is 20°C-80°C, and the activation time is 1h-24h.

10. A hydrogen production device, characterized in that: The invention comprises the multi-layer alloy electrode according to claim 1 or 2 or a multi-layer alloy electrode prepared by the method for preparing the multi-layer alloy electrode according to any one of claims 3 to 9.

Images