Porous electrode material, method for producing the same, and electrolytic device

Abstract

The application provides a porous electrode material, a preparation method thereof and an electrolytic device. The porous electrode material comprises a grid-shaped high-entropy alloy, the composition of the high-entropy alloy is Ni a Fe b Co c Cr d Al e , 30 <= a <= 37, 5 <= b <= 16.7, 5 <= c <= 16.7, 5 <= d <= 16.7, 5 <= e <= 16.7, a + b + c + d + e = 100, and the grid-shaped high-entropy alloy has pores on the surface. The porous electrode material provided by the application uses Ni, Fe, Co, Cr and Al as raw materials of a catalyst electrode, so that the prepared porous electrode material has excellent water electrolysis oxygen production activity and stability in an alkaline medium.

Description

Technical Field

[0001] This invention relates to the field of electrolytic hydrogen production technology, and more specifically, to a porous electrode material, its preparation method, and an electrolysis apparatus. Background Technology

[0002] Water electrolysis is a crucial technology for converting water into hydrogen and oxygen. It utilizes renewable energy sources such as solar and wind power to produce hydrogen, thus achieving sustainable energy development. Effective catalysts can improve the efficiency and hydrogen production rate of water electrolysis, reduce costs, and promote the development of renewable energy. Traditional water electrolysis catalysts, such as those made of precious metals like platinum and palladium, are expensive, increasing production costs and impacting the environment. Furthermore, water electrolysis catalysts can also be used to generate and store electricity, making them vital for the development of energy conversion and storage technologies. Therefore, developing inexpensive and efficient water electrolysis catalysts is of great significance. It can promote the development of sustainable energy, drive the popularization of clean energy vehicles, and advance energy conversion and storage technologies, ultimately achieving sustainable energy development.

[0003] Although researchers have developed many transition metal catalysts for water electrolysis, numerous problems still exist, such as:

[0004] 1. Powdered catalysts have poor stability. During long-term water splitting reactions, the catalyst is prone to deactivation, shedding, or premature wear, resulting in a decrease in gas production efficiency. Frequent catalyst replacement is required, which reduces economic benefits.

[0005] 2. Low selectivity; some transition metal water electrolysis catalysts may produce unwanted side reactions or products in the water splitting reaction, thereby reducing hydrogen production efficiency. Furthermore, currently commercially available nickel foam catalysts have a slow gas production rate, requiring a higher current density to achieve the same hydrogen production, thus incurring higher energy costs.

[0006] Therefore, inventing a porous electrode material that can improve hydrogen production efficiency is a technical problem that urgently needs to be solved. Summary of the Invention

[0007] In view of this, the present invention aims to solve the technical problem of low hydrogen production efficiency of existing catalyst electrodes.

[0008] The first aspect of the present invention provides a porous electrode material.

[0009] A second aspect of the present invention provides a method for preparing a porous electrode material.

[0010] A third aspect of the present invention provides an application of a porous electrode material.

[0011] A fourth aspect of the present invention provides a catalyst electrode.

[0012] The fifth aspect of the present invention provides an electrolysis apparatus.

[0013] Specifically, the present invention is achieved through the following technical solution:

[0014] A first aspect of the present invention provides a porous electrode material comprising a mesh-like high-entropy alloy, wherein the high-entropy alloy is composed of Ni. a Fe b Co c Cr d Al e , 30≤a≤37, 5≤b≤16.7, 5≤c≤16.7, 5≤d≤16.7, 5≤e≤16.7, a+b+c+d+e=100, the surface of the mesh-like high-entropy alloy has pores.

[0015] The porous electrode material provided by this invention uses five elements—Ni, Fe, Co, Cr, and Al—as raw materials for the catalyst electrode. This results in the prepared porous electrode material exhibiting excellent electrolytic oxygen production activity and stability in alkaline media. Furthermore, the porous electrode of this invention has a mesh-like structure with pores on its surface, thus increasing the active area of ​​the electrode material, exposing more catalytic active sites, and improving the porosity of the catalyst electrode, thereby enhancing the catalytic effect. It is understood that current electrode materials typically undergo electrochemical corrosion treatment of the entire bulk material, resulting in a limited corrosion area and low porosity. This invention, however, first prepares a high-entropy alloy into a mesh-like structure before electrochemical corrosion treatment, significantly increasing the contact area with the corrosion solution, improving porosity, and thus enhancing the catalytic effect.

[0016] In the above technical solution, the pore diameter is greater than or equal to 150 μm and less than or equal to 1000 μm.

[0017] In this technical solution, the pore size is limited, which can improve the catalytic activity of porous electrode materials.

[0018] In the above technical solution, the mesh size of the mesh-like high-entropy alloy is greater than or equal to 200 μm and less than or equal to 800 μm.

[0019] In this technical solution, the mesh size of the mesh-like high-entropy alloy is limited. This can avoid the mesh size being too small, which would increase the difficulty of mesh preparation, and also avoid the mesh size being too large, which would reduce porosity.

[0020] In the above technical solution, the mesh-like high-entropy alloy is formed by selective laser melting process.

[0021] In this technical solution, a grid-like high-entropy alloy can be printed using selective laser melting technology, for example, by using a laser 3D metal printing device. The porous electrode material of this invention effectively combines selective laser melting technology in the preparation process, thus overcoming the problem of low porosity caused by conventional electrochemical corrosion of bulk alloys.

[0022] In the above technical solution, the pores are formed through electrochemical corrosion treatment.

[0023] In this technical solution, the pores are formed through electrochemical etching, which improves the pore-forming efficiency. However, it is not limited to electrochemical etching; it could also be an etching process, etc.

[0024] In the above technical solution, the porous electrode material achieves a current density of 10 mA / cm² in the electrocatalytic oxygen production test. 2 The overpotential is less than or equal to 285mV, which gives the porous electrode material of the present invention good conductivity.

[0025] In the above technical solution, a = 34.4, b = 16.4, c = 16.4, d = 16.4, and e = 16.4.

[0026] In this technical solution, a = 34.4, b = 16.4, c = 16.4, d = 16.4, and e = 16.4, meaning the porous electrode material is composed of Ni. 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 By controlling the proportions of five elements—Ni, Fe, Co, Cr, and Al—the stability, conductivity, and catalytic effect of porous electrode materials in alkaline media can be maximized.

[0027] In the above technical solution, the crystal structure of the grid-like high-entropy alloy includes face-centered cubic lattice and body-centered cubic lattice.

[0028] In this technical solution, high-entropy alloys with face-centered cubic or body-centered cubic lattices have a higher active area, thereby resulting in higher catalytic efficiency.

[0029] A second aspect of this invention provides a method for preparing a porous electrode material, comprising the following steps: printing a mesh-like high-entropy alloy of a first preset size from high-entropy alloy powder using a selective laser melting process, wherein the high-entropy alloy powder is composed of Ni. a Fe b Co c Cr d Al e, 30≤a≤37, 5≤b≤16.7, 5≤c≤16.7, 5≤d≤16.7, 5≤e≤16.7, a+b+c+d+e=100; Porous electrode material is obtained by electrochemically corroding the mesh-like high-entropy alloy with a corrosive solution.

[0030] The method for preparing porous electrode materials provided by this invention involves first printing a mesh-like high-entropy alloy powder using selective laser melting (SLM), and then electrochemically etching the mesh-like high-entropy alloy with an etching solution to obtain a mesh-like porous electrode material. The mesh-like porous electrode prepared by this invention has pores on its mesh surface, thus increasing the active area of ​​the electrode material, exposing more catalytic active sites, improving the porosity of the catalyst electrode, and consequently enhancing the catalytic effect. It is understood that current electrode materials typically undergo electrochemical etching of the entire bulk material, resulting in a limited etching area and low porosity. This invention, by first preparing the high-entropy alloy into a mesh shape and then performing electrochemical etching, significantly increases the contact area with the etching solution, improves porosity, and thus enhances the catalytic effect. Furthermore, the porous electrode material of this invention effectively incorporates SLM technology during its preparation, overcoming the problem of low porosity caused by conventional electrochemical etching of bulk alloys.

[0031] In the above technical solution, the mesh size of the mesh-like high-entropy alloy is greater than or equal to 200 μm and less than or equal to 800 μm.

[0032] In this technical solution, the mesh size of the mesh-like high-entropy alloy is limited. This can avoid the mesh size being too small, which would increase the difficulty of mesh preparation, and also avoid the mesh size being too large, which would reduce porosity.

[0033] In the above technical solution, the particle size of the high-entropy alloy powder is greater than or equal to 15μm and less than or equal to 45μm.

[0034] In this technical solution, controlling the particle size of high-entropy alloy powder can accelerate the melting rate of high-entropy alloy powder and improve the printing speed.

[0035] In the above technical solution, the step of printing a grid-like high-entropy alloy of a first preset size from high-entropy alloy powder by selective laser melting process includes: drawing a grid-like structure model; importing the grid-like structure model into a laser 3D metal printing device, and printing it through the laser 3D metal printing device to obtain a grid-like high-entropy alloy of the first preset size.

[0036] In this technical solution, during the printing process of high-entropy alloy powder, a grid-like structure model can be drawn first, imported into a laser 3D metal printing device, and then printed using the laser 3D metal printing device to obtain a grid-like high-entropy alloy.

[0037] In the above technical solution, the length of the first preset dimension is greater than or equal to 40mm and less than or equal to 60mm; the width of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm; and the height of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm.

[0038] In this technical solution, the length of the first preset dimension is greater than or equal to 40mm and less than or equal to 60mm; the width of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm; and the height of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm. Furthermore, the length, width, and height of the first preset dimension are 50mm × 20mm × 20mm, meaning that during the printing process, the size of the printed mesh-like high-entropy alloy is 50mm × 20mm × 20mm. Controlling the size of the mesh-like high-entropy alloy can, on the one hand, avoid the problem of slow printing efficiency due to an excessively small size, and on the other hand, avoid the problem of poor subsequent etching effects due to an excessively large size.

[0039] In the above technical solution, after the step of printing high-entropy alloy powder into a grid-like high-entropy alloy of a first preset size by selective laser melting process, the method further includes: cutting the grid-like high-entropy alloy of the first preset size to cut the grid-like high-entropy alloy to a second preset size.

[0040] In this technical solution, after printing the mesh-like high-entropy alloy, the mesh-like high-entropy alloy is sawn, which can increase the surface area of ​​the mesh-like high-entropy alloy, thereby increasing the contact area with the corrosion liquid and improving the pore formation rate during the electrochemical corrosion process.

[0041] In the above technical solution, the length of the second preset dimension is greater than or equal to 0.5 mm and less than or equal to 1 mm; the width of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm; and the height of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm.

[0042] In this technical solution, the length of the second preset dimension is greater than or equal to 0.5 mm and less than or equal to 1 mm; the width of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm; the height of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm. Furthermore, the length, width and height of the second preset dimension are 0.8 mm × 10 mm × 10 mm, which means that the mesh-like high-entropy alloy is cut to a size of 0.8 mm × 10 mm × 10 mm, which can improve the hole-forming rate in the later stage.

[0043] In the above technical solution, the corrosive liquid includes an acid solution and ferrous sulfate.

[0044] In this technical solution, a mixture of acid solution and ferrous sulfate is selected as the etching solution. Compared with a mixture of acid solution and chromium trioxide, it has a better etching effect and can make the porous electrode material have better alkali resistance and conductivity.

[0045] In the above technical solution, the acid solution includes hydrogen chloride.

[0046] In this technical solution, hydrogen chloride has a better pore-forming effect compared to other acid solutions.

[0047] In the above technical solution, the molar ratio of hydrogen chloride and ferrous sulfate is greater than or equal to 2:1 and less than or equal to 6:1.

[0048] In this technical solution, controlling the molar ratio of hydrogen chloride and ferrous sulfate can maximize the corrosion effect and improve alkali resistance.

[0049] In the above technical solution, the concentration of hydrogen chloride is greater than or equal to 1 mol / L and less than or equal to 3 mol / L.

[0050] In this technical solution, controlling the concentration of hydrogen chloride can ensure the optimal pH value of the etching solution. If the concentration is too high, the pH value of the etching solution will be too high, which is not conducive to pore formation and will instead affect the alkali resistance stability of the porous electrode material.

[0051] In the above technical solution, the concentration of ferrous sulfate is greater than or equal to 0.3 mol / L and less than or equal to 0.8 mol / L.

[0052] In this technical solution, the concentration of ferrous sulfate is greater than or equal to 0.3 mol / L and less than or equal to 0.8 mol / L, for example, 0.5 mol / L. This can ensure the pore-forming effect and avoid the problem of wasting materials due to excessive ferrous sulfate and insignificant improvement in pore size.

[0053] In the above technical solution, the electrochemical corrosion treatment process includes the following conditions: DC current, current ≥ 1.5V and ≤ 2V, and energizing time ≥ 1 minute and ≤ 5 minutes.

[0054] In this technical solution, electrochemical corrosion is carried out by direct current. Furthermore, the current is greater than or equal to 1.5V and less than or equal to 2V, for example, the current is 1.8V, and the energizing time is greater than or equal to 1 minute and less than or equal to 5 minutes, for example, 3 minutes. By controlling the current and energizing time, the hole-forming effect can be improved while the energy utilization rate can be increased, and energy waste can be avoided.

[0055] In the above technical solution, the printing environment of the laser 3D metal printing equipment is an argon atmosphere during the printing process.

[0056] In this technical solution, the printing environment of the laser 3D metal printing equipment is an argon gas environment, which can ensure a safe printing environment.

[0057] In the above technical solution, during the printing process, the diameter of the focused laser beam of the laser 3D metal printing equipment is greater than or equal to 70μm and less than or equal to 120μm.

[0058] In this technical solution, the diameter of the focused laser beam in the laser 3D metal printing equipment is greater than or equal to 70 μm and less than or equal to 120 μm. Furthermore, the diameter of the focused laser beam in the laser 3D metal printing equipment is 90 μm. This ensures both printing speed and pore precision, thereby improving the catalytic effect of the porous electrode material.

[0059] In the above technical solution, the laser power of the laser 3D metal printing equipment is greater than or equal to 300W and less than or equal to 500W.

[0060] In this technical solution, the laser power of the laser 3D metal printing equipment is greater than or equal to 300W and less than or equal to 500W. Furthermore, the laser power of the laser 3D metal printing equipment is 400W. By controlling the laser power of the laser 3D metal printing equipment, the printing speed can be guaranteed, the precision of the pores can be ensured, and the catalytic effect of the porous electrode material can be improved.

[0061] In the above technical solution, during the printing process, the scanning speed of the laser in the laser 3D metal printing equipment is greater than or equal to 1000 mm / s and less than or equal to 1400 mm / s.

[0062] In this technical solution, during the printing process, the scanning speed of the laser in the laser 3D metal printing equipment is greater than or equal to 1000 mm / s and less than or equal to 1400 mm / s. Further, the scanning speed of the laser in the laser 3D metal printing equipment is 1200 mm / s. By controlling the scanning speed of the laser in the laser 3D metal printing equipment, both the printing rate and the quality of the porous electrode material can be guaranteed, avoiding the impact of excessively fast printing speed on the catalytic effect of the porous electrode material.

[0063] In the above technical solution, the scanning distance of the laser in the laser 3D metal printing equipment is greater than or equal to 0.05mm and less than or equal to 0.15mm.

[0064] In this technical solution, the scanning distance of the laser in the laser 3D metal printing equipment is greater than or equal to 0.05 mm and less than or equal to 0.15 mm. Furthermore, the scanning distance of the laser in the laser 3D metal printing equipment is equal to 0.09 mm. Controlling the scanning distance of the laser in the laser 3D metal printing equipment can ensure the quality of the porous electrode material and improve the catalytic effect.

[0065] In the above technical solution, the thickness of each layer printed by the laser 3D metal printing equipment is greater than or equal to 20μm and less than or equal to 40μm.

[0066] In this technical solution, the thickness of each layer printed by the laser 3D metal printing equipment is greater than or equal to 20 μm and less than or equal to 40 μm. Further, the thickness of each layer printed by the laser 3D metal printing equipment is 30 μm. Controlling the thickness of each layer printed by the laser 3D metal printing equipment can ensure the quality of the porous electrode material and improve the catalytic effect.

[0067] The third aspect of the present invention provides the application of porous electrode materials prepared by the preparation method of porous electrode materials of the first aspect of the present invention or any of the preparation methods of porous electrode materials of the second aspect of the present invention in the electrolysis of water to produce hydrogen and / or oxygen.

[0068] The fourth aspect of the present invention provides a catalyst electrode, which is prepared from a porous electrode material according to any one of the first aspects of the present invention, or from a porous electrode material prepared by a method for preparing a porous electrode material according to any one of the second aspects of the present invention.

[0069] The fifth aspect of the present invention provides an electrolysis apparatus, including a catalyst electrode as described in the fourth aspect of the present invention.

[0070] Beneficial effects: The porous electrode material provided by this invention exhibits excellent oxygen production activity and stability in alkaline media during water electrolysis, at 10 mA·cm⁻¹. -2 The required overpotential is 270mV to 280mV, and it can be within 500mA·cm. -2 It can operate continuously for 1000 hours and its performance is superior to that of nickel foam. Attached Figure Description

[0071] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0072] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or related technologies will be briefly introduced below. Obviously, those skilled in the art can obtain other drawings based on these drawings without creative effort.

[0073] Figure 1 This is a schematic flowchart of the method for preparing the porous electrode material provided in Embodiment 1 of the present invention;

[0074] Figure 2 This is a schematic flowchart of the preparation method of the porous electrode material provided in Embodiment 2 of the present invention;

[0075] Figure 3 This is a schematic flowchart of the preparation method of the porous electrode material provided in Embodiment 3 of the present invention;

[0076] Figure 4 This is a schematic flowchart of the preparation method of the porous electrode material provided in Embodiment 4 of the present invention;

[0077] Figure 5 This is a schematic flowchart of the preparation method of the porous electrode material provided in Comparative Example 1 of the present invention;

[0078] Figure 6 This is a schematic flowchart of the preparation method of the porous electrode material provided in Comparative Example 2 of the present invention;

[0079] Figure 7 Linear voltammetric scan curves of hydrogen evolution and oxygen evolution for electrochemical testing of the porous electrode material provided in Example 1 of this invention;

[0080] Figure 8 Linear voltammetric scan curves of hydrogen evolution and oxygen evolution for electrochemical testing of the porous electrode material provided in Embodiment 2 of the present invention;

[0081] Figure 9 Linear voltammetric scan curves of hydrogen evolution and oxygen evolution for electrochemical testing of the porous electrode material provided in Example 3 of this invention;

[0082] Figure 10 Scanning electron microscope (SEM) image of the porous electrode material prepared by the method for preparing porous electrode material provided in Embodiment 1 of the present invention;

[0083] Figure 11 Scanning electron microscope (SEM) image of the porous electrode material prepared by the method for preparing porous electrode material provided in Embodiment 2 of the present invention;

[0084] Figure 12 Scanning electron microscope (SEM) image of the porous electrode material prepared by the method for preparing porous electrode material provided in Embodiment 3 of the present invention;

[0085] Figure 13 This is a schematic block diagram of an electrolysis apparatus provided in an embodiment of the present invention.

[0086] in, Figure 13 The correspondence between component names and their designations is as follows:

[0087] 1. Electrolysis apparatus; 12. Catalyst electrode. Detailed Implementation

[0088] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0089] An embodiment of the first aspect of the present invention provides a porous electrode material comprising a mesh-like high-entropy alloy, wherein the high-entropy alloy is composed of Ni. a Fe b Co c Cr d Al e , 30≤a≤37, 5≤b≤16.7, 5≤c≤16.7, 5≤d≤16.7, 5≤e≤16.7, a+b+c+d+e=100, the surface of the mesh-like high-entropy alloy has pores.

[0090] The porous electrode material provided by this invention uses five elements—Ni, Fe, Co, Cr, and Al—as raw materials for the catalyst electrode. This results in the prepared porous electrode material exhibiting excellent electrolytic oxygen production activity and stability in alkaline media. Furthermore, the porous electrode of this invention has a mesh-like structure with pores on its surface, thus increasing the active area of ​​the electrode material, exposing more catalytic active sites, and improving the porosity of the catalyst electrode, thereby enhancing the catalytic effect. It is understood that current electrode materials typically undergo electrochemical corrosion treatment of the entire bulk material, resulting in a limited corrosion area and low porosity. This invention, however, first prepares a high-entropy alloy into a mesh-like structure before electrochemical corrosion treatment, significantly increasing the contact area with the corrosion solution, improving porosity, and thus enhancing the catalytic effect.

[0091] In the above embodiments, the pore diameter is greater than or equal to 150 μm and less than or equal to 1000 μm.

[0092] In this embodiment, the pore size is limited, which can improve the catalytic activity of the porous electrode material.

[0093] In the above embodiments, the mesh size of the mesh-like high-entropy alloy is greater than or equal to 200 μm and less than or equal to 800 μm.

[0094] In this embodiment, the mesh size of the mesh-like high-entropy alloy is limited. This can avoid the mesh size being too small, which would increase the difficulty of mesh preparation, and also avoid the mesh size being too large, which would reduce porosity.

[0095] In the above embodiments, the mesh-like high-entropy alloy is formed by selective laser melting process.

[0096] In this embodiment, a mesh-like high-entropy alloy can be printed using selective laser melting technology, for example, by using a laser 3D metal printing device. The porous electrode material of the present invention effectively incorporates selective laser melting technology during the preparation process, thus overcoming the problem of low porosity caused by conventional electrochemical corrosion of bulk alloys.

[0097] In the above embodiments, the pores are formed by electrochemical corrosion treatment.

[0098] In this embodiment, the pores are formed through electrochemical etching, which improves the pore-forming efficiency. However, it is not limited to electrochemical etching; it could also be an etching process, etc.

[0099] In the above embodiments, the porous electrode material was used in the electrocatalytic oxygen production test with a current density of 10 mA / cm². 2 The overpotential is less than or equal to 285mV, which gives the porous electrode material of the present invention good conductivity.

[0100] In the above embodiment, a = 34.4, b = 16.4, c = 16.4, d = 16.4, and e = 16.4.

[0101] In this embodiment, a = 34.4, b = 16.4, c = 16.4, d = 16.4, and e = 16.4, meaning the porous electrode material is composed of Ni. 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 By controlling the proportions of five elements—Ni, Fe, Co, Cr, and Al—the stability, conductivity, and catalytic effect of porous electrode materials in alkaline media can be maximized.

[0102] In the above embodiments, the crystal structure of the mesh-like high-entropy alloy includes face-centered cubic lattices and body-centered cubic lattices.

[0103] In this embodiment, high-entropy alloys with face-centered cubic or body-centered cubic lattices have a higher active area, thereby resulting in higher catalytic efficiency.

[0104] A second aspect of the present invention provides a method for preparing a porous electrode material.

[0105] Example 1

[0106] See Figure 1 This embodiment provides a method for preparing a porous electrode material, including the following steps:

[0107] S102: Draw a mesh-like structure model;

[0108] S104: Import the mesh structure model into the laser 3D metal printing equipment. Under an argon atmosphere, the high-entropy alloy powder (composed of Ni) is printed using the laser 3D metal printing equipment. 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The porous electrode material is printed by means of a laser beam with a diameter of 70 μm, a laser power of 300 W, a laser scanning speed of 1000 mm / s, a laser scanning spacing of 0.05 mm, and a printing thickness of 20 μm per layer.

[0109] S106: Cut the bulk porous electrode material to obtain a small bulk porous electrode material of 0.8mm×10mm×10mm;

[0110] S108: A porous electrode material is obtained by electrochemically etching a small block of porous electrode material using a hydrogen chloride and ferrous sulfate etching solution; wherein the molar ratio of hydrogen chloride to ferrous sulfate is 2:1, the concentration of hydrogen chloride is 1 mol / L, the concentration of ferrous sulfate is 0.3 mol / L, the current under DC is 1.5V, and the energizing time is 1 minute.

[0111] The scanning electron microscope image of the porous electrode material prepared in this embodiment is shown below. Figure 10 As shown, the electrochemical performance of the porous electrode material prepared in this embodiment was tested. The specific test steps are as follows:

[0112] The non-electrochemical testing portion of the porous electrode material prepared in this embodiment was sealed with silicone rubber, exposing a fixed area of ​​free surface for electrochemical testing. A linear voltammetric scan method was used to test the electrocatalytic material. A three-electrode system was used: the working electrode was the porous electrode material prepared in this embodiment, the reference electrode was mercury / mercuric oxide, the auxiliary electrode was a platinum sheet, and the electrolyte was a 1 mol / L potassium hydroxide solution. The obtained hydrogen evolution polarization curve is shown below. Figure 7 As shown, Figure 7 This indicates that when the current intensity reaches 10 mA / cm 2 At this point, the hydrogen evolution overpotential is 259 mV. This indicates that the porous electrode material in this embodiment exhibits superior hydrogen evolution catalytic activity.

[0113] Example 2

[0114] See Figure 2 This embodiment provides a method for preparing a porous electrode material, including the following steps:

[0115] S202: Draw a mesh-like structure model;

[0116] S204: The mesh structure model is imported into the laser 3D metal printing equipment. Under an argon atmosphere, the high-entropy alloy powder (composed of Ni) is printed using the laser 3D metal printing equipment. 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The porous electrode material is printed by means of a laser beam with a diameter of 120 μm, a laser power of 500 W, a laser scanning speed of 1400 mm / s, a laser scanning spacing of 0.15 mm, and a printing thickness of 40 μm per layer.

[0117] S206: Cut the bulk porous electrode material to obtain a small block of porous electrode material of 0.8mm×10mm×10mm;

[0118] S208: A porous electrode material is obtained by electrochemically etching a small block of porous electrode material using a hydrogen chloride and ferrous sulfate etching solution; wherein the molar ratio of hydrogen chloride to ferrous sulfate is 6:1, the concentration of hydrogen chloride is 3 mol / L, the concentration of ferrous sulfate is 0.8 mol / L, the current under DC is 2V, and the energizing time is 5 minutes.

[0119] The scanning electron microscope image of the porous electrode material prepared in this embodiment is shown below. Figure 11 As shown in the figure, 500 μm is the scale bar. The electrochemical performance of the porous electrode material prepared in this embodiment was tested. The specific test steps are as follows:

[0120] The non-electrochemical testing portion of the porous electrode material prepared in this embodiment was sealed with silicone rubber, exposing a fixed area of ​​free surface for electrochemical testing. A linear voltammetric scan method was used to test the electrocatalytic material. A three-electrode system was used: the working electrode was the porous electrode material prepared in this embodiment, the reference electrode was mercury / mercuric oxide, the auxiliary electrode was a platinum sheet, and the electrolyte was a 1 mol / L potassium hydroxide solution. The obtained hydrogen evolution polarization curve is shown below. Figure 8 As shown, Figure 8 The results show that when the current intensity reaches 10 mA / cm2, the hydrogen evolution overpotential is 273 mV, which indicates that the porous electrode material in this embodiment has excellent hydrogen evolution catalytic activity.

[0121] Example 3

[0122] See Figure 3 This embodiment provides a method for preparing a porous electrode material, including the following steps:

[0123] S302: Draw a mesh-like structure model;

[0124] S304: The mesh structure model is imported into the laser 3D metal printing equipment. Under an argon atmosphere, the high-entropy alloy powder (composed of Ni) is printed using the laser 3D metal printing equipment. 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The porous electrode material is printed by means of a laser beam with a diameter of 90 μm, a laser power of 400 W, a laser scanning speed of 1200 mm / s, a laser scanning spacing of 0.1 mm, and a printing thickness of 30 μm per layer.

[0125] S306: Cut the bulk porous electrode material to obtain a small bulk porous electrode material of 0.8mm×10mm×10mm;

[0126] S308: A porous electrode material is obtained by electrochemically etching a small block of porous electrode material using a hydrogen chloride and ferrous sulfate etching solution; wherein the molar ratio of hydrogen chloride to ferrous sulfate is 4:1, the concentration of hydrogen chloride is 2 mol / L, the concentration of ferrous sulfate is 0.5 mol / L, the current under DC is 1.8V, and the energizing time is 3 minutes.

[0127] The scanning electron microscope image of the porous electrode material prepared in this embodiment is shown below. Figure 12 As shown, the electrochemical performance of the porous electrode material prepared in this embodiment was tested. The specific test steps are as follows:

[0128] The non-electrochemical testing portion of the porous electrode material prepared in this embodiment was sealed with silicone rubber, exposing a fixed area of ​​free surface for electrochemical testing. A linear voltammetric scan method was used to test the electrocatalytic material. A three-electrode system was used: the working electrode was the porous electrode material prepared in this embodiment, the reference electrode was mercury / mercuric oxide, the auxiliary electrode was a platinum sheet, and the electrolyte was a 1 mol / L potassium hydroxide solution. The obtained hydrogen evolution polarization curve is shown below. Figure 9 As shown, Figure 9 The results show that the hydrogen evolution overpotential is 283 mV when the current intensity reaches 10 mA / cm². This indicates that the porous electrode material in this embodiment exhibits superior hydrogen evolution catalytic activity.

[0129] Example 4

[0130] See Figure 4 This embodiment provides a method for preparing a porous electrode material, including the following steps:

[0131] S402: High-entropy alloy powder is printed into a grid-like high-entropy alloy of a first preset size using a selective laser melting process, wherein the high-entropy alloy powder is composed of Ni. a Fe b Co c Cr d Al e , 30≤a≤37, 5≤b≤16.7, 5≤c≤16.7, 5≤d≤16.7, 5≤e≤16.7, a+b+c+d+e=100;

[0132] S404: A porous electrode material is obtained by electrochemically corroding a mesh-like high-entropy alloy with an etchant.

[0133] The method for preparing porous electrode materials provided by this invention first involves printing a mesh-like high-entropy alloy from high-entropy alloy powder using a selective laser melting (SLM) process. Specifically, a data model of a mesh-like molded part with pore sizes of not less than 200 micrometers is first drawn using CAD drawing software, with the output file format being STL. The data model is then imported into an SLM device for printing, producing a mesh-like NiFeCoCrAl high-entropy alloy with pore sizes ranging from 200 μm to 800 μm at room temperature. The crystal structure is mainly composed of FCC and BCC phases. Then, the mesh-like high-entropy alloy is subjected to electrochemical etching treatment using an etching solution to obtain a mesh-like porous electrode material. The mesh-like porous electrode prepared by this invention has pores on its mesh-like surface, which increases the active area of ​​the electrode material, exposes more catalytic active sites, improves the porosity of the catalyst electrode, and thus enhances the catalytic effect. Understandably, current electrode materials typically involve electrochemically etching the entire bulk material, resulting in a limited etching area and low porosity. This invention, however, first prepares a high-entropy alloy into a mesh structure before electrochemical etching, significantly increasing the contact area with the etching solution, improving porosity, and thus enhancing the catalytic effect. Furthermore, the porous electrode material of this invention effectively incorporates selective laser melting during its preparation, overcoming the problem of low porosity caused by conventional electrochemical etching of bulk alloys.

[0134] In the above embodiments, the mesh size of the mesh-like high-entropy alloy is greater than or equal to 200 μm and less than or equal to 800 μm.

[0135] In this embodiment, the mesh size of the mesh-like high-entropy alloy is limited. This can avoid the mesh size being too small, which would increase the difficulty of mesh preparation, and also avoid the mesh size being too large, which would reduce porosity.

[0136] In the above embodiments, the particle size of the high-entropy alloy powder is greater than or equal to 15 μm and less than or equal to 45 μm.

[0137] In this embodiment, controlling the particle size of the high-entropy alloy powder can accelerate the melting rate of the high-entropy alloy powder and improve the printing speed.

[0138] In the above embodiments, the step of printing a grid-like high-entropy alloy of a first preset size from high-entropy alloy powder using selective laser melting technology includes: drawing a grid-like structure model; importing the grid-like structure model into a laser 3D metal printing device; and printing it using the laser 3D metal printing device to obtain a grid-like high-entropy alloy of the first preset size.

[0139] In this embodiment, during the printing process of high-entropy alloy powder, a grid-like structure model can be drawn first, imported into a laser 3D metal printing device, and then printed using the laser 3D metal printing device to obtain a grid-like high-entropy alloy.

[0140] In the above embodiments, the length of the first preset dimension is greater than or equal to 40mm and less than or equal to 60mm; the width of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm; and the height of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm.

[0141] In this embodiment, the length of the first preset dimension is greater than or equal to 40mm and less than or equal to 60mm; the width of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm; and the height of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm. Furthermore, the length, width, and height of the first preset dimension are 50mm × 20mm × 20mm, meaning that during the printing process, the size of the printed mesh-like high-entropy alloy is 50mm × 20mm × 20mm. Controlling the size of the mesh-like high-entropy alloy can, on the one hand, avoid the problem of slow printing efficiency due to an excessively small size, and on the other hand, avoid the problem of poor subsequent etching effects due to an excessively large size.

[0142] In the above embodiments, after the step of printing a grid-shaped high-entropy alloy of a first preset size by selective laser melting process, the method further includes: cutting the grid-shaped high-entropy alloy of the first preset size to cut the grid-shaped high-entropy alloy to a second preset size.

[0143] In this embodiment, after printing the mesh-shaped high-entropy alloy, the mesh-shaped high-entropy alloy is sawn to increase the surface area of ​​the mesh-shaped high-entropy alloy, thereby increasing the contact area with the corrosion liquid and improving the pore formation rate during the electrochemical corrosion process.

[0144] In the above embodiments, the length of the second preset dimension is greater than or equal to 0.5 mm and less than or equal to 1 mm; the width of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm; and the height of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm.

[0145] In this embodiment, the length of the second preset dimension is greater than or equal to 0.5 mm and less than or equal to 1 mm; the width of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm; the height of the second preset dimension is greater than or equal to 5 mm and less than or equal to 15 mm. Furthermore, the length, width and height of the second preset dimension are 0.8 mm × 10 mm × 10 mm, which means that the mesh-like high-entropy alloy is cut to a size of 0.8 mm × 10 mm × 10 mm, which can improve the hole-forming rate in the later stage.

[0146] In the above embodiments, the corrosive solution includes an acid solution and ferrous sulfate.

[0147] In this embodiment, a mixture of hydrogen chloride and ferrous sulfate is selected as the etching solution. Compared with a mixture of hydrogen chloride and chromium trioxide, it has a better etching effect and can give the porous electrode material better alkali resistance.

[0148] In the above embodiments, the acid solution includes hydrogen chloride.

[0149] In the above embodiments, the molar ratio of hydrogen chloride to ferrous sulfate is greater than or equal to 2:1 and less than or equal to 6:1.

[0150] In this embodiment, controlling the molar ratio of hydrogen chloride and ferrous sulfate can maximize the corrosion effect and improve alkali resistance.

[0151] In the above embodiments, the concentration of hydrogen chloride is greater than or equal to 1 mol / L and less than or equal to 3 mol / L.

[0152] In this embodiment, controlling the concentration of hydrogen chloride can ensure the optimal pH value of the etching solution. If the concentration is too high, the pH value of the etching solution will be too high, which is not conducive to pore formation and will instead affect the alkali resistance stability of the porous electrode material.

[0153] In the above embodiments, the concentration of ferrous sulfate is greater than or equal to 0.3 mol / L and less than or equal to 0.8 mol / L.

[0154] In this embodiment, the concentration of ferrous sulfate is greater than or equal to 0.3 mol / L and less than or equal to 0.8 mol / L, for example, 0.5 mol / L. This ensures the pore-forming effect while avoiding the problem of wasting material due to excessive ferrous sulfate and insignificant improvement in pore size.

[0155] In the above embodiments, the electrochemical corrosion treatment conditions include: DC current, current flow greater than or equal to 1.5V and less than or equal to 2V, and current flow time greater than or equal to 1 minute and less than or equal to 5 minutes.

[0156] In this embodiment, electrochemical corrosion is performed using direct current. Furthermore, the current is greater than or equal to 1.5V and less than or equal to 2V, for example, the current is 1.8V, and the energizing time is greater than or equal to 1 minute and less than or equal to 5 minutes, for example, 3 minutes. By controlling the current and energizing time, the hole-forming effect can be improved while increasing energy utilization and avoiding energy waste.

[0157] In the above embodiments, the printing environment of the laser 3D metal printing equipment is an argon atmosphere during the printing process.

[0158] In this embodiment, the printing environment of the laser 3D metal printing equipment is an argon environment, preferably high-purity argon, which can ensure a safe printing environment.

[0159] In the above embodiments, during the printing process, the diameter of the focused laser beam of the laser 3D metal printing equipment is greater than or equal to 70 μm and less than or equal to 120 μm.

[0160] In this embodiment, the diameter of the focused laser beam in the laser 3D metal printing equipment is greater than or equal to 70 μm and less than or equal to 120 μm. Further, the diameter of the focused laser beam in the laser 3D metal printing equipment is 90 μm. This ensures both printing speed and pore precision, thereby improving the catalytic effect of the porous electrode material.

[0161] In the above embodiments, the laser power of the laser 3D metal printing equipment is greater than or equal to 300W and less than or equal to 500W.

[0162] In this embodiment, the laser power of the laser 3D metal printing equipment is greater than or equal to 300W and less than or equal to 500W. Further, the laser power of the laser 3D metal printing equipment is 400W. By controlling the laser power of the laser 3D metal printing equipment, the printing speed can be guaranteed, the precision of the pores can be ensured, and the catalytic effect of the porous electrode material can be improved.

[0163] In the above embodiments, during the printing process, the scanning speed of the laser in the laser 3D metal printing equipment is greater than or equal to 1000 mm / s and less than or equal to 1400 mm / s.

[0164] In this embodiment, during the printing process, the scanning speed of the laser in the laser 3D metal printing equipment is greater than or equal to 1000 mm / s and less than or equal to 1400 mm / s. Further, the scanning speed of the laser in the laser 3D metal printing equipment is 1200 mm / s. By controlling the scanning speed of the laser in the laser 3D metal printing equipment, both the printing rate and the quality of the porous electrode material can be guaranteed, avoiding the impact of excessively fast printing speed on the catalytic effect of the porous electrode material.

[0165] In the above embodiments, the scanning distance of the laser in the laser 3D metal printing equipment is greater than or equal to 0.05 mm and less than or equal to 0.15 mm.

[0166] In this embodiment, the scanning distance of the laser in the laser 3D metal printing equipment is greater than or equal to 0.05 mm and less than or equal to 0.15 mm. Furthermore, the scanning distance of the laser in the laser 3D metal printing equipment is equal to 0.09 mm. Controlling the scanning distance of the laser in the laser 3D metal printing equipment can ensure the quality of the porous electrode material and improve the catalytic effect.

[0167] In the above embodiments, the thickness of each layer printed by the laser 3D metal printing equipment is greater than or equal to 20 μm and less than or equal to 40 μm.

[0168] In this embodiment, the thickness of each layer printed by the laser 3D metal printing equipment is greater than or equal to 20 μm and less than or equal to 40 μm. Further, the thickness of each layer printed by the laser 3D metal printing equipment is 30 μm. Controlling the thickness of each layer printed by the laser 3D metal printing equipment can ensure the quality of the porous electrode material and improve the catalytic effect.

[0169] Comparative Example 1

[0170] See Figure 5 This comparative example provides a method for preparing an electrode material, comprising the following steps:

[0171] S502: Draw a mesh-like structure model;

[0172] S504: The mesh structure model is imported into the laser 3D metal printing equipment. Under an argon atmosphere, the high-entropy alloy powder (composed of Ni) is printed using the laser 3D metal printing equipment. 34.4 Fe 16.4 Co 16.4 Cr 16.4 Al 16.4 The porous electrode material is printed by means of a laser beam with a diameter of 90 μm, a laser power of 400 W, a laser scanning speed of 1200 mm / s, a laser scanning spacing of 0.1 mm, and a printing thickness of 30 μm per layer.

[0173] S506: Cut the bulk porous electrode material to obtain a small piece of porous electrode material of 0.8mm×10mm×10mm as the porous electrode material.

[0174] The porous electrode material prepared in this comparative example was subjected to electrochemical performance testing. The specific testing procedures were the same as those in each of the above embodiments. The results showed that when the current intensity reached 10 mA / cm², the performance was satisfactory. 2 At that time, the hydrogen evolution overpotential was 353mV, which indicates that the porous electrode material in this comparative example has poor hydrogen evolution catalytic activity. This is because it was not corroded by the corrosive liquid, so the surface of the prepared electrode material did not generate a large number of pores, resulting in low conductivity.

[0175] Comparative Example 2

[0176] See Figure 6 This comparative example provides a method for preparing a porous electrode material, comprising the following steps:

[0177] S602: A porous electrode material was obtained by electrochemically corroding the bulk high-entropy alloy obtained from S504 in Comparative Example 1 using a hydrogen chloride and ferrous sulfate etching solution. The molar ratio of hydrogen chloride to ferrous sulfate was 4:1, the concentration of hydrogen chloride was 2 mol / L, the concentration of ferrous sulfate was 0.5 mol / L, the current under DC was 1.8 V, and the energizing time was 3 minutes.

[0178] The porous electrode material prepared in this comparative example was subjected to electrochemical performance testing. The specific testing procedures were the same as those in each of the above embodiments. The results showed that when the current intensity reached 10 mA / cm², the performance was satisfactory. 2 At that time, the hydrogen evolution overpotential was 360mV, which indicates that the porous electrode material in this comparative example has poor hydrogen evolution catalytic activity. This is because although the bulk high-entropy alloy is corroded by the corrosive liquid, the contact area between the high-entropy alloy and the corrosive liquid is small during the corrosion process. This results in a low porosity of the prepared porous electrode material, which in turn results in a small active area and a small number of active sites, thus leading to low conductivity.

[0179] The third aspect of the present invention provides the application of porous electrode materials in the electrolysis of water to produce hydrogen and / or oxygen. The porous electrode material used is the porous electrode material of any embodiment of the first aspect of the present invention or the porous electrode material prepared by the preparation method of the porous electrode material of any embodiment of the second aspect of the present invention.

[0180] An embodiment of the fourth aspect of the present invention provides a catalyst electrode 12, which is prepared from a porous electrode material according to any embodiment of the first aspect of the present invention, or from a porous electrode material prepared by a method for preparing a porous electrode material according to any embodiment of the second aspect of the present invention.

[0181] See Figure 13 A fifth aspect of the present invention provides an electrolysis apparatus 1, including a catalyst electrode 12 as described in the fourth aspect of the present invention.

[0182] Beneficial effects: The porous electrode material provided by this invention exhibits excellent oxygen production activity and stability in alkaline media during water electrolysis, at 10 mA·cm⁻¹. -2 The required overpotential is 270mV to 280mV, and it can be within 500mA·cm. -2 It can operate continuously for 1000 hours and its performance is superior to that of nickel foam.

[0183] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A porous electrode material, characterized in that, This includes a high-entropy alloy with a mesh-like structure, the high-entropy alloy having a Ni composition. a Fe b Co c Cr d Al e , 30≤a≤37, 5≤b≤16.7, 5≤c≤16.7, 5≤d≤16.7, 5≤e≤16.7, a+b+c+d+e=100, the surface of the mesh-like high-entropy alloy has pores; The method for preparing the porous electrode material includes the following steps: High-entropy alloy powder is printed into a grid-like high-entropy alloy of a first preset size using a selective laser melting process, wherein the high-entropy alloy powder is composed of Ni. a Fe b Co c Cr d Al e , 30≤a≤37, 5≤b≤16.7, 5≤c≤16.7, 5≤d≤16.7, 5≤e≤16.7, a+b+c+d+e=100; The porous electrode material is obtained by electrochemically corroding the mesh-like high-entropy alloy with a corrosive solution containing hydrogen chloride and ferrous sulfate. The molar ratio of hydrogen chloride to ferrous sulfate is greater than or equal to 2:1 and less than or equal to 6:1; The concentration of the hydrogen chloride is greater than or equal to 1 mol / L and less than or equal to 3 mol / L; and / or The concentration of ferrous sulfate is greater than or equal to 0.3 mol / L and less than or equal to 0.8 mol / L.

2. The porous electrode material according to claim 1, characterized in that, The pore diameter is greater than or equal to 150 μm and less than or equal to 1000 μm.

3. The porous electrode material according to claim 1, characterized in that, The mesh-like high-entropy alloy has a mesh size greater than or equal to 200 μm and less than or equal to 800 μm; and / or The pores are formed through electrochemical corrosion treatment; and / or In the electrocatalytic oxygen production test, the porous electrode material was tested at a current density of 10 mA / cm². 2 The overpotential at that time is less than or equal to 285mV.

4. The porous electrode material according to claim 1, characterized in that, The values ​​of a=34.4, b=16.4, c=16.4, d=16.4, and e=16.4 are given.

5. The porous electrode material according to claim 1, characterized in that, The crystal structure of the grid-like high-entropy alloy includes face-centered cubic lattices and body-centered cubic lattices.

6. A method for preparing the porous electrode material according to any one of claims 1 to 5, characterized in that, Includes the following steps: High-entropy alloy powder is printed into a grid-like high-entropy alloy of a first preset size using a selective laser melting process, wherein the high-entropy alloy powder is composed of Ni. a Fe b Co c Cr d Al e , 30≤a≤37, 5≤b≤16.7, 5≤c≤16.7, 5≤d≤16.7, 5≤e≤16.7, a+b+c+d+e=100; The porous electrode material is obtained by electrochemically corroding the mesh-like high-entropy alloy with a corrosive solution containing hydrogen chloride and ferrous sulfate. The molar ratio of hydrogen chloride to ferrous sulfate is greater than or equal to 2:1 and less than or equal to 6:1; The concentration of the hydrogen chloride is greater than or equal to 1 mol / L and less than or equal to 3 mol / L; and / or The concentration of ferrous sulfate is greater than or equal to 0.3 mol / L and less than or equal to 0.8 mol / L.

7. The method for preparing porous electrode material according to claim 6, characterized in that, The high-entropy alloy powder has a particle size of ≥15μm and ≤45μm.

8. The method for preparing porous electrode material according to claim 6, characterized in that, The step of printing high-entropy alloy powder into a grid-like high-entropy alloy of a first preset size using selective laser melting technology includes: Draw a mesh-like structure model; The mesh-like structure model is imported into a laser 3D metal printing device and printed using the laser 3D metal printing device to obtain a mesh-like high-entropy alloy of the first preset size.

9. The method for preparing the porous electrode material according to claim 8, characterized in that, The length of the first preset dimension is greater than or equal to 40mm and less than or equal to 60mm; The width of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm; The height of the first preset dimension is greater than or equal to 10mm and less than or equal to 30mm.

10. The method for preparing the porous electrode material according to claim 6, characterized in that, After the step of printing a grid-like high-entropy alloy of a first preset size using selective laser melting technology, the method further includes: The first preset-size mesh-like high-entropy alloy is cut to a second preset size.

11. The method for preparing the porous electrode material according to claim 10, characterized in that, The length of the second preset dimension is greater than or equal to 0.5 mm and less than or equal to 1 mm; The width of the second preset dimension is greater than or equal to 5mm and less than or equal to 15mm; The height of the second preset dimension is greater than or equal to 5mm and less than or equal to 15mm.

12. The method for preparing porous electrode material according to claim 11, characterized in that, The second preset dimensions are 0.8mm × 10mm × 10mm.

13. The method for preparing the porous electrode material according to claim 6, characterized in that, The electrochemical corrosion treatment process includes the following conditions: DC current, current ≥ 1.5V and ≤ 2V, and current duration ≥ 1 minute and ≤ 5 minutes.

14. The method for preparing porous electrode material according to claim 8, characterized in that, In the step of printing using the laser 3D metal printing equipment, the printing environment of the laser 3D metal printing equipment is an argon atmosphere. In the step of printing using the laser 3D metal printing equipment, the diameter of the focused laser beam of the laser 3D metal printing equipment is greater than or equal to 70 μm and less than or equal to 120 μm. and / or In the step of printing using the laser 3D metal printing equipment, the laser power of the laser 3D metal printing equipment is greater than or equal to 300W and less than or equal to 500W; and / or In the step of printing using the laser 3D metal printing equipment, the scanning speed of the laser in the laser 3D metal printing equipment is greater than or equal to 1000 mm / s and less than or equal to 1400 mm / s; and / or In the step of printing using the laser 3D metal printing equipment, the scanning distance of the laser in the laser 3D metal printing equipment is greater than or equal to 0.05 mm and less than or equal to 0.15 mm; and / or In the step of printing using the laser 3D metal printing equipment, the thickness of each layer printed by the laser 3D metal printing equipment is greater than or equal to 20μm and less than or equal to 40μm.

15. The application of the porous electrode material prepared by the preparation method of the porous electrode material according to any one of claims 1 to 5 or any one of claims 6 to 14 in the electrolysis of water to produce hydrogen and / or oxygen.

16. A catalyst electrode, characterized in that, The catalyst electrode is prepared from a porous electrode material prepared according to any one of claims 1 to 5 or by any one of claims 6 to 14.

17. An electrolysis apparatus, characterized in that, include The catalyst electrode as described in claim 16.

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