Porous nickel-based alloy net or fiber cloth and preparation method thereof

Abstract

The invention discloses a porous nickel-based alloy net or fiber cloth and a preparation method thereof.The preparation method comprises the following steps that metal raw materials needed by nickel-based alloy are added into a smelting furnace to be smelted, casting is conducted after smelting is completed, and a nickel-based alloy cast ingot is obtained; wherein the nickel-based alloy at least contains metal aluminum; the nickel-based alloy cast ingot is subjected to hot forging forming, and the nickel-based alloy to be machined is obtained; the nickel-based alloy to be machined is rolled in sequence, and a nickel-based alloy plate is obtained; the nickel-based alloy plate is drawn, and a nickel-based alloy wire is obtained; the nickel-based alloy wires are woven into a nickel-based alloy net, or the nickel-based alloy wires are further drawn into nickel-based alloy fibers, and then the nickel-based alloy fibers are woven into nickel-based fiber cloth; and activating the nickel-based alloy net or fiber cloth by adopting alkali liquor to obtain the porous nickel-based alloy net or fiber cloth.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalytic materials, and particularly relates to a porous nickel-based alloy mesh or fiber cloth and a preparation method thereof. Background Art

[0002] At present, the electrode materials for large-scale industrial alkaline electrolyzed water are mostly nickel meshes or modified nickel meshes. Although nickel meshes have excellent stability, the surface of pure nickel meshes is smooth and there are few catalytic active sites, resulting in low overpotentials for hydrogen evolution and oxygen evolution, high cell voltage of the electrolytic cell, and high power consumption. Most modified nickel meshes are loaded with highly active catalysts on the nickel meshes, and the catalytic activity of the nickel meshes is improved by composition regulation and specific surface area regulation. Most modified nickel mesh electrodes use techniques such as plasma spraying, electroplating, and hydrothermal treatment to load micro-nano structured nickel-based catalysts (such as porous Raney nickel) on the nickel meshes. Although such treatment methods can effectively improve the catalytic activity of the nickel meshes; however, the catalysts are prone to fall off when loaded on the nickel meshes, resulting in insufficient catalytic stability. Even if the surface of the nickel mesh is modified (such as pickling, sandblasting, etc.) to improve the bonding force between the catalyst and the substrate, the loaded catalyst will still fall off during long-term operation under alkaline electrolyzed water, high current density, and high temperature and high pressure. Moreover, modifying the nickel mesh makes the preparation process of the electrode material more complex and increases the production cost. Summary of the Invention

[0003] The purpose of the present invention is to provide a porous nickel-based alloy mesh or fiber cloth with good catalytic activity and catalytic stability and a preparation method thereof.

[0004] In the first aspect, the present invention provides a preparation method of a porous nickel-based alloy mesh or fiber cloth, adopting the following technical solution: A preparation method of a porous nickel-based alloy mesh or fiber cloth includes the following steps: (1) Add the metal raw materials required for the nickel-based alloy into a melting furnace for melting. After melting, perform casting to obtain a nickel-based alloy ingot; wherein: the nickel-based alloy contains at least aluminum; (2) Perform hot forging on the nickel-based alloy ingot in step (1) to form a nickel-based alloy to be processed; wherein: the temperature of the hot forging is 800-1300 °C; (3) Roll the nickel-based alloy to be processed in step (2) in sequence to obtain a nickel-based alloy plate; draw the nickel-based alloy plate to obtain a nickel-based alloy wire; Wherein: the rolling is hot rolling, or cold rolling and recrystallization annealing; wherein: the temperature of the hot rolling is 800-1300 °C; in the cold rolling and recrystallization annealing, the temperature of the recrystallization annealing is 700-1050 °C; (4) Weave the nickel-based alloy wire in step (3) into a nickel-based alloy mesh; or further draw the nickel-based alloy wire to obtain nickel-based alloy fibers, and then weave the nickel alloy fibers into a nickel-based alloy fiber cloth; then subject the nickel-based alloy mesh or fiber cloth to an activation treatment with an alkali solution to obtain a porous nickel-based alloy mesh or fiber cloth.

[0005] Preferably, in the step (1), the nickel-based alloy is one of nickel-aluminum alloy, nickel-molybdenum-aluminum alloy, and nickel-iron-aluminum alloy.

[0006] More preferably, in the nickel-aluminum alloy, the mass ratio of nickel to aluminum is (85~100):(1~20); in the nickel-molybdenum-aluminum alloy, the mass ratio of nickel, molybdenum, and aluminum is (45~84):(15~40):(1~20); in the nickel-iron-aluminum alloy, the mass ratio of nickel, iron, and aluminum is (35~79):(20~50):(1~20).

[0007] Preferably, in the step (1), the melting is carried out in a vacuum or an inert atmosphere; more preferably, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.

[0008] Preferably, in the step (1), the melting temperature is 1000~1300 °C, and the number of melting times is 3~5 times.

[0009] Preferably, in the step (2), before the hot forging forming of the nickel-based alloy ingot, a homogenization annealing treatment is first carried out.

[0010] More preferably, the temperature of the homogenization annealing treatment is 1000~1300 °C, and the time of the homogenization annealing treatment is 5~60 h.

[0011] Preferably, in the step (3), multiple rollings are carried out until the thickness of the plate is 0.5~2 mm.

[0012] Preferably, in the cold rolling and recrystallization annealing in the step (3), the time of the recrystallization annealing is 0.5~3 h.

[0013] Preferably, in the step (3), multiple drawings are carried out until the diameter of the nickel-based alloy wire is 0.1~0.5 mm.

[0014] Preferably, in the steps (3) and (4), the drawing is hot drawing, or cold drawing and recrystallization annealing.

[0015] More preferably, the temperature of the hot drawing is 500~1000 °C; in the cold drawing and recrystallization annealing, the temperature of the recrystallization annealing is 700~1050 °C, and the time of the recrystallization annealing is 10~60 min.

[0016] Preferably, in the step (4), the nickel-based alloy wire is drawn to an alloy fiber with a diameter of 5-30 μm.

[0017] Preferably, in the step (4), the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution with a concentration of 5-10 mol / L; the activation treatment is to soak the nickel-based alloy mesh in the alkali solution and perform ultrasonic treatment for 0.5-3 h.

[0018] In a second aspect, the present invention provides a porous nickel-based alloy mesh or fiber cloth prepared by the aforementioned preparation method.

[0019] One or more of the above technical solutions of the present invention can achieve at least one of the following beneficial effects: (1) The nickel-based alloy of the present invention contains the Al metal element, which will dissolve out during the activation treatment, so that a porous structure will appear on the fibers of the nickel-based alloy mesh or fiber cloth, thereby increasing the catalytic active sites and activating the nickel-based alloy mesh or fiber cloth, and greatly improving the catalytic performance of the nickel mesh electrode.

[0020] (2) In the method of the present invention, the temperature of hot forging is controlled to ensure that the nickel-based alloy to be processed does not crack, so that the subsequent rolling process can be carried out smoothly; during the rolling process, the hot rolling temperature or the temperature of recrystallization annealing in cold rolling and recrystallization annealing is controlled, which can ensure that the sheet does not crack, so that the subsequent drawing process can be better carried out.

[0021] (3) After melting in the method of the present invention, homogenization annealing is carried out, which can improve the comprehensive performance of the nickel-based alloy catalytic electrode. Description of the Drawings

[0022] Figure 1 It is a physical picture of the nickel-aluminum alloy sheet prepared in Example 1.

[0023] Figure 2 It is a physical picture of the nickel-aluminum alloy ingot prepared in Comparative Example 1.

[0024] Figure 3 It is a physical picture of the nickel-aluminum alloy sheet in Comparative Example 3.

[0025] Figure 4 It is a physical picture of the nickel-aluminum alloy sheet in Comparative Example 4.

[0026] Figure 5 It is a SEM picture of the fibers of the NiAl15 fiber cloth and the fibers of the porous NiAl15 alloy fiber cloth prepared in Example 3.

[0027] Figure 6The NiAl fiber cloth and porous NiAl alloy fiber cloth prepared in Examples 1 to 3; and the OER activity curves of the nickel fiber cloth and activated nickel fiber cloth in Comparative Example 5 as catalytic electrodes.

[0028] Figure 7 SEM images of the fibers of the NiMo20Al15 fiber cloth and the fibers of the porous NiMo20Al15 alloy fiber cloth prepared in Example 7.

[0029] Figure 8 The OER activity curves of the NiMoAl alloy fiber cloth and porous NiMoAl alloy fiber cloth prepared in Examples 4, 5 and 7, and the NiMo alloy fiber cloth and activated NiMo alloy fiber cloth prepared in Comparative Example 8 as catalytic electrodes.

[0030] Figure 9 The HER activity curves of the NiMoAl alloy fiber cloth, porous NiMoAl alloy fiber cloth, unannealed porous NiMoAl alloy fiber cloth prepared in Examples 5 to 8, and the NiMo alloy fiber cloth and activated NiMo alloy fiber cloth prepared in Comparative Example 8, and the unannealed NiMo alloy fiber cloth in Comparative Example 9 as catalytic electrodes.

[0031] Figure 10 The full electrolytic cell performance test curves of the porous NiMo20Al15 alloy fiber cloth prepared in Example 7, the unannealed porous NiMo20Al15 alloy fiber cloth prepared in Example 8, and the commercial NiMo-plasma electrode prepared in Comparative Example 10 as catalytic electrodes. Detailed implementation manners

[0032] For the convenience of understanding the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with the specification drawings and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments. Unless otherwise defined, all professional terms used hereinafter have the same meaning as commonly understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments and equipment used in the present invention can be obtained through the market or can be prepared by existing methods.

[0033] As described above, the present invention provides a method for preparing a porous nickel-based alloy mesh or fiber cloth, comprising the following steps: (1) Adding the metal raw materials required for the nickel-based alloy into a melting furnace for melting. After melting, casting is carried out to obtain a nickel-based alloy ingot; wherein: the nickel-based alloy contains at least aluminum. (2) Hot forge the nickel-based alloy ingot in step (1) to obtain a nickel-based alloy to be processed; wherein: the temperature of hot forging is 800-1300 °C; (3) Roll the nickel-based alloy to be processed in step (2) successively to obtain a nickel-based alloy sheet; draw the nickel-based alloy sheet to obtain a nickel-based alloy wire; Wherein: the rolling is hot rolling, or cold rolling and recrystallization annealing; wherein: the temperature of hot rolling is 800-1300 °C; in cold rolling and recrystallization annealing, the temperature of recrystallization annealing is 700-1050 °C; (4) Weave the nickel-based alloy wire in step (3) into a nickel-based alloy mesh; or further draw the nickel-based alloy wire to obtain nickel-based alloy fibers, then weave the nickel alloy fibers into a nickel-based alloy fiber cloth; then activate the nickel-based alloy mesh or fiber cloth with an alkali solution to obtain a porous nickel-based alloy mesh or fiber cloth.

[0034] Preferably, the temperature of hot forging is 1000-1200 °C, including but not limited to 1000 °C, 1050 °C, 1100 °C, 1150 °C, 1200 °C, etc.

[0035] Preferably, the temperature of hot rolling is 900-1100 °C, including but not limited to 900 °C, 950 °C, 1000 °C, 1050 °C, 1100 °C, etc.

[0036] Preferably, in the cold rolling and recrystallization annealing, the temperature of recrystallization annealing is 850-1000 °C, including but not limited to 850 °C, 880 °C, 900 °C, 920 °C, 950 °C, 980 °C, 1000 °C, etc.

[0037] Preferably, in step (1), the nickel-based alloy is one of nickel-aluminum alloy, nickel-molybdenum-aluminum alloy, and nickel-iron-aluminum alloy.

[0038] More preferably, the mass ratio of nickel to aluminum in the nickel-aluminum alloy is (80-100):(1-20), including but not limited to 80:20, 82:18, 85:15, 88:12, 90:10, 92:8, 95:5, 98:2, etc.; the mass ratio of nickel, molybdenum to aluminum in the nickel-molybdenum-aluminum alloy is (45-84):(15-40):(1-20), including but not limited to 45:40:15, 50:40:10, 55:40:5, 60:30:10, 65:20:15, 70:20:10, 75:20:5, 80:10:10, 84:10:6, etc.; the mass ratio of nickel, iron to aluminum in the nickel-iron-aluminum alloy is (35-79):(20-50):(1-20), including but not limited to 35:50:15, 40:40:20, 55:40:5, 60:30:10, 65:20:15, 70:20:10, 75:20:5, etc.

[0039] Preferably, in the step (1), the melting is carried out in a vacuum or an inert atmosphere; more preferably, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.

[0040] Preferably, in the step (1), the melting temperature is 1000-1300 °C, including but not limited to 1000 °C, 1050 °C, 1100 °C, 1150 °C, 1200 °C, 1250 °C, 1300 °C, etc.; the number of melting times is 3-5 times, including but not limited to 3 times, 4 times, 5 times.

[0041] Preferably, in the step (2), before the nickel-based alloy ingot is hot forged into shape, a homogenization annealing treatment is first carried out.

[0042] More preferably, the temperature of the homogenization annealing treatment is 1000-1300 °C, including but not limited to 1000 °C, 1050 °C, 1100 °C, 1150 °C, 1200 °C, 1250 °C, 1300 °C, etc.; the time of the homogenization annealing treatment is 5-60 h, including but not limited to 5 h, 8 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h, 50 h, 55 h, 60 h, etc.

[0043] Preferably, in the step (3), multiple rollings are carried out until the thickness of the plate is 0.5-2 mm; including but not limited to 0.5 mm, 0.8 mm, 1.0 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2.0 mm, etc.

[0044] Preferably, in the step (3), in the cold rolling and recrystallization annealing, the time of the recrystallization annealing is 0.5-3 h, including but not limited to 0.5 h, 1.0 h, 1.5 h, 2.0 h, 2.5 h, 3.0 h, etc.

[0045] Preferably, in the step (3), multiple drawing operations are performed until the diameter of the nickel-based alloy wire is 0.1-0.5 mm, including but not limited to 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, etc.

[0046] Preferably, in the steps (3) and (4), the drawing is hot drawing, or cold drawing and recrystallization annealing.

[0047] More preferably, the temperature of the hot drawing is 500-1000 °C, including but not limited to 500 °C, 550 °C, 600 °C, 650 °C, 700 °C, 750 °C, 800 °C, 850 °C, 900 °C, 950 °C, 1000 °C, etc. In cold drawing and recrystallization annealing, the temperature of the recrystallization annealing is 700-1050 °C, including but not limited to 700 °C, 750 °C, 800 °C, 850 °C, 900 °C, 950 °C, 1000 °C, etc.; the time of the recrystallization annealing is 10-60 min, including but not limited to 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, etc.

[0048] Preferably, in the step (4), the nickel-based alloy wire is drawn until the diameter of the alloy fiber is 5-30 μm, including but not limited to 5 μm, 7 μm, 10 μm, 12 μm, 15 μm, 17 μm, 20 μm, 22 μm, 25 μm, 27 μm, 30 μm, etc.

[0049] Preferably, in the step (4), the alkaline solution is a 5-10 mol / L sodium hydroxide solution or potassium hydroxide solution; the activation treatment is to soak the nickel-based alloy mesh in the alkaline solution and perform ultrasonic treatment for 0.5-3 h.

[0050] In a second aspect, the present invention provides a porous nickel-based alloy mesh or fiber cloth prepared by the foregoing preparation method.

[0051] The test method for the half electrolytic cell test in the present invention is as follows: Cut the nickel-based alloy mesh or fiber cloth catalytic electrode into a 5 cm × 5 cm square mesh, fix it with a platinum electrode clip, and perform the test in a 0.1 mol / L KOH alkaline electrolyte solution. The counter electrode uses a carbon rod, and the reference electrode uses a saturated calomel electrode. Before the linear voltammetry scan test, first activate the material with 10 cycles of voltammetry scan, and then perform the linear voltammetry scan test at a scan rate of 5 mV / s to obtain the OER activity curve or HER activity curve of the catalytic electrode.

[0052] The full electrolytic cell test method in the present invention: Use the nickel-based alloy mesh or fiber cloth as the catalytic electrode to form an electrolytic cell with a PPS diaphragm, pump in 1 mol / L KOH electrolyte solution (20 mL / min), and perform the full electrolytic cell performance test.

[0053] Example 1 In this example, the porous nickel-based alloy fiber cloth is a porous NiAl5 alloy fiber cloth, and the specific preparation method is as follows: (1) Metals nickel and aluminum with a purity above 99wt% are added to a melting furnace according to a mass ratio of 95:5, and vacuum melting is carried out 4 times (where: the vacuum degree is 10 -1 Pa, the melting temperature is 1200 °C, and the melting time for each time is 1.5 h). After melting, casting is carried out to obtain a nickel-aluminum alloy ingot.

[0054] (2) The nickel-aluminum alloy ingot obtained in step (1) is subjected to homogenization annealing treatment at 1150 °C in a nitrogen atmosphere for 24 h to obtain a nickel-aluminum alloy ingot after homogenization annealing treatment; the nickel-aluminum alloy ingot after homogenization annealing treatment is hot forged at 1000 °C (no cracking of the ingot occurs during the hot forging process) to obtain a nickel-aluminum alloy ingot to be processed.

[0055] (3) The nickel-aluminum alloy ingot to be processed in step (2) is hot rolled at 1000 °C, and the deformation amount for each hot rolling is controlled to be 1 mm. After 20 times of hot rolling, the thickness of the plate is rolled to 1 mm (no cracking occurs during rolling), and a nickel-aluminum alloy plate is obtained.

[0056] (4) The nickel-aluminum alloy plate is subjected to 15 times of hot drawing at 900 °C (no wire breakage occurs during the hot drawing process) to obtain a nickel-aluminum alloy wire with a diameter of 0.3 mm; the nickel-aluminum alloy wire is subjected to 15 times of hot drawing at 900 °C until the fiber diameter reaches 12 μm to obtain nickel-aluminum alloy fibers.

[0057] (5) The nickel-aluminum alloy fibers in step (4) are woven into a NiAl5 alloy fiber cloth, and the alloy fiber cloth is placed in an 8 mol / L sodium hydroxide solution for ultrasonic activation treatment for 1.5 h. After taking out, cleaning and drying, a porous NiAl5 alloy fiber cloth is obtained.

[0058] In this example, the physical picture of the nickel-aluminum alloy plate prepared in step (3) is as Figure 1 shown, and it can be seen that no cracking occurs in the hot-rolled plate.

[0059] Comparative Example 1 Steps (1) and (2) are basically the same as those in Example 1, the difference being that: in step (2), the hot forging temperature is 700 °C. During the hot forging process in step (2), ingot cracking occurs (specifically visible Figure 2 ), and subsequent hot rolling and drawing processes cannot be carried out.

[0060] Comparative Example 2 Steps (1) and (2) are basically the same as those in Example 1, except that: in step (2), the hot forging temperature is 1400 °C. During the hot forging process in step (2), the ingot also cracked, and the subsequent hot rolling and drawing processes could not be carried out.

[0061] Comparative Example 3 Steps (1) to (3) are basically the same as those in Example 1, except that: in step (3), the hot rolling temperature is 700 °C. The physical drawing of the nickel-aluminum alloy sheet obtained in step (3) is as Figure 3 shown. It can be seen that obvious cracks appeared on the sheet, and the subsequent drawing process could not be carried out.

[0062] Comparative Example 4 Steps (1) to (3) are basically the same as those in Example 1, except that: in step (3), the hot rolling temperature is 1400 °C. After hot rolling, the nickel-aluminum alloy sheet is visible Figure 4 , and obvious cracks appeared on the nickel-aluminum alloy sheet, and the subsequent drawing process could not be carried out.

[0063] Example 2 In this example, the prepared porous nickel-based alloy fiber cloth is a porous NiAl10 alloy fiber cloth. The preparation method is basically the same as that in Example 1, except that: in step (1), the mass ratio of metallic nickel to metallic aluminum is 90:10.

[0064] Example 3 In this example, the prepared porous nickel-based alloy fiber cloth is a porous NiAl15 alloy fiber cloth. The preparation method is basically the same as that in Example 1, except that: in step (1), the mass ratio of metallic nickel to metallic aluminum is 85:15.

[0065] The fibers in the NiAl15 alloy fiber cloth without alkali activation treatment and the fibers in the porous NiAl5 alloy fiber cloth in this example were observed by SEM micro-morphology. The results are visible Figure 5 ; it can be seen that after alkali activation treatment, more fine pore structures appeared on the surface of the fibers in the porous NiAl5 alloy fiber cloth, while the surface of the fibers without alkali activation treatment was smooth and had no micropore structure.

[0066] Comparative Example 5 (1) Add metallic nickel with a purity of more than 99 wt% to a melting furnace for vacuum melting 4 times (where: the vacuum degree is 10 -1 Pa, the melting temperature is 1200 °C, and the melting time for each time is 1.5 h). After melting, casting is carried out to obtain a nickel ingot.

[0067] (2) The nickel ingot obtained in step (1) is subjected to homogenization annealing treatment at a temperature of 1150°C in a nitrogen atmosphere for 24 h to obtain a nickel ingot after homogenization annealing treatment; the nickel ingot after homogenization annealing treatment is hot forged at 1000°C (no ingot cracking occurs during the hot forging process) to obtain a nickel ingot to be processed.

[0068] (3) The nickel ingot to be processed in step (2) is hot rolled at 1000°C, and the deformation amount of each hot rolling is controlled to be 1 mm; after 20 times of hot rolling, the thickness of the plate is rolled to 1 mm to obtain a nickel plate.

[0069] (4) The nickel plate is subjected to the 15th hot drawing at 900°C to obtain a nickel wire with a diameter of 0.5 mm; the nickel wire is subjected to the 15th hot drawing at 900°C to obtain nickel fibers with a diameter of 12 μm (no wire breakage occurs during the hot drawing process).

[0070] (5) The nickel fibers in step (4) are woven into a nickel fiber cloth, and the nickel fiber cloth is placed in a 6 mol / L sodium hydroxide solution for ultrasonic activation treatment for 1.5 h. After taking out, washing and drying, an activated nickel fiber cloth is obtained.

[0071] The NiAl alloy fiber cloth, porous NiAl alloy fiber cloth prepared in Examples 1 to 3, the nickel fiber cloth in Comparative Example 5, and the activated nickel fiber cloth are subjected to a half-electrolytic cell test, and the obtained OER activity curve is visible Figure 6 .

[0072] From Figure 6 it can be seen that the OER activity of the nickel fiber cloth and the activated nickel fiber cloth in Comparative Example 5 basically does not change. The OER activity of the NiAl alloy fiber cloth in Examples 1 to 3 is very low; however, compared with the NiAl alloy fiber cloth, the OER activity of the porous NiAl alloy fiber cloth in Examples 1 to 3 is greatly improved, indicating that its catalytic activity is further improved.

[0073] Example 4 In this example, the porous nickel-based alloy fiber cloth is a porous NiMo20Al5 alloy fiber cloth, and the specific preparation method is as follows: (1) Metals nickel, molybdenum and aluminum with a purity of more than 99 wt% are added to a melting furnace according to a mass ratio of 75:20:5, and vacuum melting is carried out 4 times (where: the vacuum degree is 10 -1 Pa, the melting temperature is 1200°C, and the melting time for each time is 2 h). After melting, casting is carried out to obtain a nickel-molybdenum-aluminum alloy ingot.

[0074] (2) The nickel-molybdenum-aluminum alloy obtained in step (1) is subjected to homogenization annealing treatment at 1100 °C under a nitrogen atmosphere for 30 h to obtain a nickel-molybdenum-aluminum alloy ingot after homogenization annealing treatment; the nickel-molybdenum-aluminum alloy ingot after homogenization annealing treatment is hot forged at 1200 °C (no cracking of the ingot occurs during the hot forging process) to obtain a nickel-molybdenum-aluminum alloy ingot to be processed.

[0075] (3) The nickel-molybdenum-aluminum alloy ingot to be processed in step (2) is cold rolled (controlling the deformation amount of each cold rolling to be 1 mm), and after cold rolling, it is subjected to recrystallization annealing at 900 °C for 1.5 h; the cold rolling + recrystallization annealing process is cycled 5 times until the thickness of the sheet is 0.2 mm to obtain a nickel-molybdenum-aluminum alloy sheet (no cracking occurs in the sheet).

[0076] (4) The nickel-molybdenum-aluminum alloy sheet in step (2) is cold drawn, and after cold drawing, it is subjected to recrystallization annealing at 900 °C for 1.5 h. The cold drawing + recrystallization annealing process is cycled 6 times, and the diameter of the cold drawn wire is 0.3 mm to obtain a nickel-molybdenum-aluminum alloy wire; then the nickel-molybdenum-aluminum alloy wire is cold drawn, and after cold drawing, it is subjected to recrystallization annealing at 900 °C for 1.5 h. The cold drawing + recrystallization annealing process is cycled 4 times, and the diameter of the cold drawn fiber is 10 μm to obtain a nickel-molybdenum-aluminum alloy fiber.

[0077] (5) The nickel-molybdenum-aluminum alloy fibers in step (4) are woven into a NiMo20Al5 alloy fiber cloth, and the NiMo20Al5 alloy fiber cloth is placed in a 7 mol / L sodium hydroxide solution for ultrasonic activation treatment for 2 h. After taking it out, washing and drying, a porous NiMo20Al5 alloy fiber cloth is obtained.

[0078] Comparative Example 6 Steps (1) to (3) are basically the same as those in Example 4, except that: in step (3), the recrystallization annealing temperature is 600 °C, and during the cold rolling process, the sheet cracks and the subsequent drawing process cannot be carried out.

[0079] Comparative Example 7 Steps (1) to (3) are basically the same as those in Example 4, except that: in step (3), the recrystallization annealing temperature is 1100 °C, and during the cold rolling process, the nickel-molybdenum-aluminum alloy sheet cracks and the subsequent drawing process cannot be carried out.

[0080] Example 5 The porous nickel-based alloy fiber cloth prepared in this example is a porous NiMo20Al10 alloy fiber cloth, and the preparation method is basically the same as that in Example 4, except that: in step (1), the mass ratio of metallic nickel, metallic molybdenum and metallic aluminum is 70:20:10.

[0081] Example 6 Basically the same as Example 5, with the difference that: in step (2), homogenization annealing treatment is not carried out, and the nickel-molybdenum-aluminum alloy ingot is directly hot forged into shape; correspondingly, an unannealed porous NiMo20Al10 alloy fiber cloth is prepared.

[0082] Example 7 In this example, the prepared porous nickel-based alloy fiber cloth is a porous NiMo20Al15 alloy fiber cloth, and the preparation method is basically the same as that of Example 4, with the difference that: in step (1), the mass ratio of metallic nickel, metallic molybdenum and metallic aluminum is 65:20:15.

[0083] Perform SEM microscopic morphology observation on the fibers in the NiMo20Al15 alloy fiber cloth without alkali activation treatment and the fibers in the porous NiMoAl15 alloy fiber cloth in this example, and the results are as follows Figure 7 ; it can be seen that after alkali activation treatment, there are many fine pore structures on the surface of the fibers in the porous NiMoAl5 alloy fiber cloth, while the surface of the fibers in the NiMoAl5 alloy fiber cloth without alkali activation treatment is smooth and there are no micropore structures.

[0084] Example 8 Basically the same as Example 7, with the difference that: in step (2), homogenization annealing treatment is not carried out, and the nickel-molybdenum-aluminum alloy ingot is directly hot forged into shape; correspondingly, an unannealed porous NiMo20Al15 alloy fiber cloth is prepared.

[0085] Comparative Example 8 The nickel-based alloy fiber cloth prepared in this comparative example is an activated NiMo20 nickel-based alloy fiber cloth, and the preparation method is basically the same as that of Example 4, with the difference that: in step (1), the mass ratio of metallic nickel and metallic molybdenum is 80:20.

[0086] Comparative Example 9 This comparative example is basically the same as Comparative Example 8, with the difference that: in step (2), homogenization annealing treatment is not carried out, and the nickel-molybdenum alloy ingot is directly hot forged into shape; correspondingly, an unannealed NiMo20 alloy fiber cloth is prepared.

[0087] Comparative Example 10 Adopt a traditional nickel mesh electrode, and the specific preparation method is: obtain a Ni / Mo / Al three-metal mixed powder with nickel: molybdenum: aluminum = 65:20:15 (mass ratio) by physical methods, spray the metal mixed powder on a nickel mesh substrate by plasma spraying, and then soak and dissolve Al with KOH to obtain a nickel mesh plasma-sprayed NiMo porous electrode material (NiMo-plasma).

[0088] The NiMoAl alloy fiber cloths, porous NiMoAl alloy fiber cloths prepared in Example 4, Example 6 and Example 8, as well as the NiMo alloy fiber cloth and the activated NiMo alloy fiber cloth in Comparative Example 8 were used as catalytic electrodes for half - electrolytic cell tests, and the measured OER activity curves are shown Figure 8 .

[0089] It can be seen from Figure 8 that the OER catalytic activity of the activated NiMo alloy fiber cloth in Comparative Example 8 is slightly improved compared with the NiMo alloy fiber cloth. The OER catalytic activity of the porous NiMoAl alloy fiber cloths in Example 4, Example 6 and Example 8 is greatly improved compared with the NiMoAl alloy fiber cloths; among them, the OER catalytic activity of the porous NiMoAl15 alloy fiber cloth prepared in Example 8 is the best.

[0090] The NiMoAl alloy fiber cloths, porous NiMoAl alloy fiber cloths, unannealed porous NiMoAl alloy fiber cloths prepared in Examples 5 - 8, the NiMo alloy fiber cloth and the activated NiMo alloy fiber cloth in Comparative Example 8, and the unannealed NiMo alloy fiber cloth in Comparative Example 9 were subjected to half - cell tests; the measured HER activity curves are shown Figure 9 .

[0091] It can be seen from Figure 9 that the HER catalytic activity of the unannealed porous NiMoAl alloy fiber cloths in Example 6 and Example 8 is improved compared with the NiMoAl alloy fiber cloths in Example 5 and Example 7 respectively; however, compared with the porous NiMoAl alloy fiber cloths in Example 5 and Example 7 respectively, their HER catalytic activity decreases; this shows that the homogenization annealing treatment can further improve the catalytic activity of the porous NiMoAl alloy fiber cloths.

[0092] From the comparison results of the NiMo alloy fiber cloth, the activated NiMo alloy fiber cloth in Comparative Example 8 and the unannealed NiMo alloy fiber cloth in Comparative Example 9, the HER activity of the unannealed NiMo alloy fiber cloth in Comparative Example 9 is basically unchanged compared with the NiMo alloy fiber cloth in Comparative Example 8; the HER activity of the activated NiMo alloy fiber cloth in Comparative Example 8 is slightly improved compared with the NiMo alloy fiber cloth in Comparative Example 8.

[0093] The porous NiMoAl15 alloy fiber cloth in Example 7, the unannealed porous NiMoAl15 alloy fiber cloth in Example 8 and the NiMo - plasma in Comparative Example 10 were subjected to full - electrolytic cell tests, and the results are as Figure 10 shown.

[0094] It can be seen from Figure 10It can be seen that the catalytic activities of the porous NiMoAl15 alloy fiber cloth in Example 7 and the unannealed porous NiMoAl15 alloy fiber cloth in Example 8 are both superior to those of the NiMo-plasma electrode in Comparative Example 10, and the catalytic activity of the porous NiMoAl15 alloy fiber cloth in Example 7 is the best.

[0095] Example 9 In this example, the porous nickel-based alloy mesh is a porous NiFe20Al10 alloy mesh, and the specific preparation method is as follows: (1) Metals nickel, iron, and aluminum with a purity above 99 wt% are added to a melting furnace in a mass ratio of 80:10:10 and subjected to vacuum melting 4 times (where: the vacuum degree is 10 -1 Pa, the melting temperature is 1000 °C, and the melting time for each time is 1 h). After melting, casting is carried out to obtain a nickel-iron-aluminum alloy ingot.

[0096] (2) The nickel-iron-aluminum alloy ingot obtained in step (1) is subjected to homogenization annealing treatment at 1000 °C in a nitrogen atmosphere for 50 h to obtain a homogenization annealed nickel-iron-aluminum alloy ingot; the homogenization annealed nickel-iron-aluminum alloy ingot is hot forged at 800 °C (no cracking of the ingot occurs during the hot forging process) to obtain a nickel-iron-aluminum alloy ingot to be processed.

[0097] (3) The nickel-iron-aluminum alloy ingot to be processed in step (2) is hot rolled at 800 °C (no cracking of the plate occurs during the hot rolling process). The deformation amount of each hot rolling is controlled to be 1 mm. After 10 times of hot rolling, the thickness of the plate is rolled to 1.5 mm to obtain a nickel-iron-aluminum alloy plate.

[0098] (4) The nickel-iron-aluminum alloy plate in step (3) is hot drawn 10 times at 800 °C (no wire breakage occurs during the hot drawing process), and the wire diameter is drawn to 0.2 mm to obtain a nickel-iron-aluminum alloy wire.

[0099] (5) The nickel-iron-aluminum alloy wire in step (4) is woven into a NiFe20Al10 alloy mesh, and the alloy mesh is ultrasonically activated in a 6 mol / L sodium hydroxide solution for 1.5 h. After taking it out, cleaning and drying are carried out to obtain a porous NiFe10Al10 alloy mesh.

[0100] Example 10 In this example, the porous nickel-based alloy mesh is a porous NiMo15Al15 alloy mesh, and the specific preparation method is as follows: (1) Add metallic nickel, metallic molybdenum, and metallic aluminum with a purity above 99 wt% into a melting furnace according to a mass ratio of 70:15:15, and conduct melting 3 times in a nitrogen atmosphere (where the melting temperature is 1300 °C and the melting time for each time is 1 h). After melting, perform casting to obtain a nickel-molybdenum-aluminum alloy ingot.

[0101] (2) Conduct homogenization annealing treatment on the nickel-molybdenum-aluminum alloy ingot obtained in step (1) for 10 h in a nitrogen atmosphere at a temperature of 1300 °C to obtain a nickel-molybdenum-aluminum alloy ingot after homogenization annealing treatment; perform hot forging on the nickel-molybdenum-aluminum alloy ingot after homogenization annealing treatment at 1300 °C (no cracking of the ingot occurred during the hot forging process) to obtain a nickel-molybdenum-aluminum alloy ingot to be processed.

[0102] (3) Perform hot rolling on the nickel-molybdenum-aluminum alloy ingot to be processed in step (2) at 1300 °C (no cracking of the plate occurred during the hot rolling process), and control the deformation amount for each hot rolling to be 1 mm; after 10 times of hot rolling, the thickness of the rolled plate is 1 mm to obtain a nickel-molybdenum-aluminum alloy plate.

[0103] (4) Perform the 8th hot drawing on the nickel-molybdenum-aluminum alloy plate in step (3) at a temperature of 1000 °C (no wire breakage occurred during the hot drawing process), and draw it to a wire diameter of 0.4 mm to obtain a nickel-molybdenum-aluminum alloy wire.

[0104] (5) Weave the nickel-molybdenum-aluminum alloy wire in step (4) into a NiMo15Al15 alloy mesh, place the alloy mesh in a 6 mol / L potassium hydroxide solution for ultrasonic activation treatment for 3 h, take it out, clean, and dry it to obtain a porous NiMo15Al15 alloy mesh.

[0105] Example 11 In this example, the porous nickel-based alloy mesh is a porous NiFe20Al5 alloy mesh, and the specific preparation method is as follows: (1) Add metallic nickel, metallic iron, and metallic aluminum with a purity above 99 wt% into a melting furnace according to a mass ratio of 75:20:5, and conduct vacuum melting 5 times (where: the vacuum degree is 10 -1 Pa, the melting temperature is 1000 °C, and the melting time for each time is 3 h). After melting, perform casting to obtain a nickel-iron-aluminum alloy ingot.

[0106] (2) Conduct homogenization annealing treatment on the nickel-iron-aluminum alloy obtained in step (1) for 50 h in a nitrogen atmosphere at a temperature of 1000 °C to obtain a nickel-iron-aluminum alloy ingot after homogenization annealing treatment; perform hot forging on the nickel-iron-aluminum alloy ingot after homogenization annealing treatment at 800 °C (no cracking of the ingot occurred during the hot forging process) to obtain a nickel-iron-aluminum alloy ingot to be processed.

[0107] (3) Cold-roll the nickel-iron-aluminum alloy ingot to be processed in step (2), controlling the deformation amount of each cold rolling to be 1 mm; after cold rolling, perform recrystallization annealing at 1050 °C for 30 min; repeat the cold rolling + recrystallization annealing process 4 times, and the thickness of the rolled sheet is 2 mm; obtain a nickel-iron-aluminum alloy sheet (no cracking of the sheet occurs during the cold rolling process).

[0108] (4) Cold-draw the nickel-molybdenum-aluminum alloy sheet in step (2), and perform recrystallization annealing at 1050 °C for 15 min after cold drawing; repeat the cold drawing + recrystallization annealing process 4 times, and cold-draw to a wire diameter of 0.2 mm to obtain a nickel-iron-aluminum alloy wire (no fracture of the wire occurs during cold drawing).

[0109] (5) Weave the nickel-iron-aluminum alloy wire in step (4) into a NiFe20Al5 alloy mesh, place the NiFe20Al5 alloy mesh in a 10 mol / L sodium hydroxide solution for ultrasonic activation treatment for 30 min, take it out, wash and dry it to obtain a porous NiFe20Al5 alloy mesh.

[0110] Example 12 In this example, the porous nickel-based alloy mesh is a porous NiFe20Al15 alloy mesh, and the specific preparation method is as follows: (1) Add metallic nickel, metallic iron, and metallic aluminum with a purity of more than 99 wt% in a mass ratio of 75:10:15 to a melting furnace for vacuum melting 5 times (where: the vacuum degree is 10 -1 Pa, the melting temperature is 1100 °C, and the melting time for each time is 2 h), and perform casting after melting to obtain a nickel-iron-aluminum alloy ingot.

[0111] (2) Perform homogenization annealing treatment on the nickel-iron-aluminum alloy obtained in step (1) in a nitrogen atmosphere at a temperature of 1000 °C for 25 h to obtain a nickel-iron-aluminum alloy ingot after homogenization annealing treatment; perform hot forging on the nickel-iron-aluminum alloy ingot after homogenization annealing treatment at 1300 °C (no cracking of the ingot occurs during the hot forging process) to obtain a nickel-iron-aluminum alloy ingot to be processed.

[0112] (3) Cold-roll the nickel-iron-aluminum alloy ingot to be processed in step (2), controlling the deformation amount of each cold rolling to be 0.8 mm; after cold rolling, perform recrystallization annealing at 700 °C for 3 h; repeat the cold rolling + recrystallization annealing process 6 times, and the thickness of the rolled sheet is 2 mm to obtain a nickel-iron-aluminum alloy sheet (no cracking of the sheet occurs during the cold rolling process).

[0113] (4) Cold-draw the nickel-iron-aluminum alloy sheet in step (2), perform recrystallization annealing at 700 °C for 60 min after cold drawing, repeat the cold drawing + recrystallization annealing process 7 times, and cold-draw to a wire diameter of 0.3 mm to obtain a nickel-iron-aluminum alloy wire.

[0114] (5) Weave the nickel-iron-aluminum alloy wire in step (4) into a NiFe20Al15 alloy mesh, place the alloy mesh in a 6 mol / L sodium hydroxide solution for ultrasonic activation treatment for 3 h, take it out, clean it, and dry it to obtain a porous NiFe10Al15 alloy mesh (no wire breakage occurred during cold drawing).

[0115] The above embodiments are only for illustrating the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A preparation method of a porous nickel-based alloy mesh or fiber cloth, characterized in that, It includes the following steps: (1) Add the metal raw materials required for the nickel-based alloy into a melting furnace for melting. After melting, carry out casting to obtain a nickel-based alloy ingot; wherein: the nickel-based alloy contains at least aluminum; (2) Hot forge the nickel-based alloy ingot in step (1) to form a nickel-based alloy to be processed; wherein: the temperature of hot forging is 800 - 1300 °C; (3) Roll the nickel-based alloy to be processed in step (2) successively to obtain a nickel-based alloy sheet; draw the nickel-based alloy sheet to obtain a nickel-based alloy wire; The rolling is hot rolling, or cold rolling and recrystallization annealing; wherein: the temperature of hot rolling is 800 - 1300 °C; In cold rolling and recrystallization annealing, the temperature of recrystallization annealing is 700 - 1050 °C; (4) Weave the nickel-based alloy wire in step (3) into a nickel-based alloy mesh; or further draw the nickel-based alloy wire to obtain nickel-based alloy fibers, then weave the nickel alloy fibers into a nickel-based alloy fiber cloth; then activate the nickel-based alloy mesh or fiber cloth with an alkali solution to obtain a porous nickel-based alloy mesh or fiber cloth.

2. The preparation method of the porous nickel-based alloy mesh or fiber cloth according to claim 1, characterized in that, In step (1), the nickel-based alloy is one of nickel-aluminum alloy, nickel-molybdenum-aluminum alloy, and nickel-iron-aluminum alloy; wherein: in the nickel-aluminum alloy, the mass ratio of nickel to aluminum is (85 - 100):(1 - 20); in the nickel-molybdenum-aluminum alloy, the mass ratio of nickel, molybdenum, and aluminum is (45 - 84):(15 - 40):(1 - 20); in the nickel-iron-aluminum alloy, the mass ratio of nickel, iron, and aluminum is (35 - 79):(20 - 50):(1 - 20).

3. The preparation method of the porous nickel-based alloy mesh or fiber cloth according to claim 1 or 2, characterized in that, In step (1), the melting is carried out in a vacuum or an inert atmosphere, and the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; the melting temperature is 1000 - 1300 °C, and the number of melting times is 3 - 5 times.

4. The preparation method of the porous nickel-based alloy mesh or fiber cloth according to claim 1, characterized in that, In step (2), before hot forging the nickel-based alloy ingot, carry out homogenization annealing treatment first.

5. The preparation method of the porous nickel-based alloy mesh or fiber cloth according to claim 4, characterized in that, The temperature of the homogenization annealing treatment is 1000 - 1300 °C, and the time of the homogenization annealing treatment is 5 - 60 h.

6. The method for preparing the porous nickel-based alloy mesh or fiber cloth according to claim 1 or 2, characterized in that In step (3), carry out multiple rollings until the thickness of the sheet is 0.5 - 2 mm; in cold rolling and recrystallization annealing, the time of recrystallization annealing is 0.5 - 3 h.

7. The preparation method of the porous nickel-based alloy mesh or fiber cloth according to claim 1, characterized in that In step (3), carry out multiple drawings until the diameter of the nickel-based alloy wire is 0.1 - 0.5 mm.

8. The method for preparing the porous nickel-based alloy mesh or fiber cloth according to claim 1 or 7, characterized in that, In steps (3) and (4), the drawing is hot drawing, or cold drawing and recrystallization annealing; wherein: the temperature of hot drawing is 500 - 1000 °C; in cold drawing and recrystallization annealing, the temperature of recrystallization annealing is 700 - 1050 °C; the time of recrystallization annealing is 10 - 60 min.

9. The method for preparing the porous nickel-based alloy mesh or fiber cloth according to claim 1, wherein In step (4), draw the nickel-based alloy wire until the diameter of the nickel-based alloy fiber is 5 - 30 μm; the alkali solution is a 5 - 10 mol / L sodium hydroxide solution or potassium hydroxide solution; the activation treatment is to soak the nickel-based alloy mesh in the alkali solution and carry out ultrasonic treatment for 0.5 - 3 h.

10. A porous nickel-based alloy mesh or fiber cloth, characterized in that, Prepared by using the preparation method described in any one of claims 1 - 9.

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