Preparation method of porous metal film coated metal hydrogen storage material block
By tightly coating the surface of the hydrogen storage material block with a porous metal film, the volume expansion and pulverization problems of the hydrogen storage material block during the hydrogen absorption and desorption cycle are solved, and stable hydrogen transportation is achieved.
Patent Information
- Application Number
- CN202510978088.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-16
- Publication Date
- 2025-10-10
AI Technical Summary
The significant volume change of hydrogen storage material blocks due to phase change during the hydrogen absorption and desorption cycle leads to pulverization and poor heat and mass transfer, hindering the large-scale and long-distance transportation of hydrogen.
During the pressing and molding process of the hydrogen storage material powder, the porous metal film is tightly wrapped on the surface of the hydrogen storage material block through ultra-high pressing pressure, forming a good interface bonding force and inhibiting volume expansion and pulverization.
It effectively suppresses the pulverization of hydrogen storage material blocks, maintains good hydrogen absorption and desorption kinetics, and meets the needs of large-scale and long-distance transportation.
Smart Images
Figure CN120755350A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of metal hydrogen storage material block forming and preparation, and in particular relates to a method for preparing a porous metal film-coated metal hydrogen storage material block. Background Art
[0002] Metal hydrogen storage materials include magnesium-based, titanium-based, vanadium-based and rare earth-based hydrogen storage materials. Among them, magnesium is recognized as a very promising hydrogen storage alloy system. The theoretical mass hydrogen storage density of its hydride (MgH2) is as high as 7.6 wt% H2, and the energy density is as high as 9MJ / kg Mg. In addition, magnesium is abundant in nature and has the characteristics of low price and non-toxicity. However, its stable thermodynamic enthalpy value, slow kinetics and storage and transportation safety hazards limit its application. At present, a lot of research has been carried out on the improvement of its hydrogen storage thermodynamics and kinetics, and a series of Mg-based hydrogen storage alloys with better performance have been obtained. For example, the Mg-based hydrogen storage alloy developed by Shanghai Jiaotong University 90 Ni 10 The alloy can release hydrogen at 180°C, and the cycle stability is improved to 800 times. A ton-level solid-state hydrogen storage demonstration vehicle has been developed.
[0003] Compared to powdered hydrogen storage materials, blocks are more conducive to heat conduction and safer transportation, and they prevent powdered materials from clumping. However, during the hydrogen absorption and desorption cycles, the blocks undergo significant volume changes due to phase transitions. After multiple cycles, the pressed blocks undergo significant volume expansion and even pulverization. This pulverization hinders heat and mass transfer, significantly degrading the hydrogen absorption and desorption kinetics, and is a bottleneck hindering the large-scale, long-distance storage and transportation of hydrogen. Summary of the Invention
[0004] In order to solve the above problems, the present invention provides a novel preparation method of a porous metal film coated metal hydrogen storage material block. The method is to compact the metal hydrogen storage material powder while using ultra-high pressing pressure to tightly coat the porous metal film on the surface of the hydrogen storage material block, thereby solving the volume expansion and pulverization of the hydrogen storage material block caused by the phase change of the hydrogen storage material during the hydrogen absorption and desorption cycle, while maintaining the good hydrogen absorption and desorption kinetics of the metal hydrogen storage material block.
[0005] To achieve the above object, the technical solution adopted by the present invention is: A method for preparing a porous metal film-coated metal hydrogen storage material block includes one of the following two methods: Method 1: First lay a layer of porous metal film on the bottom and inner wall of the mold, then add metal hydrogen storage material powder, and then cover the surface of the powder with a layer of porous metal film, press into shape, and finally demold to obtain a porous metal film-coated metal hydrogen storage material block.
[0006] Method 2: First, the metal hydrogen storage material powder is pressed into a block, and then a layer of porous metal film is wrapped on the surface of the pressed block, and finally pressed into shape in a mold to obtain a porous metal film-coated metal hydrogen storage material block.
[0007] Furthermore, the metal hydrogen storage material powder includes but is not limited to powder of at least one of magnesium-based hydrogen storage material, titanium-based hydrogen storage material, vanadium-based hydrogen storage material and rare earth hydrogen storage material.
[0008] Furthermore, the porous metal film is a metal foam or a metal mesh. The metal foam includes, but is not limited to, at least one of nickel foam, copper foam, iron foam, aluminum foam, cobalt foam, zinc foam, titanium foam, silver foam, and zirconium foam; the metal mesh includes, but is not limited to, at least one of nickel mesh, copper mesh, iron mesh, aluminum mesh, cobalt mesh, zinc mesh, titanium mesh, silver mesh, and zirconium mesh. The porous metal film is made of a pure metal or an alloy.
[0009] Furthermore, the mesh size of the foam metal is between 100-1000 meshes, the mesh size of the metal mesh is between 10-2000 meshes, and the pore size of the porous metal film is smaller than the particle size of the metal hydrogen storage material powder.
[0010] Furthermore, the thickness of the porous metal film is 0.02-2 mm.
[0011] Furthermore, the compression molding pressure in both Method 1 and Method 2 is 50-1000 MPa. In porous metal film-coated metal hydrogen storage material blocks prepared at different compression pressures, the interfacial bonding strength between the metal film and the hydrogen storage material block varies, resulting in varying effectiveness in suppressing block pulverization. Higher pressures increase interfacial bonding strength, which is more effective in suppressing powder pulverization.
[0012] Compared with the prior art, the present invention has the following beneficial effects: The present invention utilizes a high-pressure pressing process to evenly and tightly coat the porous metal film on the surface of the metal hydrogen storage material block, thereby forming a good interface bonding force between the porous metal film and the metal hydrogen storage material block, generating a strong restraining force on the surface of the metal hydrogen storage material block, effectively suppressing the volume expansion caused by hydrogen absorption and desorption, solving the problem of pulverization of the block material, and meeting the needs of the metal hydrogen storage material block in the large-scale and long-distance transportation of hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS
[0013] Figure 1 Schematic diagram of one-step molding preparation of a porous metal film-coated metal hydrogen storage material block provided by the present invention; Figure 2 Schematic diagram of the two-step molding preparation of the porous metal film-coated metal hydrogen storage material block provided by the present invention; Figure 3 SEM characterization of the porous nickel foam film coated magnesium alloy hydrogen storage block obtained in Example 1; Figure 4 SEM characterization of the porous copper mesh film coated magnesium alloy hydrogen storage block obtained in Example 2; Figure 5 SEM characterization of the porous stainless steel mesh film coated magnesium alloy hydrogen storage block obtained in Example 3; Figure 6 SEM characterization of the porous nickel mesh film coated magnesium alloy hydrogen storage block obtained in Example 4; Figure 7 SEM characterization of the porous aluminum mesh film coated magnesium alloy hydrogen storage block obtained in Example 5. DETAILED DESCRIPTION
[0014] The technical solutions of the present application are described in further detail below with reference to the accompanying drawings and examples.
[0015] The present application provides two preparation methods of porous metal film coated metal hydrogen storage material block, as shown in Figure 1 and Figure 2 .
[0016] As shown in Figure 1 , the first preparation method of the porous metal film coated metal hydrogen storage material block disclosed by the present application is one-step forming method, comprising the following steps: Step 1, select a porous metal film with a thickness of 0.02-2mm, according to the size of the inner wall of the mold, cut the porous metal film with appropriate size, and paste it on the inner wall and lower surface of the mold.
[0017]
[0017] Step 2, put the metal hydrogen storage material powder into the mold described in step 1 in the glove box, then cover a layer of cut porous metal film with appropriate size on the surface of the powder, and press form under high pressure (forming pressure is 50-1000MPa), finally demold to obtain the porous metal film coated metal hydrogen storage material block.
[0018] As shown in Figure 2 , the second preparation method of the porous metal coated metal hydrogen storage material block disclosed by the present application is two-step forming method, comprising the following steps: Step 1, put the metal hydrogen storage material powder into the mold in the glove box, and press form by high pressure (forming pressure is 50-1000MPa) to obtain the metal hydrogen storage material block.
[0019] Step 2, select a porous metal film with a thickness of 0.02-2mm, according to the size of the metal hydrogen storage material block, cut the porous metal film with appropriate size, and wrap it on the surface of the metal hydrogen storage material block by hand.
[0020] Step 3: Place the metal hydrogen storage material block with the surface wrapped with a porous metal film into a mold in a glove box, press it into shape under high pressure (molding pressure is 50-1000 MPa), and finally demold it to obtain the porous metal film-coated metal hydrogen storage material block.
[0021] In both of the aforementioned methods, the porous metal film comprises one of a metal foam (e.g., at least one of nickel foam, copper foam, iron foam, aluminum foam, cobalt foam, zinc foam, titanium foam, silver foam, zirconium foam, etc., with a mesh size between 100 and 1000 mesh) and a metal mesh (e.g., at least one of nickel mesh, copper mesh, iron mesh, aluminum mesh, cobalt mesh, zinc mesh, titanium mesh, silver mesh, zirconium mesh, etc., with a mesh size between 10 and 2000 mesh). The porous metal film is made of pure metal or various alloys.
[0022] The cross-sectional shape of the mold can be set as needed, including but not limited to circle, semicircle, quarter circle, square, diamond, etc. The mold size is between 5mm-150mm.
[0023] Example 1 This embodiment includes the following steps: Step 1. Select nickel foam with a thickness of 0.25mm and a mesh size of 150 mesh. According to the mold size of 10mm diameter, cut two 10mm diameter nickel foam discs and a 31.4mm long and 6mm wide rectangular foam copper sheet. Then stick the 10mm nickel foam disc to the bottom of the mold and the 31.4mm long and 6mm wide rectangular nickel foam sheet to the inner wall.
[0024] Step 2: In a glove box, place the magnesium alloy (Mg92Ni5Y2Nd1) hydrogen storage material powder into the mold with nickel foam in step 1, then cover the surface of the magnesium alloy hydrogen storage material powder with a cut 10 mm diameter nickel foam disc, press into shape at a molding pressure of 200 MPa, and finally demold to obtain a nickel foam-coated magnesium alloy hydrogen storage material block.
[0025] The SEM characterization of the porous nickel foam film-coated magnesium alloy hydrogen storage block obtained in this example is as follows Figure 3 As shown in the figure, after high-pressure pressing, there are a large number of irregular pores at the micron level on the surface of the block.
[0026] Example 2 This embodiment includes the following steps: Step 1. Select a copper mesh with a thickness of 0.25mm and a mesh size of 100. According to the mold size of 10mm diameter, cut two 10mm diameter copper mesh discs and a 31.4mm long and 6mm wide rectangular copper mesh. Then stick the 10mm copper mesh disc to the bottom of the mold and the 31.4mm long and 6mm wide rectangular copper mesh to the inner wall.
[0027] Step 2: Place the magnesium alloy (Mg92Ni5Y2Nd1) hydrogen storage material powder into the copper mesh mold in step 1 in a glove box, then cover the surface of the magnesium alloy hydrogen storage material powder with a cut copper mesh disc with a diameter of 10 mm, press into shape at a molding pressure of 200 MPa, and finally demold to obtain a copper mesh-coated alloy-based hydrogen storage material block.
[0028] The SEM characterization of the porous copper mesh film-coated magnesium alloy hydrogen storage block obtained in this example is as follows Figure 4 As shown in the figure, after high-pressure pressing, the copper mesh wires are deformed, and 200 μm regular grid-like pores are evenly distributed on the surface of the block.
[0029] Example 3 This embodiment includes the following steps: Step 1: Place magnesium alloy (Mg92Ni5Y2Nd1) hydrogen storage material powder into a mold with a diameter of 10 mm in a glove box, press it under a molding pressure of 200 MPa, and obtain a magnesium alloy hydrogen storage material block with a diameter of 10 mm and a height of 5 mm by demolding.
[0030] Step 2. Select a stainless steel mesh with a thickness of 0.25 mm and a mesh size of 200. According to the size of the magnesium alloy hydrogen storage material block with a diameter of 10 mm and a height of 5 mm, cut two 10 mm diameter stainless steel mesh discs and a 31.4 mm long and 6 mm wide rectangular stainless steel mesh, and manually wrap them on the surface of the magnesium alloy hydrogen storage material block.
[0031] Step 3: Place the magnesium alloy hydrogen storage material block with the surface wrapped with stainless steel mesh obtained in step 2 into a mold in a glove box, press it into shape at a pressure of 200 MPa, and finally demold it to obtain the stainless steel mesh-coated magnesium alloy hydrogen storage material block.
[0032] The SEM characterization of the porous stainless steel mesh film-coated magnesium alloy hydrogen storage block obtained in this embodiment is as follows: Figure 5 As shown in the figure, after high-pressure pressing, 100 μm regular grid-like pores are evenly distributed on the surface of the block.
[0033] Example 4 This embodiment includes the following steps: Step 1: Place magnesium alloy (Mg92Ni5Y2Nd1) hydrogen storage material powder into a mold with a diameter of 10 mm in a glove box, press it under a molding pressure of 200 MPa, and obtain a magnesium alloy hydrogen storage material block with a diameter of 10 mm and a height of 5 mm by demolding.
[0034] Step 2: Select a nickel mesh with a thickness of 0.25 mm and a mesh size of 100. According to the size of the magnesium alloy hydrogen storage material block with a diameter of 10 mm and a height of 5 mm, cut two nickel mesh discs with a diameter of 10 mm and a rectangular nickel mesh with a length of 31.4 mm and a width of 6 mm, and manually wrap them on the surface of the magnesium alloy hydrogen storage material block.
[0035] Step 3: Place the magnesium alloy hydrogen storage material block with the surface coated with nickel mesh obtained in step 2 into a mold in a glove box, press it into shape at a pressure of 200 MPa, and finally demold it to obtain the nickel mesh-coated magnesium alloy hydrogen storage material block.
[0036] The SEM characterization of the porous nickel foam film-coated magnesium alloy hydrogen storage block obtained in this example is as follows Figure 6 As shown in the figure, after high-pressure pressing, 200 μm regular grid-like pores are evenly distributed on the surface of the block.
[0037] Example 5 This embodiment includes the following steps: Step 1: Place magnesium alloy (Mg92Ni5Y2Nd1) hydrogen storage material powder into a mold with a diameter of 10 mm in a glove box, press it under a molding pressure of 200 MPa, and obtain a magnesium alloy hydrogen storage material block with a diameter of 10 mm and a height of 5 mm by demolding.
[0038] Step 2: Select an aluminum mesh with a thickness of 0.25 mm and a mesh size of 100 mesh. According to the size of the magnesium alloy hydrogen storage material block with a diameter of 10 mm and a height of 5 mm, cut two 10 mm diameter aluminum mesh discs and a 31.4 mm long and 6 mm wide rectangular aluminum mesh, and manually wrap them on the surface of the magnesium alloy hydrogen storage material block.
[0039] Step 3: Place the magnesium alloy hydrogen storage material block with the surface wrapped with aluminum mesh obtained in step 2 into a mold in a glove box, press it into shape at a pressure of 200 MPa, and finally demold it to obtain the aluminum mesh-coated magnesium alloy hydrogen storage material block.
[0040] The SEM characterization of the porous nickel foam film-coated magnesium alloy hydrogen storage block obtained in this embodiment is as follows: Figure 7 As shown in the figure, after high-pressure pressing, the aluminum mesh wires are severely deformed, but there are still 200μm irregular grid-like pores on the surface of the block.
[0041] The above description is merely an exemplary embodiment of the present invention, and while the description is relatively specific and detailed, it should not be construed as limiting the scope of the patent. It should be noted that those skilled in the art may make various improvements and equivalent substitutions without departing from the principles of the present invention, and such improvements and substitutions should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a porous metal film-coated metal hydrogen storage material block, characterized in that: This includes one of the following two methods: Method 1: First, lay a layer of porous metal film on the bottom and inner wall of the mold, then add metal hydrogen storage material powder, and then cover the surface of the powder with a layer of porous metal film, press into shape, and finally demold to obtain a porous metal film-coated metal hydrogen storage material block; Method 2: First, the metal hydrogen storage material powder is pressed into a block, and then a layer of porous metal film is wrapped on the surface of the pressed block, and finally pressed into shape in a mold to obtain a porous metal film-coated metal hydrogen storage material block.
2. The method for preparing a porous metal film-coated metal hydrogen storage material block according to claim 1, characterized in that: The metal hydrogen storage material powder is powder of at least one of magnesium-based hydrogen storage material, titanium-based hydrogen storage material, vanadium-based hydrogen storage material and rare earth hydrogen storage material.
3. The method for preparing a porous metal film-coated metal hydrogen storage material block according to claim 1, characterized in that: The porous metal film is foam metal or metal mesh.
4. The method for preparing a porous metal film-coated metal hydrogen storage material block according to claim 3, characterized in that: The foam metal is at least one of foam nickel, foam copper, foam iron, foam aluminum, foam cobalt, foam zinc, foam titanium, foam silver, and foam zirconium; the metal mesh is at least one of nickel mesh, copper mesh, iron mesh, aluminum mesh, cobalt mesh, zinc mesh, titanium mesh, silver mesh, and zirconium mesh.
5. The method for preparing a porous metal film-coated metal hydrogen storage material block according to claim 3 or 4, characterized in that: The mesh number of the foam metal is between 100-1000 meshes, and the mesh number of the metal mesh is between 10-2000 meshes.
6. The method for preparing a porous metal film-coated metal hydrogen storage material block according to claim 5, characterized in that: The pore size of the porous metal film is smaller than the particle size of the metal hydrogen storage material powder.
7. The method for preparing a porous metal film-coated metal hydrogen storage material block according to claim 1, characterized in that: The thickness of the porous metal film is 0.02-2 mm.
8. The method for preparing a porous metal film-coated metal hydrogen storage material block according to claim 1, characterized in that: The pressure of the compression molding in both method 1 and method 2 is 50-1000 MPa.