Solid hydrogen storage device and manufacturing method thereof

Abstract

The solid hydrogen storage device comprises a shell and a cavity defined by the shell, the interior of the cavity is divided by partition plates to form a plurality of independent spaces, the cross sections of the independent spaces are arranged in a cellular array mode, one end of each independent space is fixedly connected with the bottom face of the shell, the other end of each independent space is open, and the independent spaces are filled with hydrogen storage material powder. A layer of nickel filter screen is arranged at the opening end of the independent space, an opening hole is formed in the shell close to the nickel filter screen, and an internal thread used for being connected with a valve is arranged on the opening hole. According to the solid hydrogen storage device, structure and function integrated Al-5Ce-2Ni-0.5 Zr alloy powder with high heat conductivity, high toughness and high creep resistance serves as a raw material, the solid hydrogen storage device is integrally formed through the selective laser melting technology, the weight percentage of the hydrogen storage material is increased to 95% or above from 70%-80% of a traditional solid hydrogen storage device, the hydrogen storage amount is increased by 15% or above, the highest pressure bearing capacity reaches 15 MPa, and the hydrogen storage effect is good. The hydrogen storage device has the remarkable advantages and characteristics of safety, high efficiency, high production efficiency and low cost.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen energy storage, and in particular relates to a solid-state hydrogen storage device and a manufacturing method thereof. Background Art

[0002] As an energy source, hydrogen has outstanding advantages. First, hydrogen is widely distributed, accounting for about 81.75% of the total amount of matter in the universe, and is abundant in the water bodies of the earth; second, the calorific value of hydrogen is high, which is 3 times that of gasoline, 3.9 times that of alcohol, and 4.5 times that of coke; third, the product of hydrogen combustion is only one - water. Today, when advocating green development, the development and utilization of hydrogen energy has received unprecedented attention. In recent years, my country's hydrogen energy technology and industry have developed rapidly. As a clean energy, hydrogen energy has injected strong impetus into economic and social development.

[0003] In the hydrogen energy industry chain, the storage link is particularly critical, as it connects the upstream hydrogen production and the downstream hydrogen use. At present, there are three main ways to store hydrogen: high-pressure gas, liquid and solid. Among them, solid-state hydrogen storage technology is considered to be the most promising hydrogen storage technology due to its high volume hydrogen storage density, excellent safety and long-term storage capacity. The solid-state hydrogen storage process involves the classic "three transfers and one reaction" theory in the traditional chemical industry, that is, it is based on the kinetics of hydrogenation and dehydrogenation reactions, and is based on momentum transfer, heat transfer and mass transfer. At the same time, it has the new "three transfers and one reaction" typical characteristics of electron transfer, proton transfer, molecular transfer and catalytic reaction. The design ideas and manufacturing processes of existing solid-state hydrogen storage devices, whether water-jacket type, spiral tube type, rib plate type, multi-tube bundle fin type or microchannel type, etc., all follow the traditional "three transmission and one reverse" design theory and method of chemical tank devices. The hydrogen storage efficiency is low, which weakens the advantage of solid-state hydrogen storage with high hydrogen storage density. More importantly, the thermal effect during the hydrogen absorption and desorption process can easily cause deformation or even cracking of the hydrogen storage device, resulting in premature scrapping of the hydrogen storage device, or even hydrogen leakage due to damage to the device, posing a major safety hazard. Summary of the invention

[0004] The object of the present invention is to provide a solid-state hydrogen storage device and a manufacturing method thereof to achieve more efficient and safe hydrogen storage.

[0005] In order to achieve the above-mentioned purpose, the following technical solution is provided.

[0006] A solid-state hydrogen storage device comprises a shell, the shell is surrounded by a cavity, the cavity is divided by a partition to form a plurality of independent spaces, the cross-sections of the plurality of independent spaces are arranged in a cellular array, one end of each independent space is fixedly connected to the bottom surface of the shell, and the other end is open, the independent space is filled with hydrogen storage material powder, a layer of nickel filter is arranged at the open end of the independent space, an opening is arranged in the shell near the nickel filter, and the opening is provided with an internal thread for connecting a valve.

[0007] The cellular array is a cellular, honeycomb, or leaf-shaped array; the hydrogen storage material is any one of rare earth AB5, titanium AB2, titanium-vanadium solid solution, magnesium-based hydrogen storage alloy, coordinated hydride, and metal nitrogen hydride, or a composite material formed by a combination of the above-mentioned multiple hydrogen storage materials; and the nickel filter mesh number is 400 to 600 meshes.

[0008] The appearance of the shell includes: a cube, a column, a cone, a sphere, an ellipsoid, or other ergonomic shapes.

[0009] Correspondingly, a method for manufacturing a solid-state hydrogen storage device is also disclosed, which comprises the following steps in sequence: Step S1: Prepare aluminum alloy powder with a size range of 40 μm to 65 μm, and the components in the powder are 100% by weight. The proportion is: Ce: 5%, Ni: 2%, Zr: 0.5%, and the balance is Al, recorded as Al-5Ce-2Ni-0.5Zr; Step S2: Establish a three-dimensional data model of the solid-state hydrogen storage device, import the slice file of the three-dimensional data model into the laser selective melting equipment, load Al-5Ce-2Ni-0.5Zr alloy powder, and adjust the process parameters as follows: laser power is 200-400W, scanning speed is 800-1500mm / s, scanning spacing is 20-40μm, slice layer thickness is 20-30μm, and spot diameter is 30-50μm; Step S3: Under an argon protective atmosphere, turn on the laser to perform laser selective melting layer by layer along the Z-axis direction until the cellular array structure is formed, take out the structure from the laser selective melting equipment, load the hydrogen storage material into the cellular array, and cover it with a nickel filter; the mesh size of the nickel filter is smaller than the particle size of the hydrogen storage material powder and the aluminum alloy powder.

[0010] Step S4: moving the structure obtained in S3 into a laser selective melting device, refilling the Al-5Ce-2Ni-0.5Zr alloy powder, turning on the laser to perform laser selective melting molding layer by layer along the Z-axis direction until the shell and the internal thread are formed; Step S5: Take the structure obtained in S4 out of the laser selective melting equipment, fix it on the operating table, use ultrasonic vibration to eliminate the internal stress of the structure, and at the same time cooperate with compressed air flow and external blowing and suction of an industrial vacuum cleaner to completely empty the aluminum alloy powder in the shell.

[0011] Step S6: Install a valve into the internal thread of the structure obtained in S5 to obtain the solid-state hydrogen storage device.

[0012] Furthermore, in step S3, the wall thickness of the cellular array structure is 100-200 μm.

[0013] Furthermore, in step S4, the thickness of the shell is 1 to 2 mm.

[0014] Furthermore, in step S5, the rated voltage of the ultrasonic generator is 220V, and the single-channel output power is 300W, the operating frequency range is 20-40KHz, and the ultrasonic vibration time is 60-120min.

[0015] Compared with the prior art, the present invention, on the basis of breaking the traditional "three transfers and one reaction" solid-state hydrogen storage device design concept and manufacturing method, proposes a new "three transfers and one reaction" solid-state hydrogen storage device design concept and laser selective melting manufacturing method based on electron transfer, proton transfer, molecular transfer and catalytic reaction, and uses Al-5Ce-2Ni-0.5Zr alloy with high thermal conductivity, high toughness and high creep resistance to manufacture solid-state hydrogen storage device. The high thermal conductivity with a thermal conductivity of more than 195W / m•k comes from the extremely low content of alloying elements Ce, Ni and Zr in aluminum. The low solid solubility can ensure that the high thermal conductivity of the aluminum matrix will not be greatly reduced, so that the heat generated in the hydrogen storage process can be quickly discharged. At the same time, a large number of second phases formed by Al, Ce, Ni, and Zr produce dislocation motion impedance during creep deformation, which improves the mechanical properties of the alloy while further improving the thermal conductivity of the alloy. In addition, Ce, Ni, and Zr are all active catalytic components of hydrogen, which can effectively activate hydrogen molecules to dissociate into hydrogen atoms, accelerate the electron transfer, proton transfer, and molecular transfer rate in the hydrogen storage process, and improve the hydrogen storage kinetics. The inner cavity of the hydrogen storage device is transformed into a honeycomb unit array composed of intersecting nodes and shells, and the near-net-shape laser selective melting technology is used to realize the "arbitrary" manufacturing of the internal structure and appearance of the solid-state hydrogen storage device. It is especially suitable for the appearance requirements under complex working conditions, such as miniaturized solid-state hydrogen storage devices that meet the ergonomic characteristics of the shoulder and back curved surfaces of individual soldiers, lightweight mobile special-shaped hydrogen storage devices such as vehicle-mounted, ship-mounted, and airborne. The weight percentage of hydrogen storage materials is increased from 70% to 80% of traditional solid-state hydrogen storage devices to more than 95%, and the hydrogen storage capacity is increased by more than 15%; and the device has multiple independent inner cavity spaces The pressure-bearing capacity comes from the inner cavity cell array and high-strength shell, instead of the traditional hydrogen storage device simply relying on the shell strength of 10 to 20 mm thickness. The inner cavity cell array feature effectively shares the internal pressure borne by the shell, with a maximum pressure bearing capacity of 15MPa, while the internal pressure of the solid hydrogen storage bottle under actual working conditions does not exceed 5MPa, avoiding the safety hazards of deformation, cracking and hydrogen leakage of the hydrogen storage device. Under the same volume and hydrogen storage capacity, the structural weight is only 20% to 30% of the traditional solid hydrogen storage device structure, and the cost of mass production is only 50% of the traditional solid hydrogen storage device structure. Compared with the modular honeycomb structure, the present invention adopts the laser selective melting process to manufacture the shell and the inner cavity cell array structure, which can realize the diversification of the shell shape, the internal partition can be thinner, the molded product is lighter, and the material is saved. It is suitable for manufacturing miniaturized solid hydrogen storage devices and can realize the large-scale solid hydrogen storage devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is a structural schematic diagram of a solid-state hydrogen storage device provided in an embodiment; Figure 2 For the embodiment Figure 1Schematic diagram of the cross-sectional structure of the AA section line in FIG. Figure 3 This is a scanning electron microscope morphology of the Al-5Ce-2Ni-0.5Zr powder in the embodiment; In the figure, the shell 1; the valve 2; the internal thread 3; the nickel filter 4; the hydrogen storage material powder 5; and the partition 6. DETAILED DESCRIPTION

[0017] In order to better understand the present invention, the technical solutions in the embodiments of the present invention are described in detail below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] As attached Figure 1 As shown, in one embodiment of the present invention, the solid-state hydrogen storage device includes a shell 1, the shell surrounds a cavity, the cavity is divided by a partition 6 to form a plurality of independent spaces, and the cross-sections of the plurality of independent spaces are arranged in a honeycomb array (see FIG. Figure 2 As shown in the figure, one end of each independent space is fixedly connected to the bottom surface of the shell, and the other end is open. The independent space is filled with hydrogen storage material powder 5. A layer of nickel filter 4 is provided at the open end of the independent space. The shell near the nickel filter is provided with an opening, and the opening is provided with an internal thread 3 for connecting the valve 2. The hydrogen storage material is titanium AB2 material with a particle size of 56 to 78 μm; the nickel filter mesh number is 400 to 600 meshes, and the mesh size is smaller than the hydrogen storage material powder and aluminum alloy powder particles (attached Figure 3 The shell has a rounded rectangular appearance. The laser selective melting equipment is a German EOS M290 industrial-grade 3D metal printer, with a maximum product size of 2500x1300x2190mm and a maximum scanning speed of 7000mm / s.

[0019] In this technical solution, the shape can be designed according to the requirements of the use environment, etc. The hydrogen storage device in the present invention is not limited to the shape shown in the figure, but can be designed into any other special shape, which is convenient for installation and use in actual use and improves space utilization. In view of this structural feature, the present invention adopts a laser selective melting process to process and manufacture the complex inner cavity structure of the present invention, but the present invention is not limited to this manufacturing method. Other technologies such as plasma beam and electron beam selective melting technology can also be used, but they are less efficient and more costly than the laser selective melting manufacturing method, which is not conducive to large-scale production.

[0020] An embodiment of a method for manufacturing a solid-state hydrogen storage device of the present invention comprises the following steps in sequence: Step S1: screening the selected aluminum alloy powder to select aluminum alloy powder with a size range of 40 μm to 65 μm, wherein the chemical formula of each component in the powder is Al-5Ce-2Ni-0.5Zr by weight percentage; Step S2: Establish a three-dimensional data model of the solid-state hydrogen storage device, import the slice file of the three-dimensional data model into the laser selective melting equipment, load Al-5Ce-2Ni-0.5Zr alloy powder, and adjust the process parameters as follows: laser power is 200-400W, scanning speed is 800-1500mm / s, scanning spacing is 20-40μm, slice layer thickness is 20-30μm, and spot diameter is 30-50μm; Step S3: under an argon protective atmosphere, turning on the laser to perform laser selective melting layer by layer along the Z-axis direction until the honeycomb unit structure is formed, taking the structure out of the laser selective melting device, filling the hydrogen storage material into the honeycomb unit, and covering it with a nickel filter, wherein the mesh size of the nickel filter is smaller than the particle size of the hydrogen storage material powder and the aluminum alloy powder; the wall thickness of the honeycomb unit is 100-200 μm; Step S4: moving the structure obtained in S3 into a laser selective melting device, refilling the Al-5Ce-2Ni-0.5Zr alloy powder, turning on the laser to perform laser selective melting layer by layer along the Z-axis direction until the shell and the internal thread are formed, and the thickness of the shell is 1 to 2 mm; Step S5: Take the structure obtained in S4 out of the laser selective melting equipment, fix it on the operating table and use ultrasonic vibration to eliminate the internal stress of the structure. The rated voltage of the ultrasonic generator is 220V, the single-channel output power is 300W, the operating frequency range is 20-40KHz, and the ultrasonic vibration time is 60-120min. At the same time, the compressed air flow and the external blowing and suction of the industrial vacuum cleaner are used to completely empty the aluminum alloy powder in the shell.

[0021] Step S6: Install a valve into the opening of the structure obtained in S5 to obtain the solid-state hydrogen storage device.

[0022] Compared with the prior art, the weight percentage of hydrogen storage materials in the solid-state hydrogen storage device of the present invention is increased from 70% to 80% of traditional solid-state hydrogen storage devices to more than 95%, and the hydrogen storage capacity is increased by more than 15%; and the device has a multi-independent space structure with a complex inner cavity, and the pressure-bearing capacity comes from the inner cavity honeycomb unit array and the high-strength shell, rather than the traditional hydrogen storage device that simply relies on the shell strength of 5 to 20 mm thickness. The inner cavity honeycomb unit array feature effectively shares the internal pressure borne by the shell, and the maximum pressure-bearing capacity reaches 15 MPa, while the pressure in the solid-state hydrogen storage bottle under actual working conditions does not exceed 5 MPa, avoiding the safety hazards of deformation, cracking and hydrogen leakage of the hydrogen storage device. Under the same volume and hydrogen storage capacity, the structural weight is only 20% to 30% of that of the traditional solid-state hydrogen storage device structure, and the cost of mass production is only 50% of that of the traditional solid-state hydrogen storage device structure.

Claims

1. A solid-state hydrogen storage device, characterized in that: The hydrogen storage device includes a shell, which is surrounded by a cavity. The cavity is divided by a partition to form a plurality of independent spaces. The cross-sections of the plurality of independent spaces are arranged in a cellular array. One end of each independent space is fixedly connected to the bottom surface of the shell, and the other end is open. The independent space is filled with hydrogen storage material powder. A layer of nickel filter is provided at the open end of the independent space. An opening is provided in the shell near the nickel filter, and an internal thread for connecting a valve is provided on the opening.

2. The solid-state hydrogen storage device according to claim 1, characterized in that: The cellular array is one of a cellular, honeycomb, and leaf-shaped array; the hydrogen storage material is any one of rare earth AB5, titanium AB2, titanium-vanadium solid solution, magnesium-based hydrogen storage alloy, coordinated hydride, metal nitrogen hydride, or a composite material formed by a combination of the above-mentioned multiple hydrogen storage materials.

3. A method for manufacturing a solid-state hydrogen storage device as claimed in claim 1 or 2, characterized in that: The steps include: Step S1: preparing aluminum alloy powder with a size range of 40 μm to 65 μm, wherein the components in the powder are as follows by weight percentage: Ce: 5%, Ni: 2%, Zr: 0.5%, and the balance is Al, recorded as Al-5Ce-2Ni-0.5Zr; Step S2: Establish a three-dimensional data model of the solid-state hydrogen storage device, import the slice file of the three-dimensional data model into the laser selective melting equipment, load Al-5Ce-2Ni-0.5Zr alloy powder, and adjust the process parameters as follows: laser power is 200-400W, scanning speed is 800-1500mm / s, scanning spacing is 20-40μm, slice layer thickness is 20-30μm, and spot diameter is 30-50μm; Step S3: under an argon protective atmosphere, turning on the laser to perform laser selective melting layer by layer along the Z-axis direction until the cellular array structure is formed, taking the structure out of the laser selective melting device, loading the hydrogen storage material powder into the cellular array, and covering it with a nickel filter; the mesh size of the nickel filter is smaller than the particle size of the hydrogen storage material powder and the aluminum alloy powder; Step S4: moving the structure obtained in S3 into a laser selective melting device, refilling the Al-5Ce-2Ni-0.5Zr alloy powder, turning on the laser to perform laser selective melting molding layer by layer along the Z-axis direction until the shell and the internal thread are formed; Step S5: taking out the structure obtained in S4 from the laser selective melting device, fixing it on an operating table, and eliminating the internal stress of the structure by ultrasonic vibration, while simultaneously using compressed air flow and external blowing and suction of an industrial vacuum cleaner to completely empty the aluminum alloy powder in the shell; Step S6: Install a valve into the internal thread of the structure obtained in S5 to obtain the solid-state hydrogen storage device.

4. The method for manufacturing a solid-state hydrogen storage device according to claim 3, characterized in that: In the step S3, the wall thickness of the cellular array structure is 100-200 μm.

5. The method for manufacturing a solid-state hydrogen storage device according to claim 3, characterized in that: In step S4, the thickness of the shell is 1 to 2 mm.

6. The method for manufacturing a solid-state hydrogen storage device according to claim 3, characterized in that: In step S5, the rated voltage of the ultrasonic generating device is 220V, the single-channel output power is 300W, the operating frequency range is 20-40KHz, and the ultrasonic vibration time is 60-120min.

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