Hydrogen storage module based on 3D printing technology and preparation method and hydrogen charging and discharging method thereof

Abstract

The invention discloses a hydrogen storage module based on a 3D printing technology, a preparation method of the hydrogen storage module and a hydrogen charging and discharging method. The hydrogen storage module is mainly a product obtained by sintering a hydrogen storage module blank at high temperature, the hydrogen storage module blank is generated by 3D printing of a mixture of hollow borosilicate glass microspheres and a binder, a base material of the hydrogen storage module is the hollow borosilicate glass microspheres, the hydrogen storage module is of a porous micro-channel structure, a micro-channel penetrates through all symmetrical faces of the hydrogen storage module, the pore volume of the module is 30-50 vol%, and the average pore size is 0.5-2 cm. The hydrogen charging and discharging method of the hydrogen storage module comprises the steps that the hydrogen storage module is assembled and then fixed to a partition plate in the hydrogen storage container, and the hydrogen charging process is completed by controlling the temperature of compressed hydrogen to range from 150 DEG C to 400 DEG C and the pressure to range from 5 MPa to 100 MPa; during hydrogen desorption, the hydrogen storage container is pumped to negative pressure, and then the temperature is gradually increased to enable the hydrogen storage module to desorb hydrogen. The hydrogen filling rate and efficiency can be increased, rapid hydrogen filling and discharging are achieved, the device can flexibly adapt to the shape of a container, and the high volume ratio is achieved.

Description

Technical Field

[0001] This invention relates to the field of hydrogen storage materials technology, specifically to a hydrogen storage module based on 3D printing technology, its preparation method, and its hydrogen filling and discharging method. Background Technology

[0002] Hydrogen energy is considered to play a vital role in future energy utilization and sustainable development due to its advantages such as high energy density, cleanliness, environmental friendliness, renewability, convenient storage and transportation, and diverse applications. The storage and transportation of hydrogen is a key factor determining its economic viability, and mainly includes high-pressure gaseous hydrogen storage, cryogenic liquid hydrogen storage, solid-state hydrogen storage, and organic-liquid hydrogen storage. Among these, solid-state hydrogen storage, which stores hydrogen in solid materials through physical or chemical adsorption, high-pressure compression, etc., offers advantages such as high hydrogen storage density, good safety, and long storage time, and is considered the most promising hydrogen storage technology.

[0003] Hollow glass microspheres are an important solid hydrogen storage material, with individual spheres ranging from 10 to 250 μm in diameter and 0.5 to 2 μm in wall thickness. Under high temperature and pressure conditions, hydrogen diffuses through the porous walls of the microspheres, cools, and is then stored in the hollow portion of the microspheres. However, the hydrogen filling process requires temperatures of 200–350 °C to achieve a rapid filling rate. Traditional heating methods primarily use electric heating rods and heat transfer oil to heat the hydrogen storage container, but due to the low thermal conductivity of hollow glass microspheres, these heat conduction-based heating methods are time-consuming. Simultaneously, there are significant temperature differences at different locations within the hydrogen storage container, with higher temperatures near heat exchange tubes or heating rods and lower temperatures further away, hindering uniform heating and hydrogen filling. Furthermore, the dense packing of micron-sized microspheres within the hydrogen storage container impedes hydrogen diffusion, slows down the filling and discharging rates, and easily clogs the gas passages during filling and discharging. Summary of the Invention

[0004] To address the technical problems of long hydrogen charging and discharging processes and easy blockage of gas pipelines in existing technologies, this invention provides a hydrogen storage module and hydrogen charging and discharging method based on 3D printing technology.

[0005] The hydrogen storage module based on 3D printing technology provided by this invention is mainly a product of high-temperature sintering of a hydrogen storage module preform generated by 3D printing of a mixture of hollow borosilicate glass microspheres and binder. The matrix material is hollow borosilicate glass microspheres. The hydrogen storage module is cubic in shape and has a porous microchannel structure. The microchannels run through each symmetry plane of the hydrogen storage module. The module pore volume is 30-50 vol%, and the average pore diameter is 0.5-2 cm.

[0006] This invention also provides a method for preparing a hydrogen storage module based on 3D printing technology, comprising the following steps:

[0007] 1) Printing green body: Hollow borosilicate glass microspheres with a particle size of 10-250 μm and a wall thickness of 0.5-2 μm are added to a binder jet 3D printing equipment. The binder saturation is set to 40-90%, the printed layer thickness is 50-800 μm, the recoating speed is 50-200 mm / s, the oscillator speed is 1200-2500 rpm, the powder bed temperature is 30-80℃, and the drying time is 5-20 s. A hydrogen storage module green body with a porous microchannel structure is prepared by binder jet process. The pore volume of the hydrogen storage module green body is 30-50 vol%, and the average pore diameter is 0.5-2 cm.

[0008] 2) Curing and sintering: The printed hydrogen storage module blank is placed in a curing chamber and cured at 100-200℃ for 2-4 hours to remove moisture from the binder; then, it is transferred to a sintering furnace and sintered at 700-900℃ in an argon atmosphere for 5-10 hours to obtain a hollow glass microsphere hydrogen storage module.

[0009] The adhesive is mainly one of water-soluble adhesives such as vinyl alcohol polymers, water-based epoxy polymers, and alkaline silica sol.

[0010] The overall dimensions of the hydrogen storage module are adjusted according to the specifications of the working chamber of the binder jet 3D printing equipment. The side length of the hydrogen storage module is generally 10-50cm.

[0011] This invention also provides a method for charging and discharging hydrogen in a hydrogen storage module based on 3D printing technology, comprising the following steps:

[0012] 1) Hydrogen charging of the hydrogen storage module

[0013] After assembling the hydrogen storage module, fix it to the partition inside the hydrogen storage container. High-temperature compressed hydrogen is introduced into the hydrogen storage container through the inlet valve. The hydrogen temperature is controlled between 150 and 400°C. The pressure inside the hydrogen storage container is controlled between 5 and 100 MPa by adjusting the inlet and outlet valves. After the hydrogen storage module is filled with hydrogen to saturation, the hydrogen storage container is cooled to below 100°C, preferably to room temperature, to complete the hydrogen filling process.

[0014] 2) Hydrogen release from the hydrogen storage module

[0015] When releasing hydrogen, the hydrogen storage container is first evacuated to a negative pressure, and then the temperature is gradually increased to 150-400°C to release hydrogen from the hydrogen-saturated storage module.

[0016] The present invention has the following beneficial effects:

[0017] 1) Compared with the traditional close-packed form, the hydrogen storage module with porous microchannel structure prepared by the binder jet 3D printing technology of this invention will not hinder the flow and diffusion of hydrogen in the hydrogen storage material during the hydrogen charging and discharging process, and can significantly increase the contact area between hydrogen and hydrogen storage material. This not only accelerates the hydrogen charging rate and efficiency and realizes rapid hydrogen charging and discharging, but also ensures that the hydrogen storage material is heated uniformly as a whole.

[0018] 2) Compared with traditional particulate hydrogen storage materials, the modular structure can avoid the hydrogen storage material from clogging the gas pipeline and being lost during the hydrogen charging and discharging process.

[0019] 3) The modular design of the hydrogen storage unit makes it easier to flexibly adapt to the shape of the container and achieve a high volumetric efficiency through combination and assembly. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the hydrogen storage module of the present invention;

[0021] Figure 2 This is a schematic diagram of the hydrogen storage module of the present invention after being assembled and filled into the hydrogen storage container.

[0022] In the diagram: 1-Inlet valve, 2-Hydrogen storage container, 3-Hydrogen storage module assembly layer, 4-Outlet valve. Detailed Implementation

[0023] To facilitate understanding by those skilled in the art, the present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0024] Hydrogen storage module preparation:

[0025] 1) Printing green body: Hollow borosilicate glass microspheres with a particle size of 150 μm and a wall thickness of 1.0 μm were added to a binder jet 3D printing equipment. The saturation of the 8% (w / w) polyvinyl alcohol aqueous solution binder was set to 70%, the printing layer thickness was 500 μm, the recoating speed was 100 mm / s, the oscillator speed was 2500 rpm, the powder bed temperature was 60℃, and the drying time was 15 s. A hydrogen storage module green body with a porous microchannel structure was prepared by the binder jet process. The side length of the hydrogen storage module green body was 50 cm, the pore volume was 50 vol%, and the average pore diameter was 1 cm.

[0026] 2) Curing and Sintering: The printed hydrogen storage module preform was placed in a curing chamber and cured at 150℃ for 4 hours to remove moisture from the binder. Subsequently, it was transferred to a sintering furnace and sintered at 720℃ in an argon atmosphere for 10 hours to obtain a hollow glass microsphere hydrogen storage module with a side length of 50cm, a pore volume of 50 vol%, and an average pore diameter of 1cm. A schematic diagram of the hydrogen storage module is shown below. Figure 1 As shown.

[0027] Of course, depending on the need, the adhesive may also be a water-based epoxy polymer or an alkaline silica sol.

[0028] Hydrogen charging and discharging methods for hydrogen storage modules:

[0029] like Figure 2 As shown, Figure 1 The hydrogen storage modules shown are assembled to form a hydrogen storage module assembly layer 3. The hydrogen storage module assembly layer 3 is fixed to the partition inside the hydrogen storage container 2. High-temperature compressed hydrogen gas at 260°C is introduced into the hydrogen storage container 2 through the inlet valve 1. The pressure inside the hydrogen storage container 2 is controlled to 50MPa by adjusting the inlet valve 1 and the outlet valve 4. Because the hollow borosilicate glass microspheres of the hydrogen storage module have a very high contact area with the rapidly flowing hot hydrogen gas, the hydrogen storage module can be uniformly heated to 260°C within 3 minutes, achieving rapid saturation hydrogen filling. The rapid flow of hydrogen gas will not cause the hollow borosilicate glass microspheres of the hydrogen storage module to fly into the exhaust pipe, and will not cause pipe blockage or loss of hydrogen storage material. After the hydrogen storage module is saturated with hydrogen, the hydrogen storage container 2 is cooled to room temperature to complete the hydrogen filling process. When releasing hydrogen, the hydrogen storage container 2 is first evacuated to negative pressure, and then the temperature is gradually increased to 150-400°C to release hydrogen from the hydrogen-saturated hydrogen storage module.

[0030] In contrast, if the same amount of hollow borosilicate glass microspheres are directly loaded into a hydrogen storage container, and compressed hydrogen gas at 260°C is introduced into the container, and the pressure inside the container is controlled to 50 MPa by adjusting the inlet and outlet valves, the hollow borosilicate glass microspheres cannot be prevented from rapidly entering the exhaust pipe with the hydrogen flow during the filling process, resulting in the loss of hydrogen storage material. When the outlet valve is closed and the inlet valve is opened, because the hot hydrogen gas inside the storage container is in a non-flowing state and the hollow borosilicate glass microspheres have low thermal conductivity, the microspheres cannot reach the set temperature of 260°C, thus reducing the hydrogen filling efficiency.

Claims

1. A hydrogen storage module based on 3D printing technology, characterized in that: The hydrogen storage module is a product of a hydrogen storage module green body generated by 3D printing of a mixture of hollow borosilicate glass microspheres and a binder and high-temperature sintering, the matrix material of the hydrogen storage module is hollow borosilicate glass microspheres, the hydrogen storage module is in the shape of a cube, has a porous microchannel structure, the microchannels penetrate through the symmetrical faces of the hydrogen storage module, the pore volume of the module is 30-50 vol%, and the average pore diameter is 0.5-2 cm.

2. The 3D printing technology based hydrogen storage module as claimed in claim 1, wherein: The binder is one of a vinyl alcohol polymer, a water-based epoxy polymer and an alkaline silica sol.

3. The 3D printing technology based hydrogen storage module as claimed in claim 1, wherein: The hydrogen storage module has a side length of 10-50 cm.

4. A method for producing a hydrogen storage module based on 3D printing technology according to any one of claims 1 to 3, characterized in that The method comprises the following steps: 1) printing a green body: hollow borosilicate glass microspheres with a particle size of 10-250 μm and a wall thickness of 0.5-2 μm are added to a binder jetting 3D printing device, the saturation of the binder is set to 40-90%, the printing layer thickness is set to 50-800 μm, the re-coating speed is set to 50-200 mm / s, the oscillator speed is set to 1200-2500 rpm, the powder bed temperature is set to 30-80°C, and the drying time is set to 5-20 s, a hydrogen storage module green body with a porous microchannel structure is prepared by a binder jetting process, the pore volume of the hydrogen storage module green body is 30-50 vol%, and the average pore diameter is 0.5-2 cm; 2) curing and sintering: the printed hydrogen storage module green body is placed in a curing box and cured at 100-200°C for 2-4 hours to remove the water in the binder; then, the hydrogen storage module green body is placed in a sintering furnace and sintered at 700-900°C in an argon atmosphere for 5-10 hours to obtain a hollow glass microsphere hydrogen storage module.

5. The method of claim 4, wherein: The binder is one of a vinyl alcohol polymer, a water-based epoxy polymer and an alkaline silica sol.

6. A method for charging and discharging hydrogen of the hydrogen storage module based on 3D printing technology according to any one of claims 1 to 3, characterized in that The method comprises the following steps: 1) hydrogen charging of the hydrogen storage module After the hydrogen storage modules are assembled, they are fixed on a partition plate in a hydrogen storage container, high-temperature compressed hydrogen is introduced into the hydrogen storage container through an inlet valve, the hydrogen temperature is controlled at 150-400°C, the pressure in the hydrogen storage container is controlled at 5-100 MPa by adjusting the inlet valve and an outlet valve of the hydrogen storage container, the hydrogen storage modules are saturated with hydrogen, the hydrogen storage container is then lowered to below 100°C, and the hydrogen charging process is completed; 2) hydrogen discharging of the hydrogen storage module During hydrogen discharging, the hydrogen storage container is first pumped to a negative pressure, and then gradually heated to 150-400°C to make the hydrogen-saturated hydrogen storage modules discharge hydrogen.

7. The method of claim 6, wherein: After the hydrogen storage modules are saturated with hydrogen, the hydrogen storage container is lowered to room temperature, and the hydrogen charging process is completed.

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