A method of filling a solid state hydrogen storage cylinder

Abstract

The application discloses a solid-state hydrogen storage cylinder filling method, and relates to the technical field of hydrogen storage cylinder filling, which comprises the following steps: preparing hydrogen storage alloy powder, thermosetting epoxy resin, dispersing liquid and heat transfer material; mixing the thermosetting epoxy resin and a curing agent uniformly in proportion to obtain a thermosetting epoxy resin mixed liquid; then mixing the hydrogen storage alloy powder, the dispersing liquid, the heat transfer material and the thermosetting epoxy resin mixed liquid uniformly in proportion to obtain a mixture; and finally filling the mixture into a hydrogen storage cylinder and allowing the mixture to solidify in an activation process. The application has the advantages that the design is reasonable, the possibility of uneven heat exchange caused by uneven distribution of internal materials of the hydrogen storage cylinder during use is improved, and the heat value transmission efficiency of the solid-state hydrogen storage cylinder is enhanced; the solidified epoxy resin can play a certain buffering role on hydrogen absorption expansion of the hydrogen storage alloy powder, and stress concentration caused by accumulation of the hydrogen storage alloy powder is reduced.

Description

Technical Field

[0001] This invention relates to the field of hydrogen storage cylinder filling technology, and more specifically to the field of a solid hydrogen storage cylinder filling method. Background Technology

[0002] The current traditional method for filling hydrogen storage cylinders includes procedures such as mixing, alloy block forming, alloy block drying, crushing, screening, and filling. Existing patents disclose the following technologies:

[0003] Patent publication number CN114151722A, entitled "A Vehicle-Mounted Metal Hydride Composite Hydrogen Storage Device," discloses the following: A vehicle-mounted metal hydride composite hydrogen storage device includes a hydrogen storage cylinder unit module and a semiconductor unit module. The hydrogen storage cylinder unit module includes a hydrogen storage cylinder filled with hydrogen storage material. The semiconductor unit module includes a semiconductor chip in contact with the hydrogen storage cylinder and is connected to a power line. The semiconductor chip can heat or cool the hydrogen storage cylinder. This device features rapid dynamic response to hydrogen absorption and desorption, efficient energy utilization, and no corrosion to pipelines. It also offers easy thermal conversion, simple operation, and convenient application and promotion in vehicle systems.

[0004] The patent with publication number CN102751522A, entitled "A Mobile Power Generation System for a Fuel Cell Using Hydrogen as Fuel," discloses the following: The hydrogen supply module stores hydrogen through a metal hydride hydrogen storage method, or through methanol reforming to produce hydrogen, or through a high-pressure steel cylinder hydrogen storage method; in the metal hydride hydrogen storage method, a hydrogen storage alloy is filled into a hydrogen storage cylinder, and several hydrogen storage cylinders form a group. The hydrogen storage cylinders are fitted with heat sinks, and the hydrogen storage cylinders are connected by a manifold. One end of the manifold is equipped with a rupture disc, and the other end is equipped with a ball valve and a hydrogen pressure reducing valve; the connection between the hydrogen supply module and the vehicle transportation module is a movable connection. The aluminum alloy frame of each group of hydrogen storage cylinders can be directly inserted into the track of the vehicle transportation module. To prevent the frame of the hydrogen storage cylinder group from sliding, both ends of the frame are secured with easily detachable retaining rings.

[0005] The aforementioned patented and traditional methods result in excessively time-consuming processes for each step of the hydrogen storage cylinder filling process, leading to an overall lengthy production time. To ensure the filling volume, in addition to using automated equipment, manual replenishment is also necessary, which is cumbersome and prone to damaging the cylinder. Traditional filling methods also result in the hydrogen storage material turning into a very fine powder after activation, which can easily lead to powder spraying during hydrogen release. Furthermore, the activated hydrogen storage material is prone to accumulation, causing stress concentration. Summary of the Invention

[0006] The purpose of this invention is to provide a method for filling solid hydrogen storage cylinders in order to solve the above-mentioned technical problems.

[0007] To achieve the above objectives, the present invention specifically adopts the following technical solution:

[0008] This invention provides a method for filling solid hydrogen storage cylinders, comprising the following steps:

[0009] S1. Materials to be prepared: hydrogen storage alloy powder, thermosetting epoxy resin, dispersion, and heat transfer material (the hydrogen storage alloy powder is one of AB2 type, AB5 type, or BCC type hydrogen storage alloy powder; the dispersion is PTFE or CMC solution; the heat transfer material is one or more of aluminum powder, graphite, or carbon nanotubes).

[0010] S2. Mix the thermosetting epoxy resin and the curing agent evenly according to the ratio to obtain a thermosetting epoxy resin mixture liquid;

[0011] S3. Then, the hydrogen storage alloy powder, dispersion, heat transfer material and thermosetting epoxy resin mixture are mixed evenly according to the proportion to obtain a mixture.

[0012] S4. Finally, fill the mixture into the hydrogen storage bottle and allow it to solidify during the activation process.

[0013] Specifically, this solution eliminates unnecessary steps, directly loading the hydrogen storage cylinder after mixing. The process is simple and ensures that the hydrogen storage alloy powder is exposed to air for a short time, preventing oxidation of the hydrogen storage alloy.

[0014] This solution eliminates steps such as alloy block forming, drying, crushing, and screening, significantly reducing the overall production time of the hydrogen storage cylinder by two-thirds; it also solves the problem of excessively time-consuming production processes.

[0015] This solution changes the production method of hydrogen storage cylinders, and the entire production process will be carried out by automated equipment, reducing human intervention and eliminating the manual feeding step, ensuring that the cylinder body will not be scratched due to feeding; thus solving the problem of manual feeding.

[0016] Add a dispersion to ensure uniform mixing and uniform heating of the hydrogen storage alloy powder.

[0017] In one embodiment, in step S2, the thermosetting epoxy resin liquid and the curing agent are mixed evenly in a ratio range of 1:0.2 to 1:0.6 to obtain a two-component thermosetting epoxy resin mixed liquid.

[0018] Adding a certain amount of two-component thermosetting epoxy resin allows the mixed material to cure during the activation process, eliminating the need for a drying step.

[0019] In one embodiment, in step S3, the mixture obtained by mixing hydrogen storage alloy powder, dispersion, heat transfer material and thermosetting epoxy resin mixture has a certain fluidity.

[0020] Specifically, the mixed material exhibits a certain degree of fluidity, which facilitates filling and ensures that it solidifies into a cohesive whole within the bottle without dispersing.

[0021] A mixture of thermosetting epoxy resin, PTFE dispersion, heat transfer material, and hydrogen storage alloy powder in appropriate proportions is prepared into a fluid mixture and then placed in a hydrogen storage bottle. During the activation process, the epoxy resin will cure, which can solve the problems of powder spraying, easy accumulation, and stress concentration of the activated hydrogen storage alloy powder.

[0022] In one embodiment, in step S3, the hydrogen storage alloy powder, dispersion, heat transfer material and two-component thermosetting epoxy resin mixture are mixed evenly in a ratio of 0.855:0.02:0.035:0.09 to obtain a mixture.

[0023] In one embodiment, in step S3, the hydrogen storage alloy powder, dispersion, heat transfer material and two-component thermosetting epoxy resin mixture are mixed evenly in a ratio of 0.89:0.02:0.04:0.05 to obtain a mixture.

[0024] In one embodiment, in step S3, the hydrogen storage alloy powder, dispersion, heat transfer material and two-component thermosetting epoxy resin mixture are mixed evenly in a ratio of 0.915:0.01:0.025:0.05 to obtain a mixture.

[0025] In one embodiment, in step S4, the cured mixture exhibits a honeycomb structure after activation.

[0026] Specifically, it can reduce stress concentration caused by the accumulation of hydrogen storage alloy powder, and also reduce the possibility of uneven heat exchange caused by uneven internal material distribution during the use of hydrogen storage cylinders.

[0027] In one embodiment, in step S1, the heat transfer material used is a heat transfer material that has been sieved through a 30-mesh sieve.

[0028] Specifically, the heat transfer material used is a 30-mesh sieve, which can ensure the filling amount while maintaining the heat transfer effect of the hydrogen storage cylinder.

[0029] In one embodiment, in step S4, the mixture is filled into a hydrogen storage bottle by an automated filling device, allowing it to solidify during the activation process.

[0030] Specifically, the cured epoxy resin can buffer the hydrogen absorption and expansion of the hydrogen storage alloy powder.

[0031] The beneficial effects of this invention are as follows:

[0032] 1. This invention is rationally designed, and the cured mixture exhibits a honeycomb structure after activation. This reduces stress concentration caused by the accumulation of hydrogen storage alloy powder; the addition of a dispersion liquid ensures uniform mixing and heating of the hydrogen storage alloy powder, reducing the possibility of uneven heat exchange caused by uneven material distribution inside the hydrogen storage cylinder during use; the cured epoxy resin can also buffer the hydrogen absorption and expansion of the hydrogen storage alloy powder.

[0033] 2. This solution eliminates unnecessary steps, allowing direct loading into the hydrogen storage cylinder after mixing. The process is streamlined and ensures the hydrogen storage alloy powder is exposed to air for a shorter time, preventing oxidation. This solution also eliminates steps such as alloy block forming, drying, crushing, and sieving, significantly reducing the overall production time of the hydrogen storage cylinder by four-fifths; thus solving the problem of excessively time-consuming production processes.

[0034] 3. After changing the production method of hydrogen storage cylinders, this solution will enable the entire production process to be carried out by automated equipment, reducing manual intervention and eliminating the manual feeding step, thus ensuring that the cylinder body will not be scratched due to feeding; and solving the problem of manual feeding. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0036] Therefore, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0037] Example 1

[0038] This embodiment provides a method for filling a solid hydrogen storage cylinder, including the following steps:

[0039] S1. Materials preparation: hydrogen storage alloy powder, thermosetting epoxy resin, dispersion and graphite. The heat transfer material used is graphite that has been sieved through 30 mesh.

[0040] S2. Mix the thermosetting epoxy resin liquid and the curing agent in a ratio of 1:0.2 to obtain a two-component thermosetting epoxy resin mixture liquid.

[0041] S3. The hydrogen storage alloy powder, dispersion, heat transfer material and two-component thermosetting epoxy resin mixture are mixed evenly in a ratio of 0.855:0.02:0.035:0.09 to obtain a mixture with fluidity.

[0042] S4. The mixture is filled into the hydrogen storage cylinder using automated filling equipment, allowing it to solidify during the activation process. The solidified mixture exhibits a honeycomb structure after activation. This reduces stress concentration caused by the accumulation of hydrogen storage alloy powder and also reduces the possibility of uneven heat exchange caused by uneven material distribution inside the hydrogen storage cylinder during use. The solidified epoxy resin can also buffer the hydrogen absorption and expansion of the hydrogen storage alloy powder.

[0043] Example 2

[0044] This embodiment provides a method for filling a solid hydrogen storage cylinder, including the following steps:

[0045] S1. Materials preparation: hydrogen storage alloy powder, thermosetting epoxy resin, dispersion and graphite. The heat transfer material used is graphite that has been sieved through 30 mesh.

[0046] S2. Mix the thermosetting epoxy resin liquid and the curing agent in a ratio of 1:0.2 to obtain a two-component thermosetting epoxy resin mixture liquid.

[0047] S3. The hydrogen storage alloy powder, dispersion, heat transfer material and two-component thermosetting epoxy resin mixture are mixed evenly in a ratio of 0.89:0.02:0.04:0.05 to obtain a mixture with fluidity.

[0048] S4. The mixture is filled into the hydrogen storage cylinder using automated filling equipment, allowing it to solidify during the activation process. The solidified mixture exhibits a honeycomb structure after activation. This reduces stress concentration caused by the accumulation of hydrogen storage alloy powder and also reduces the possibility of uneven heat exchange caused by uneven material distribution inside the hydrogen storage cylinder during use. The solidified epoxy resin can also buffer the hydrogen absorption and expansion of the hydrogen storage alloy powder.

[0049] Example 3

[0050] This embodiment provides a method for filling a solid hydrogen storage cylinder, including the following steps:

[0051] S1. Materials preparation: hydrogen storage alloy powder, thermosetting epoxy resin, dispersion and graphite. The heat transfer material used is graphite that has been sieved through 30 mesh.

[0052] S2. Mix the thermosetting epoxy resin liquid and the curing agent in a ratio of 1:0.2 to obtain a two-component thermosetting epoxy resin mixture liquid.

[0053] S3. The hydrogen storage alloy powder, dispersion, heat transfer material and two-component thermosetting epoxy resin mixture are mixed evenly in a ratio of 0.915:0.01:0.025:0.05 to obtain a mixture with fluidity.

[0054] S4. The mixture is filled into the hydrogen storage cylinder using automated filling equipment, allowing it to solidify during the activation process. The solidified mixture exhibits a honeycomb structure after activation. This reduces stress concentration caused by the accumulation of hydrogen storage alloy powder and also reduces the possibility of uneven heat exchange caused by uneven material distribution inside the hydrogen storage cylinder during use. The solidified epoxy resin can also buffer the hydrogen absorption and expansion of the hydrogen storage alloy powder.

[0055] Comparison of experimental results:

[0056] The first aspect: Taking a 1L solid hydrogen storage cylinder as an example, the alloy filling amount of different solid hydrogen storage cylinders is shown in Table 1:

[0057] Table 1: Packing Density of Hydrogen Storage Beds with Different Packing Methods

[0058]

[0059] The second aspect: 4MPa, 10℃ hydrogen charging; 25℃, 0.2MPa cutoff, 4SLM hydrogen release; the thermal conductivity, hydrogen charging rate, and hydrogen release rate of the hydrogen storage bed are shown in Table 2:

[0060] Table 2: Comparison of heat transfer and hydrogen absorption / desorption data for different filling methods

[0061]

[0062]

[0063] According to Tables 1 and 2, combined with the packing density and hydrogen absorption and release data of solid hydrogen storage cylinders, although the packing density of pure alloy is high, its heat exchange is extremely poor and the effective hydrogen release is too small to be practical for engineering use. The alloy packing density of this patent is slightly lower than that of the traditional packing method, but its advantage is that the improved mixed alloy powder will solidify into a whole inside the cylinder, which will reduce the problem of stress concentration.

[0064] The third aspect: Strain comparison of solid hydrogen storage cylinders is shown in Table 3:

[0065] Table 3: Comparison of strain in different solid hydrogen storage cylinders

[0066]

[0067] As can be seen from Table 3, the traditional filling method, which uses dry powder, is prone to uneven density distribution of the hydrogen storage bed in the solid hydrogen storage cylinder due to the filling process. This results in strain deviations at different locations and tends to cause large strains in the middle of the cylinder, leading to cylinder deformation. The filling method of this patent effectively solves the problem of uneven density distribution of the hydrogen storage bed in the solid hydrogen storage cylinder, and avoids cylinder deformation caused by local strain concentration due to powder expansion.

[0068] The fourth aspect: Comparison of loading times is shown in Table 4:

[0069] Table 4 Comparison of loading times:

[0070]

[0071] As can be seen from Table 4, in terms of filling time, based on a batch of 60 1L solid hydrogen storage cylinders, the traditional filling method takes 5.5 days, with an average of 60 minutes per cylinder. In addition, manual assistance is required to ensure the filling volume, and the process is complicated. In contrast, this patent can complete the filling in just 1 day, with an average of only 12 minutes per cylinder. Moreover, it can be filled directly after mixing, with a simple process and no need for manual filling.

Claims

1. A method for filling a solid hydrogen storage cylinder, characterized in that, Includes the following steps: S1. Materials preparation: hydrogen storage alloy powder, thermosetting epoxy resin, dispersion and heat transfer material; S2. Mix the thermosetting epoxy resin liquid and the curing agent in a ratio range of 1:0.2~1:0.6 to obtain a two-component thermosetting epoxy resin mixture liquid. S3. Then, the hydrogen storage alloy powder, dispersion, heat transfer material and two-component thermosetting epoxy resin mixture are mixed evenly in a ratio of 0.8~0.95:0.01~0.05:0.01~0.05:0.03~0.15 to obtain a mixture with a certain fluidity. S4. Finally, fill the mixture into the hydrogen storage bottle and allow it to solidify during the activation process.

2. The method for filling a solid hydrogen storage cylinder according to claim 1, characterized in that, In step S1, the hydrogen storage alloy powder is one of AB2 type hydrogen storage alloy powder, AB5 type hydrogen storage alloy powder, or BCC type hydrogen storage alloy powder.

3. The method for filling a solid hydrogen storage cylinder according to claim 1, characterized in that, In step S1, the dispersion is a PTFE or CMC solution.

4. The method for filling a solid hydrogen storage cylinder according to claim 1, characterized in that, In step S1, the heat transfer material is one or more of aluminum powder, graphite, or carbon nanotubes.

5. The method for filling a solid hydrogen storage cylinder according to claim 1, characterized in that, In step S1, the heat transfer material used is a heat transfer material that has been sieved through a 30-100 mesh.

6. The method for filling a solid hydrogen storage cylinder according to claim 1, characterized in that, In step S4, the cured mixture exhibits a honeycomb structure after activation.

7. The method for filling a solid hydrogen storage cylinder according to claim 1, characterized in that, In step S4, the mixture is filled into the hydrogen storage bottle by an automated filling device, allowing it to solidify during the activation process.

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