Solid hydrogen storage device

Abstract

This invention discloses a solid hydrogen storage device, comprising a vertical tank, a hydrogen distribution and collection box, and a hydrogen filling / discharging liner. The hydrogen distribution and collection box has a hydrogen inlet and a hydrogen outlet, and its bottom plate has a connecting hole connecting the hydrogen distribution and collection box and the hydrogen filling / discharging liner. The top of the hydrogen filling / discharging liner has a hydrogen storage material inlet pipe, and the bottom has a hydrogen storage material outlet pipe that forms a sliding seal with the vertical tank. The wall of the hydrogen filling / discharging liner has an expansion joint, and the liner is filled with solid hydrogen storage material. The inner wall of the vertical tank and the outer wall of the hydrogen filling / discharging liner form a teacup-shaped gap, and the vertical tank wall corresponding to the teacup-shaped gap has a heat exchange medium inlet and a heat exchange medium outlet. This invention simultaneously solves the heat and volume compensation problems during the hydrogen filling and discharging process, improving the reliability of the device.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen storage technology, and specifically relates to a solid hydrogen storage device. Background Technology

[0002] Hydrogen is considered one of the cleanest and most efficient energy sources because its combustion process does not release greenhouse gases such as carbon dioxide and it has a high calorific value. The utilization of hydrogen is inseparable from its storage, which currently includes three main methods: gaseous hydrogen storage, liquid hydrogen storage, and solid-state hydrogen storage. Solid-state hydrogen storage involves storing hydrogen in the lattice of a solid hydrogen storage alloy material (such as rare earth compounds (LaNi5)), and achieving physically reversible hydrogen addition and release processes by changing the temperature and pressure under certain temperature and pressure conditions. Compared to gaseous and liquid hydrogen storage, solid-state hydrogen storage does not require excessive energy consumption and has advantages such as higher volumetric hydrogen storage density, safety and efficiency, and a stable hydrogen release rate, making it a promising hydrogen storage technology.

[0003] Solid hydrogen storage materials typically expand in volume when absorbing hydrogen and contract in volume when releasing hydrogen. Furthermore, they release a significant amount of heat during hydrogen absorption and require substantial heat replenishment during hydrogen release. Temperature also significantly impacts the hydrogen absorption and desorption rates of the storage material. Therefore, to ensure the long-term use of hydrogen storage materials and the rapid and efficient absorption and desorption of hydrogen, it is essential to simultaneously address the heat and volume changes during hydrogen absorption and desorption, designing hydrogen storage devices with high-efficiency heat exchange performance and volume compensation. Otherwise, the absorption and desorption efficiency of solid hydrogen storage will decrease, and with each hydrogen charge and discharge cycle, the expansion and compression of the solid hydrogen storage alloy will cause lattice deformation, leading to a rapid decrease in its capacity. Additionally, the expansion of the solid hydrogen storage material subjects the storage shell to significant stress, posing a risk of bulging and cracking. Solving the problems of heat absorption / desorption and volume changes during the hydrogen absorption and desorption process of solid hydrogen storage is crucial for ensuring high absorption and desorption rates and directly affects the cost and safety of the hydrogen storage device.

[0004] Patent CN117307953A discloses a hydrogen storage and release device that facilitates the replacement of hydrogen storage materials. After the hydrogen storage alloy's hydrogen charging and releasing capacity deteriorates, a new hydrogen storage alloy is injected through the jacket inlet to replace the original hydrogen storage alloy without moving the entire device. This method is convenient and low-cost. However, the volume expansion absorption of the hydrogen storage alloy during the charging and releasing process is poor, and the capacity of the solid hydrogen storage material may decay rapidly. Patent CN103883874B discloses a hydrogen storage tank with an external heat exchange structure. Its structure is simple, easy to manufacture, and low-cost. It has a better heat exchange effect and excellent hydrogen release performance. However, this hydrogen storage tank only has a heat exchange effect and cannot absorb the volume expansion of the solid hydrogen storage material during the hydrogen absorption and release process. Therefore, it cannot simultaneously solve the problems of volume expansion and heat release, and the tank body is at risk of bulging and rupture. Summary of the Invention

[0005] To address the technical problems of poor absorption efficiency due to volume expansion during hydrogen charging and discharging in existing solid hydrogen storage devices, and the inability to simultaneously solve the problems of volume expansion and heat release during absorption, this invention provides a solid hydrogen storage device that solves the problems of volume expansion and heat release during solid hydrogen storage.

[0006] This invention provides a solid hydrogen storage device, comprising a vertical tank, a hydrogen distribution and collection box coaxially arranged from top to bottom within the vertical tank, and a hydrogen filling and discharging liner; the hydrogen distribution and collection box is cylindrical and is formed by the inner wall of the vertical tank, the top plate of the vertical tank, and the bottom plate of the hydrogen distribution and collection box; the hydrogen filling and discharging liner is cylindrical and suspended below the bottom plate of the hydrogen distribution and collection box, the bottom plate of the hydrogen distribution and collection box and the inner wall of the hydrogen filling and discharging liner forming a closed space, and a teacup-shaped gap is formed between the outer wall of the hydrogen filling and discharging liner and the inner wall of the vertical tank; a heat exchange medium inlet and a heat exchange medium outlet are provided on the vertical tank wall corresponding to the teacup-shaped gap;

[0007] A hydrogen storage material inlet pipe is located at the top center of the hydrogen filling / discharging inner liner, connecting to the inner liner. This inlet pipe passes through the hydrogen distribution and collection box and extends to the outside of the top plate of the vertical tank. A hydrogen storage material outlet pipe is located at the bottom center of the inner liner, connecting to the inner liner. This outlet pipe passes through the bottom of a teacup-shaped gap and extends to the outside of the bottom plate of the vertical tank. A sliding seal is provided between the outer wall of the outlet pipe and the bottom plate of the vertical tank, allowing it to move axially. One or more expansion joints are provided on the cylindrical wall of the inner liner, allowing them to extend or contract axially. The inner liner is filled with solid hydrogen storage material.

[0008] The vertical tank containing the hydrogen distribution and collection box has a hydrogen inlet and a hydrogen outlet on its wall. A connecting hole is opened on the bottom plate of the hydrogen distribution and collection box in the area of ​​the hydrogen filling and discharging liner. The connecting hole connects the hydrogen distribution and collection box and the hydrogen filling and discharging liner, ensuring that hydrogen can enter or leave the hydrogen filling and discharging liner evenly. The heat exchange medium inlet, the teacup-shaped gap between the outer wall of the hydrogen filling and discharging liner and the inner wall of the vertical tank, and the heat exchange medium outlet form a closed and connected cavity, which allows the heat exchange medium to remove heat from the solid hydrogen storage material filled in the hydrogen filling and discharging liner or to replenish the solid hydrogen storage material.

[0009] The connecting holes are arranged in a ring, equilateral triangle, or regular quadrilateral pattern on the bottom plate of the hydrogen distribution and collection tank. The connecting holes are preferably circular, with a diameter of 19–60 mm. When the connecting holes are evenly distributed in a ring, the circumferential spacing between the holes should be 30–80 mm, and the radial spacing should be 40–60 mm. When the connecting holes are evenly distributed in equilateral triangles, the side length of the equilateral triangles should be 20–60 mm; when the connecting holes are evenly distributed in regular quadrilaterals, the side length of the regular quadrilaterals should be 20–100 mm.

[0010] When loading solid hydrogen storage material, the outlet pipe is closed and the inlet pipe is open. Under gravity, the solid hydrogen storage material enters the charging / discharging liner through the inlet pipe and is stored there. When the solid hydrogen storage material needs replacement due to its lifespan decline, the outlet pipe is opened, and under gravity, the solid hydrogen storage material in the charging / discharging liner leaves the hydrogen storage device through the outlet pipe. The inlet and outlet pipes should preferably be cylindrical with a diameter of 50–400 mm.

[0011] The sliding seal between the outer wall of the hydrogen storage material outlet pipe and the bottom plate of the vertical tank, which moves axially along the vertical tank, can be a packing seal. The packing seal ensures that the hydrogen storage material outlet pipe can maintain a tight seal with the bottom of the vertical tank as it extends and retracts downward along with the hydrogen filling and discharging inner liner.

[0012] Depending on the different needs of hydrogen filling and discharging, during hydrogen filling, a low-temperature heat exchange medium enters from the heat exchange medium inlet into the teacup-shaped gap between the outer wall of the hydrogen filling / discharging inner liner and the inner wall of the vertical tank. Through heat transfer via the inner liner wall, the heat released by the solid hydrogen storage material absorbing hydrogen is absorbed, and the medium exits the hydrogen storage device through the heat exchange medium outlet, thus lowering the temperature of the solid hydrogen storage material. When hydrogen needs to be released from the solid hydrogen storage material, a high-temperature heat exchange medium enters from the heat exchange medium inlet into the teacup-shaped gap between the outer wall of the hydrogen filling / discharging inner liner and the inner wall of the vertical tank. Through heat transfer via the inner liner wall, heat is provided to the solid hydrogen storage material within the inner liner, causing the material to absorb heat and release hydrogen. The heat exchange medium, after releasing heat, exits the hydrogen storage device through the heat exchange medium outlet. By using the heat exchange medium to remove heat from the hydrogen storage device or replenish it, the hydrogen absorption and release process can proceed at a high rate. Fluids such as water, nitrogen, and air can be used as the heat exchange medium.

[0013] The diameter of the hydrogen filling / discharging liner should preferably be 0.6 to 0.9 times the diameter of the vertical tank. The expansion joints on the liner wall can extend or contract axially to change the axial length of the liner and adjust its storage volume, accommodating volume changes caused by the solid hydrogen storage material during filling and discharging. When expansion joints are manufactured as a single layer, elastic alloys should be used to give them good resilience. Copper-based, iron-based, and nickel-based high-elasticity alloys are suitable, utilizing their low elastic modulus and high elastic limit to provide high resilience. When expansion joints are made of multiple layers through stamping, they can be constructed with separate pressure-bearing and resilience layers. The pressure-bearing layer bears the pressure of the hydrogen storage system, while the resilience layer provides the resilience. The resilience layer should preferably be made of an elastic alloy, ensuring that the material maintains a certain tensile stress after stamping, creating a spring-like effect that allows the expansion joint to maintain its original shape and rebound when the external force is removed. When expansion joints are made of multiple layers, springs can be added between the layers to enhance resilience. In short, the goal is to ensure the expansion joint has optimal resilience. An expansion joint can consist of one or more expansion waves, with a wave height of 30–300 mm and a wave spacing of 50–200 mm. When multiple expansion joints are set in the inner wall of the hydrogen filling and discharging liner, the multiple expansion joints are evenly distributed on the axis of the hydrogen filling and discharging liner to ensure that the volume expansion at different positions on the axis of the hydrogen filling and discharging liner can be better absorbed.

[0014] As a preferred option, a filter screen, such as a wire mesh, can be installed in the perforated area of ​​the section where the hydrogen storage liner is located on the bottom plate of the hydrogen distribution and collection tank to prevent small, broken solid hydrogen storage material particles from leaving the hydrogen storage liner with the hydrogen. The pore size of the filter screen should be smaller than the minimum particle size of the solid hydrogen storage material, preferably 10% to 30% of the minimum particle size of the solid hydrogen storage material.

[0015] As a preferred option, a hydrogen distribution and collection pipe can be installed in the connecting hole on the bottom plate of the hydrogen distribution and collection tank. The hydrogen distribution and collection pipe hangs inside the hydrogen filling and discharging liner and is embedded in the solid hydrogen storage material. The length of the hydrogen distribution and collection pipe should preferably be 80-95% of the length of the hydrogen filling and discharging liner. The lower end of the hydrogen distribution and collection pipe is sealed with a sealing plate, and one or more layers of hydrogen pores are formed on the pipe wall. Each layer typically has 2-6 hydrogen pores, and the spacing between layers should preferably be 50-150 mm. The diameter of the hydrogen pores is smaller than the minimum particle size of the solid hydrogen storage material. Alternatively, hydrogen pores can also be formed on the sealing plate at the lower end of the hydrogen distribution and collection pipe, in which case no hydrogen pores are required on the pipe wall. The advantage of the hydrogen distribution and collection pipe is that it allows for better introduction and extraction of hydrogen into and out of the hydrogen filling and discharging liner along its axis.

[0016] As a preferred solution, to ensure that all solid hydrogen storage material is filled within the expandable hydrogen filling / discharging liner and to prevent the solid hydrogen storage material from expanding and clogging the hydrogen storage material outlet pipe during hydrogen filling, a hydrogen storage material outlet plug can be installed inside the outlet pipe. The outlet plug consists of a baffle, a packing seal, a baffle cylinder, a handle, and an installation ring. The baffle cylinder is a cylindrical tube with an outer diameter smaller than the inner diameter of the hydrogen storage material outlet pipe, typically 4-10 mm smaller. One end of the baffle cylinder is closed by the baffle, while the other end is open. The baffle end is inserted into the hydrogen storage material outlet pipe to prevent solid hydrogen storage material from entering the outlet pipe when not unloading. The baffle has the same shape as the bottom of the filling / discharging liner. A handle, which can be made of round steel or angle steel, is provided at the open end for easy installation and removal of the hydrogen storage material outlet plug. The gap between the hydrogen storage material outlet pipe and the hydrogen storage material outlet plug is sealed with filler such as ceramic fiber rope to prevent solid hydrogen storage material from entering the gap between them. The diameter of the ceramic fiber rope should be 5-11 mm. To ensure that the hydrogen storage material outlet plug is fixed inside the hydrogen storage material outlet pipe, an installation ring is set at the open end. The installation ring is a circular ring that is fitted over the baffle. A circular hole is made on the installation ring, and a threaded hole is made at the same position on the hydrogen storage material outlet pipe so that the installation ring can be fixed to the hydrogen storage material outlet pipe with screws.

[0017] As a preferred option, the expansion wave of the expansion joint should be set to be concave towards the inner side of the hydrogen filling and discharging liner. This has the advantage that it can not only extend along the axial direction of the tank to increase the internal volume, but also expand outward from the expansion wave to release the axial space here, so as to better cope with the volume expansion of the solid hydrogen storage material.

[0018] As a preferred option, to ensure that the solid hydrogen storage material in the hydrogen filling and discharging liner can be smoothly discharged, the lower part of the hydrogen filling and discharging liner should be set as a cone with a cone angle of 20 to 60 degrees, and the hydrogen storage material outlet pipe should be located at the top of the cone so that the solid hydrogen storage material can be discharged smoothly.

[0019] As a preferred solution, to avoid problems such as caking or poor flowability of the solid hydrogen storage material in the hydrogen filling and discharging liner, which may cause difficulties in unloading, a loosening air inlet can be installed on the wall of the hydrogen filling and discharging liner. During the unloading process of the solid hydrogen storage material, inert gases such as high-pressure nitrogen and carbon dioxide can be introduced to allow the solid hydrogen storage material to be discharged more smoothly.

[0020] As a preferred solution, a limiting hinge can be installed on the wall of the hydrogen filling / discharging liner. The limiting hinge consists of a connecting rod and a connecting hinge. The connecting rod is connected via the connecting hinge and can rotate around the hinge. The initial position of the limiting hinge installation is when the connecting rods are at a certain angle, preferably 30–60 degrees. The limiting hinge moves downwards as the hydrogen filling / discharging liner expands and elongates. When the connecting rods overlap and form a straight line, i.e., the angle between the two connected rods is 0 degrees, the limiting hinge reaches its limiting termination position and restricts further downward movement and elongation of the hydrogen filling / discharging liner. It is preferable to have two or more limiting hinges evenly distributed around the circumference of the hydrogen filling / discharging liner to ensure the liner is in a uniformly limited state.

[0021] As a preferred embodiment, a rebound device is installed inside the vertical tank, below the hydrogen filling / discharging liner. The rebound device consists of a mounting top plate, a rebound spring, and a mounting base plate from top to bottom. The mounting top plate is fixed below the hydrogen filling / discharging liner, and the mounting base plate is mounted on the bottom plate of the vertical tank. The upper and lower ends of the rebound spring are connected to the mounting top plate and the mounting base plate, respectively. When one rebound device is installed, it is located at the bottom center of the hydrogen filling / discharging liner, with the hydrogen storage material outlet pipe fitted inside. If two or more rebound devices are installed, they are evenly distributed along the lower edge of the hydrogen filling / discharging liner. The function of the rebound device is to assist the expansion joint in rebounding, ensuring that after the solid hydrogen storage material releases hydrogen, the expansion joint is in a contracted state, allowing it to expand during the next hydrogen filling. When the hydrogen storage device is not storing hydrogen, the return spring is in a natural or appropriately compressed state. When the solid hydrogen storage material begins to absorb hydrogen, its volume expands, causing the expansion joint to extend downwards. This increases the storage volume of the hydrogen filling / discharging liner while simultaneously compressing the return spring, allowing the spring to accumulate elastic potential energy. When the solid hydrogen storage material in the filling / discharging liner begins to release hydrogen, its volume decreases, and it no longer exerts a downward force on the return spring. At this point, the elastic potential energy accumulated in the spring begins to be released, applying a force to the filling / discharging liner. The expansion joint of the filling / discharging liner absorbs the compressive stress, causing the expansion joint to contract in preparation for the next hydrogen storage and release cycle.

[0022] As a better solution, when the limiting hinge is not used, a limiting rod can be installed inside the spring of the rebound device. The limiting rod is fixed to the mounting base and kept vertical. The limiting rod can be cylindrical, square, or angle iron, with an outer diameter smaller than the inner diameter of the spring so that it can be installed inside the spring. After installation, the height difference between the spring and the limiting rod should be 60% to 90% of the maximum downward displacement of the hydrogen filling / discharging liner. The purpose of the limiting rod is to restrict the downward movement of the hydrogen filling / discharging liner. Once the liner reaches the limiting rod, it will stop moving downward. At this point, a stress sensor or contact sensor can be installed on the limiting rod. When the limiting rod begins to generate stress or contact with the liner is detected, an alarm is triggered or the process settings stop the storage of hydrogen in the hydrogen storage device. The advantage of the limiting rod is that it ensures that the hydrogen storage device will not be damaged by overfilling or excessive expansion of the solid hydrogen storage material.

[0023] When filling the hydrogen storage device with solid hydrogen storage material, open the hydrogen storage material inlet pipe and close the hydrogen storage material outlet pipe to fill the charging / discharging liner with solid hydrogen storage material. Keep the hydrogen storage material inlet and outlet pipes closed during the charging / discharging process. When unloading the solid hydrogen storage material from the hydrogen storage device, open the hydrogen storage material outlet pipe to unload the solid hydrogen storage material from the charging / discharging liner. When unloading the solid hydrogen storage material, the hydrogen storage material inlet pipe can also be opened as a vent. The purpose of opening the hydrogen storage material inlet pipe is to maintain the pressure balance of the liner and prevent the formation of negative pressure in the charging / discharging liner when the solid hydrogen storage material is rapidly unloaded, which would make it difficult to unload the solid hydrogen storage material or cause the charging / discharging liner to collapse. If the solid hydrogen storage material has poor flowability and cannot be unloaded due to caking, compression, or other reasons, the loosening air inlet can be opened and inert gas such as nitrogen can be introduced to loosen the solid hydrogen storage material and unload it more smoothly from the charging / discharging liner.

[0024] During hydrogen filling, the hydrogen inlet of this solid hydrogen storage device is opened and the hydrogen outlet is closed, forming a sealed cavity where hydrogen can only enter and not exit. Hydrogen enters the hydrogen distribution and collection box through the hydrogen inlet, and then flows into the filling / discharging liner through the connecting holes on the bottom plate of the distribution and collection box and the hydrogen distribution and collection pipe. Under pressure, the hydrogen is stored in the solid hydrogen storage material within the filling / discharging liner. During filling, the volume of the solid hydrogen storage material increases, causing the expansion joint to extend towards the outlet pipe of the hydrogen storage material. This increase in the volume of the filling / discharging liner compensates for the increase in the volume of the solid hydrogen storage material, preventing the risk of bulging. Because the solid hydrogen storage material releases heat during the absorption of hydrogen, once the heat released during hydrogen filling reaches a certain level, the temperature inside the hydrogen filling / discharging liner rises. At this point, a low-temperature medium is introduced into the teacup-shaped gap between the outer wall of the hydrogen filling / discharging liner and the inner wall of the vertical tank through the heat exchange medium inlet. The heat released by the solid hydrogen storage material absorbing hydrogen in the hydrogen filling / discharging liner is absorbed through the heat transfer effect of the liner wall and then leaves the hydrogen storage device through the heat exchange medium outlet, thus reducing the temperature of the solid hydrogen storage material in the hydrogen filling / discharging liner.

[0025] When releasing hydrogen, this solid hydrogen storage device opens the hydrogen outlet and closes the hydrogen inlet, creating a sealed cavity that allows only outflow of hydrogen. Hydrogen is released from the solid hydrogen storage material and enters the hydrogen distribution and collection pipe, then flows through the connecting holes to fill the hydrogen distribution and collection box. Once a certain pressure is established, the hydrogen leaves the storage device through the outlet, supplying downstream devices or external equipment. After releasing hydrogen, the solid hydrogen storage material decreases in volume, and the expansion joint contracts due to its resilience, restoring the inner tank to its pre-filling / discharging state. Since the solid hydrogen storage material needs to absorb heat to release the stored hydrogen, a high-temperature heat exchange medium enters through the heat exchange medium inlet into the cup-shaped gap between the outer wall of the inner tank and the inner wall of the vertical tank. Through heat transfer from the inner tank wall, heat is transferred to the solid hydrogen storage material, causing it to absorb heat and release hydrogen. The heat exchange medium, after releasing heat, leaves the storage device through the heat exchange medium outlet.

[0026] The same medium can be used during hydrogen charging and discharging. By setting up external heaters or coolers, the heat exchange medium is cooled during hydrogen charging and heated during hydrogen discharging, so as to achieve the purpose of recycling.

[0027] The present invention has the following beneficial effects:

[0028] 1) By storing hydrogen in solid hydrogen storage materials, there is no need for harsh conditions such as high pressure or low temperature. The hydrogen storage process does not require excessive energy consumption, and it is safe, efficient and has a stable hydrogen release rate.

[0029] 2) By setting expansion elements and heat exchange elements, the heat and volume compensation problems in the hydrogen charging and discharging process are solved at the same time, so that the hydrogen charging and discharging can be carried out at a higher rate; the expansion elements reduce the mutual expansion and compression of solid hydrogen storage alloy materials, and the internal lattice of solid hydrogen storage alloy materials can still maintain a good morphology after more hydrogen charging and discharging cycles, resulting in slower decay of hydrogen storage capacity and longer life of solid hydrogen storage materials.

[0030] 3) By creating an internal volume change through expansion elements, the stress applied to the hydrogen storage shell caused by volume expansion is greatly reduced, avoiding risks such as bulging and cracking of the solid hydrogen storage shell. Furthermore, by setting a limiting device, the safety and reliability of solid hydrogen storage are improved, and the cost of solid hydrogen storage is reduced. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the solid hydrogen storage device of the present invention;

[0032] Figure 2 yes Figure 1 A top view of the structure along the central AA direction;

[0033] Figure 3 yes Figure 1 A schematic diagram of a structure for plugging the outlet of hydrogen storage material;

[0034] Figure 4 yes Figure 1 A schematic diagram of a type of mid-limit hinge;

[0035] Figure 5 yes Figure 1 A schematic diagram of a rebound device.

[0036] In the diagram: 1-Hydrogen storage material inlet pipe, 2-Hydrogen distribution and collection box, 3-Hydrogen inlet, 4-Hydrogen outlet, 5-Connecting hole, 6-Heat exchange medium inlet, 7-Heat exchange medium outlet, 8-Vertical tank, 9-Hydrogen distribution and collection pipe, 10-Hydrogen hole, 11-Hydrogen filling / discharging inner liner, 12-Sliding seal, 13-Hydrogen storage material outlet pipe, 14-Hydrogen storage material outlet plug, 15-Solid hydrogen storage material, 16-Rebound device, 17-Loosening air inlet, 18-Limiting hinge, 19-Expansion joint, 20-Baffle, 21-Stuffing seal, 22-Baffle cylinder, 23-Handle, 24-Mounting ring, 25-Connecting rod, 26-Connecting hinge, 27-Mounting top plate, 28-Limiting rod, 29-Rebound spring, 30-Mounting bottom plate. Detailed Implementation

[0037] The present invention will now be described in detail with reference to the accompanying drawings.

[0038] like Figure 1 and Figure 2As shown, the solid hydrogen storage device provided by the present invention includes a vertical tank 8, a hydrogen distribution and collection box 2 and a hydrogen filling and discharging liner 11 arranged coaxially with the vertical tank 8 from top to bottom inside the vertical tank 8; the hydrogen distribution and collection box 2 is cylindrical and is formed by the inner wall of the vertical tank 8, the top plate of the vertical tank 8 and the bottom plate of the hydrogen distribution and collection box 2; the hydrogen filling and discharging liner 11 is cylindrical and suspended below the bottom plate of the hydrogen distribution and collection box 2. The bottom plate of the hydrogen distribution and collection box 2 and the inner wall of the hydrogen filling and discharging liner 11 form a closed space, and a teacup-shaped gap is formed between the outer wall of the hydrogen filling and discharging liner 11 and the inner wall of the vertical tank 8; a heat exchange medium inlet 6 and a heat exchange medium outlet 7 are provided on the tank wall of the vertical tank 8 corresponding to the teacup-shaped gap.

[0039] A hydrogen storage material inlet pipe 1 is located at the top center of the hydrogen filling / discharging inner liner 11, connected to the inner liner 11. The hydrogen storage material inlet pipe 1 passes through the hydrogen distribution and collection box 2 and extends to the outside of the top plate of the vertical tank 8. A hydrogen storage material outlet pipe 13 is located at the bottom center of the hydrogen filling / discharging inner liner 11, connected to the inner liner 11. The hydrogen storage material outlet pipe 13 passes through the bottom of the teacup-shaped gap and extends to the outside of the bottom plate of the vertical tank 8. A groove is provided between the outer wall of the hydrogen storage material outlet pipe 13 and the bottom plate of the vertical tank 8. The tank body 8 has an axially movable sliding seal 12; the cylindrical wall of the hydrogen filling / discharging inner liner 11 is provided with one or more expansion joints 19, which can extend or contract axially; the hydrogen filling / discharging inner liner 11 is filled with solid hydrogen storage material 15; the outer side of the wall of the hydrogen filling / discharging inner liner 11 is provided with a limiting hinge 18 along the axial direction; a rebound device 16 is provided inside the vertical tank body 8 and below the hydrogen filling / discharging inner liner 11; and a loosening air inlet 17 is provided on the wall of the hydrogen filling / discharging inner liner 11.

[0040] The vertical tank 8 containing the hydrogen distribution and collection box 2 has a hydrogen inlet 3 and a hydrogen outlet 4 on its tank wall. A connecting hole 5 is opened on the bottom plate of the hydrogen distribution and collection box 2 in the area within the cross-section of the hydrogen filling and discharging liner 11. A hydrogen distribution and collection pipe 9 is installed on the connecting hole 5, which is suspended inside the hydrogen filling and discharging liner 11 and closed at the bottom. The hydrogen distribution and collection pipe 9 is buried in the solid hydrogen storage material 15. A hydrogen hole 10 is opened on the pipe wall of the hydrogen distribution and collection pipe 9 to connect the hydrogen distribution and collection box 2 and the hydrogen filling and discharging liner 11, so as to ensure that hydrogen can enter or leave the hydrogen filling and discharging liner 11 evenly. The heat exchange medium inlet 6, the teacup-shaped gap between the outer wall of the hydrogen filling and discharging liner and the inner wall of the vertical tank, and the heat exchange medium outlet 7 form a closed and connected cavity, which allows the heat exchange medium to remove heat from the solid hydrogen storage material 15 filled in the hydrogen filling and discharging liner 11 or to replenish heat to the solid hydrogen storage material 15.

[0041] Figure 3 yes Figure 1A schematic diagram of a structure for a hydrogen storage material outlet plug. As shown in the figure, the hydrogen storage material outlet plug includes a baffle 20, a packing seal 21, a baffle cylinder 22, a handle 23, and an installation ring 24. The baffle cylinder 22 is a cylindrical tube with an outer diameter smaller than the inner diameter of the hydrogen storage material outlet pipe 13, typically 4-10 mm smaller. One end of the baffle cylinder 22 is closed by the baffle 20, while the other end is open. The baffle end is inserted into the hydrogen storage material outlet pipe 13 to prevent solid hydrogen storage material from entering the outlet pipe 13 when not unloading. The baffle 20 is aligned with the bottom of the filling / discharging inner liner 11. The shape is consistent; a handle 23 is provided at the open end of the baffle 22, which can be round steel or angle steel, etc.; the gap between the hydrogen storage material outlet pipe 13 and the hydrogen storage material outlet plug is filled with filler such as ceramic fiber rope and sealed 21, the diameter of the ceramic fiber rope should be 5-11mm; the mounting ring 24 is a circular ring, which is fitted outside the baffle 22, and a circular hole is opened on the mounting ring 24. A threaded hole is opened at the same position on the hydrogen storage material outlet pipe 13 so that the mounting ring 24 can be fixed on the hydrogen storage material outlet pipe 13 with screws.

[0042] Figure 4 yes Figure 1 A schematic diagram of a limiting hinge structure. As shown in the figure, the limiting hinge consists of connecting rods 25 and connecting hinges 26, with the connecting rods 25 connected via the connecting hinges 26. The initial installation position of the limiting hinge is such that the connecting rods 25 are at a certain angle, with the included angle between the connected rods preferably being 30 to 60 degrees. It is preferable to have two or more limiting hinges, evenly distributed around the circumference of the hydrogen filling / discharging liner, to ensure that the hydrogen filling / discharging liner is in a uniformly limited position.

[0043] Figure 5 yes Figure 1 A schematic diagram of the rebound device is shown. As illustrated, the rebound device consists of a mounting top plate 27, a rebound spring 29, and a mounting base plate 30 from top to bottom. When one rebound device is installed, it is located at the bottom center of the hydrogen filling / discharging liner, with the hydrogen storage material outlet pipe fitted inside. If two or more rebound devices are installed, they are evenly distributed along the lower edge of the hydrogen filling / discharging liner. When no limiting hinge is installed, a limiting rod 28 can be installed inside the rebound spring. The purpose of the limiting rod is to restrict the downward movement of the hydrogen filling / discharging liner. Once the hydrogen filling / discharging liner reaches the limiting rod 28, it will no longer move downwards.

[0044] The operation process of the present invention will be described below with reference to the accompanying drawings:

[0045] 1) Loading and unloading of solid hydrogen storage materials

[0046] Close the hydrogen storage material outlet pipe 13 and open the hydrogen storage material inlet pipe 1. Under the influence of gravity, the hydrogen storage material 15 enters the hydrogen filling / discharging liner 11 from the hydrogen storage material inlet pipe 1 and is stored in the hydrogen filling / discharging liner. When the solid hydrogen storage material 15 needs to be replaced due to the decline in its lifespan, open the hydrogen storage material outlet pipe 13. Under the influence of gravity, the solid hydrogen storage material 15 in the hydrogen filling / discharging liner 11 leaves the hydrogen storage device from the hydrogen storage material outlet pipe 13. If the solid hydrogen storage material 15 cannot be discharged due to poor flowability caused by caking, compression, etc., the loosening air inlet 17 can be opened and inert gases such as nitrogen can be introduced to loosen the solid hydrogen storage material 15 and discharge it more smoothly from the hydrogen filling / discharging liner 11.

[0047] 2) Hydrogen charging of solid hydrogen storage materials

[0048] Simultaneously close hydrogen outlet 4, hydrogen storage material inlet pipe 1, hydrogen storage material outlet pipe 13, and loosening air inlet 17, and open hydrogen inlet 3. Hydrogen enters hydrogen distribution and collection box 2 through hydrogen inlet 3, and enters hydrogen filling and discharging liner 11 through connecting hole 5, hydrogen distribution and collection pipe 9, and hydrogen hole 10, where it is absorbed and stored by solid hydrogen storage material 15. During hydrogen filling, low-temperature heat exchange medium enters from heat exchange medium inlet 6 and fills the teacup-shaped gap formed by the inner wall of vertical tank 8 and the outer wall of hydrogen filling and discharging liner 11. After absorbing the heat released by the solid hydrogen storage material 15 in the hydrogen filling and discharging liner 11 due to the absorption of hydrogen, it leaves the hydrogen storage device through heat exchange medium outlet 7. During hydrogen filling, the volume of solid hydrogen storage material 15 increases, causing expansion joint 19 to extend towards hydrogen storage material outlet pipe 13. The volume of hydrogen filling and discharging liner 11 increases, compensating for the increase in the volume of solid hydrogen storage material 15, and preventing the risk of bulging in the hydrogen filling and discharging liner 11.

[0049] 3) Hydrogen release from solid hydrogen storage materials

[0050] Simultaneously close hydrogen inlet 3, hydrogen storage material inlet pipe 1, hydrogen storage material outlet pipe 13, and loosening air inlet 17, and open hydrogen outlet 4. High-temperature heat exchange medium enters through heat exchange medium inlet 6 and fills the teacup-shaped gap formed by the inner wall of the vertical tank 8 and the outer wall of the hydrogen filling / discharging liner 11, providing heat to the solid hydrogen storage material 15 in the liner 11. The solid hydrogen storage material 15 absorbs heat and releases hydrogen gas, which exits the hydrogen storage device through hydrogen outlet 4; the heat exchange medium, after releasing heat, exits the hydrogen storage device through heat exchange medium outlet 7. After releasing hydrogen, the solid hydrogen storage material 15 decreases in volume, and the expansion joint 19 contracts under elastic force, allowing the hydrogen filling / discharging liner 11 to return to its pre-filling state as much as possible. Of course, to ensure the contraction of the hydrogen filling / discharging liner 11, a limiting hinge 18 can be used to prevent excessive deformation of the expansion joint 19, and a springback device 16 can be used to assist the contraction of the expansion joint 19. Alternatively, without setting a limiting hinge, a limiting rod 28 can be set inside the spring spring of the rebound device to prevent excessive deformation of the expansion joint 19.

Claims

1. A solid hydrogen storage device, characterized in that: The system includes a vertical tank, a hydrogen distribution and collection box coaxially arranged from top to bottom within the vertical tank, and a hydrogen filling and discharging liner. The hydrogen distribution and collection box is cylindrical and is formed by the inner wall of the vertical tank, the top plate of the vertical tank, and the bottom plate of the hydrogen distribution and collection box. The hydrogen filling and discharging liner is cylindrical and suspended below the bottom plate of the hydrogen distribution and collection box. The bottom plate of the hydrogen distribution and collection box and the inner wall of the hydrogen filling and discharging liner form a closed space, and a teacup-shaped gap is formed between the outer wall of the hydrogen filling and discharging liner and the inner wall of the vertical tank. A heat exchange medium inlet and a heat exchange medium outlet are provided on the vertical tank wall corresponding to the teacup-shaped gap. A hydrogen storage material inlet pipe is located at the top center of the hydrogen filling / discharging inner liner, connecting to the inner liner. This inlet pipe passes through the hydrogen distribution and collection box and extends to the outside of the top plate of the vertical tank. A hydrogen storage material outlet pipe is located at the bottom center of the inner liner, connecting to the inner liner. This outlet pipe passes through the bottom of a teacup-shaped gap and extends to the outside of the bottom plate of the vertical tank. A sliding seal is provided between the outer wall of the outlet pipe and the bottom plate of the vertical tank, allowing it to move axially. One or more expansion joints are provided on the cylindrical wall of the inner liner, allowing them to extend or contract axially. The inner liner is filled with solid hydrogen storage material. The vertical tank containing the hydrogen distribution and collection box has a hydrogen inlet and a hydrogen outlet on its wall. A connecting hole is opened on the bottom plate of the hydrogen distribution and collection box in the area of ​​the hydrogen filling and discharging liner. The connecting hole connects the hydrogen distribution and collection box and the hydrogen filling and discharging liner, ensuring that hydrogen can enter or leave the hydrogen filling and discharging liner evenly. The heat exchange medium inlet, the teacup-shaped gap between the outer wall of the hydrogen filling and discharging liner and the inner wall of the vertical tank, and the heat exchange medium outlet form a closed and connected cavity, which allows the heat exchange medium to remove heat from the solid hydrogen storage material filled in the hydrogen filling and discharging liner or to replenish the solid hydrogen storage material.

2. The solid hydrogen storage device according to claim 1, characterized in that: The outlet pipe of the hydrogen storage material is equipped with a hydrogen storage material outlet plug.

3. The solid hydrogen storage device according to claim 2, characterized in that: The hydrogen storage material outlet plug includes a baffle, a packing seal, a baffle cylinder, and a handle. The baffle cylinder is a cylindrical tube with an outer diameter smaller than the inner diameter of the hydrogen storage material outlet pipe. One end of the baffle cylinder is closed with a baffle, and the other end is open. The baffle end is inserted into the hydrogen storage material outlet pipe to prevent solid hydrogen storage material from entering the outlet pipe when not unloading. The baffle has the same shape as the bottom of the hydrogen filling / discharging liner. A handle is provided at the open end, which can be a round steel or angle steel, to facilitate the installation and removal of the hydrogen storage material outlet plug. A packing seal is provided in the gap between the hydrogen storage material outlet pipe and the hydrogen storage material outlet plug to prevent solid hydrogen storage material from entering the gap between them.

4. The solid hydrogen storage device according to claim 3, characterized in that: The baffle is provided with a mounting ring at the open end. The mounting ring is a circular ring that is fitted over the baffle. A circular hole is made on the mounting ring, and a threaded hole is made at the same position on the hydrogen storage material outlet pipe so that the mounting ring can be fixed to the hydrogen storage material outlet pipe with screws.

5. The solid hydrogen storage device according to claim 1, characterized in that: Limit hinges are installed on the inner wall of the hydrogen filling / discharging liner.

6. The solid hydrogen storage device according to claim 5, characterized in that: The limiting hinge consists of a connecting rod and a connecting hinge. The connecting rod is connected by the connecting hinge and can rotate around the connecting hinge. The initial position of the limiting hinge is when the connecting rods are at a certain angle. The limiting hinge moves downward as the inner wall of the hydrogen filling and discharging liner expands and elongates. When the connecting rods overlap and form a straight line, that is, when the included angle between the two connected connecting rods is 0 degrees, the limiting hinge reaches the limiting termination position and restricts the inner wall of the hydrogen filling and discharging liner from continuing to move downward and elongate.

7. The solid hydrogen storage device according to claim 1, characterized in that: A rebound device is installed inside the vertical tank, below the hydrogen filling / discharging liner.

8. The solid hydrogen storage device according to claim 7, characterized in that: The rebound device consists of a mounting top plate, a rebound spring, and a mounting bottom plate from top to bottom. The mounting top plate is fixed below the hydrogen filling / discharging inner liner, and the mounting bottom plate is installed on the bottom plate of the vertical tank. The upper and lower ends of the rebound spring are connected to the mounting top plate and the mounting bottom plate, respectively.

9. The solid hydrogen storage device according to claim 8, characterized in that: The rebound device has a limiting rod inside the rebound spring. The limiting rod is cylindrical or square, and its outer diameter is smaller than that of the rebound spring. The height of the limiting rod is lower than that of the rebound spring in its natural state. The limiting rod restricts the downward movement of the hydrogen filling / discharging liner. When the hydrogen filling / discharging liner moves down to contact the limiting rod, it will no longer move downward.

10. The solid hydrogen storage device according to claim 5, characterized in that: A rebound device is installed inside the vertical tank, below the hydrogen filling / discharging liner.

11. The solid hydrogen storage device according to claim 1, characterized in that: A hydrogen distribution and collection pipe is installed in the connecting hole on the bottom plate of the hydrogen distribution and collection box. The hydrogen distribution and collection pipe is suspended inside the hydrogen filling and discharging liner and buried in the solid hydrogen storage material. The lower end of the hydrogen distribution and collection pipe is sealed with a sealing plate. Hydrogen holes are opened on the pipe wall, and the diameter of the hydrogen holes is smaller than the minimum particle size of the solid hydrogen storage material.

12. The solid hydrogen storage device according to claim 1, characterized in that: A hydrogen distribution and collection pipe is installed in the connecting hole on the bottom plate of the hydrogen distribution and collection box. The hydrogen distribution and collection pipe is suspended inside the hydrogen filling and discharging liner and buried in the solid hydrogen storage material. The lower end of the hydrogen distribution and collection pipe is sealed with a sealing plate. The sealing plate has hydrogen holes with a diameter smaller than the minimum particle size of the solid hydrogen storage material.

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