A solid-state hydrogen storage device and method thereof

Abstract

The present invention discloses a solid-state hydrogen storage device and a method thereof. The present invention uses a thermochemical heat storage device with a high heat storage density as the heat source when the solid-state hydrogen storage device releases hydrogen, without potential hazards such as combustion and explosion, and can greatly improve the safety and storage weight ratio parameters of the solid-state hydrogen storage device. By indirectly adjusting the contact area between the energy storage type heating block and the liquid adsorbent through a mechanical adjusting rod, and further controlling the vaporization amount of the adsorbent, precise regulation of the heat release amount of the thermochemical adsorption bed can be achieved. During the hydrogen charging process of the solid-state hydrogen storage device, heat storage can be completed by adding liquid adsorbent to the liquid storage tank, which has characteristics such as simple operation and short time consumption, and significantly enhances the applicability of the solid-state hydrogen storage device on hydrogen energy vehicles.

Description

Technical Field

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

[0002] Solid-state hydrogen storage refers to storing hydrogen in a solid-state hydrogen storage material medium through physical or chemical adsorption. This new type of hydrogen storage technology has advantages such as high volumetric hydrogen storage density, convenient storage and transportation, and good safety performance, so it is considered to be the most promising hydrogen storage method. The hydrogen storage mechanism of solid materials can generally be divided into two categories, namely physical hydrogen storage and chemical hydrogen storage. Physical hydrogen storage materials include carbonaceous adsorption materials, metal-organic frameworks, and zeolites, etc. Hydrogen is adsorbed on the micropores, frameworks, or tube structures of the materials without the occurrence of chemical reactions. For chemical hydrogen storage, the materials mainly include various metal alloys, metal hydrides, coordination hydrides, and hydrogen hydrates, etc., with chemical reactions occurring, and hydrogen is stored in the alloy lattice of metal hydrides. Among them, due to its rich reserves, high theoretical hydrogen storage capacity (7.6 wt%), and volumetric hydrogen storage density (110 kg / m 3 H2), low cost, and the fact that elemental magnesium can react with hydrogen at high temperatures to form MgH2, the MgH2 / Mg system is considered to be one of the most promising hydrogen storage systems. However, solid-state hydrogen storage requires a certain amount of heat during the hydrogen release process. Conventional electric heating methods mainly have two deficiencies. One is that it will reduce the energy utilization rate of solid-state hydrogen storage vehicles, and using methods such as storage batteries will significantly increase the volume and weight of the solid-state hydrogen storage device. The other is that there are obvious safety hazards in electric heating and other methods, and accidents such as combustion and explosion are likely to occur. Summary of the Invention

[0003] The purpose of the present invention is to provide a solid-state hydrogen storage device that uses a thermochemical heat storage technology with a high heat storage density (800 - 1000 kJ / kg) as the heat source of the solid-state hydrogen storage device, greatly improving the safety and storage weight ratio parameters of the solid-state hydrogen storage device. In addition, during the hydrogen charging process of the solid-state hydrogen storage device, heat storage can be completed by injecting a liquid adsorption working medium, which has the characteristics of simple and fast operation, and improves the applicability of the solid-state hydrogen storage device on hydrogen energy vehicles.

[0004] The present invention intends to achieve the purpose of the present invention with the following technical solutions:

[0005] In a first aspect, the present invention provides a solid-state hydrogen storage device, which includes an adiabatic hydrogen storage chamber and an adiabatic heat storage chamber;

[0006] The hydrogen storage chamber is filled with a hydrogen storage alloy, and a hydrogen pipeline with a hydrogen valve penetrates from the outside of the hydrogen storage chamber into the inside of the hydrogen storage chamber; the hydrogen pipeline inputs hydrogen into the hydrogen storage alloy for storage during the hydrogen charging stage and discharges hydrogen from the hydrogen storage alloy during the hydrogen release stage;

[0007] A thermochemical adsorption bed is arranged inside the hydrogen storage alloy. The thermochemical adsorption bed forms a heat exchange contact with the hydrogen storage alloy but cannot exchange substances. During the hydrogen charging stage, the thermochemical adsorption bed realizes the desorption of the gaseous adsorption working medium and the regeneration of the adsorption bed by absorbing the heat in the hydrogen storage alloy. During the hydrogen release stage, the thermochemical adsorption bed releases heat to the hydrogen storage alloy by adsorbing the externally input gaseous adsorption working medium.

[0008] An electric heating component for auxiliary heating is arranged on the surface of the thermochemical adsorption bed. The thermochemical adsorption bed is provided with a working medium inlet and outlet, and the working medium inlet and outlet are connected to one end of the adsorption working medium pipeline. The other end of the adsorption working medium pipeline is connected to the heat storage cavity. A liquid storage device is arranged inside the heat storage cavity. The liquid storage device is connected with the adsorption working medium pipeline and the filling pipeline. The adsorption working medium pipeline is sequentially connected to the top gas phase space of the liquid storage device, a regulating valve, and the other end of the adsorption working medium pipeline, so as to input the gaseous adsorption working medium in the liquid storage device into the thermochemical adsorption bed when the regulating valve is opened. One end of the filling pipeline is connected to the top gas phase space of the liquid storage device, and the other end passes through the heat storage cavity and is connected to an external filling valve, which is used to fill the liquid storage device with liquid adsorption working medium when the filling valve is opened. The regeneration pipeline is sequentially connected to the other end of the adsorption working medium pipeline and a regeneration pump, then passes through the heat storage cavity and is connected to an external regeneration valve, which is used to discharge the gaseous adsorption working medium generated by the regeneration desorption of the thermochemical adsorption bed when the regeneration valve is opened. A heat storage type heating block fixed to the upper permanent magnet is arranged inside the liquid storage device. The outer surface of the heat storage type heating block can directly exchange heat with the liquid adsorption working medium. A lower permanent magnet with controllable spatial position is arranged outside the liquid storage device. The heating area of the heat storage type heating block in the liquid adsorption working medium is adjusted by the mutual acting force between the two permanent magnets.

[0009] As a preference of the above first aspect, the electric heating component is an electric heating film attached to the surface of the thermochemical adsorption bed. The power supply wire of the electric heating film passes through the shell of the solid hydrogen storage device and is connected to a power supply.

[0010] As a preference of the above first aspect, the lower permanent magnet is installed below the liquid storage device in the heat storage cavity, and the spatial position relative to the upper permanent magnet is controlled by a mechanical adjusting rod extending out of the heat storage cavity.

[0011] As a preference of the above first aspect, a guiding frame extending from the inside to the outside is installed in the liquid storage device. The upper permanent magnet, the heat storage type heating block, and the lower permanent magnet are all installed on the guiding frame. The guiding frame restricts the three to only slide vertically up and down. The immersion depth of the heat storage type heating block in the liquid adsorption working medium is positively correlated with its heating area.

[0012] Preferably, as the first aspect described above, the energy storage heating block can float in the liquid adsorption working medium inside the liquid storage container. The upper permanent magnet and the lower permanent magnet are opposite in poles and thus attract each other. During the process that the lower permanent magnet moves downward away from the upper permanent magnet, the immersion depth of the energy storage heating block gradually decreases. During the process that the lower permanent magnet moves upward close to the upper permanent magnet, the immersion depth of the energy storage heating block gradually increases.

[0013] Preferably, as the first aspect described above, the energy storage heating block is a latent heat type phase change heat storage module or a magnetothermal heating module, and is installed in the liquid storage container in a replaceable form.

[0014] Preferably, as the first aspect described above, the hydrogen storage alloy is selected as a magnesium-based hydrogen storage alloy.

[0015] Preferably, as the first aspect described above, the outlet end of the regeneration pipeline is externally connected to a refrigeration device for liquefying and recycling the discharged gaseous adsorption working medium.

[0016] Preferably, as the first aspect described above, the thermochemical adsorption bed is filled with a solid thermochemical adsorbent, and the adsorption working medium is of a working medium type that matches the thermochemical adsorbent to form thermochemical heat storage.

[0017] In the second aspect, the present invention provides an operation method of a solid hydrogen storage device according to any one of the above first aspect solutions, which includes an alternately performed hydrogen charging stage and a hydrogen releasing stage;

[0018] In the hydrogen charging stage, the thermochemical adsorption bed is in an adsorption saturation state, and its operation process is as follows:

[0019] Open the regeneration valve, start the regeneration pump, and keep the inside of the thermochemical adsorption bed initially in a negative pressure state; then open the hydrogen valve, and let the external hydrogen enter the hydrogen storage alloy through the hydrogen pipeline for hydrogen storage in the form of a compound. Meanwhile, the reaction heat is released and the thermochemical adsorption bed is heated. The thermochemical adsorption bed is regenerated by desorption and the released gaseous adsorption working medium enters the regeneration pipeline, and is discharged after passing through the regeneration pump and the regeneration valve in sequence; if the reaction heat during the hydrogen storage process is not enough to complete the regeneration of the thermochemical adsorption bed, then turn on the electric heating component to assist in heating the thermochemical adsorption bed; when the hydrogen charging is completed and the thermochemical adsorption bed is regenerated, close the regeneration valve and the hydrogen valve, stop the regeneration pump, then open the filling valve, and let the external liquid adsorption working medium enter the liquid storage container through the filling pipeline. After reaching the specified liquid level, close the filling valve. The energy storage heating block accumulates heat through input heat or direct replacement, completes the hydrogen charging stage, and enters the hydrogen releasing stage;

[0020] The operation process of the hydrogen releasing stage is as follows:

[0021] Open the hydrogen valve and the regulating valve. By controlling the position of the lower permanent magnet relative to the upper permanent magnet, the energy storage type heating block is gradually immersed in the liquid adsorption working medium to heat the liquid adsorption working medium. The gaseous adsorption medium generated by the vaporization of the liquid adsorption working medium enters the thermochemical adsorption bed through the adsorption working medium pipeline and reacts with the thermochemical adsorbent in the thermochemical adsorption bed. The released adsorption heat heats the hydrogen storage alloy. After the hydrogen storage alloy reaches the corresponding temperature, it starts to release hydrogen, and the hydrogen is supplied to the outside through the hydrogen pipeline. When the hydrogen flow needs to be adjusted, the heating area of the energy storage type heating block in the liquid adsorption working medium is changed by controlling the position of the lower permanent magnet relative to the upper permanent magnet, so as to change the flow rate of the gaseous adsorption working medium transported to the thermochemical adsorption bed, and thus change the hydrogen release amount of the hydrogen storage alloy based on the regulation of the heat release amount of the thermochemical adsorption bed.

[0022] The prominent and beneficial technical effects of the present invention compared with the prior art are as follows: Using a thermochemical energy storage device with a high heat storage density as the heat source when the solid hydrogen storage device releases hydrogen, there are no potential hazards such as combustion and explosion, and the safety and storage weight ratio parameters of the solid hydrogen storage device can be greatly improved. By indirectly adjusting the contact area between the energy storage type heating block and the liquid adsorption working medium through a mechanical adjusting rod, and then controlling the vaporization amount of the adsorption working medium, the precise regulation of the heat release amount of the thermochemical adsorption bed can be realized. During the hydrogen charging process of the solid hydrogen storage device, heat storage can be completed by adding liquid adsorption working medium to the liquid storage tank, which has the characteristics of simple operation and short time consumption, significantly enhancing the applicability of the solid hydrogen storage device on hydrogen energy vehicles. In addition, the thermochemical adsorption bed is regenerated simultaneously, absorbing a large amount of reaction heat during the hydrogen charging of the solid hydrogen storage device, increasing the hydrogen charging amount, and greatly reducing the external heat consumption, simplifying the system operation process.

[0023] The following will further illustrate the concept, specific structure and technical effects of the present invention with reference to the drawings to fully understand the purpose, features and effects of the present invention. Description of the Drawings

[0024] Figure 1 is a schematic structural diagram of a solid hydrogen storage device of the present invention.

[0025] Figure 1 In the figure: hydrogen storage chamber 1, heat storage chamber 2, hydrogen pipeline 3, hydrogen valve 4, hydrogen storage alloy 5, thermochemical adsorption bed 6, electric heating film 7, power cord 8, adsorption working medium pipeline 9, regulating valve 10, liquid storage device 11, guide frame 12, upper permanent magnet 13, energy storage type heating block 14, lower permanent magnet 15, mechanical adjusting rod 16, regeneration pipeline 17, regeneration pump 18, regeneration valve 19, filling pipeline 20, filling valve 21. Detailed Embodiments

[0026] To make the above objects, features, and advantages of the present invention more apparent and understandable, the following will describe the specific embodiments of the present invention in detail with reference to the accompanying drawings. Many specific details are set forth in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below. The technical features in the various embodiments of the present invention can be combined correspondingly without conflict.

[0027] In the description of the present invention, it should be understood that when an element is considered to be "connected" to another element, it can be directly connected to the other element or indirectly connected, that is, there is an intermediate element. On the contrary, when an element is referred to as being "directly" connected to another element, there is no intermediate element.

[0028] In the description of the present invention, it should be understood that the terms "first" and "second" are only used for the purpose of distinguishing descriptions, and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of the features.

[0029] See Figure 1 , in a preferred embodiment of the present invention, a solid-state hydrogen storage device is provided. The components of the device include a hydrogen storage chamber 1, a heat storage chamber 2, a hydrogen pipeline 3, a hydrogen valve 4, a hydrogen storage alloy 5, a thermochemical adsorption bed 6, an electric heating film 7, a power cord 8, an adsorption working medium pipeline 9, a regulating valve 10, a liquid storage device 11, a guiding frame 12, an upper permanent magnet 13, an energy storage type heating block 14, a lower permanent magnet 15, a mechanical regulating rod 16, a regeneration pipeline 17, a regeneration pump 18, a regeneration valve 19, a filling pipeline 20, a filling valve 21, etc. The following will describe in detail the cooperation and actuation relationship between the components in the solid-state hydrogen storage device.

[0030] In the solid-state hydrogen storage device, the hydrogen storage chamber 1 is used to store the hydrogen medium, and the heat storage chamber 2 is used to install the heat storage components. Together, they form the main part of the chemical heat storage type solid-state hydrogen storage device.

[0031] The hydrogen storage chamber 1 is filled with a hydrogen storage alloy 5. The hydrogen storage alloy 5 is a hydrogen storage alloy that can reversibly store hydrogen. The principle of its hydrogen storage is that the alloy reacts with hydrogen to form an alloy hydride, but this reaction is a reversible process. The forward reaction is hydrogen absorption and heat release; the reverse reaction is hydrogen release and heat absorption. Therefore, by changing the temperature and pressure conditions, the reaction can be carried out forward and backward repeatedly to achieve the hydrogen absorption and release function of the material. There are currently many existing hydrogen storage alloys. In the embodiments of the present invention, a magnesium-based hydrogen storage alloy, such as the MgH2 / Mg system, is preferably used.

[0032] To control the input and output of hydrogen, a hydrogen pipeline 3 with a hydrogen valve 4 can be passed from outside the hydrogen storage chamber 1 into the inside of the hydrogen storage chamber 1. The hydrogen valve 4 can be arranged outside the hydrogen storage chamber 1 for convenient control. The hydrogen pipeline 3 inputs hydrogen into the hydrogen storage alloy 5 for storage during the hydrogen charging stage, and discharges hydrogen from the hydrogen storage alloy 5 into the hydrogen-consuming equipment during the hydrogen release stage.

[0033] The desorption of hydrogen from the hydrogen storage alloy 5 depends on heat. Therefore, a thermochemical adsorption bed 6 is arranged inside the hydrogen storage alloy 5. The thermochemical adsorption bed 6 is in heat exchange contact with the hydrogen storage alloy 5. There is good thermal conductivity between the hydrogen storage alloy 5 and the thermochemical adsorption bed 6, but there is no mass exchange between the two, and they are isolated from each other. During the hydrogen charging stage, the thermochemical adsorption bed 6 realizes the desorption of the gaseous adsorption medium and the regeneration of the adsorption bed by absorbing the heat in the hydrogen storage alloy 5. During the hydrogen release stage, the thermochemical adsorption bed 6 releases heat to the hydrogen storage alloy 5 by adsorbing the externally input gaseous adsorption medium.

[0034] The thermochemical adsorption bed 6 in the present invention is based on the thermochemical adsorption heat storage technology. The thermochemical energy storage system stores energy in stable chemical materials, namely thermochemical adsorbents. The thermochemical energy storage system converts thermal energy into chemical potential energy during the reversible reaction, thereby storing or releasing heat in the adsorbent material. Therefore, the thermochemical adsorption bed 6 in the present invention is filled with a thermochemical adsorbent. The thermochemical adsorbent can adopt any adsorbent that can realize the corresponding thermochemical energy storage, preferably a solid adsorbent type, such as hydrates of salts, ammonia compounds (NH3 / N2), metal hydrides, hydroxides (Ca(OH)2 / CaO / H2O system), and carbonates (PbCO3, CaCO3), etc. The adsorption medium adopts a medium type that matches the thermochemical adsorbent to form thermochemical heat storage. The specific adsorbents and adsorption media for thermochemical adsorption heat storage exist in the prior art and can be selected according to needs. The heat storage density of the thermochemical adsorption bed 6 should be as high as possible, preferably 800 - 1000 kJ / kg.

[0035] Since the thermochemical adsorption bed 6 is arranged inside the hydrogen storage alloy 5, heat can be provided during the hydrogen release stage, and the heat generated during hydrogen charging can be utilized to promote the regeneration of the thermochemical adsorption bed and increase the hydrogen charging amount. Considering the stability under some special operating conditions, an electric heating component needs to be arranged on the surface of the thermochemical adsorption bed 6 in the present invention to provide heat for the regeneration of the thermochemical adsorption bed under special conditions and assist in providing the heat required for the desorption and regeneration of the thermochemical adsorption bed 6. The form of the electric heating component is not limited. In the embodiment of the present invention, the electric heating component is an electric heating film 7 attached to the surface of the thermochemical adsorption bed 6, and the power cord 8 of the electric heating film 7 passes through the shell of the solid hydrogen storage device to connect to the power supply. However, the electric heating film 7 is not always turned on and only needs to be turned on and operated when necessary.

[0036] The thermochemical adsorption bed 6 is provided with a working medium inlet and outlet, and the working medium inlet and outlet are connected to one end of the adsorption working medium pipeline 9. The other end of the adsorption working medium pipeline 9 is connected to the heat storage cavity 2 for the inflow and outflow of the gaseous adsorption working medium. A liquid storage device 11 is arranged inside the heat storage cavity 2. The liquid storage device 11 is connected to the adsorption working medium pipeline 9 and the filling pipeline 20, corresponding to the evaporation and filling functions of the adsorption working medium respectively.

[0037] During the operation of the liquid storage device 11, liquid adsorption working medium will be stored inside, so a gas phase space in the upper part and a liquid phase space in the lower part will be formed with the liquid level as the boundary. The adsorption working medium pipeline 9 is sequentially connected to the top gas phase space of the liquid storage device 11, the regulating valve 10, and the other end of the adsorption working medium pipeline 9, so as to input the gaseous adsorption working medium in the liquid storage device 11 into the thermochemical adsorption bed 6 when the regulating valve 10 is opened.

[0038] In addition, one end of the filling pipeline 20 is connected to the top gas phase space of the liquid storage device 11, and the other end passes through the heat storage cavity 2 and is connected to an external filling valve 21 for filling liquid adsorption working medium into the liquid storage device 11 when the filling valve 21 is opened.

[0039] The regeneration pipeline 17 is sequentially connected to the other end of the adsorption working medium pipeline 9 and the regeneration pump 18, then passes through the heat storage cavity 2 and is connected to an external regeneration valve 19. When the thermochemical adsorption bed is regenerated, gaseous adsorption working medium will be generated, so the gaseous adsorption working medium generated by the regeneration and desorption of the thermochemical adsorption bed 6 can be discharged through the regeneration pipeline 17 when the regeneration valve 19 is opened. In addition, if there is a need to recover the gaseous adsorption working medium, a refrigeration device can be externally connected to the outlet end of the regeneration pipeline 20 to liquefy and reuse the discharged gaseous adsorption working medium and replenish it back into the liquid storage device 11.

[0040] An energy storage type heating block 14 fixed to the upper permanent magnet 13 is arranged inside the liquid storage device 11. The outer surface of the energy storage type heating block 14 can directly exchange heat with the liquid adsorption working medium; a lower permanent magnet 15 with controllable spatial position is arranged outside the liquid storage device 11, and the heating area of the energy storage type heating block 14 in the liquid adsorption working medium is adjusted through the interaction force between the two permanent magnets.

[0041] The energy storage type heating block 14 is a latent heat type phase change energy storage module or a magnetothermal type heating module, and is installed in the liquid storage device 11 in a replaceable form. A large amount of heat can be stored inside the energy storage type heating block 14. When it is immersed in the liquid adsorption working medium in the liquid storage device 11, the heat inside can be released, causing the liquid adsorption working medium to gradually vaporize into a gaseous adsorption working medium. The gaseous adsorption working medium enters the inside of the thermochemical adsorption bed filled with the thermochemical adsorbent, and then the heat required for the desorption of hydrogen by the hydrogen storage alloy 5 can be generated. This method does not require using electric energy to provide the heat required for the desorption of hydrogen by the hydrogen storage alloy 5. Therefore, the energy utilization rate of the solid hydrogen storage vehicle can be ensured. Moreover, if the storage battery required for heating the hydrogen storage alloy 5 does not need to be carried, the volume and weight of the solid hydrogen storage device can be significantly reduced. At the same time, this heating method will not cause accidents such as combustion and explosion, and has extremely high safety. In addition, since the energy storage type heating block 14 is installed in the liquid storage device 11 in a replaceable form, heat can be input into it for energy storage, or a fully charged energy storage type heating block 14 can be directly replaced, which is convenient for selection according to different usage scenarios.

[0042] It should be noted that the above-mentioned energy storage type heating block 14 realizes the regulation of the heating power by changing the heating area in the liquid adsorption working medium, and further realizes the regulation of the output amount of the gaseous adsorption working medium. Since the energy storage type heating block 14 needs to be arranged inside the liquid storage device 11 and is difficult to be directly controlled, an upper permanent magnet 13 and a lower permanent magnet 15 are introduced in the present invention to adjust it. The upper permanent magnet 13 is fixed on the energy storage type heating block 14, and the two move synchronously. Therefore, the lower permanent magnet 15 can apply a force to the upper permanent magnet 13 and the energy storage type heating block 14 through repulsion or attraction. Theoretically, when the magnetic force of the lower permanent magnet 15 is large enough, it can be installed outside the heat storage cavity 2. However, in order to minimize the possibility of using a relatively large and heavy lower permanent magnet 15 as much as possible, the lower permanent magnet 15 in the present invention is installed below the liquid storage device 11 in the heat storage cavity 2, and the spatial position relative to the upper permanent magnet 13 is controlled by a mechanical adjusting rod 16 extending out of the heat storage cavity 2. The mechanical adjusting rod 16 is a rod body that can directly act on the lower permanent magnet 15 and apply an up and down driving force to it.

[0043] In addition, continue to refer to Figure 1As shown, in an embodiment of the present invention, in order to ensure the controllability of the spatial positions among the upper permanent magnet 13, the energy storage type heating block 14, and the lower permanent magnet 15, a guide frame 12 extending from the inside to the outside is installed in the liquid storage tank 11, and the guide frame 12 can be in the form of one or more vertically arranged guide rods. The upper permanent magnet 13, the energy storage type heating block 14, and the lower permanent magnet 15 are all installed on the guide frame 12, and the guide frame 12 restricts the three to only slide up and down vertically. Thus, the immersion depth of the energy storage type heating block 14 in the liquid adsorption working medium is positively correlated with its heating area, and the heating area can be adjusted by changing the immersion depth of the energy storage type heating block 14 in the liquid adsorption working medium, thereby changing its heating power.

[0044] In addition, theoretically, the upper permanent magnet 13 and the lower permanent magnet 15 can interact with each other through both repulsive force and attractive force. In an embodiment of the present invention, the energy storage type heating block 14 can float in the liquid adsorption working medium inside the liquid storage tank 11, and the upper permanent magnet 13 and the lower permanent magnet 15 are opposite in polarity and thus attract each other. Thus, during the process of the lower permanent magnet 15 moving downward away from the upper permanent magnet 13, the immersion depth of the energy storage type heating block 14 gradually decreases, and during the process of the lower permanent magnet 15 moving upward close to the upper permanent magnet 13, the immersion depth of the energy storage type heating block 14 gradually increases.

[0045] In another embodiment of the present invention, based on Figure 1 the solid hydrogen storage device shown, a method for operating the device is also provided, and its operation process is mainly divided into two stages. The first stage is the hydrogen charging stage, and the second stage is the hydrogen release stage.

[0046] First, assume that all valves are in the closed state, dynamic equipment such as the regeneration pump 18 is in the stopped state, the thermochemical adsorption bed 6 is in the adsorption saturation state, and the liquid adsorption working medium inside the liquid storage tank 11 has been completely consumed.

[0047] The first stage, the hydrogen charging stage:

[0048] (1) Open the regeneration valve 19, start the regeneration pump 18, the inside of the thermochemical adsorption bed 6 starts to be in a negative pressure state, and then open the hydrogen valve 4. External hydrogen enters the hydrogen storage alloy 5 through the hydrogen pipeline 3 and is stored in the form of a compound, while releasing reaction heat. Subsequently, the reaction heat heats the thermochemical adsorption bed 6, and the thermochemical adsorption bed 6 releases the gaseous adsorption working medium, which enters the regeneration pipeline 17 and is discharged after passing through the regeneration pump 18 and the regeneration valve 19 in sequence. In addition, if the reaction heat during the hydrogen storage process is not enough, and the reaction heat during the hydrogen storage process alone is not sufficient to complete the regeneration of the thermochemical adsorption bed 6, electrical energy can be supplied to the electric heating film 7 through the power line 8, and the thermochemical adsorption bed 6 can be assisted heated by the electric heating film 7.

[0049] (2) The above process continues until the hydrogen filling is completed and the regenerative thermochemical adsorption bed 6 is regenerated. At this time, the regeneration valve 19 and the hydrogen valve 4 are closed, the regeneration pump 18 is stopped, and then the filling valve 21 is opened. The external liquid adsorbent enters the liquid storage device 11 through the filling pipeline 20. After reaching the specified liquid level, the filling valve 21 is closed. Finally, heat is input into the energy storage heating block 14 or the energy storage heating block 14 is directly replaced.

[0050] After the above steps (1) and (2) are completed, the chemical heat storage type solid hydrogen storage device completes hydrogen filling and heat storage and enters the next stage.

[0051] The second stage is the hydrogen release stage:

[0052] Open the hydrogen valve 4 and the regulating valve 10. By controlling the position of the lower permanent magnet 15 relative to the upper permanent magnet 13, the energy storage heating block 14 is gradually immersed in the liquid adsorbent to heat the liquid adsorbent. The gaseous adsorbent generated by the vaporization of the liquid adsorbent enters the thermochemical adsorption bed 6 through the adsorbent pipeline 9 and reacts with the thermochemical adsorbent in the thermochemical adsorption bed 6. The released adsorption heat heats the hydrogen storage alloy 5. After the hydrogen storage alloy 5 reaches the corresponding temperature, it starts to release hydrogen and supplies hydrogen to the outside through the hydrogen pipeline 3. When hydrogen flow regulation is required, the heating area of the energy storage heating block 14 in the liquid adsorbent is changed by controlling the position of the lower permanent magnet 15 relative to the upper permanent magnet 13, so as to change the flow rate of the gaseous adsorbent transported to the thermochemical adsorption bed 6, and thus change the hydrogen release amount of the hydrogen storage alloy 5 based on the regulation of the heat release amount of the thermochemical adsorption bed 6. Specifically, based on Figure 1 the specific device structure, its control method can be carried out in the following way:

[0053] (1) Open the hydrogen valve 4 and the regulating valve 10. Control the position of the lower permanent magnet 15 on the guide frame 12 through the mechanical adjusting rod 16. Under the action of the magnetic field forces of the upper permanent magnet 13 and the lower permanent magnet 15, the energy storage heating block 14 is gradually immersed in the liquid adsorbent to heat it. Subsequently, the liquid adsorbent vaporizes and enters the thermochemical adsorption bed 6 through the adsorbent pipeline 9, reacts with the adsorbent in the thermochemical adsorption bed 6, releases a large amount of high-grade adsorption heat and heats the hydrogen storage alloy 5. After the hydrogen storage alloy 5 reaches the set temperature, it starts to release hydrogen and supplies hydrogen to the outside through the hydrogen pipeline 3.

[0054] (2) The above-mentioned solid-state hydrogen storage device can also adjust the hydrogen flow rate: when it is necessary to increase the hydrogen supply, the lower permanent magnet 15 is moved upward by the mechanical adjusting rod 16 to increase the immersion depth of the energy storage type heating block 14 in the liquid adsorption working medium, thereby increasing the vaporization amount of the liquid adsorption working medium. Subsequently, by increasing the opening degree of the regulating valve 10, the gaseous adsorption working medium is transported to the thermochemical adsorption bed 6 to make it release more adsorption heat, and finally the hydrogen release amount of the hydrogen storage alloy 5 is increased. When it is necessary to reduce the hydrogen supply, the lower permanent magnet 15 is moved downward by the mechanical adjusting rod 16 to reduce the immersion depth of the energy storage type heating block 14 in the liquid adsorption working medium, thereby reducing the vaporization amount of the liquid adsorption working medium. Subsequently, by reducing the opening degree of the regulating valve 10, the gaseous adsorption working medium is transported to the thermochemical adsorption bed 6 to make it release less adsorption heat, and finally the hydrogen release amount of the hydrogen storage alloy 5 is reduced.

[0055] The above-mentioned stage one and stage two run reciprocally to form the overall operation process of the above-mentioned solid-state hydrogen storage device.

[0056] The above is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A solid-state hydrogen storage device, characterized in that, It includes an adiabatic hydrogen storage chamber (1) and an adiabatic heat storage chamber (2); The hydrogen storage chamber (1) is filled with a hydrogen storage alloy (5), and a hydrogen pipeline (3) with a hydrogen valve (4) penetrates from the outside of the hydrogen storage chamber (1) into the inside of the hydrogen storage chamber (1); during the hydrogen filling stage, the hydrogen pipeline (3) inputs hydrogen into the hydrogen storage alloy (5) for storage, and during the hydrogen release stage, the hydrogen pipeline (3) discharges hydrogen from the hydrogen storage alloy (5); A thermochemical adsorption bed (6) is arranged inside the hydrogen storage alloy (5), and the thermochemical adsorption bed (6) forms a heat exchange contact with the hydrogen storage alloy (5) but there is no mass exchange; during the hydrogen filling stage, the thermochemical adsorption bed (6) realizes the desorption of the gaseous adsorption working medium and the regeneration of the adsorption bed by absorbing the heat in the hydrogen storage alloy (5), and during the hydrogen release stage, the thermochemical adsorption bed (6) releases heat to the hydrogen storage alloy (5) by adsorbing the externally input gaseous adsorption working medium; An electric heating component for auxiliary heating is arranged on the surface of the thermochemical adsorption bed (6); there are working medium inlets and outlets on the thermochemical adsorption bed (6), and one end of the working medium pipeline (9) is connected to the working medium inlets and outlets, and the other end of the working medium pipeline (9) is connected to the heat storage chamber (2); a liquid storage device (11) is arranged inside the heat storage chamber (2), and the liquid storage device (11) is connected with the working medium pipeline (9) and the filling pipeline (20); the working medium pipeline (9) is sequentially connected to the top gas phase space of the liquid storage device (11), a regulating valve (10), and the other end of the working medium pipeline (9), so as to input the gaseous adsorption working medium in the liquid storage device (11) into the thermochemical adsorption bed (6) when the regulating valve (10) is opened; one end of the filling pipeline (20) is connected to the top gas phase space of the liquid storage device (11), and the other end passes through the heat storage chamber (2) and is connected to an external filling valve (21) for filling the liquid storage device (11) with liquid adsorption working medium when the filling valve (21) is opened; the regeneration pipeline (17) is sequentially connected to the other end of the working medium pipeline (9) and a regeneration pump (18), then passes through the heat storage chamber (2) and is connected to an external regeneration valve (19) for discharging the gaseous adsorption working medium generated by the regeneration desorption of the thermochemical adsorption bed (6) when the regeneration valve (19) is opened; a heat storage type heating block (14) fixed to the upper permanent magnet (13) is arranged inside the liquid storage device (11), and the outer surface of the heat storage type heating block (14) can directly exchange heat with the liquid adsorption working medium; a lower permanent magnet (15) with controllable spatial position is arranged outside the liquid storage device (11), and the heating area of the heat storage type heating block (14) in the liquid adsorption working medium is adjusted by the mutual acting force between the two permanent magnets.

2. The solid-state hydrogen storage device according to claim 1, characterized in that, The electric heating component is an electric heating film (7) attached to the surface of the thermochemical adsorption bed (6), and the power cord (8) of the electric heating film (7) passes through the shell of the solid hydrogen storage device and is connected to a power supply.

3. The solid-state hydrogen storage device according to claim 1, wherein The lower permanent magnet (15) is installed below the liquid storage device (11) in the heat storage chamber (2), and the spatial position relative to the upper permanent magnet (13) is controlled by a mechanical adjusting rod (16) extending out of the heat storage chamber (2).

4. The solid-state hydrogen storage device according to claim 3, characterized in that A guide frame (12) extending from the inside to the outside is installed in the liquid storage device (11). The upper permanent magnet (13), the energy storage type heating block (14), and the lower permanent magnet (15) are all installed on the guide frame (12). The guide frame (12) restricts the three to only slide up and down vertically. The immersion depth of the energy storage type heating block (14) in the liquid adsorption working medium is positively correlated with its heating area.

5. The solid hydrogen storage device according to claim 4, wherein The energy storage type heating block (14) can float in the liquid adsorption working medium inside the liquid storage device (11). The upper permanent magnet (13) and the lower permanent magnet (15) are opposite in polarity and attract each other. During the process that the lower permanent magnet (15) moves downward away from the upper permanent magnet (13), the immersion depth of the energy storage type heating block (14) gradually decreases. During the process that the lower permanent magnet (15) moves upward close to the upper permanent magnet (13), the immersion depth of the energy storage type heating block (14) gradually increases.

6. The solid-state hydrogen storage device according to claim 1, wherein The energy storage type heating block (14) is a latent heat type phase change heat storage module or a magnetothermal type heating module, and is installed in the liquid storage device (11) in a replaceable form.

7. The solid-state hydrogen storage device according to claim 1, characterized in that, The hydrogen storage alloy (5) is selected as a magnesium-based hydrogen storage alloy.

8. The solid-state hydrogen storage device according to claim 1, wherein The outlet end of the regeneration pipeline (20) is externally connected to a refrigeration device for liquefying and recycling the discharged gaseous adsorption working medium.

9. The solid-state hydrogen storage device according to claim 1, wherein The thermochemical adsorption bed (6) is filled with a solid thermochemical adsorbent, and the adsorption working medium adopts a working medium type that matches the thermochemical adsorbent to form thermochemical heat storage.

10. A method for operating a solid-state hydrogen storage device according to any one of claims 1 to 9, characterized in that, Including an alternating hydrogen charging stage and a hydrogen releasing stage; During the hydrogen charging stage, the thermochemical adsorption bed (6) is in an adsorption saturation state, and its operation process is as follows: Open the regeneration valve (19), start the regeneration pump (18), and keep the inside of the thermochemical adsorption bed (6) initially in a negative pressure state; then open the hydrogen valve (4), and pass the external hydrogen into the hydrogen storage alloy (5) through the hydrogen pipeline (3) for hydrogen storage in the form of a compound. At the same time, reaction heat is released and the thermochemical adsorption bed (6) is heated. The thermochemical adsorption bed (6) is regenerated by desorption, and the released gaseous adsorption working medium enters the regeneration pipeline (17), and is discharged after passing through the regeneration pump (18) and the regeneration valve (19) in sequence; If the reaction heat during the hydrogen storage process is not enough to complete the regeneration of the thermochemical adsorption bed (6), turn on the electric heating component to assist in heating the thermochemical adsorption bed (6); When the hydrogen charging is completed and the thermochemical adsorption bed (6) is regenerated, close the regeneration valve (19) and the hydrogen valve (4), stop the regeneration pump (18), then open the filling valve (21), pass the external liquid adsorption working medium into the liquid storage device (11) through the filling pipeline (20), and close the filling valve (21) after reaching the specified liquid level. The energy storage type heating block (14) accumulates heat through input heat or direct replacement, completes the hydrogen charging stage, and enters the hydrogen releasing stage; The operation process of the hydrogen releasing stage is as follows: Open the hydrogen valve (4) and the regulating valve (10). By controlling the position of the lower permanent magnet (15) relative to the upper permanent magnet (13), gradually immerse the energy storage type heating block (14) in the liquid adsorbent working medium to heat the liquid adsorbent working medium. The gaseous adsorbent working medium generated by the vaporization of the liquid adsorbent working medium enters the thermochemical adsorption bed (6) through the adsorbent working medium pipeline (9), reacts with the thermochemical adsorbent in the thermochemical adsorption bed (6), and the released adsorption heat heats the hydrogen storage alloy (5). After the hydrogen storage alloy (5) reaches the corresponding temperature, it starts to release hydrogen and supplies hydrogen to the outside through the hydrogen pipeline (3); when hydrogen flow regulation is required, by controlling the position of the lower permanent magnet (15) relative to the upper permanent magnet (13), change the heating area of the energy storage type heating block (14) in the liquid adsorbent working medium, thereby changing the flow rate of the gaseous adsorbent working medium transported to the thermochemical adsorption bed (6), and thus changing the hydrogen release amount of the hydrogen storage alloy (5) based on the regulation of the heat release amount of the thermochemical adsorption bed (6).

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