Composite solid hydrogen storage device with gradient temperature field coupled annular layered structure

Abstract

The invention discloses a composite solid hydrogen storage device with a gradient temperature field coupled annular layered structure. The composite solid hydrogen storage device comprises a hydrogen storage cavity, a heating rod and a hydrogen cylinder, a plurality of radial heat-conducting separation layers are arranged in the hydrogen storage cavity from inside to outside in a sleeving manner; a gap is reserved between every two adjacent radial heat conduction separation layers, and the radial heat conduction separation layers divide the interior of the hydrogen storage cavity into a plurality of annular hydrogen storage chambers; air holes for hydrogen to pass through are formed in the surface of the radial heat-conducting separation layer; the heating rod is arranged in the center of the hydrogen storage cavity, and heat is sequentially and radially transferred from inside to outside; the working temperatures of the hydrogen storage materials in the plurality of hydrogen storage chambers are sequentially reduced from inside to outside; independent hydrogen conveying pipelines are communicated with the interiors of the hydrogen storage chambers, and the hydrogen conveying pipelines are communicated with a hydrogen cylinder. The solid hydrogen storage device can precisely regulate and control the heat transfer path in the reactor based on the working temperature gradient of different hydrogen storage materials.

Description

Technical Field

[0001] This invention relates to the field of hydrogen energy storage technology, and more specifically to a composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure. Background Technology

[0002] Solid-state hydrogen storage, with its core advantages such as high volumetric hydrogen storage density, excellent safety, and convenient storage and transportation, has become a highly promising technology for large-scale hydrogen energy storage and transportation, with broad application prospects in fuel cells, distributed energy supply, and energy storage power stations. Currently, mainstream solid-state hydrogen storage systems mainly include magnesium-based (MgH2), titanium-iron-based (TiFe), and lanthanum-nickel-based (LaNi5) metal / alloy hydrogen storage materials. The thermodynamic and kinetic characteristics of hydrogen absorption and desorption vary significantly among different systems: magnesium-based materials have high theoretical hydrogen storage capacity and low cost, but poor hydrogen desorption kinetics, typically requiring temperatures above 300℃ for effective hydrogen release; TiFe-based alloys have a moderate hydrogen desorption temperature (around 100℃) and balanced overall performance; LaNi5-based rare earth alloys can complete hydrogen absorption and desorption cycles at room temperature or even near room temperature, exhibiting fast response and mild operating conditions.

[0003] Traditional solid-state hydrogen storage devices typically employ a single hydrogen storage material homogeneously filled within the reactor, relying on a central heating rod to uniformly heat the entire tank during hydrogen release. This structural approach suffers from inherent technical bottlenecks that are difficult to overcome through material modification, severely limiting system energy efficiency and practicality. For example:

[0004] 1. Low heat utilization efficiency: In order to meet the high-temperature hydrogen release requirements of high-melting-point materials such as magnesium-based materials, the entire reactor needs to be heated to the target high temperature. This will cause overheating in the low-temperature active material area such as LaNi5 inside the tank, resulting in a large amount of high-quality heat energy being wasted ineffectively.

[0005] 2. Significant system heat loss: The overall high temperature operation of the reactor results in an excessively high surface temperature of the shell, a large temperature difference between the reactor and the environment, severe heat loss through convection and radiation, and further reduction in the energy efficiency of the device.

[0006] 3. Difficulty in synergizing material properties: A single material system cannot simultaneously achieve complementary performance of high hydrogen storage capacity (advantage of magnesium-based materials) and low-temperature rapid hydrogen release (advantage of LaNi5) in the same reactor. The system is difficult to balance between hydrogen storage density, operating temperature and response rate, resulting in insufficient overall performance.

[0007] Therefore, developing a composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-layered structure that can precisely control the heat transfer path inside the reactor based on the working temperature gradient of different hydrogen storage materials is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0008] In view of this, the present invention provides a composite solid hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure, which can precisely control the heat transfer path inside the reactor based on the working temperature gradient of different hydrogen storage materials.

[0009] To achieve the above objectives, the present invention adopts the following technical solution: A composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-layered structure includes: The hydrogen storage cavity has multiple radial thermally conductive partition layers arranged from the inside to the outside. There are gaps between adjacent radial thermally conductive partition layers, and the multiple radial thermally conductive partition layers divide the interior of the hydrogen storage cavity into multiple annular hydrogen storage chambers. The surface of the radial thermally conductive partition layers has pores for hydrogen to pass through. A heating rod is positioned at the center of the hydrogen storage cavity, and heat is transferred radially from the inside to the outside; the operating temperature of the hydrogen storage material in the multiple hydrogen storage chambers decreases sequentially from the inside to the outside. The hydrogen cylinder has multiple hydrogen storage chambers, each connected to an independent hydrogen delivery pipeline, and the multiple hydrogen delivery pipelines are connected to the hydrogen cylinder.

[0010] Preferably, a solenoid valve is installed on the hydrogen delivery pipeline.

[0011] Preferably, a temperature sensor is installed in the hydrogen storage chamber.

[0012] Preferably, the solid hydrogen storage device also includes a control cabinet, and the temperature sensor and solenoid valve are connected to the control cabinet.

[0013] Preferably, the hydrogen storage material contains a highly thermally conductive material.

[0014] Preferably, the hydrogen storage cavity is provided with an insulation layer on the outside.

[0015] Preferably, the top and bottom of the hydrogen storage cavity are both connected to flanges.

[0016] As can be seen from the above technical solution, compared with the prior art, the present invention discloses a composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure, which has the following advantages: (1) When absorbing hydrogen, the outer hydrogen storage material absorbs hydrogen and releases heat, and the heat can be transferred inward to assist the inner medium and high temperature material in absorbing hydrogen and realize the recovery of reaction heat; when releasing hydrogen, the central heating rod provides high temperature heat, which is transferred outward in a radial manner, driving the inner high temperature material, the middle medium temperature material, and the outer low temperature material to release hydrogen in sequence, thus realizing the graded supply and utilization of heat. (2) The device only heats the center and the heat is used in a radial gradient. It does not require overall high-temperature heating and has low energy consumption. At the same time, the heat released by hydrogen is used in a gradient and the heat of hydrogen absorption reaction is recovered, which significantly reduces heat loss. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0018] Figure 1 This is a schematic diagram of the solid hydrogen storage device provided by the present invention; Figure 2 An internal top view of the hydrogen storage cavity provided by the present invention; Figure 3 This is an internal cross-sectional view of the hydrogen storage cavity provided by the present invention.

[0019] In the figure, 1-Hydrogen storage chamber; 2-Radial thermally conductive partition layer; 3-Hydrogen storage chamber; 4-Heating rod; 5-Hydrogen cylinder; 6-Hydrogen delivery pipeline; 7-Solenoid valve; 8-Temperature sensor; 9-Flange. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1: This invention discloses a composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-layered structure, comprising: The hydrogen storage chamber 1 has multiple radial thermally conductive partition layers 2 arranged from the inside to the outside. There are gaps between adjacent radial thermally conductive partition layers 2. The multiple radial thermally conductive partition layers 2 divide the interior of the hydrogen storage chamber 1 into multiple annular hydrogen storage chambers 3. The surface of the radial thermally conductive partition layers 2 is provided with pores for hydrogen to pass through. Heating rod 4 is located at the center of hydrogen storage chamber 1, and heat is transferred radially from the inside to the outside; the working temperature of the hydrogen storage material in the multiple hydrogen storage chambers 3 decreases sequentially from the inside to the outside. The hydrogen cylinder 5 and multiple hydrogen storage chambers 3 are each connected to an independent hydrogen delivery pipeline 6, and the multiple hydrogen delivery pipelines 6 are connected to the hydrogen cylinder 5.

[0022] This device can be used in scenarios such as stationary hydrogen storage stations, vehicle-mounted hydrogen storage systems, and thermal and hydrogen storage coupling devices.

[0023] In one embodiment, the hydrogen storage material in the hydrogen storage chamber 3 at the center of the hydrogen storage cavity 1 is in close contact with the heating rod 4 to ensure radial heat conduction, so that the temperature can reach the hydrogen storage material and then release hydrogen; the highest heating temperature at the center is ≥500℃, providing a stable heat source for the system.

[0024] In one embodiment, the hydrogen storage chamber 3 is filled with the following layers from the inside out: the first layer (innermost) is filled with a magnesium-based solid hydrogen storage material with a high hydrogen release temperature. This material can be further modified to ensure that the hydrogen release temperature is ≤300℃. The second layer is filled with a TiFe-based hydrogen storage alloy with an operating temperature of 100-120℃. The third layer is filled with a TiMn-based hydrogen storage alloy with an operating temperature of 40-100℃. The outermost layer can be filled with a LaNi5-based material with an operating temperature of room temperature -60℃. The number of layers can be designed according to the temperature gradient, such as a fifth or nth layer. The radial thickness of each annular layer is designed according to the radial temperature gradient of the central heating rod, so that the ambient temperature of each layer exactly matches the hydrogen absorption and desorption operating temperature of the corresponding hydrogen storage material. Each layer operates at a suitable temperature, avoiding overheating and degradation, and improving cycle stability.

[0025] In one embodiment, the thickness of the hydrogen storage chamber 3 is precisely designed based on the heat dissipation temperature gradient of the heating rod 4, so that the average temperature of each layer is exactly matched with the hydrogen absorption and desorption temperature of the corresponding material, and an insulation layer is provided on the outer layer to reduce external heat dissipation.

[0026] In one embodiment, the radial thermally conductive separator 2 is used to isolate different types of solid hydrogen storage materials to prevent cross-contamination. It is made of copper with a porosity of 30% and a thickness of 5 mm, and does not react with the hydrogen storage materials. The radial thermally conductive separator 2 has a certain thermal conductivity, which can maintain the radial temperature gradient, and the pores allow hydrogen gas to pass through while limiting the cross-layering of hydrogen storage material powder.

[0027] In one embodiment, a solenoid valve 7 is installed on the hydrogen delivery pipeline 6. Each hydrogen storage chamber 3 has an independent hydrogen delivery pipeline 6, which is then merged to supply hydrogen in a unified manner. The hydrogen delivery pipeline 6 of each layer and the hydrogen pipeline after merging are all controlled by the corresponding solenoid valve 7 to control the filling and releasing of hydrogen.

[0028] In one embodiment, a temperature sensor 8 is installed inside the hydrogen storage chamber 3.

[0029] In one embodiment, the solid-state hydrogen storage device further includes a control cabinet, to which temperature sensor 8 and solenoid valve 7 are connected. The control cabinet is a PLC control cabinet, which controls solenoid valve 7 to regulate hydrogen release, and uses temperature sensor 8 to monitor the temperature of each layer of hydrogen storage material, thereby adjusting the power of heating rod 4 to reach the temperature required for hydrogen release from that layer of material.

[0030] In one embodiment, a high thermal conductivity material is mixed into the hydrogen storage material. The high thermal conductivity material, such as expanded graphite powder, is used to dope the hydrogen storage material powder to improve the internal thermal conductivity of the layer, ensuring uniform temperature of the layer and enabling it to smoothly reach the hydrogen release temperature.

[0031] In one embodiment, an insulation layer is provided on the outside of the hydrogen storage chamber 1. The insulation layer can reduce heat loss to the outside.

[0032] In one embodiment, flanges 9 are connected to both the top and bottom of the hydrogen storage chamber 1. Flanges 9 facilitate connection to external components.

[0033] Example 2: Four independent annular hydrogen storage chambers 3 are arranged radially from the inside to the outside along the cylindrical hydrogen storage cavity 1. The radial thickness of each layer is precisely designed according to the radial temperature gradient of the heating rod 4. Adjacent hydrogen storage chambers 3 are isolated by radially heat-conducting partition layers 2, which not only achieves physical isolation between adjacent hydrogen storage chambers 3 to prevent cross-contamination of hydrogen storage powder, but also ensures radial heat transfer while allowing hydrogen gas to pass freely through the pores. The parameters of each layer are as follows: First layer (innermost layer): 100mm radial thickness, filled with modified magnesium-based hydrogen storage material. After modification, the hydrogen release temperature is reduced to 280℃, and the theoretical hydrogen storage capacity is 6.0wt%. Second layer: 120mm radial thickness, filled with TiFe-based hydrogen storage alloy, operating temperature 100-120℃, hydrogen storage capacity 1.8wt%; Third layer: 150mm radial thickness, filled with TiMn-based hydrogen storage alloy, operating temperature 40-100℃, hydrogen storage capacity 2.0wt%; The fourth layer (outermost layer): 180 mm in radial thickness, filled with LaNi5-based hydrogen storage alloy, operating temperature 25℃-60℃, hydrogen storage capacity 1.4 wt%.

[0034] Hydrogen gathering and temperature control system: Each layer of annular hydrogen storage chamber 3 is equipped with an independent hydrogen delivery pipeline 6. All hydrogen delivery pipelines 6 are connected to the main hydrogen gathering pipeline. Each layer of hydrogen delivery pipeline 6 and the main gathering pipeline are equipped with a solenoid valve 7. The solenoid valve 7 is normally closed. Temperature sensors 8 are embedded in the hydrogen storage material of each layer. The temperature sensors 8 are electrically connected to the external PLC control cabinet (control unit). The control cabinet is also linked with the central heating rod 4 and each solenoid valve 7 to realize intelligent control of temperature and hydrogen charging and discharging.

[0035] (a) Hydrogen absorption process The main collection and transmission pipeline and each layer of solenoid valve 7 are opened by the PLC control cabinet. The hydrogen in the external hydrogen cylinder enters the fourth, third, second and first layer hydrogen storage chambers in sequence through the hydrogen transmission pipeline 6. The outer LaNi5 material is the first to absorb hydrogen. The hydrogen absorption reaction is an exothermic reaction. The released heat is transferred inward step by step through the radial heat-conducting partition layer 2. Heat recovery and utilization: The outer low-temperature material absorbs hydrogen and releases heat, raising the temperature of the middle TiMn and TiFe material region to 40-120℃, which meets the medium-temperature hydrogen absorption temperature requirement and does not require additional heating; the inner magnesium-based material, with the help of the heat transferred inward and its own slight hydrogen absorption and heat release, raises the temperature to 150-200℃. If the temperature is insufficient, heating rod 4 can be used to supplement the heat. Hydrogen absorption complete: When the temperature sensors 8 of each layer detect that the material temperature tends to stabilize and the hydrogen pressure no longer drops, the PLC control cabinet sequentially closes the solenoid valves 7 of each layer, and the hydrogen absorption process ends. At this time, all materials in each layer of the device have completed hydrogen storage, realizing the full-process recovery of reaction heat.

[0036] (II) Hydrogen release process Initiating hydrogen release: Based on the hydrogen supply demand, the PLC control cabinet starts the central heating rod 4, sets the heating power, and raises the temperature of the outer wall of the heating rod 4 to 300°C. The heat is transferred to the first layer of magnesium-based material through thermal conduction to meet its hydrogen release temperature requirements. Heat cascade transfer: While the first layer of magnesium-based material releases hydrogen, the unused heat is transferred outward through the radial thermally conductive partition layer 2, causing the temperature of the second TiFe-based material region to rise to 100-120℃, triggering its temperature-induced hydrogen release; the unused heat in the second layer continues to be transferred outward, causing the temperature of the third TiMn-based material region to rise to 40-100℃, and the fourth layer, with the help of ambient temperature and internal heat transfer, maintains the hydrogen release conditions at room temperature -60℃, thus achieving cascade hydrogen release from the inside out; Hydrogen gathering and transportation: The hydrogen released from each layer of material flows into the main gathering and transportation pipeline through the independent hydrogen transportation pipeline 6. According to the hydrogen supply pressure demand, the PLC control cabinet adjusts the opening of each solenoid valve 7 to achieve stable hydrogen output. Process control: Temperature sensor 8 feeds back the temperature of each layer of material to the PLC control cabinet in real time. The control cabinet dynamically adjusts the power of the central heating rod 4 according to the temperature data to ensure that the temperature of each layer always matches the hydrogen release working temperature of the corresponding material, and avoids overheating or insufficient temperature. Hydrogen release complete: When the temperature sensors 8 of each layer detect a drop in material temperature and the hydrogen pressure approaches zero, it indicates that the hydrogen storage material has finished releasing hydrogen. The PLC control cabinet then shuts off the central heating rod 4 and all solenoid valves 7, and the hydrogen release process ends.

[0037] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0038] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-layered structure, characterized in that, include: The hydrogen storage cavity has multiple radial thermally conductive partition layers arranged from the inside to the outside. There are gaps between adjacent radial thermally conductive partition layers, and the multiple radial thermally conductive partition layers divide the interior of the hydrogen storage cavity into multiple annular hydrogen storage chambers. The surface of the radial thermally conductive partition layers has pores for hydrogen to pass through. A heating rod is positioned at the center of the hydrogen storage cavity, and heat is transferred radially from the inside to the outside; the operating temperature of the hydrogen storage material in the multiple hydrogen storage chambers decreases sequentially from the inside to the outside. The hydrogen cylinder has multiple hydrogen storage chambers, each connected to an independent hydrogen delivery pipeline, and the multiple hydrogen delivery pipelines are connected to the hydrogen cylinder.

2. The composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure according to claim 1, characterized in that, A solenoid valve is installed on the hydrogen delivery pipeline.

3. The composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure according to claim 2, characterized in that, A temperature sensor is installed in the hydrogen storage chamber.

4. The composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure according to claim 3, characterized in that, The solid hydrogen storage device also includes a control cabinet, and the temperature sensor and solenoid valve are all connected to the control cabinet.

5. The composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure according to claim 1, characterized in that, The hydrogen storage material contains a highly thermally conductive material.

6. The composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure according to claim 1, characterized in that, The hydrogen storage cavity is provided with an insulation layer on the outside.

7. The composite solid-state hydrogen storage device with a gradient temperature field coupled to a ring-shaped layered structure according to claim 6, characterized in that, Flanges are connected to both the top and bottom of the hydrogen storage chamber.

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