A solid state hydrogen storage device

Abstract

This invention relates to a solid-state hydrogen storage device, comprising a tank, valves, and a filter. The tank contains hydrogen storage materials, including hydrogen storage material A and hydrogen storage material B. The solid-state hydrogen storage materials used in this invention are common and readily available, requiring no special processing or the addition of other non-hydrogen storage catalysts. The device is simple to operate and reduces costs and energy consumption.

Description

Technical Field

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

[0002] Hydrogen energy plays a vital role in promoting low-carbon and environmentally friendly economic and social development. However, challenges remain in hydrogen production, storage, and application, and the construction of hydrogen energy systems needs further improvement. Hydrogen storage and transportation technology is a relatively weak link in hydrogen energy development and is crucial for the practical application, large-scale production, and industrialization of hydrogen energy utilization. Compared to high-pressure gaseous hydrogen storage and cryogenic liquid hydrogen storage, solid-state hydrogen storage materials offer advantages such as high volumetric hydrogen storage density, good safety, and mild operating conditions, and have gradually gained attention and are being put into practical use. Currently, the application of solid-state hydrogen storage technologies and devices still faces the following problems:

[0003] (1) Activation problem of high-density hydrogen storage materials

[0004] Ti-based and V-based BCC high-capacity hydrogen storage materials, represented by AB and AB2 types, are very difficult to activate in the initial hydrogen absorption stage. They generally require high temperature or long-term incubation to gradually activate, which poses a significant challenge to the practical application of solid-state hydrogen storage devices.

[0005] (2) Poisoning problem of hydrogen storage materials

[0006] Currently, impurities in commercially available hydrogen can react on the surface of hydride particles in hydrogen storage materials, reducing the rate and amount of hydrogen absorption and release. This phenomenon is called "surface poisoning." The existence of this phenomenon can cause problems for the utilization of hydrides that are repeatedly absorbed and released using new hydrogen. Different types and contents of impurities have different degrees of poisoning on different hydrogen storage materials. Therefore, in practical applications, the allowable amount of impurities in hydrogen is one of the important criteria for selecting hydrogen storage material systems and types.

[0007] (3) Regeneration of hydrogen storage materials

[0008] After hydrogen storage materials are poisoned, they need to be reactivated, also known as "regeneration". After regeneration, the hydrogen storage materials can recover their activity to varying degrees. In practical applications, the hydrogen storage materials absorb and desorb hydrogen in a cycle that uses pure hydrogen. Alloy poisoning cannot be completely avoided. However, when the alloy is frequently poisoned, it is easy to regenerate if it is cleaned with ultra-high purity hydrogen gas and heated to vacuum. If the hydrogen storage material is made into a hydrogen storage device and regenerated by high-temperature heating, the regeneration temperature of titanium-based hydrogen storage alloys can even reach 400~500℃, which can pose a great challenge to the sealing and safety reliability of the hydrogen storage device.

[0009] In summary, the key to realizing the high-value application of solid-state hydrogen storage technology lies in solving the problems of activation, regeneration, and cycle life of solid-state hydrogen storage materials and devices under relatively mild and simple conditions. Summary of the Invention

[0010] To address the problems of existing technologies, the technical problem to be solved by the present invention is to provide a solid hydrogen storage device that improves the activation speed and hydrogen absorption / desorption cycle life of the solid hydrogen storage device.

[0011] The present invention discloses a solid hydrogen storage device, the device comprising: a hydrogen storage tank 1, a valve 2, and a filter 3. The hydrogen storage tank 1 is provided with hydrogen storage material, which includes hydrogen storage material A 4 and hydrogen storage material B 5. The hydrogen storage material A 4 and hydrogen storage material B 5 are filled in layers but in direct contact at the interface. The hydrogen storage material A 4 is filled in the upper part of the hydrogen storage tank 1 near the valve end, and the hydrogen storage material B 5 is filled in the lower part of the hydrogen storage tank 1.

[0012] Preferably, the activation, hydrogen absorption and desorption cycle, and regeneration of the hydrogen storage device tank 1 can be completed in a water bath environment of room temperature to 100°C, which is easy to implement and does not increase the safety and reliability risks in solid-state hydrogen storage technology.

[0013] Preferably, the solid hydrogen storage device tank is generally made of aluminum alloy or stainless steel.

[0014] Preferably, the hydrogen in the hydrogen storage device tank 1 enters and exits only through valve 2, and filter 3 is used to separate the hydrogen storage material powder and hydrogen.

[0015] Preferably, the filter 3 is disposed between the valve 2 and the hydrogen storage material A 4, and is fixed on the vent of the valve 2.

[0016] Preferably, the filter element 3 is made of metal powder metallurgy sintering or metal wire mesh pressing, and the filtration accuracy is 0.5~3μm; a sealing gasket is provided on the top of the filter element 3 to improve the sealing performance, wherein the sealing gasket material is including but not limited to one or more of polytetrafluoroethylene and fluororubber.

[0017] Preferably, by weight percentage, the hydrogen storage material A4 accounts for 5% to 50% of the total hydrogen storage material, and the hydrogen storage material B5 accounts for 50% to 95% of the total hydrogen storage material.

[0018] Preferably, the hydrogen storage material A4 and hydrogen storage material B5 are granules or powders.

[0019] Furthermore, both hydrogen storage material A4 and hydrogen storage material B5 are in powder form.

[0020] Preferably, the hydrogen storage material A4 is a rare earth-based material with low hydrogen storage density but fast activation speed and easy pulverization and regeneration, such as AB5 (A side is generally one or more rare earth elements, and B side is generally one or more elements selected from Ni, Co, Mn, Al, Cu, Fe, etc.), AB3 (A side is generally one or more rare earth elements and Mg, Ca, etc., and B side is generally one or more elements selected from Ni, Co, Mn, Al, Cu, Fe, etc.), AB... 3.5 (Side A is generally one or more elements from rare earth elements and Mg, Ca, etc., and side B is generally one or more elements from Ni, Co, Mn, Al, Cu, Fe, etc.) type hydrogen storage materials with a weight hydrogen storage density of 1.4wt~1.7wt%.

[0021] Preferably, the regeneration treatment temperature after activation and poisoning of the hydrogen storage material A is ≤100℃, which can be achieved under hydrothermal conditions.

[0022] Preferably, the hydrogen storage material B5 is one or more of the following: titanium-based AB (A side is generally composed of one or two elements, Ti and Zr, and B side is generally composed of one or more elements, Mn, Cr, Co, and rare earth elements), AB2 (A side is generally composed of one or two elements, Ti and Zr, and B side is generally composed of one or more elements, Mn, Cr, Co, V, and rare earth elements), and V-based BCC type (generally a solid solution composed of V and one or more elements, such as Ti, Zr, Fe, Cr, and Mn), which have a hydrogen storage density of 1.8 wt% to 3.8 wt%.

[0023] Preferably, the hydrogen storage material B is difficult to activate and the regeneration treatment temperature after poisoning is ≥100℃, which is difficult to achieve under general hydrothermal conditions.

[0024] This invention discloses a solid-state hydrogen storage device comprising two or more metallic hydrogen storage materials with different hydrogen storage densities, cycle lives, activation performance, and regeneration performance. A hydrogen storage material A, with a lower hydrogen storage density but better cycle life and activation / regeneration performance, is filled at the hydrogen charging / discharging interface of the device. A hydrogen storage material B, with a higher hydrogen storage density but poorer cycle life and activation / regeneration performance, is filled at the bottom of the device. During hydrogen charging, hydrogen molecules are first decomposed into hydrogen atoms by material A. Material A catalyzes the activation of material B, significantly increasing its activation rate and lowering its activation temperature to below 100°C. This facilitates activation of the solid-state hydrogen storage device without compromising its safety and reliability. Simultaneously, impurities in the hydrogen gas are preferentially absorbed by material A, leading to partial oxidation or poisoning and a decrease in its hydrogen absorption / discharge cycle performance, while improving the cycle performance of material B. During hydrogen discharge, the ultra-high purity hydrogen gas released by material B passes through material A, purifying and regenerating it, partially or completely restoring its hydrogen absorption / discharge performance. This repeated cycle significantly improves the activation rate and cycle stability of the solid-state hydrogen storage device.

[0025] Beneficial effects

[0026] (1) The hydrogen storage materials A and B involved in this invention have independent hydrogen absorption and desorption functions. While increasing the hydrogen storage density, they can also promote each other synergistically. During the hydrogen filling process, material A, which is close to the bottle opening, preferentially absorbs hydrogen and is activated, while acting as a catalyst for material B, reducing the activation difficulty of material B. Since hydrogen storage material A first absorbs hydrogen and pulverizes, it will also preferentially adsorb impurity gases in the hydrogen, thereby increasing the purity of the hydrogen reacting with hydrogen storage material B and reducing the risk of poisoning of hydrogen storage material B. During the hydrogen release process, the ultra-high purity hydrogen released by material B passes through hydrogen storage material A, which can wash and purify hydrogen storage material A, playing a role in regeneration and restoring its hydrogen absorption and desorption performance. Therefore, the entire hydrogen storage device exhibits characteristics and functions such as faster activation speed, improved cycle life, and self-cleaning regeneration, which greatly improves the safety, reliability, and service life of the solid hydrogen storage device. However, if the upper layer is hydrogen storage material B and the lower layer is hydrogen storage material A, the activation speed of the hydrogen storage device can also be improved, but the cycle life cannot be significantly improved.

[0027] (2) Compared with other existing technologies, the solid hydrogen storage material of the present invention is common and readily available, and does not require special treatment or the addition of other non-hydrogen storage material catalysts. It is simple to operate and can reduce costs and energy consumption. Attached Figure Description

[0028] Figure 1 A schematic diagram of the device structure required for improving the activation rate and hydrogen absorption / desorption cycle life of solid-state hydrogen storage devices;

[0029] The attached diagram is labeled as follows: 1-hydrogen storage tank, 2-valve, 3-filter, 4-hydrogen storage material A, 5-hydrogen storage material B;

[0030] Figure 2 The graphs show the activation rate and cycle life decay curves of Examples 1, 2, and 3 of the present invention. Detailed Implementation

[0031] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0032] Example 1

[0033] like Figure 1 As shown, a method for improving the activation rate and hydrogen absorption / desorption cycle life of a solid hydrogen storage device according to a preferred embodiment of the present invention includes a hydrogen storage device tank 1, a valve 2, a filter 3, hydrogen storage material A 4, and hydrogen storage material B 5. Hydrogen storage material A 4 is filled in the upper part of the hydrogen storage device tank 1 near the valve end, and hydrogen storage material B 5 is filled in the lower part of the hydrogen storage device tank 1. Both hydrogen storage material A 4 and hydrogen storage material B 5 are in granular or powder form. Hydrogen storage material A 4 and hydrogen storage material B 5 are filled in layers but in direct contact at the interface.

[0034] The hydrogen storage device tank 1 forms the outer shell structure of the entire device. In this embodiment, the hydrogen storage device tank 1 is preferably made of 6061 aluminum alloy, which has good thermal conductivity. The outer diameter φ of the tank 1 is 60mm, the height is 330mm, the wall thickness is 4mm, and the volume is 0.6L.

[0035] The filter element 3 is disposed between the valve 2 and the hydrogen storage material A4 and is fixed to the vent hole of the valve 2 with hollow bolts. It is used to filter dust from the hydrogen storage material. In this embodiment, the filter element is a small round disc sintered from brass powder metallurgy. The filter element has a diameter of 8mm, a thickness of 1mm, and a filtration accuracy of 3μm. A φ8*2mm fluororubber ring is provided on the top of the filter element for sealing.

[0036] Hydrogen storage material A4 is rare earth AB5 (MmNi) 4.4 Mn 0.1 Co 0.5 Mm on side A is a mixed rare earth element containing 27% La by mass. The material has a hydrogen storage density ≥1.50wt%. It should be understood that other easily activated rare earth hydrogen storage materials can also be used in this invention.

[0037] Hydrogen storage material A5 is a titanium-based AB (TiFe) 0.96 Mn （0.04-x） Co x (x=0~0.02) type, the hydrogen storage density of the material is ≥1.80wt%. It should be understood that other titanium-based AB2 and V-based BCC type hydrogen storage materials that are difficult to activate can also be used in this invention.

[0038] Hydrogen storage materials A4 and A5 were both sieved through a 6-mesh sieve. 2375g (95%) of hydrogen storage material B was weighed and filled at the bottom of the aforementioned hydrogen storage tank, and 125g (5%) of hydrogen storage material A was weighed and filled at the top of the hydrogen storage device tank. The total filling amount was 2500g, with a filling density of 4.167g / cm³. 3 .

[0039] For the activation treatment of the hydrogen storage device, place the hydrogen storage device in a water bath at 60℃~80℃ and evacuate it for 30 minutes. Then, after cooling to room temperature, introduce hydrogen gas with a purity of 99.999% at a pressure of 4 MPa (hydrogen impurity content: O2≤1PPM, N2≤5PPM, CO≤1PPM, CO2≤1PPM, CH4≤1PPM, H2O≤3PPM). Maintain the pressure in the 80℃ water bath for 2 hours, then release the hydrogen gas and evacuate it for 30 minutes. Repeat the above steps until the activation is complete.

[0040] The hydrogen storage device cycle life test involves placing the activated hydrogen storage device in room temperature tap water to purge hydrogen for 1 hour, then placing it in 45°C hot water to release hydrogen, recording the amount of hydrogen released, and repeating this cycle 200 times.

[0041] The device reached a maximum hydrogen release capacity of 495L after nine cycles of repeated vacuuming and hydrogen absorption / desorption activation. After 200 cycles of hydrogen absorption / desorption, the hydrogen release capacity remained at 395L, with a lifespan decay rate of 20.20%.

[0042] Example 2

[0043] Compared with Example 1, in Example 2, the hydrogen storage material B was filled with 2000g (80%), the hydrogen storage material A was filled with 500g (20%), and the rest was exactly the same as in Example 1. After repeated vacuuming and hydrogen absorption and desorption activation treatments 7 times, the device reached the maximum hydrogen release capacity of 479L. After 200 hydrogen absorption and desorption cycles, the hydrogen release capacity remained at 421L, and the lifespan decay rate was 12.11%.

[0044] Example 3

[0045] Compared with Example 1, in Example 3, the hydrogen storage material B was filled with 1250g (50%), the hydrogen storage material A was filled with 1250g (50%), and the rest was exactly the same as in Example 1. After repeated vacuuming and hydrogen absorption and desorption activation treatments 4 times, the device reached the maximum hydrogen release capacity of 462L. After 200 hydrogen absorption and desorption cycles, the hydrogen release capacity remained at 434L, and the lifespan decay rate was 6.06%.

[0046] Comparative Example 1

[0047] Compared with Example 1, the hydrogen storage material B in Comparative Example 1 was filled with 2500g (100%), and the rest was exactly the same as in Example 1. The device showed no signs of activation after more than 10 repeated vacuuming and hydrogen absorption and desorption activation treatments, indicating that although the material has a high hydrogen storage density, it is difficult to activate.

[0048] Comparative Example 2

[0049] Compared with Example 1, Comparative Example 2 directly mixed hydrogen storage materials A and B, and the rest of the components were exactly the same as in Example 1. The device was activated on the 14th time after repeated vacuuming and hydrogen absorption and desorption activation treatments, indicating that the directly mixed A and B could also be activated slowly. However, after 200 cycles, the lifespan decreased by 26.88%.

[0050] The activation and cycle life test curves of Examples 1, 2, 3 and Comparative Example 2 are as follows: Figure 2 As shown in the figure, the results indicate that the method of improving the activation speed and hydrogen absorption / desorption cycle life of a solid hydrogen storage device according to the present invention can significantly reduce the activation difficulty of the hydrogen storage device while further improving its cycle life, thereby reducing the energy consumption and cost of using the solid hydrogen storage device.

Claims

1. A solid-state hydrogen storage device, the device comprising: The hydrogen storage device comprises a tank body (1), a valve (2), and a filter (3), characterized in that the tank body (1) is provided with hydrogen storage materials, including hydrogen storage material A (4) and hydrogen storage material B (5), wherein hydrogen storage material A (4) and hydrogen storage material B (5) are layered but in direct contact at the interface, wherein hydrogen storage material A (4) is filled in the upper part of the hydrogen storage device tank body (1) near the valve end, and hydrogen storage material B (5) is filled in the lower part of the hydrogen storage device tank body (1); wherein the filtration accuracy of the filter (3) is 0.5~3μm; wherein the hydrogen storage material A (4) is a rare earth series AB5, AB3, AB 3.5 One or more of the following hydrogen storage materials; the hydrogen storage material B (5) is one or more of the following: titanium-based AB, AB2, and V-based BCC type hydrogen storage materials; The activation, hydrogen absorption and desorption cycle, and regeneration treatment of the hydrogen storage device tank (1) are carried out in a water bath environment at room temperature to 100°C.

2. The solid-state hydrogen storage device according to claim 1, characterized in that, The filter (3) is located between the valve (2) and the hydrogen storage material A (4), and is fixed on the vent of the valve (2).

3. The solid-state hydrogen storage device according to claim 1, characterized in that, Hydrogen gas in the tank (1) of the hydrogen storage device enters and exits only through valve (2), and filter (3) is used to separate hydrogen storage material powder and hydrogen gas; The filter (3) is made of metal powder metallurgy sintering or metal wire mesh pressing; a sealing gasket is provided on the top of the filter (3).

4. The solid-state hydrogen storage device according to claim 1, characterized in that, By weight percentage, hydrogen storage material A (4) accounts for 5%~50% and hydrogen storage material B (5) accounts for 50%~95%.

5. The solid-state hydrogen storage device according to claim 1, characterized in that, The hydrogen storage material A (4) and hydrogen storage material B (5) are granules or powders.

6. The solid-state hydrogen storage device according to claim 1, characterized in that, The hydrogen storage material A (4) has a weight hydrogen storage density of 1.4wt to 1.7wt%.

7. The solid-state hydrogen storage device according to claim 1, characterized in that, The regeneration treatment temperature of the hydrogen storage material A after activation and poisoning is ≤100℃.

8. The solid-state hydrogen storage device according to claim 1, characterized in that, The hydrogen storage material B (5) has a weight hydrogen storage density of 1.8wt to 3.8wt%.

9. The solid-state hydrogen storage device according to claim 1, characterized in that, The hydrogen storage material B is difficult to activate, and the regeneration treatment temperature after poisoning is ≥100℃.

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