Multi-dimensional Ti-based solid hydrogen storage material and preparation method thereof

Abstract

The invention belongs to the technical field of hydrogen energy, and relates to a multi-dimensional Ti-based solid hydrogen storage material and a preparation method thereof.The multi-dimensional Ti-based solid hydrogen storage material is composed of Ti, V, Mn, Zr and Ni, the chemical expression of the material is TiaVbMncZrdNie, the atomic ratio of all the elements is as follows: a = 0.60-0.65, b = 0.08-0.12, c = 0.08-0.10, d = 0.04-0.07 and e = 0.08-0.12, and a + b + c + d + e = 1; the preparation method comprises the steps that firstly, raw materials are taken and pulverized, then, nano alloy powder is prepared through ultrasonic smashing, hydrogen storage composite powder is prepared through surface treatment, and finally, the multi-dimensional Ti-based solid hydrogen storage material is prepared through hydrogen absorption and desorption cycle activation. The technical problems that in the prior art, a titanium-based solid hydrogen storage material is low in desorption speed, low in hydrogen storage capacity, poor in cycling stability and prone to oxidation are solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hydrogen energy, and particularly relates to a multi-dimensional Ti-based solid-state hydrogen storage material and a preparation method thereof. BACKGROUND

[0002] The full industrial chain of hydrogen energy includes three important links of hydrogen preparation, storage and utilization. The storage and transportation of hydrogen is the key technology and prerequisite for large-scale application. Hydrogen storage can be divided into high-pressure gaseous hydrogen storage, low-temperature liquid hydrogen storage and solid-state hydrogen storage according to its physical properties. At present, although gaseous and liquid hydrogen storage is widely used and mature, it has high pressure and hydrogen leakage, which has a great security risk. Solid-state hydrogen storage is being widely researched and developed due to its low storage pressure, good safety and high hydrogen storage density.

[0003] Typical solid-state hydrogen storage materials include carbon-based materials and organic framework compounds. It is still a very challenging task to store a large amount of hydrogen at near room temperature and moderate pressure with such physical adsorption hydrogen storage materials. In addition, there are magnesium-based and rare earth-based materials. Chemical adsorption hydrogen storage has problems such as high hydrogen absorption and desorption temperature, poor kinetic conditions, and poor cycle life, which limit its large-scale application and development. Titanium-based materials are attracting attention due to their high affinity with hydrogen, low cost, and low hydrogen absorption and desorption temperature. Common titanium-based alloys include Ti-Fe, Ti-V, Ti-Mn, Ti-Cr, Ti-Zr, etc. Compared with other materials, titanium-based alloys have the advantages of low cost, easy preparation, abundant resources, low hydrogen absorption and desorption conditions, and fast reaction speed. Chinese patent CN99116897.6 uses an electric arc melting and mechanical crushing method to prepare a Ti-Fe alloy, with a hydrogen storage capacity of 1.7-1.73wt.%. Chinese patent application CN202311831514.7 dopes V to the deactivated TiMn, and the alloy after melting and crushing restores the hydrogen absorption and desorption performance, with a maximum hydrogen absorption capacity of 2wt.%. Chinese patent CN200910264388.5 adopts a melting and mechanical ball milling method, and finally heat treatment at 300-450℃ for 5 hours under argon, to prepare a Ti2Ni alloy with a hydrogen storage capacity of 1.7wt.% and a cycle rate of 91.0%; Ti-V alloy (Ti 0.76 V 0.24 , Ti0.51V 0.49 and Ti 0.25 V 0.75All of them have a BCC (body-centered cubic) structure. At temperatures below 150°C, their initial hydrogen absorption value without activation can reach 2 wt.%, and the hydrogen equilibrium pressure is less than 1 Pa. Meanwhile, the Ti-V series alloys prepared by the suspension melting and mechanical crushing method in Chinese patent CN03141849.X, after annealing at 950°C, have a BCC main phase and a maximum hydrogen storage capacity of 3.8 wt.%. However, problems still exist, such as low hydrogen storage density, easy pulverization, poor hydrogen desorption kinetics, severe hysteresis, and short cycle life. Therefore, it is necessary to develop ternary or multi-component alloys, such as Ti-Cr-V and Ti-Mn-V ternary alloys. The main phase is the BCC solid solution phase (the BCC structure has more tetrahedral and octahedral voids, providing more storage space for hydrogen atoms). The introduction of the secondary Laves phase into the solid solution promotes activation (Laves-phase hydrogen storage alloys have more hydrogen atom diffusion channels; the combination of BCC and C14Laves phases can improve the overall performance of hydrogen storage alloys). For example, the Ti-Mn-V alloy prepared by scholar XYChen... 23 V 40 Mn 37 The maximum hydrogen storage capacity can reach 3.5 wt.%. The maximum and effective hydrogen storage capacities of the Ti-32V-Mn-20Cr alloy 353K developed by scholars Yu Xuebin et al. are 3.5% and 2.4%, respectively. Scholars Li Jigang et al. discovered that (Ti... 1－x Zrx) 1.1 Cr 1.9 V 0.1 The cell parameters of the alloys (x = 0.05, 0.1, 0.2) continuously increase with the increase of Zr substitution for Ti, the hydrogen absorption / desorption plateau pressure continuously decreases, and the maximum hydrogen storage capacity continuously increases, reaching a maximum of 1.85%. Scholar Hangzhou Ming studied Ti alloys smelted using magnetic levitation. 10 V 83－x Fe6ZrMn x The alloys (x = 0, 2, 4, 6) can rapidly absorb hydrogen without inoculation at room temperature and 4 MPa hydrogen pressure; the maximum hydrogen absorption capacities of the alloys at room temperature are 3.66%, 3.61%, 2.77%, and 2.25%, respectively. Chen et al. prepared a high-entropy alloy TiZrFeMnCrV with a single C14Laves structure by arc melting and mechanical ball milling, achieving a hydrogen storage capacity of 1.80 wt%, but its activation and kinetic properties were poor. Chinese patent CN202310514733.6 proposes adding Hf and Cr to TiVMn, Ti... 19 Hf4V 40 Mn 35 Cr y(x = 0, 2, 4, 6), composed of C14Laves phase and BCC, with hydrogen storage capacity increasing with Cr content as follows: 2.15 wt.%, 2.09 wt.%, 2.03 wt.%, and 1.98 wt.%. Chinese Patent CN201810333474.6 describes ZrTi prepared by arc melting and heat treatment. 0.4 Cr 0.1 V 1.8 The hydrogen absorption capacity at 25℃ is 2.70 wt%, and it takes 600 seconds to complete 90% of the hydrogen absorption. The TiZrFeMnCrV alloy prepared by Chinese patent CN202111657219.5 has a C14Laves single-phase structure, with hydrogen storage capacities of 1.90 wt.% and 1.84 wt.% at 30℃ and 50℃, respectively. It is evident that although multi-component alloys are potential hydrogen storage materials, they still suffer from technical problems such as slow desorption rates, low hydrogen storage capacity, and poor cycle stability. Summary of the Invention

[0004] The purpose of this invention is to provide a multi-dimensional Ti-based solid hydrogen storage material and its preparation method, so as to solve the technical problems of slow desorption rate, low hydrogen storage capacity, poor cycle stability and easy oxidation in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] This invention provides a multidimensional Ti-based solid-state hydrogen storage material, which is composed of Ti, V, Mn, Zr, and Ni elements. The chemical formula of this material is Ti a V b Mn c Zr d Ni e The atomic ratios of each element are a = 0.60-0.65, b = 0.08-0.12, c = 0.08-0.10, d = 0.04-0.07, e = 0.08-0.12, and a+b+c+d+e = 1.

[0007] This invention also provides a method for preparing a multidimensional Ti-based solid hydrogen storage material as described above, comprising the following steps:

[0008] S1: Take raw materials and perform vacuum melting and gas atomization powder production;

[0009] S2: Ultrasonic grinding to prepare nano-alloy powder;

[0010] S3: Surface treatment to prepare hydrogen storage composite powder;

[0011] S4: Multidimensional Ti-based solid hydrogen storage material prepared by hydrogen absorption and desorption cycle activation.

[0012] Furthermore, the specific steps of S1 are as follows:

[0013] S1.1: Take TiZr master alloy and Ti, V, Mn and Ni metal blocks as raw materials, and put them into the melting crucible in descending order of melting point. Close the atomization chamber and evacuate.

[0014] S1.2: When the vacuum degree reaches 10 -1 -10 -3 At Pa, the temperature is increased to melt the raw materials. When the temperature reaches 1700-1900℃, inert gas is introduced and the temperature is maintained until the raw materials are completely melted to obtain an alloy melt.

[0015] S1.3: Adjust the inert gas atomization pressure to 5-7 MPa, atomize the alloy melt through a water-cooled copper crucible connected to the bottom of the tundish, collect the atomization products, and obtain alloy powder with a particle size of 50-150 μm.

[0016] Furthermore, the specific steps of S2 are as follows:

[0017] The alloy powder obtained by S1 is transferred to a sealed chamber containing argon gas, and an ultrasonic probe with a threaded connection to a moving rod is inserted into the alloy powder and filled with inert gas. The alloy powder is then ultrasonically pulverized and sieved to obtain alloy powder with a particle size of no more than 500 nm. The alloy powder with a particle size of more than 500 nm is ultrasonically pulverized again.

[0018] Furthermore, the specific steps of S3 are as follows:

[0019] S3.1: Take boron powder with a particle size of 50-100nm and white oil at a mass ratio of 1:2 and place it in a slurry crucible. Then place it on a stirrer and stir at a speed of 500-1000rpm for 1-2 hours to obtain a uniform boron slurry.

[0020] S3.2: Mix the nano-alloy powder obtained in S2 with boron slurry at a volume ratio of 1:2, stir for 2-3 hours until the mixture is uniform, and transfer the mixture to a vacuum furnace;

[0021] S3.3: Set the heating rate of the vacuum furnace to 5-10℃ / min, heat to 300-500℃ under a vacuum of 0.1-1Pa, hold at this temperature for 2-3 hours, and then cool naturally to room temperature to obtain hydrogen storage composite powder.

[0022] Furthermore, the specific steps of S4 are as follows:

[0023] S4.1: Place the hydrogen storage composite powder in a resistance heating furnace and evacuate it to below 1×10-3 Pa;

[0024] S4.2: Heat the sample chamber in the resistance heating furnace to 473-500K, close the sample valve, and fill it with hydrogen gas at a pressure of 4MPa-6MPa. Then open the sample valve, record the experimental data, and plot the hydrogen absorption curve.

[0025] S4.3: Determine whether the hydrogen absorption curve plotted in S4.2 is stable. If it is stable, close the sample valve and evacuate to 1×10⁻⁶. -3 Below Pa, record the experimental data and plot the hydrogen release curve; if it is not stable, return to S4.2;

[0026] S4.4: Repeat S4.2 to S4.3 to determine the overlap between the hydrogen absorption curve and the hydrogen release curve. If the overlap is ≥95%, a multi-dimensional Ti-based solid hydrogen storage material is obtained. If the overlap is <95%, repeat S4.2 to S4.4 until the overlap is ≥95%.

[0027] The beneficial effects of this invention are as follows: 1. This invention introduces elements such as V, Mn, Zr, and Ni into Ti-based hydrogen storage materials to form a multi-component high-entropy alloy containing a multiphase structure of BCC and Laves phases. The solid solution, lattice distortion, and slow diffusion effect generated by the high-entropy effect significantly increase the interstitial sites and diffusion channels for hydrogen. Simultaneously, the alloy possesses both crystalline and amorphous structures: the crystalline state provides hydrogen absorption and desorption stability, while the disordered arrangement of the amorphous state accelerates hydrogen diffusion, reducing stress, strain, and pulverization problems, thereby improving cycle life; 2. This invention employs a gas atomization and ultrasonic composite process, shortening the gas flow distance through a confined nozzle and combining cavitation effects to efficiently prepare fine-particle powder. The technology is highly mature and suitable for large-scale production; 3. This invention, by coating with a moderately dense boron film, both isolates oxygen and allows hydrogen to diffuse through the pores. Furthermore, the hydrogenation characteristics of boron (forming BH4) further increase the hydrogen storage capacity, achieving a dual effect of protection and performance enhancement. Attached Figure Description

[0028] 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 some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a flowchart of a method for preparing a multi-dimensional Ti-based solid hydrogen storage material according to the present invention;

[0030] Figure 2 This is a schematic diagram of the vacuum induction melting gas atomization device in this invention;

[0031] Figure 3 This is a schematic diagram of the ultrasonic pulverizing device in this invention;

[0032] Figure 4 This is a schematic diagram of the surface treatment (patina) device in this invention;

[0033] Figure 5 This is a scanning electron microscope image of the nanopowder obtained in Example 1 of this invention after coating treatment;

[0034] Figure 6 The XRD (X-ray Diffraction) pattern before hydrogen storage in Example 1 of this invention;

[0035] Figure 7 The XRD pattern after hydrogen storage in Example 1 of this invention;

[0036] Figure 8 This is an activation curve of the hydrogen storage material in Example 1 of the present invention;

[0037] Figure 9 This is a PCT (Pressure-Composition-Temperature) curve of the hydrogen storage material after activation in Example 1 of the present invention;

[0038] Figure 10 This is a cycle curve diagram of the hydrogen storage material after activation in Example 1 of the present invention;

[0039] Figure 11 These are electron microscope images of the hydrogen storage powder prepared in Example 1 of this invention;

[0040] Figure 12 This is the activation curve of the hydrogen storage material in Example 2 of the present invention;

[0041] Figure 13 This is a PCT curve of the hydrogen storage material after activation in Example 2 of the present invention;

[0042] Figure 14 This is a PCT curve of the hydrogen storage material after activation in Example 3 of the present invention;

[0043] Figure 15 This is a PCT curve of the hydrogen storage material after activation in Example 4 of the present invention;

[0044] Figure 16 This is a PCT curve of the hydrogen storage material after activation in Example 5 of the present invention;

[0045] Figure 17 This is a PCT curve of the hydrogen storage material after activation in Example 6 of the present invention;

[0046] Figure 18 This is a PCT curve of the hydrogen storage material after activation in Example 7 of the present invention;

[0047] Figure 19 This is a PCT curve of the hydrogen storage material after activation in Example 8 of the present invention.

[0048] In the figure, 1. melting crucible, 2. melting chamber, 3. tundish, 4. atomizing nozzle, 5. atomizing chamber, 6. powder collection tank, 7. water-cooled copper crucible, 8. inert gas, 9. moving rod, 10. ultrasonic probe, 11. alloy powder, 12. stirrer; 13. slurry crucible. Detailed Implementation

[0049] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0050] The inventive concept and principle of this invention are as follows: This invention targets Ti-based hydrogen storage materials and constructs a multi-component high-entropy alloy by introducing multiple elements such as V, Mn, Zr, and Ni. This effectively alleviates stress-strain and pulverization problems during charge-discharge processes, thereby significantly improving the material's cycle life. Simultaneously, by coating the alloy surface with a moderately dense boron film, oxygen is isolated and oxidation is prevented, while the micropores allow hydrogen diffusion. Furthermore, the hydrogenation properties of boron can form BH4 groups, further increasing the overall hydrogen storage capacity, achieving a dual effect of material protection and performance enhancement. The "multi-dimensional" composite nature of this invention is reflected in several aspects: in terms of composition, it consists of a composite of five metallic elements and one non-metallic element; in terms of powder scale, it is a mixture of nano- and micron-level particles; the phase structure encompasses BCC, FCC, and Laves phases; and in terms of structural form, it employs a coating strategy to synergistically optimize hydrogen storage performance.

[0051] A multidimensional Ti-based solid-state hydrogen storage material is proposed, which is composed of Ti, V, Mn, Zr, and Ni elements. The chemical formula of this material is Ti a V b Mn c Zr d Ni e The atomic ratios of each element are a = 0.60-0.65, b = 0.08-0.12, c = 0.08-0.10, d = 0.04-0.07, and e = 0.08-0.12, and a+b+c+d+e = 1. The Zr element is derived from the TiZr master alloy, in which the mass ratio of Ti to Zr is 1:1. The multidimensional Ti-based solid hydrogen storage material contains BCC phase and Laves phase.

[0052] The reason for selecting a TiZr master alloy with a Ti to Zr mass ratio of 1:1 is as follows: 1) Zirconium has an extremely high melting point (over 2000℃). If it is added directly to the alloy system, it will easily cause other alloying elements to volatilize severely at high temperatures, thus making the actual composition unable to meet the preset ratio. Using zirconium master alloys can not only effectively reduce the melting temperature and avoid compositional deviations, but also significantly improve the uniformity of element distribution in composite materials; 2) Ti and Zr belong to the same group IVB transition metals in the periodic table and have highly similar electronic configurations and crystal structures. When the mass ratio of Ti to Zr is 1:1, the corresponding atomic ratio is about 2:1 (Ti:Zr≈1.91:1). This ratio falls exactly within the continuous solid solution range of the Ti-Zr binary alloy (rather than forming a multiphase mixture), avoiding the precipitation of α phase, β phase or intermetallic compounds (such as Ti2Zr, TiZr2) due to compositional deviations, reducing phase boundary defects, forming a uniform single solid solution phase, providing a consistent lattice environment for the uniform diffusion and storage of hydrogen atoms, and avoiding local differences in hydrogen storage performance.

[0053] A multidimensional Ti-based solid-state hydrogen storage material includes the following steps, such as: Figure 1 As shown, at the beginning of powder preparation, the atomization chamber 5 of the vacuum melting gas atomization equipment is cleaned with inert argon gas. The melting crucible 1 and the water-cooled copper crucible 7 used for preparation are baked to remove moisture from the crucible and refractory materials. The alternating magnetic field induces strong eddy currents in the metal material. These eddy currents generate Joule heat, causing the metal material to heat up rapidly and melt. At the same time, the multiple segments of cooling water in the cold copper crucible circulate, absorbing the heat from the crucible wall and carrying it away, thereby keeping the temperature of the crucible wall relatively low. This cooling method can effectively avoid direct contact between the crucible wall and the molten metal, reducing contamination.

[0054] S1: Take raw materials and use them Figure 2 The vacuum induction melting gas atomization device shown is used for vacuum melting gas atomization powder production;

[0055] The specific steps for S1 are as follows:

[0056] S1.1: Take TiZr master alloy and Ti, V, Mn and Ni metal blocks as raw materials, and put them into the melting crucible 1 in descending order of melting point. Close the atomization chamber 5 and evacuate.

[0057] S1.2: When the vacuum degree reaches 10 -1 -10 -3 When Pa, the temperature is increased to melt the raw material. When the temperature reaches 1700-1900℃, inert gas 8 is introduced and the temperature is maintained until the raw material is completely melted to obtain the alloy melt.

[0058] S1.3: Adjust the atomization pressure of the inert gas 8 to 5-7 MPa, atomize the alloy melt through a water-cooled copper crucible connected to the bottom of the tundish 3, collect the atomization products, and obtain alloy powder with a particle size of 50-150 μm.

[0059] In this embodiment, the alloy melt is cooled and atomized by passing through an intermediate ladle 3 with a bottom aperture of 3-5 mm and a water-cooled copper crucible 7 connected below. The alloy melt is impacted and atomized by inert gas 8 at the atomizing nozzle 4. The atomized product is collected in the atomizing chamber 5 to obtain alloy powder 11 with a particle size of 50-150 μm. The alloy powder 11 falls into the powder collection tank 6.

[0060] S2: Use Figure 3 The ultrasonic pulverization device shown is used to prepare nano-alloy powder;

[0061] S2 specifically involves: transferring the alloy powder 11 obtained in S1 into a sealed chamber containing argon gas, inserting the ultrasonic probe 10 with a threaded connection to the moving rod 9 into the alloy powder 11 and filling it with inert gas (argon gas), and then ultrasonically pulverizing the alloy powder 11. The ultrasonic treatment source is a high-frequency ultrasonic generator (frequency greater than 10MHz). After sieving, alloy powder with a particle size of no more than 500nm is obtained. The alloy powder with a particle size greater than 500nm is ultrasonically pulverized again.

[0062] The reason for selecting alloy powder with a particle size of no more than 500 nm is that alloy powder of this size is rapidly activated, has a high hydrogen absorption and desorption capacity, and is also beneficial for subsequent dispersion and surface treatment.

[0063] The principle of ultrasonic pulverization is as follows: Under the action of ultrasound, small bubbles will be formed, that is, cavitation. These cavitation bubbles will expand rapidly under the action of sound pressure, generating instantaneous high temperature and high pressure, causing the target material to be subjected to strong impact and shearing, thus being broken into nanoscale particles.

[0064] S3: Use Figure 4 The surface treatment (patina) apparatus shown is used to prepare hydrogen storage composite powder by surface treatment of alloy powder with a particle size of no more than 500 nm obtained by S2.

[0065] The specific steps for S3 are as follows:

[0066] S3.1: Take boron powder with a particle size of 50-100 nm and white oil (low viscosity mineral oil, density 0.82-0.85 g / cm³). 3 Low-viscosity mineral oil is easier to mix and stir evenly, reducing agglomeration. If boron powder agglomerates severely, it should be heated (heating temperature should not exceed 50℃). Mix the boron powder at a mass ratio of 1:2 and place it in a slurry crucible 13. Then place it on a stirrer 12 and stir at a speed of 500-1000 rpm for 1-2 hours to obtain a uniform boron slurry.

[0067] S3.2: Mix the alloy powder with a particle size of no more than 500 nm obtained in S2 with boron slurry at a volume ratio of 1:2, stir for 2-3 hours until the mixture is uniform, and transfer the mixture to a vacuum furnace.

[0068] S3.3: The vacuum furnace is heated at a rate of 5–10 °C / min, and the temperature is raised to 300–500 °C under a vacuum of 0.1–1 Pa. The mixture is then held at this temperature for 2–3 hours, and then allowed to cool naturally to room temperature to obtain hydrogen storage composite powder. Figure 5 As shown.

[0069] S4: Multidimensional Ti-based solid hydrogen storage material prepared by hydrogen absorption and desorption cycle activation.

[0070] The specific steps for S4 are as follows:

[0071] S4.1: Place the hydrogen storage composite powder in a resistance heating furnace and evacuate it to below 1×10-3 Pa;

[0072] S4.2: Heat the sample chamber in the resistance heating furnace to 473-500K, close the sample valve, and fill it with hydrogen gas at a pressure of 4MPa-6MPa. Then open the sample valve, record the experimental data, and plot the hydrogen absorption curve.

[0073] S4.3: Determine whether the hydrogen absorption curve plotted in S4.2 is stable. If it is stable, close the sample valve and evacuate to 1×10⁻⁶. -3 Below Pa, record the experimental data and plot the hydrogen release curve; if it is not stable, return to S4.2;

[0074] S4.4: Determine whether the hydrogen absorption curve and the hydrogen release curve overlap. If the overlap is ≥95%, a multi-dimensional Ti-based solid hydrogen storage material is obtained. If the overlap is <95%, repeat S4.2 to S4.3 until the overlap is ≥95%.

[0075] In specific embodiments of the present invention: Ti and V are the main components of the titanium-based hydrogen storage alloy. This is because Ti and V are the main hydrogen-absorbing elements, and the BCC structure ensures a large hydrogen storage capacity. However, excessive Ti leads to an overly brittle and hard alloy, reducing its toughness and processing performance. Insufficient Ti and V affects the structural stability and hydrogen storage performance of the alloy, causing a decrease in its hydrogen storage capacity. The addition of Mn introduces the secondary Laves phase into the solid solution (Laves-phase hydrogen storage alloys have more hydrogen atom diffusion channels; the combination of BCC and Laves phases can improve the overall performance of the hydrogen storage alloy). Zr is used to adjust the phase structure of the alloy (replacing some Ti with Zr can increase the alloy's lattice parameters and reduce the hydrogen absorption plateau pressure), improving hydrogen storage performance. However, excessive Zr leads to brittleness, and excessive precious metals are too expensive. Insufficient Zr leads to an unstable phase structure, affecting hydrogen storage performance. Ni can generate a body-centered cubic TiNi secondary phase in the Ti alloy, increasing the phase interface and catalyzing the entry and exit channels of hydrogen atoms, reducing the hydrogenation incubation period of the alloy. However, excessive Ni will reduce the proportion of the hydrogen-absorbing main phase, leading to a decrease in capacity; insufficient Ni may prevent the shortening of the incubation period from being achieved. Finally, the solid solution structure of the multi-component alloy provides a large number of interstitial sites, while lattice distortion and slow diffusion effects provide additional sites for hydrogen diffusion channels, thus benefiting hydrogen storage performance. Therefore, by appropriately proportioning the five elements in a multi-component system, not only is hydrogen storage performance guaranteed, but the cost of the alloy is also controlled.

[0076] Example 1: A hydrogen storage alloy Ti 0.65 V 0.12 Mn 0.10 Zr 0.05 Ni 0.08 Preparation method of .

[0077] S1: Take raw materials and perform vacuum melting and gas atomization powder production;

[0078] S1.1: Calculate the amount of each raw material according to the atomic ratio Ti:V:Mn:Zr:Ni = 0.65:0.12:0.10:0.05:0.08. Take a 1:1 TiZr master alloy and Ti, V, Mn and Ni metal blocks as raw materials, and put them into the melting crucible 1 in descending order of melting point. Close the atomization chamber 5 and evacuate the vacuum.

[0079] S1.2: When the vacuum degree reaches 10 -3 When Pa, the temperature is increased and the raw material is melted. When the temperature reaches 1700℃, inert gas 8 is introduced and the temperature is maintained until the raw material is completely melted to obtain an alloy melt.

[0080] S1.3: Adjust the atomization pressure of the inert gas 8 to 5 MPa, and atomize the alloy melt through the water-cooled copper crucible 7 connected to the bottom of the tundish 3. Collect the atomization products to obtain alloy powder 11 with a particle size of 150 μm.

[0081] S2: Ultrasonic pulverization to prepare nanopowder; the alloy powder 11 obtained in S1 is transferred to a sealed chamber with argon gas, and an ultrasonic probe 10 with a threaded moving rod 9 is inserted into the alloy powder 11 and filled with inert gas. The alloy powder 11 is then ultrasonically pulverized, and after sieving, alloy powder with a particle size of no more than 500 nm is obtained. The alloy powder with a particle size of more than 500 nm is ultrasonically pulverized again.

[0082] S3: Surface treatment to prepare hydrogen storage composite powder;

[0083] S3.1: Take boron powder with a particle size of 100nm and mix it with white oil at a mass ratio of 1:2. Place it in a slurry crucible 13 and then place it on a stirrer 12 and stir at 1000rpm for 2 hours to obtain a uniform boron slurry.

[0084] S3.2: Mix the nano-alloy powder obtained in S2 with boron slurry at a volume ratio of 1:2, stir for 3 hours until the mixture is uniform, and transfer the mixture to a vacuum furnace;

[0085] S3.3: Set the heating rate of the vacuum furnace to 10℃ / min, heat to 500℃ under a vacuum of 0.1Pa, keep the mixture at this temperature for 3 hours, and then cool it naturally to room temperature to obtain hydrogen storage composite powder.

[0086] S4: Multidimensional Ti-based solid hydrogen storage material prepared by hydrogen absorption and desorption cycle activation.

[0087] S4.1: Place the hydrogen storage composite powder in a resistance heating furnace and evacuate it to below 1×10-3 Pa;

[0088] S4.2: Heat the sample chamber in the resistance heating furnace to 473K, close the sample valve, and fill it with hydrogen gas at a pressure of 6MPa. Then open the sample valve, record the experimental data, and plot the hydrogen absorption curve.

[0089] S4.3: Determine whether the hydrogen absorption curve plotted in S4.2 is stable. If it is stable, close the sample valve and evacuate to 1×10⁻⁶. -3 Below Pa, record the experimental data and plot the hydrogen release curve. If it is not stable, return to S4.2.

[0090] S4.4: Determine whether the hydrogen absorption curve and the hydrogen release curve overlap. If the overlap is ≥95%, a multi-dimensional Ti-based solid hydrogen storage material is obtained. If the overlap is <95%, repeat S4.2 to S4.3 until the overlap is ≥95%.

[0091] Figure 6 The XRD pattern before hydrogen storage in Example 1 of this invention is shown below. Figure 6 It can be seen that the characteristic diffraction peaks of the BCC phase mainly appear around 2θ≈40°, 60°, and 80°, corresponding to the (110), (200), and (211) crystal plane diffraction of the body-centered cubic structure; the characteristic peaks of the Laves phase are concentrated in the region of 2θ≈35°, 42°, 58°, and 70°. The diffraction peaks of the two phases do not overlap or interfere with each other, indicating good phase separation; using the diffraction peak intensity ratio (I 相 / ∑I 总 Preliminary estimation of phase content: if the intensity of the strongest peak (2θ≈40°) of the BCC phase is I1 and the intensity of the strongest peak (2θ≈42°) of the Laves phase is I2, then I1:I2≈3:2. Combining the difference in crystallinity between the two phases (similar peak sharpness), it can be inferred that the BCC phase accounts for about 60% and the Laves phase accounts for about 40%. This ratio is consistent with the design goal of "multi-dimensional structure" in Example 1, that is, the BCC phase provides high hydrogen storage capacity, the Laves phase optimizes hydrogen diffusion kinetics, and the two work together to improve the overall performance.

[0092] Figure 7 The XRD pattern after hydrogen storage in Example 1 of this invention is shown below. Figure 7 It can be seen that after hydrogen storage, the main phases of the material in Example 1 are the Laves phase and the FCC phase. The FCC phase is obtained by the change of the BCC phase before hydrogen storage.

[0093] Figure 8 This is the activation curve of the hydrogen storage material in Example 1 of the present invention. Figure 8 It can be seen that in the 0-200s period, both the first and second activation curves rise rapidly, indicating that the hydrogen absorption reaction rate is fast in the initial stage, and the active sites on the material surface quickly combine with hydrogen. The slope of the first activation curve is larger, reflecting that the initial hydrogen absorption rate is higher in the first activation than in the second. In the 500-1000s period, the two curves gradually flatten out, indicating that the material has reached a saturated state for hydrogen absorption. At this time, the sites inside the material that can store hydrogen are basically filled, and the saturated hydrogen absorption capacity of the first activation is higher than that of the second.

[0094] Figure 9 This is a PCT curve of the hydrogen storage material after activation in Example 1 of the present invention. Figure 9It can be seen that after activation, during the hydrogen absorption process, the hydrogen pressure rises slowly as the hydrogen absorption capacity increases in the initial low hydrogen pressure region. When the hydrogen absorption capacity approaches 2.5 wt.% of the hydrogen storage capacity, the hydrogen pressure rises sharply to reach hydrogen absorption saturation. During the hydrogen release process, the hydrogen pressure decreases as the hydrogen release capacity increases. The hydrogen absorption and release curves show a plateau segment and a hysteresis loop. The plateau reflects the hydrogen absorption and release equilibrium under specific conditions, which is beneficial for stable pressure control of hydrogen storage and release. The hysteresis stems from kinetic resistance and thermodynamic irreversibility, reflecting the reversibility and kinetic difficulty of hydrogen absorption and release. In terms of quantitative performance, the hydrogen absorption capacity under the test conditions is 2.41 wt.%.

[0095] Figure 10 This is a cycle curve diagram of the hydrogen storage material after activation in Example 1 of the present invention. Figure 10 It can be seen that the maximum hydrogen storage capacity of the alloy remains relatively stable during cycling, with a slight decrease in effective hydrogen storage capacity after each cycle. After 10 hydrogen absorption cycles, the hydrogen storage capacity of the alloy decreased from 1.92 wt.% to 1.85 wt.%. It can be calculated that the capacity retention rate of the alloy after 10 hydrogen absorption / desorption cycles is 96.35%, demonstrating excellent cycle stability.

[0096] Figure 11 These are electron microscope images of the hydrogen storage powder prepared in Example 1 of this invention. Figure 11 It can be seen that the powder particles exhibit an irregular morphology, with obvious blocky and fragmented structures, and the particle size is in the nanometer range (using a scale). The surface is rough and has features such as pores and cracks.

[0097] Example 2: A hydrogen storage alloy Ti 0.62 V 0.12 Mn 0.10 Zr 0.04 Ni 0.12 Preparation method of .

[0098] S1: Take raw materials and perform vacuum melting and gas atomization powder production;

[0099] S1.1: Calculate the amount of each raw material according to the atomic ratio Ti:V:Mn:Zr:Ni = 0.62:0.12:0.10:0.04:0.12. Take TiZr master alloy and Ti, V, Mn and Ni metal blocks with a mass ratio of 1:1 as raw materials, and put them into the melting crucible 1 in descending order of melting point. Close the atomization chamber 5 and evacuate.

[0100] S1.2: When the vacuum degree reaches 10 -3 When Pa, the temperature is increased and the raw material is melted. When the temperature reaches 1800℃, inert gas 8 is introduced and the temperature is maintained until the raw material is completely melted to obtain an alloy melt.

[0101] S1.3: Adjust the atomization pressure of the inert gas 8 to 6 MPa, and atomize the alloy melt through the water-cooled copper crucible 7 connected to the bottom of the tundish 3. Collect the atomization products to obtain alloy powder 11 with a particle size of 150 μm.

[0102] S2: Ultrasonic pulverization to prepare nanopowder; the alloy powder 11 obtained in S1 is transferred to a sealed chamber with argon gas, and an ultrasonic probe 10 with a threaded moving rod 9 is inserted into the alloy powder 11 and filled with inert gas. The alloy powder 11 is then ultrasonically pulverized, and after sieving, alloy powder with a particle size of no more than 500 nm is obtained. The alloy powder with a particle size of more than 500 nm is ultrasonically pulverized again.

[0103] S3: Surface treatment to prepare hydrogen storage composite powder;

[0104] S3.1: Take boron powder with a particle size of 50nm and mix it with white oil at a mass ratio of 1:2. Place it in a slurry crucible 13 and then place it on a stirrer 12 and stir at 500rpm for 1h to obtain a uniform boron slurry.

[0105] S3.2: Mix the nano-alloy powder obtained in S2 with boron slurry at a volume ratio of 1:2, and stir while mixing for 2 hours to obtain a mixture and transfer it to a vacuum furnace;

[0106] S3.3: Set the heating rate of the vacuum furnace to 5℃ / min, heat to 300℃ under a vacuum of 0.1Pa, keep the mixture at this temperature for 2 hours, and then cool it naturally to room temperature to obtain hydrogen storage composite powder.

[0107] S4: Multidimensional Ti-based solid hydrogen storage material prepared by hydrogen absorption and desorption cycle activation.

[0108] S4.1: Place the hydrogen storage composite powder in a resistance heating furnace and evacuate it to below 1×10-3 Pa;

[0109] S4.2: Heat the sample chamber in the resistance heating furnace to 486.5K, close the sample valve, and fill it with hydrogen gas at a pressure of 4MPa. Then open the sample valve, record the experimental data, and plot the hydrogen absorption curve.

[0110] S4.3: Determine whether the hydrogen absorption curve plotted in S4.2 is stable. If it is stable, close the sample valve and evacuate to 1×10⁻⁶. -3 Below Pa, record the experimental data and plot the hydrogen release curve. If it is not stable, return to S4.2.

[0111] S4.4: Determine whether the hydrogen absorption curve and the hydrogen release curve overlap. If the overlap is ≥95%, a multi-dimensional Ti-based solid hydrogen storage material is obtained. If the overlap is <95%, repeat S4.2 to S4.3 until the overlap is ≥95%.

[0112] Figure 12 The figure shows the activation curve of the hydrogen storage material in Example 2 of this invention. It can be seen that during the period of 0 to 500 seconds, both the first and second activation curves rise rapidly, indicating that the hydrogen absorption reaction rate is fast in the initial stage. After 500 seconds, the two curves gradually flatten out, indicating that the material has reached the saturation state for hydrogen absorption. At this time, the sites inside the material that can store hydrogen are basically filled, and the saturation hydrogen absorption of the first activation is higher than that of the second activation.

[0113] Figure 13 This is the PCT curve of the hydrogen storage material after activation in Example 2 of the present invention. Figure 13 It can be seen that after activation, the hydrogen pressure gradually increases with the increase of hydrogen storage capacity during hydrogen absorption and decreases accordingly during hydrogen release. There is a clear plateau segment in the process (hydrogen storage capacity range of about 0.5-2.5 wt.%), which shows typical thermodynamic equilibrium characteristics. This is beneficial for stable pressure control of hydrogen storage and release in practical applications. At the same time, the hydrogen absorption and release curves form a hysteresis loop, which is due to the asymmetry of hydrogen absorption and release kinetics and thermodynamic irreversibility. This reflects the reversibility of hydrogen absorption and release and the degree of kinetic difficulty. Under the test conditions, the hydrogen absorption capacity can reach 2.5 wt.%.

[0114] Example 3: A hydrogen storage alloy Ti 0.65 V 0.10 Mn 0.1 Zr 0.05 Ni 0.10 Preparation method of .

[0115] S1: Take raw materials and perform vacuum melting and gas atomization powder production;

[0116] S1.1: Calculate the amount of each raw material according to the atomic ratio Ti:V:Mn:Zr:Ni = 0.65:0.10:0.1:0.05:0.10. Take TiZr master alloy and Ti, V, Mn and Ni metal blocks with a mass ratio of 1:1 as raw materials, and put them into the melting crucible 1 in descending order of melting point. Close the atomization chamber 5 and evacuate.

[0117] S1.2: When the vacuum degree reaches 10-3 Pa, the temperature is increased and the raw material is melted. When the temperature reaches 1900℃, inert gas 8 is introduced and the temperature is maintained until the raw material is completely melted to obtain the alloy melt.

[0118] S1.3: Adjust the atomization pressure of the inert gas 8 to 7 MPa, and atomize the alloy melt through the water-cooled copper crucible 7 connected to the bottom of the tundish 3. Collect the atomization products to obtain alloy powder 11 with a particle size of 150 μm.

[0119] S2: Ultrasonic pulverization to prepare nanopowder; the alloy powder 11 obtained in S1 is transferred to a sealed chamber with argon gas, and an ultrasonic probe 10 with a threaded moving rod 9 is inserted into the alloy powder 11 and filled with inert gas. The alloy powder 11 is then ultrasonically pulverized, and after sieving, alloy powder with a particle size of no more than 500 nm is obtained. The alloy powder with a particle size of more than 500 nm is ultrasonically pulverized again.

[0120] S3: Surface treatment to prepare hydrogen storage composite powder;

[0121] S3.1: Take boron powder with a particle size of 77nm and mix it with white oil at a mass ratio of 1:2. Place it in a slurry crucible 13 and then place it on a stirrer 12 and stir at a speed of 750rpm for 1.5h to obtain a uniform boron slurry.

[0122] S3.2: Mix the nanopowder obtained in S2 with boron slurry at a volume ratio of 1:2, stirring continuously for 2.5 hours until the mixture is homogeneous, and transfer the mixture to a vacuum furnace;

[0123] S3.3: Set the heating rate of the vacuum furnace to 7.5℃ / min, heat to 400℃ under a vacuum of 0.45Pa, keep the mixture at this temperature for 2.5 hours, and then cool it naturally to room temperature to obtain hydrogen storage composite powder.

[0124] S4: Multidimensional Ti-based solid hydrogen storage material prepared by hydrogen absorption and desorption cycle activation.

[0125] S4.1: Place the hydrogen storage composite powder in a resistance heating furnace and evacuate it to 1×10⁻⁶. -3 Below Pa;

[0126] S4.2: Heat the sample chamber in the resistance heating furnace to 500K, close the sample valve, and fill it with hydrogen gas at a pressure of 5MPa. Then open the sample valve, record the experimental data, and plot the hydrogen absorption curve.

[0127] S4.3: Determine whether the hydrogen absorption curve plotted in S4.2 is stable. If it is stable, close the sample valve and evacuate to 1×10⁻⁶. -3 Below Pa, record the experimental data and plot the hydrogen release curve. If it is not stable, return to S4.2.

[0128] S4.4: Determine whether the hydrogen absorption curve and the hydrogen release curve overlap. If the overlap is ≥95%, a multi-dimensional Ti-based solid hydrogen storage material is obtained. If the overlap is <95%, repeat S4.2 to S4.3 until the overlap is ≥95%.

[0129] Figure 14 This is the PCT curve of the hydrogen storage material after activation in Example 3 of the present invention. Figure 14As can be seen, after the hydrogen storage material in Example 3 is activated, the hydrogen pressure rises rapidly with the capacity during hydrogen absorption and then plateaus. The pressure drops accordingly during hydrogen release. The existence of a hysteresis loop reflects the irreversibility of hydrogen absorption and release and the difference in kinetics. The hydrogen absorption capacity reaches approximately 2.18 wt.%.

[0130] Example 4: A hydrogen storage alloy Ti 0.65 V 0.08 Mn 0.08 Zr 0.07 Ni 0.12 Preparation method of .

[0131] The difference from Example 3 is that in S1.1, the amount of each raw material is calculated according to the atomic ratio Ti:V:Mn:Zr:Ni = 0.65:0.08:0.08:0.07:0.12. The TiZr master alloy and Ti, V, Mn and Ni metal blocks with a mass ratio of 1:1 are used as raw materials and are loaded into the water-cooled copper crucible in order of melting point from high to low. The atomization chamber door is closed and a vacuum is drawn.

[0132] Everything else is the same as in Example 3.

[0133] Figure 15 This is the PCT curve of the hydrogen storage material after activation in Example 4 of the present invention. Figure 15 It can be seen that after the material is activated, there are adsorption (hydrogen absorption) and desorption (hydrogen release) processes. Both processes increase with the increase of hydrogen storage capacity and hydrogen pressure. The adsorption curve and desorption curve do not coincide, forming a hysteresis loop, which reflects the kinetic asymmetry and thermodynamic irreversibility of hydrogen adsorption and desorption, indicating that there is energy loss in hydrogen adsorption-desorption. Under the test conditions, the hydrogen absorption capacity can reach 1.79 wt.%.

[0134] Example 5: A hydrogen storage alloy Ti 0.65 V 0.08 Mn 0.08 Zr 0.09 Ni 0.1 Preparation method of .

[0135] The difference from Example 3 is that in S2, nanoparticles are prepared by ultrasonic pulverization. The alloy powder obtained in S1 is transferred to a sealed chamber under an argon protective atmosphere, and an ultrasonic probe 10 is inserted into the alloy powder 11 and filled with inert gas 8. The alloy powder 11 is then ultrasonically pulverized and sieved to obtain alloy powder 11 with a particle size of about 50 nm.

[0136] Everything else is the same as in Example 3.

[0137] Figure 16 This is the PCT curve of the hydrogen storage material after activation in Example 5 of the present invention. Figure 16It can be seen that after the material is activated, there are adsorption (hydrogen absorption) and desorption (hydrogen release) processes. Both processes increase with the increase of hydrogen storage capacity and hydrogen pressure. The adsorption curve and desorption curve do not coincide, forming a hysteresis loop, which reflects the kinetic asymmetry and thermodynamic irreversibility of hydrogen adsorption and desorption, indicating that there is energy loss in hydrogen adsorption-desorption. Under the test conditions, the hydrogen absorption capacity can reach 1.9 wt.%.

[0138] Example 6: A hydrogen storage alloy Ti 0.62 V 0.08 Mn 0.1 Zr 0.07 Ni 0.12 Preparation method of .

[0139] The difference from Example 3 is that in S2, nanoparticles are prepared by ultrasonic pulverization. The alloy powder obtained in S1 is transferred to a sealed chamber under an argon protective atmosphere, and an ultrasonic probe 10 is inserted into the alloy powder 11 and filled with inert gas 8. The alloy powder 11 is then ultrasonically pulverized and sieved to obtain alloy powder 11 with a particle size of about 500 nm.

[0140] Everything else is the same as in Example 3.

[0141] Figure 17 This is the PCT curve of the hydrogen storage material after activation in Example 6 of the present invention. Figure 17 It can be seen that after the material is activated, there are adsorption (hydrogen absorption) and desorption (hydrogen release) processes. Both processes increase with the increase of hydrogen storage capacity and hydrogen pressure. The adsorption curve and desorption curve do not coincide, forming a hysteresis loop, which reflects the kinetic asymmetry and thermodynamic irreversibility of hydrogen adsorption and desorption, indicating that there is energy loss in hydrogen adsorption-desorption. Under the test conditions, the hydrogen absorption capacity can reach 1.56 wt.%.

[0142] Example 7: A hydrogen storage alloy Ti 0.65 V 0.1 Mn 0.08 Zr 0.07 Ni 0.1 Preparation method of .

[0143] The difference from Example 3 is that in S4.2, the sample chamber in the resistance heating furnace is heated to 227°C, the sample valve is closed, and hydrogen gas at a pressure of 4 MPa is introduced. Then the sample valve is opened, the experimental data is recorded, and the hydrogen absorption curve is plotted.

[0144] Everything else is the same as in Example 3.

[0145] Figure 18 This is the PCT curve of the hydrogen storage material after activation in Example 7 of the present invention. Figure 18It can be seen that after the material is activated, there are adsorption (hydrogen absorption) and desorption (hydrogen release) processes. Both processes increase with the increase of hydrogen storage capacity and hydrogen pressure. The adsorption curve and desorption curve do not coincide, forming a hysteresis loop, which reflects the kinetic asymmetry and thermodynamic irreversibility of hydrogen adsorption and desorption, indicating that there is energy loss in hydrogen adsorption-desorption. Under the test conditions, the hydrogen absorption capacity can reach 1.7 wt.%.

[0146] Example 8: A hydrogen storage alloy Ti 0.65 V 0.11 Mn 0.1 Zr 0.05 Ni 0.09 Preparation method of .

[0147] The difference from Example 3 is that in S4.2, the sample chamber in the resistance heating furnace is heated to 227°C, the sample valve is closed, and hydrogen gas at a pressure of 6MPa is introduced. Then the sample valve is opened, the experimental data is recorded, and the hydrogen absorption curve is plotted.

[0148] Everything else is the same as in Example 3.

[0149] Figure 19 This is the PCT curve of the hydrogen storage material after activation in Example 8 of the present invention. Figure 19 It can be seen that after the material is activated, there are adsorption (hydrogen absorption) and desorption (hydrogen release) processes. Both processes increase with the increase of hydrogen storage capacity, and the hydrogen pressure gradually increases. The adsorption curve and the desorption curve do not coincide, forming a hysteresis loop, which reflects the kinetic asymmetry and thermodynamic irreversibility of hydrogen adsorption and desorption, indicating that there is energy loss in hydrogen adsorption-desorption. Under the test conditions, the hydrogen absorption capacity can reach 2.2 wt.%.

[0150] Comparative Example 1: A hydrogen storage alloy Ti 0.65 Zr 0.05 Mn 0.15 Cr 0.07 V 0.08 Preparation method of .

[0151] The difference from Example 1 is that in S1.1, the amount of each raw material is calculated according to the atomic ratio Ti:Zr:Mn:Cr:V = 0.65:0.05:0.15:0.07:0.08. Ti, Zr, Mn, Cr and V metal blocks are taken as raw materials and loaded into the melting crucible 1 in order of melting point from high to low. The atomization chamber 5 is closed and a vacuum is drawn.

[0152] Everything else is the same as in Example 1.

[0153] Comparative Example 2: A hydrogen storage alloy Ti 0.6 Zr 0.1 Cr 0.08 Mn 0.08 V 0.08 Ni 0.06Preparation method of .

[0154] The difference from Example 1 is that in S1.1, the amount of each raw material is calculated according to the atomic ratio Ti:Zr:Cr:Mn:V:Ni = 0.6:0.1:0.08:0.08:0.08:0.06. Ti, Zr, Cr, Mn, V and Ni metal blocks are taken as raw materials and loaded into the melting crucible 1 in descending order of melting point. The atomization chamber 5 is closed and a vacuum is drawn.

[0155] Everything else is the same as in Example 1.

[0156] Comparative Example 3: A hydrogen storage alloy Ti1.2Fe0.8Mn0.2+1wt.%La(Ti 1.2 Fe 0.8 Mn 0.2 La 0.008 Preparation method of ).

[0157] The difference from Example 1 is that in S1.1, the amount of each raw material is calculated according to the atomic ratio Ti:Fe:Mn:La = 1.2:0.8:0.2:0.008, and Ti, Fe, Mn and La metal blocks are taken as raw materials and loaded into the melting crucible 1 in order of melting point from high to low. The atomization chamber 5 is closed and vacuum is performed.

[0158] Everything else is the same as in Example 1.

[0159] Comparative Example 4: A hydrogen storage alloy Ti 29 V 25 Mn 46 Preparation method of .

[0160] The difference from Example 1 is that in S1.1, the amount of each raw material is calculated according to the atomic ratio Ti:V:Mn = 29:25:46, and Ti, V and Mn metal blocks are taken as raw materials and loaded into the melting crucible 1 in order of melting point from high to low. The atomization chamber 5 is closed and vacuum is performed.

[0161] Everything else is the same as in Example 1.

[0162] Comparative Example 5: A hydrogen storage alloy Ti 45 Zr 27 Ni 20 Preparation method of V8.

[0163] The difference from Example 1 is that in S1.1, the amount of each raw material is calculated according to the atomic ratio Ti:Zr:Ni:V = 45:27:20:8, and Ti, Zr, Ni and V metal blocks are taken as raw materials and loaded into the melting crucible 1 in order of melting point from high to low. The atomization chamber 5 is closed and vacuum is performed.

[0164] Everything else is the same as in Example 1.

[0165] Comparative Example 6: A hydrogen storage alloy Ti 0.65 V 0.12 Mn 0.09 Zr 0.05 Ni 0.09 Preparation method of .

[0166] The difference from Example 1 is that in S1.1, the amount of each raw material is calculated according to the atomic ratio Ti:V:Mn:Zr:Ni = 0.65:0.12:0.09:0.05:0.09. TiZr master alloy with a mass ratio of 3:1 and Ti, V, Mn and Ni metal blocks are used as raw materials and loaded into the melting crucible 1 in descending order of melting point. The atomization chamber 5 is closed and a vacuum is drawn.

[0167] Everything else is the same as in Example 1.

[0168] Comparative Example 7: A hydrogen storage alloy Ti 0.65 V 0.12 Mn 0.09 Zr 0.05 N i0.09 Preparation method.

[0169] The difference from Example 1 is that S3 in Example 1 is not performed, but everything else is the same as in Example 1.

[0170] Everything else is the same as in Example 1.

[0171] Comparative Example 8: A hydrogen storage alloy Ti 0.65 V 0.12 Mn 0.09 Zr 0.05 N i0.09 Preparation method of .

[0172] In step S1.2 of Example 1, when the vacuum degree reaches 10... -3 When Pa, the temperature is increased and the raw materials are melted. When the temperature reaches 1550°C, inert gas 8 is introduced and the temperature is maintained until the raw materials are completely melted to obtain an alloy melt. The rest is the same as in Example 1.

[0173] Everything else is the same as in Example 1.

[0174] Comparative Example 9: A hydrogen storage alloy Ti 0.65 V 0.12 Mn 0.09 Zr 0.05 N i0.09 Preparation method of .

[0175] The difference from Example 1 is as follows: In S4.2, the sample chamber in the resistance heating furnace is heated to 213°C, the sample valve is closed, and hydrogen gas at a pressure of 2MPa is introduced. Then the sample valve is opened, the experimental data is recorded, and the hydrogen absorption curve is plotted. The rest is the same as in Example 1.

[0176] Comparative Example 10: A hydrogen storage alloy Ti 0.65 V 0.12 Mn 0.09 Zr 0.05 N i0.09 Preparation method.

[0177] The difference from Example 1 is that S2 in Example 1 is not performed, but everything else is the same as in Example 1.

[0178] Table 1 Performance test results of Examples 1-8

[0179]

[0180]

[0181] Table 2 Performance test results for Comparative Examples 1-10

[0182]

[0183] Table 1 shows the performance test results of Examples 1-8, and Table 2 shows the performance test results of Comparative Examples 1-10. It can be seen that the multi-dimensional Ti-based solid hydrogen storage material proposed in this invention (Examples 1-8) exhibits significant advantages in phase composition (BCC+Laves), hydrogen absorption performance, and activation characteristics. Compared with the comparative examples, the maximum hydrogen absorption capacity of Examples 1-8 (1.8-2.56 wt.%) is generally higher than that of Comparative Examples 1-5 (1.79-2.14 wt.%), with Example 2 reaching the highest value of 2.56 wt.%. Furthermore, all examples can achieve hydrogen absorption and desorption under mild conditions of 293 K, far superior to the high temperature of 573 K required for Comparative Example 5. In addition, Example 1 only requires one activation cycle to achieve a high activation capacity of 2.98 wt.%, significantly better than Comparative Example 1 (1.83 wt.%) and Comparative Example 4 (requiring three cycles to reach 2.14 wt.%). It is particularly noteworthy that Comparative Examples 1-2 have lower hydrogen absorption capacities due to containing only the Laves phase, while Comparative Example 5, with its single BCC phase and requirement for high-temperature operation, has limited practicality. In summary, this invention, through the synergistic effect of the BCC and Laves phases, exhibits significant advantages in low-temperature high-efficiency hydrogen absorption, low activation difficulty, and high capacity, thus significantly improving the overall performance of the material.

[0184] The various embodiments in this specification are described in a related manner. Similar or identical parts between embodiments can be referred to mutually. Each embodiment focuses on describing the differences from other embodiments. In particular, the system embodiments are basically similar to the method embodiments, so the description is relatively simple; relevant parts can be referred to the descriptions of the method embodiments.

[0185] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention are included within the scope of protection of the present invention.

Claims

1. A multi-dimensional Ti-based solid-state hydrogen storage material, characterized in that, This multidimensional Ti-based solid-state hydrogen storage material is composed of Ti, V, Mn, Zr, and Ni elements. The chemical formula for this material is Ti. a V b Mn c Zr d Ni e The atomic ratios of each element are a = 0.60-0.65, b = 0.08-0.12, c = 0.08-0.10, d = 0.04-0.07, e = 0.08-0.12, and a+b+c+d+e = 1.

2. The multi-dimensional Ti-based solid hydrogen storage material according to claim 1, characterized in that, The multidimensional Ti-based solid hydrogen storage material contains BCC phase and Laves phase.

3. A method for preparing a multidimensional Ti-based solid hydrogen storage material according to any one of claims 1 or 2, characterized in that, Includes the following steps: S1: Take raw materials and perform vacuum melting and gas atomization powder production; S2: Ultrasonic grinding to prepare nano-alloy powder; S3: Surface treatment to prepare hydrogen storage composite powder; S4: Multidimensional Ti-based solid hydrogen storage material prepared by hydrogen absorption and desorption cycle activation.

4. The method for preparing a multi-dimensional Ti-based solid hydrogen storage material according to claim 3, characterized in that, The specific steps of S1 are as follows: S1.1: Take TiZr master alloy and Ti, V, Mn and Ni metal blocks as raw materials, and put them into the melting crucible (1) according to the melting point from high to low. Close the atomization chamber (5) and evacuate. S1.2: When the vacuum degree reaches 10 -1 -10 -3 When Pa, the temperature is increased to melt the raw material. When the temperature reaches 1700-1900℃, inert gas (8) is introduced and the temperature is maintained until the raw material is completely melted to obtain the alloy melt. S1.3: Adjust the atomization pressure of the inert gas (8) to 5-7 MPa, atomize the alloy melt through the water-cooled copper crucible (7) connected to the bottom of the tundish (3), collect the atomization products, and obtain alloy powder (11) with a particle size of 50-150 μm.

5. The preparation method of a multi-dimensional Ti-based solid hydrogen storage material according to claim 3, characterized in that, The specific steps of S2 are as follows: The alloy powder (11) obtained by S1 is transferred to a sealed chamber with argon gas, and an ultrasonic probe (10) with a threaded moving rod (9) is inserted into the alloy powder (11) and filled with inert gas. The alloy powder (11) is then ultrasonically pulverized and sieved to obtain alloy powder with a particle size of no more than 500 nm. The alloy powder with a particle size of more than 500 nm is ultrasonically pulverized again.

6. The method for preparing a multi-dimensional Ti-based solid hydrogen storage material according to claim 3, characterized in that, The specific steps of S3 are as follows: S3.1: Take boron powder with a particle size of 50-100nm and white oil, mix them in a mass ratio of 1:2, place them in a slurry crucible (13), and then place them on a stirrer (12) and stir at a speed of 500-1000rpm for 1-2 hours to obtain a uniform boron slurry; S3.2: Mix the nano-alloy powder obtained in S2 with boron slurry at a volume ratio of 1:2, stir for 2-3 hours until the mixture is uniform, and transfer the mixture to a vacuum furnace; S3.3: Set the heating rate of the vacuum furnace to 5-10℃ / min, heat to 300-500℃ under a vacuum of 0.1-1Pa, hold at this temperature for 2-3 hours, and then cool naturally to room temperature to obtain hydrogen storage composite powder.

7. The method for preparing a multi-dimensional Ti-based solid hydrogen storage material according to claim 3, characterized in that, The specific steps of S4 are as follows: S4.1: Place the hydrogen storage composite powder in a resistance heating furnace and evacuate it to below 1×10-3 Pa; S4.2: Heat the sample chamber in the resistance heating furnace to 473-500K, close the sample valve, and fill it with hydrogen gas at a pressure of 4MPa-6MPa. Then open the sample valve, record the experimental data, and plot the hydrogen absorption curve. S4.3: Determine whether the hydrogen absorption curve plotted in S4.2 is stable. If it is stable, close the sample valve and evacuate to 1×10⁻⁶. -3 Below Pa, record the experimental data and plot the hydrogen release curve; if it is not stable, return to S4.2; S4.4: Repeat S4.2 to S4.3 to determine the overlap between the hydrogen absorption curve and the hydrogen release curve. If the overlap is ≥95%, a multi-dimensional Ti-based solid hydrogen storage material is obtained. If the overlap is <95%, repeat S4.2 to S4.4 until the overlap is ≥95%.

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