Activation-free high-capacity Ti-Zr-Ni quasi-crystal / amorphous complex phase hydrogen storage alloy and preparation method thereof

Abstract

The invention relates to an activation-free high-capacity Ti-Zr-Ni quasicrystal / amorphous complex phase hydrogen storage alloy, which belongs to the technical field of hydrogen storage alloy materials, and the system can form a quasicrystal structure with high-density tetrahedral gaps, and provides a new direction for solid hydrogen storage materials. The invention provides a Ti-Zr-Ni-based hydrogen storage alloy, the chemical formula of the hydrogen storage alloy is Ti < x > Zr < y > Ni < z >, x, y and z in the formula are percentages, x is equal to 40, y is greater than or equal to 30 and less than or equal to 50, z is greater than or equal to 10 and less than or equal to 30, and x + y + z is equal to 100. According to the Ti-Zr-Ni-based hydrogen storage alloy provided by the invention, the hydrogen storage titanium alloy with high activation performance and high hydrogen absorption capacity is obtained by means of component design and preparation process improvement, and the hydrogen absorption capacity within 60s reaches up to 85% of the maximum hydrogen storage capacity.

Description

Technical Field

[0001] This invention relates to the field of hydrogen storage alloy materials technology, and in particular to a high-capacity Ti-Zr-Ni quasi-crystalline / amorphous multiphase hydrogen storage alloy that does not require activation and its preparation method. Background Technology

[0002] Titanium-based hydrogen storage alloys have attracted much attention due to their excellent hydrogen storage performance, low cost, and flexible design, making them a promising solid-state hydrogen storage material. Their main systems include Ti-Fe, Ti-Cr, Ti-Mn, Ti-Zr, and Ti-V, but they suffer from problems such as difficult activation and significant hysteresis effects.

[0003] Ti-based quasicrystalline alloys are the second largest quasicrystalline system after Al-based quasicrystalline alloys. Extensive research has shown that they possess excellent properties such as low friction coefficient, low surface energy, low expansion coefficient, high hardness, high wear resistance, and hydrogen storage capacity. Recently, Ti / Zr-based quasicrystalline alloys and their approximations have attracted attention as novel candidate materials for hydrogen storage applications due to their recent discovery of reversible large-volume hydrogen absorption at low temperatures and pressures. TiZrNi alloys, due to their ability to form simple and complex polyhedral crystals, quasicrystalline phases, and amorphous phases, with their Burgmann bishell clusters containing 20 inner-shell tetrahedral interstices and 120 intershell tetrahedral interstices, are even more conducive to hydrogen storage.

[0004] Quasicrystalline structures can be obtained by controlling alloy composition and cooling rate or preparation process. In TiZrNi quasicrystalline structures, both Ti / Zr components have a strong chemical affinity for hydrogen, while Ni has a weaker chemical affinity for hydrogen. This allows Ni to promote the decomposition of hydrogen molecules into hydrogen atoms, playing a catalytic role similar to LaNi. Furthermore, this unique quasicrystalline structure has many tetrahedral interstitials, theoretically giving it a high hydrogen storage capacity. Summary of the Invention

[0005] The purpose of this invention is to provide a high-capacity Ti-Zr-Ni quasi-crystalline / amorphous multiphase hydrogen storage alloy that does not require activation and its preparation method, so as to overcome the shortcomings of the prior art.

[0006] To achieve the objectives of the above invention, the present invention provides the following technical solution:

[0007] A high-capacity Ti-Zr-Ni quasi-crystalline / amorphous multiphase hydrogen storage alloy requiring no activation, wherein the chemical composition of the hydrogen storage alloy is as follows: Ti x Zr y Ni z In the formula, x, y, z represent the atomic percentages of the corresponding components Ti, Zr, and Ni, respectively, where x = 40, 30 ≤ y ≤ 50, 10 ≤ z ≤ 30, and x + y + z = 100.

[0008] Furthermore, when the atomic ratio of the alloy elements is x=40, 35≤y≤45, and 15≤z≤25, the resulting Ti-Zr-Ni alloy ribbon has a quasi-crystalline / amorphous multiphase structure.

[0009] Furthermore, the hydrogen storage alloy has a nanocrystalline structure with an average grain size of 25~35nm.

[0010] A method for preparing a high-capacity Ti-Zr-Ni quasi-crystalline / amorphous multiphase hydrogen storage alloy without activation includes the following steps:

[0011] Step 1: Convert the characteristic composition of the alloy from atomic percentage to mass percentage, and weigh each component elemental metal raw material to prepare the alloy.

[0012] Step Two: Place the proportioned raw materials from Step One into a vacuum arc melting furnace, and evacuate the furnace to achieve a vacuum level of 4×10⁻⁶. -3 ~5×10 -3 Pa, then argon gas is introduced as a protective gas; the alloy ingot is repeatedly melted 5 times to ensure uniform alloy composition, and after the alloy ingot is cooled to room temperature in the furnace, it is taken out to obtain the master alloy ingot;

[0013] Step 3: Cut the master alloy ingot into blocks using a wire EDM machine, remove them and place them in a quartz tube with an open bottom. Place the quartz tube and the alloy raw material together into a melt quenching equipment, and evacuate to achieve a vacuum degree of 1~2×10⁻⁶ inside the melt quenching equipment. -2 Pa, then argon gas is filled in as a protective gas; the rotation speed of the single-roller copper wheel is set to 30m / s and the induction heating current is set to 33A to melt the cut block sample, and then argon gas is filled in and pressurized to spray the molten alloy from the bottom opening of the quartz tube onto the high-speed rotating single-roller copper wheel, thereby obtaining a continuous and flexible Ti-Zr-Ni quasi-crystalline / amorphous hydrogen storage alloy thin strip.

[0014] Step 4: Cut the Ti-Zr-Ni quasi-crystalline / amorphous hydrogen storage alloy thin strip prepared in Step 3 into pieces, then vacuum-storage it for subsequent hydrogen storage experiments.

[0015] Furthermore, in step two, the arc current is adjusted to 600A and the magnetic stirring current is adjusted to 6A for melting.

[0016] Application of a high-capacity Ti-Zr-Ni quasi-crystalline / amorphous multiphase hydrogen storage alloy that requires no activation in solid-state hydrogen storage materials.

[0017] Furthermore, the hydrogen storage alloy can achieve a hydrogen absorption capacity of 1.41~2.05 wt.% without activation under conditions of 350°C and hydrogen pressure of 4 MPa.

[0018] This invention provides a high-capacity Ti-Zr-Ni quasicrystalline / amorphous multiphase hydrogen storage alloy that requires no activation. It forms a unique quasicrystalline structure with numerous tetrahedral interstitials. Both Ti and Zr components exhibit strong chemical affinity for hydrogen, while Ni has a weaker affinity but can promote the decomposition of hydrogen molecules into hydrogen atoms, acting as a catalytic agent similar to LaNi, theoretically possessing high hydrogen storage capacity. Furthermore, this hydrogen storage alloy requires no activation and exhibits a rapid hydrogen charging rate, providing a new direction for solid-state hydrogen storage materials.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] 1. Quasicrystalline structure: The hydrogen storage alloy is further improved by arc melting followed by a secondary melting process using a strip spinning method, which can further improve the uniform distribution of alloying elements. The strip spinning method also accelerates the cooling rate and directly forms this quasicrystalline structure with unique high-density tetrahedral interstices from the liquid phase.

[0021] 2. Rapid hydrogen absorption: The hydrogen storage alloy has a nanocrystalline structure with an average grain size of 25~35nm. This fine-grained structure increases the number of grain boundaries, vacancies, and defects in the alloy, which is more conducive to hydrogen diffusion, resulting in a very fast hydrogen absorption rate. Within 60 seconds, the hydrogen absorption capacity reaches 85% of the maximum capacity.

[0022] 3. High capacity without activation: The hydrogen storage alloy possesses a unique quasi-crystalline structure, combining the strong hydrogen affinity of Ti / Zr with the catalytic effect of Ni to achieve high-capacity hydrogen storage performance without activation. The initial hydrogen storage capacity at 350℃ / 4MPa is 1.41–2.05 wt.%;

[0023] 4. Low cost: The alloying elements used in the hydrogen storage alloy are inexpensive, and its preparation process is simple with few steps and no activation is required, which saves the activation treatment and can further reduce its production cost, and also has the potential for large-scale application. Attached Figure Description

[0024] Figure 1 Ti in Embodiment 1 of the present invention 40 Zr 45 Ni 15 Macroscopic photograph of alloy strip;

[0025] Figure 2 Ti in Embodiment 2 of the present invention 40 Zr 40 Ni 20 XRD pattern of the alloy;

[0026] Figure 3 Ti in Embodiment 4 of the present invention 40 Zr 30 Ni 30 XRD pattern of the alloy;

[0027] Figure 4 The hydrogen absorption kinetics diagrams are shown for the amorphous / quasicrystalline thin strips in Examples 1-4. Detailed Implementation

[0028] To further illustrate the present invention, the following description, in conjunction with embodiments and accompanying drawings, is provided. It should be understood that these embodiments are implemented based on the technical solutions of the present invention, providing detailed implementation methods and specific operating procedures. They are merely for further illustrating the features and advantages of the present invention and are not intended to limit the scope of the claims. The protection scope of the present invention should include all the contents of the claims and is not limited to the following embodiments.

[0029] Example 1

[0030] Preparation of Ti of the present invention 40 Zr 45 Ni 15 Quasicrystalline / amorphous multiphase alloys

[0031] Step 1: Place Ti 40 Zr 45 Ni 15 The characteristic composition of the alloy is converted from atomic percentage to mass percentage, and the elemental metal raw materials of each component are weighed using a balance to prepare the alloy.

[0032] Step 2: Place the proportioned raw materials from Step 1 into a vacuum arc melting furnace, and evacuate the furnace to achieve a vacuum level of 4×10⁻⁶. -3 ~5×10 -3 Pa, then argon gas is introduced as a protective gas; the arc current is adjusted to 600A and the magnetic stirring current is 6A. The alloy ingot is repeatedly melted 5 times to ensure uniform alloy composition. After the alloy ingot is cooled to room temperature with the furnace, it is taken out to obtain the master alloy ingot.

[0033] Step 3: Cut the master alloy ingot into 4×8×30mm blocks using a wire EDM machine. Take about 6 grams from each block and place it in a quartz tube with an open bottom. Place the quartz tube and the alloy raw material together into the melt quenching equipment, adjusting the distance between the bottom opening of the quartz tube and the surface of the copper wheel to about 1mm. Evacuate the equipment to achieve a vacuum degree of 1~2×10⁻⁶. -2 Pa, then argon gas was introduced as a protective gas; the rotation speed of the single-roller copper wheel was set to 30 m / s and the induction heating current to 33 A to melt the cut block sample. Then, argon gas was introduced and pressurized to spray the molten alloy from the bottom opening of the quartz tube onto the high-speed rotating single-roller copper wheel, thereby obtaining Ti. 40 Zr 45 Ni 15 Quasicrystalline / amorphous hydrogen storage alloy strips ( Figure 1 );

[0034] Step 4: Process the prepared Ti 40 Zr 45 Ni 15 X-ray diffraction (XRD) analysis was performed on the as-cast alloy sample and the thin ribbon sample. The as-cast sample showed crystalline diffraction peaks mainly containing α-(Ti,Zr) phase and C14 laves phase. The XRD pattern of the thin ribbon sample, which was formed at a rapid cooling rate, showed obvious amorphous diffraction structure characteristics and also had quasicrystalline 20 / 32 peaks at a diffraction angle of 38°, proving that it is a quasicrystalline / amorphous multiphase structure.

[0035] Example 2

[0036] Preparation of Ti of the present invention 40 Zr 40 Ni 20 Quasicrystalline / amorphous multiphase alloys

[0037] Step 1: Place Ti 40 Zr 40 Ni 20 The characteristic composition of the alloy is converted from atomic percentage to mass percentage, and the elemental metal raw materials of each component are weighed using a balance to prepare the alloy.

[0038] Step 2: Place the proportioned raw materials from Step 1 into a vacuum arc melting furnace, and evacuate the furnace to achieve a vacuum level of 4×10⁻⁶. -3 ~5×10 -3 Pa, then argon gas is introduced as a protective gas; the arc current is adjusted to 550A and the magnetic stirring current to 6A. The alloy ingot is repeatedly melted 5 times to ensure uniform alloy composition. After the alloy ingot is cooled to room temperature with the furnace, it is taken out to obtain the master alloy ingot;

[0039] Step 3: Cut the master alloy ingot into 4×8×30mm blocks using a wire EDM machine. Take about 6 grams from each block and place it in a quartz tube with an open bottom. Place the quartz tube and the alloy raw material together into the melt quenching equipment, adjusting the distance between the bottom opening of the quartz tube and the surface of the copper wheel to about 1mm. Evacuate the equipment to achieve a vacuum degree of 1~2×10⁻⁶. -2 Pa, then argon gas was introduced as a protective gas; the rotation speed of the single-roller copper wheel was set to 30 m / s and the induction heating current to 33 A to melt the cut block sample. Then, argon gas was introduced and pressurized to spray the molten alloy from the bottom opening of the quartz tube onto the high-speed rotating single-roller copper wheel, thereby obtaining Ti. 40 Zr 40 Ni 20 Quasicrystalline / amorphous hydrogen storage alloy strips;

[0040] Step 4: Process the prepared Ti 40 Zr 40 Ni 20X-ray diffraction (XRD) analysis was performed on the alloy as-cast sample and the thin strip sample respectively. Figure 2 The as-cast sample exhibits crystalline diffraction peaks mainly containing α-(Ti,Zr) phase and C14 laves phase. The XRD pattern of the thin ribbon sample formed by rapid cooling shows obvious quasicrystalline three strong peaks (18 / 29, 20 / 32, and 52 / 83) at diffraction angles of 36°, 38°, and 64°, and also shows a small amount of amorphous diffraction structure characteristics, proving that it is a quasicrystalline / amorphous multiphase structure.

[0041] Example 3

[0042] Preparation of Ti of the present invention 40 Zr 35 Ni 25 Quasicrystalline / amorphous multiphase alloys

[0043] Step 1: Place Ti 40 Zr 35 Ni 25 The characteristic composition of the alloy is converted from atomic percentage to mass percentage, and the elemental metal raw materials of each component are weighed using a balance to prepare the alloy.

[0044] Step 2: Place the proportioned raw materials from Step 1 into a vacuum arc melting furnace, and evacuate the furnace to achieve a vacuum level of 4×10⁻⁶. -3 ~5×10 -3 Pa, then argon gas is introduced as a protective gas; the arc current is adjusted to 500A and the magnetic stirring current to 6A. The alloy ingot is repeatedly melted 5 times to ensure uniform alloy composition. After the alloy ingot is cooled to room temperature with the furnace, it is taken out to obtain the master alloy ingot.

[0045] Step 3: Cut the master alloy ingot into 4×8×30mm blocks using a wire EDM machine. Take about 6 grams from each block and place it in a quartz tube with an open bottom. Place the quartz tube and the alloy raw material together into the melt quenching equipment, adjusting the distance between the bottom opening of the quartz tube and the surface of the copper wheel to about 1mm. Evacuate the equipment to achieve a vacuum degree of 1~2×10⁻⁶. -2 Pa, then argon gas was introduced as a protective gas; the rotation speed of the single-roller copper wheel was set to 30 m / s and the induction heating current to 33 A to melt the cut block sample. Then, argon gas was introduced and pressurized to spray the molten alloy from the bottom opening of the quartz tube onto the high-speed rotating single-roller copper wheel, thereby obtaining Ti. 40 Zr 35 Ni 25 Quasicrystalline / amorphous hydrogen storage alloy strips;

[0046] Step 4: Process the prepared Ti 40 Zr 35 Ni 25X-ray diffraction (XRD) analysis was performed on the as-cast alloy sample and the thin ribbon sample. The as-cast sample showed crystalline diffraction peaks mainly containing α-(Ti,Zr) phase and C14 laves phase. The XRD pattern of the thin ribbon sample, which was formed at a rapid cooling rate, showed obvious quasicrystalline three strong peaks (18 / 29, 20 / 32, and 52 / 83) at diffraction angles of 36°, 38°, and 64°, and also exhibited obvious amorphous diffraction structure characteristics, proving that it is a quasicrystalline / amorphous multiphase structure.

[0047] Example 4

[0048] Preparation of Ti of the present invention 40 Zr 30 Ni 30 Amorphous alloy

[0049] Step 1: Place Ti 40 Zr 30 Ni 30 The characteristic composition of the alloy is converted from atomic percentage to mass percentage, and the elemental metal raw materials of each component are weighed using a balance to prepare the alloy.

[0050] Step 2: Place the proportioned raw materials from Step 1 into a vacuum arc melting furnace, and evacuate the furnace to achieve a vacuum level of 4×10⁻⁶. -3 ~5×10 -3 Pa, then argon gas is introduced as a protective gas; the arc current is adjusted to 450A and the magnetic stirring current to 6A. The alloy ingot is repeatedly melted 5 times to ensure uniform alloy composition. After the alloy ingot is cooled to room temperature with the furnace, it is taken out to obtain the master alloy ingot.

[0051] Step 3: Cut the master alloy ingot into 4×8×30mm blocks using a wire EDM machine. Take about 6 grams from each block and place it in a quartz tube with an open bottom. Place the quartz tube and the alloy raw material together into the melt quenching equipment, adjusting the distance between the bottom opening of the quartz tube and the surface of the copper wheel to about 1mm. Evacuate the equipment to achieve a vacuum degree of 1~2×10⁻⁶. -2 Pa, then argon gas was introduced as a protective gas; the rotation speed of the single-roller copper wheel was set to 30 m / s and the induction heating current to 33 A to melt the cut block sample. Then, argon gas was introduced and pressurized to spray the molten alloy from the bottom opening of the quartz tube onto the high-speed rotating single-roller copper wheel, thereby obtaining Ti. 40 Zr 30 Ni 30 Amorphous hydrogen storage alloy thin strip;

[0052] Step 4: Process the prepared Ti 40 Zr 30 Ni 30X-ray diffraction (XRD) analysis was performed on the as-cast alloy sample and the thin ribbon sample. The as-cast sample showed crystalline diffraction peaks, mainly containing α-(Ti,Zr) phase and C14 laves phase, as well as a small amount of Ti2Ni phase. The XRD pattern of the thin ribbon sample, which was formed at a rapid cooling rate, showed a broad diffuse scattering peak and no crystalline diffraction peaks, proving that it is an amorphous structure.

[0053] Example 5

[0054] Step 1: Cut the Ti-Zr-Ni quasi-crystalline / amorphous hydrogen storage alloy strips prepared in Examples 1-4 into small pieces for hydrogen storage experiments.

[0055] Step 2: The hydrogen absorption performance, hydrogen storage capacity, and hydrogen absorption / desorption kinetics of the Ti-Zr-Ni quasi-crystalline / amorphous hydrogen storage alloy fragments prepared in Examples 1-4 were measured using a Quantum H-Sorb 2600 High Pressure Ads. Analyzer. Approximately 0.6000g of alloy was used for each test. Before the experiment, the hydrogen storage reaction tube was ultrasonically cleaned with alcohol and dried. During assembly, attention was paid to the sealing performance of the device to prevent leakage. The hydrogen absorption conditions were as follows: helium as the calibration gas, hydrogen absorption temperature of 350℃, heating rate of 10℃ / min, and hydrogen pressure of 4MPa.

[0056] Step 3: Figure 4 The hydrogen absorption kinetics curves for the first hydrogen absorption of the Ti-Zr-Ni quasicrystalline / amorphous hydrogen storage alloy ribbons prepared in Examples 1-4 are shown. The hydrogen storage alloys absorb hydrogen for 300 min at 350℃ and a hydrogen pressure of 4 MPa, achieving a hydrogen absorption capacity of 1.41-2.05 wt.% without activation. This demonstrates excellent activation performance and high hydrogen absorption capacity, significantly reducing activation costs.

[0057] Table 1 shows the hydrogen absorption of Ti-Zr-Ni quasi-crystalline / amorphous hydrogen storage alloy strips prepared in Examples 1-4 one minute prior.

[0058]

[0059] As shown in Table 1, the Ti-Zr-Ni quasi-crystalline / amorphous hydrogen storage alloy ribbons prepared in Examples 1-4 exhibit rapid hydrogen absorption rates, reaching approximately 85% of their maximum hydrogen absorption capacity within 1 minute. Furthermore, the preparation method of this invention is simple in process, low in cost, and conducive to large-scale production, demonstrating promising prospects for industrial application.

Claims

1. A high-capacity Ti-Zr-Ni-based quasicrystal / amorphous composite hydrogen storage alloy without activation, characterized in that, The chemical composition expression of the hydrogen storage alloy is: Ti x Zr y Ni z , wherein x, y, z respectively represent the atomic percentage of each corresponding component Ti, Zr, Ni, wherein x = 40, 30 ≤ y ≤ 50, 10 ≤ z ≤ 30, and x + y + z = 100.

2. The non-activated high-capacity Ti-Zr-Ni-based quasicrystal / amorphous composite hydrogen storage alloy of claim 1, wherein, The hydrogen storage alloy has a nanocrystalline structure, and the average grain size is 25-35 nm.

3. The preparation method of the non-activated high-capacity Ti-Zr-Ni-based quasicrystal / amorphous composite phase hydrogen storage alloy according to claim 1 or 2, characterized in that, The method comprises the following steps: Step one: converting the characteristic components of the alloy from atomic percentage to mass percentage, and weighing each component of the elemental metal raw material to prepare the alloy; Step two: put the raw materials prepared in step one into a vacuum arc melting furnace, vacuumize the furnace to reach a vacuum degree of 4x10 -3 5x10 -3 Pa, then fill in argon as a protective gas; repeatedly melt the alloy ingot for 5 times to ensure the uniformity of the alloy composition, and take out the alloy ingot after the alloy ingot cools down with the furnace to room temperature to obtain a mother alloy ingot; Step three: cut the master alloy ingot into blocks with a wire cutting machine, take out and place in a quartz tube with an open bottom, and put the quartz tube and the alloy raw material into a melt-spinning device as a whole, vacuumize to make the vacuum degree in the cavity of the melt-spinning device reach 1-2×10 -2 Pa, then fill in argon as a protective gas; set the rotating speed of the single-copper-wheel to be 30 m / s and the inductive heating current to be 33 A to melt the cut block-shaped sample, then fill in argon to pressurize, and spray the melted alloy from the bottom opening of the quartz tube to the high-speed rotating single-copper-wheel, so as to obtain a continuous and flexible Ti-Zr-Ni-based quasicrystal / amorphous hydrogen storage alloy ribbon. Step four: shearing the Ti-Zr-Ni quasicrystal / amorphous hydrogen storage alloy ribbon prepared in step three, and then vacuumizing and storing for subsequent hydrogen storage test.

4. The production method according to claim 3, characterized by, In step two, the arc current is adjusted to 600 A, and the magnetic stirring current is adjusted to 6 A for melting.

5. Application of the non-activated high-capacity Ti-Zr-Ni quasicrystal / amorphous composite hydrogen storage alloy of claim 1 or 2 in solid-state hydrogen storage material.

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