High-entropy alloy capable of rapidly absorbing hydrogen at room temperature and preparation method of high-entropy alloy

Abstract

The invention relates to a high-entropy alloy capable of rapidly absorbing hydrogen at room temperature and a preparation method of the high-entropy alloy, and aims to solve the problems of high hydrogen absorption temperature and low hydrogen absorption rate of a hydrogen storage alloy. The high-entropy alloy is composed of Zr, T, V, Fe and Cu, the chemical formula of the high-entropy alloy is (Ti0. 30Zr0. 25Fe0. 25V0. 20) 100-xCux, and the chemical formula of the high-entropy alloy is (Ti0. 30Zr0. 25Fe0. 25V0. 20) 100-xCux, wherein x ranges from 5 to 20. According to the invention, crushing and ball milling are carried out after non-self-consumption vacuum arc melting. Compared with other alloys, the prepared high-entropy alloy has lower hydrogen absorption temperature and hydrogenation pressure and higher hydrogen absorption rate, and the problems of high hydrogen absorption temperature and low hydrogen absorption rate are solved. The invention is applied to the technical field of hydrogen storage alloys.

Description

Technical Field

[0001] The invention relates to a high entropy alloy capable of rapidly absorbing hydrogen at room temperature and a preparation method thereof. Background Art

[0002] Energy is closely related to the development of human society. With the increasing prominence of energy crisis and environmental problems, the development and utilization of green new energy has become particularly urgent. Among many new energy sources, such as solar energy, geothermal energy, tidal energy, nuclear energy, hydrogen energy, etc., hydrogen energy has been favored by researchers due to its many advantages such as cleanliness, pollution-free and renewable. However, the development and utilization of hydrogen energy is a huge system engineering, involving three key technologies: large-scale preparation, storage, transportation and application of hydrogen, among which the storage and transportation of hydrogen are the most critical.

[0003] At present, storage technology has become a bottleneck hindering the application of hydrogen energy and must be solved. High-pressure gaseous hydrogen storage, low-temperature liquefied hydrogen storage and hydride hydrogen storage are the three mainstream hydrogen storage methods. Hydride hydrogen storage has been widely studied due to its high safety, high hydrogen storage density and ease of use. Designing hydrogen storage alloys that can store large amounts of hydrogen at room temperature is crucial for the widespread application of hydrogen.

[0004] In recent years, the concept of high entropy alloys has broken the design concept of traditional alloys and opened up a new path for alloy design. Therefore, studying a high-performance hydrogen storage high entropy alloy will provide better hydrogen carrier materials for the future hydrogen energy field and further promote the practical application of high entropy alloys and hydrogen. Summary of the invention

[0005] The purpose of the present invention is to solve the problems of high hydrogen absorption temperature and slow hydrogen absorption rate of hydrogen storage alloys, and propose a high entropy alloy that can quickly absorb hydrogen at room temperature and a preparation method thereof.

[0006] The invention discloses a high entropy alloy capable of rapidly absorbing hydrogen at room temperature, which is composed of Zr, T, V, Fe, and Cu, and has the chemical formula (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x , where x ranges from 5 to 20.

[0007] The preparation method of a high entropy alloy capable of rapidly absorbing hydrogen at room temperature of the present invention is carried out according to the following steps:

[0008] 1. Weighing Zr, Ti, V, Fe and Cu metal single substance particles according to the alloy atomic percentage to obtain raw materials;

[0009] 2. Place the raw materials in a crucible of a melting furnace, evacuate and fill with argon, and then perform non-consumable vacuum arc melting to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x High entropy alloy ingots;

[0010] 3. The obtained (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x The high entropy alloy ingot is polished to obtain a polished alloy ingot;

[0011] 4. Mechanically crushing the polished alloy ingot to obtain alloy particles;

[0012] 5. Ball mill the alloy particles to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x High entropy alloy ball milled powder.

[0013] The present invention has the following beneficial effects:

[0014] 1. In the high entropy alloy of the present invention, Zr, Ti, and V are strong hydrogenating elements, and Cu and Fe have superior performance in destabilizing hydrides and enhancing dehydrogenation kinetics. By rationally selecting alloy elements, a high entropy alloy with the ability to rapidly absorb hydrogen at room temperature and low pressure is prepared.

[0015] Second, the size of the alloy is reduced by ball milling, the surface area of ​​the alloy is increased, and the reaction area between hydrogen and the alloy is increased, further achieving the effect of increasing the hydrogen absorption rate of the alloy. Compared with other alloys, the high entropy alloy of the present invention has a lower hydrogen absorption temperature and hydrogenation pressure, a faster hydrogen absorption rate, and solves the problems of high hydrogen absorption temperature and slow hydrogen absorption rate.

[0016] 3. The present invention 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x The alloy has the ability to quickly absorb hydrogen at room temperature and low pressure, and is a high entropy alloy with the potential to store hydrogen. The alloy preparation method and process of the invention are simple, short in cycle, and easy to implement, and is a high entropy alloy with the potential to store hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The (Ti prepared in Example 1 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 95 SEM microstructure of Cu5 high entropy alloy;

[0018] Figure 2 The (Ti prepared in Example 2 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 90 Cu 10 SEM microstructure of high entropy alloy;

[0019] Figure 3 The (Ti prepared in Example 3 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 80 Cu 20 SEM microstructure of high entropy alloy;

[0020] Figure 4 It can absorb hydrogen rapidly at room temperature (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x XRD diagram of high entropy alloy; 1 is example 1, 2 is example 2, and 3 is example 3;

[0021] Figure 5 It is a (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x Isothermal hydrogen absorption curve of high entropy alloy at room temperature and 1MPa hydrogen pressure; 1 is example one, 2 is example two, and 3 is example three. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is not limited to the specific implementation modes listed below, but also includes any combination of the specific implementation modes.

[0023] Specific implementation method 1: In this implementation method, a high entropy alloy that can quickly absorb hydrogen at room temperature is composed of Zr, T, V, Fe, and Cu, and the chemical formula is (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 )100-x Cu x , where x ranges from 5 to 20.

[0024] Specific embodiment 2: This embodiment is different from the specific embodiment 1 in that the high entropy alloy is composed of 23.75% Zr, 28.50% Ti, 19% V, 23.75% Fe and 5% Cu in atomic percentage, and the chemical formula is (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 95 Cu5. Others are the same as those in the first specific implementation mode.

[0025] Specific embodiment 3: This embodiment is different from specific embodiment 1 or 2 in that: the high entropy alloy is composed of 22.5% Zr, 27.0% Ti, 18.0% V, 22.5% Fe and 10% Cu in atomic percentage, and the chemical formula is (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 90 Cu 10 . The rest is the same as the specific implementation mode 1 or 2.

[0026] Specific embodiment 4: This embodiment is different from the specific embodiments 1 to 3 in that the high entropy alloy is composed of 20% Zr, 24% Ti, 16% V, 20% Fe and 20% Cu in atomic percentage, and the chemical formula is (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 80 Cu 20 . The rest is the same as that of Specific Implementation Methods 1 to 3.

[0027] Specific implementation method 5: In this implementation method, a method for preparing a high entropy alloy that can quickly absorb hydrogen at room temperature is carried out according to the following steps:

[0028] 1. Weighing Zr, Ti, V, Fe and Cu metal single substance particles according to the alloy atomic percentage to obtain raw materials;

[0029] 2. Place the raw materials in a crucible of a melting furnace, evacuate and fill with argon, and then perform non-consumable vacuum arc melting to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x High entropy alloy ingots;

[0030] 3. The obtained (Ti0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x The high entropy alloy ingot is polished to obtain a polished alloy ingot;

[0031] 4. Mechanically crushing the polished alloy ingot to obtain alloy particles;

[0032] 5. Ball mill the alloy particles to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x High entropy alloy ball milled powder.

[0033] Specific implementation method 6: This implementation method is different from the specific implementation method 5 in that: Step 2 is to vacuumize to 3×10 -3 Pa. The rest is the same as the fifth specific implementation method.

[0034] Specific embodiment 7: This embodiment differs from specific embodiment 5 or 6 in that: in step 2, argon gas is introduced to a pressure of 0.05 MPa. The rest is the same as specific embodiment 5 or 6.

[0035] Specific embodiment 8: This embodiment is the same as any one of specific embodiments 5 to 7 in that: in step 5, a planetary ball mill is used for ball milling, high-purity argon gas is filled into the ball milling tank, the ball-to-material ratio is 10:1, and the rotation speed is 200 rpm. Other aspects are the same as any one of specific embodiments 5 to 7.

[0036] Specific embodiment 9: This embodiment is the same as any one of specific embodiments 5 to 8 in that the ball milling time in step 5 is 2 hours. Other aspects are the same as any one of specific embodiments 5 to 8.

[0037] Specific implementation method 10: This implementation method is the same as any one of the specific implementation methods 5 to 9: Step 5 obtains (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x The mesh number of the high entropy alloy ball-milled powder is less than 200 meshes. The rest is the same as that of any one of the fifth to ninth embodiments.

[0038] The following examples are used to verify the beneficial effects of the present invention:

[0039] Example 1: A (Ti) that can quickly absorb hydrogen at room temperature 0.30 Zr 0.25 Fe 0.25 V0.20 ) 95 Cu5 high entropy alloy and preparation method thereof

[0040] (1) Raw material preparation: 23.75% Zr, 28.50% Ti, 19% V, 23.75% Fe and 5% Cu are mixed according to atomic percentage to obtain raw materials; considering the volatilization and burning loss during the smelting process, the ingredients should be weighed according to 102% of the components, and the mass should be accurate to two decimal places after the nominal composition, wherein the metal raw material Ti is sponge titanium, and Zr, V, Fe and Cu are all small columnar particles.

[0041] (2) Arc melting: The raw materials are placed in the same crucible of the melting furnace. The Zr and V metals with higher melting temperatures are placed on the top layer of the water-cooled copper crucible, and the Ti, Fe, and Cu metals with lower melting temperatures are placed on the bottom layer of the crucible (the specific order from top to bottom is V, Zr, Ti, Fe, and Cu). The vacuum is pumped to 5 Pa by a mechanical pump, then filled with argon to 0.2 MPa, and then pumped to 5 Pa again. The vacuum is then pumped to 3×10 -3 Pa, the protective gas argon was introduced to 0.05MPa for arc melting. To ensure uniform distribution of alloy elements, the melting was repeated 5 times to finally obtain a button-shaped high-entropy alloy ingot.

[0042] (3) Polishing: The obtained high entropy alloy ingot was polished with 400-mesh sandpaper to remove surface stains and surface oxide scale, and then placed in acetone for ultrasonic cleaning.

[0043] (4) Mechanical crushing: The alloy ingots after grinding and cleaning are mechanically crushed into particles less than 2 mm.

[0044] (5) Ball milling: The mechanically crushed alloy particles are placed in the ball mill of a planetary ball mill with a ball-to-material ratio of 10:1. High-purity argon (purity 99.999%) is filled into the ball mill as a protective gas. The rotation speed is 200 rpm and the ball milling time is 2 hours. The alloy particles are crushed to less than 200 mesh to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 95 Cu5 high entropy alloy ball milled powder.

[0045] pass Figure 1 (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 95 The microstructure of Cu5 shows that the alloy consists of three phases. Figure 4 It can be seen that (Ti 0.30 Zr0.25 Fe 0.25 V 0.20 ) 95 Cu5 is composed of C14 Laves phase, α-Ti phase and α-Zr phase. Figure 5 It can be seen that at room temperature, the alloy absorbs 1.50wt.% of hydrogen within 75 minutes. The C14 Laves phase has good hydrogen storage capacity at room temperature and low pressure. In summary, the high entropy alloy prepared by arc melting in this embodiment has novel microstructure characteristics, has the ability to quickly absorb hydrogen at room temperature, and has a hydrogen storage capacity of 1.50wt.%.

[0046] Example 2: A (Ti) that can quickly absorb hydrogen at room temperature 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 90 Cu 10 High entropy alloy and preparation method thereof

[0047] (1) Raw material preparation: 22.5% Zr, 27.0% Ti, 18.0% V, 22.5% Fe and 10% Cu are mixed according to atomic percentage to obtain raw materials; considering the volatilization and burning loss during the smelting process, the ingredients should be weighed according to 102% of the components, and the mass should be accurate to two decimal places after the nominal composition, wherein the metal raw material Ti is sponge titanium, and Zr, V, Fe and Cu are all small columnar particles.

[0048] (2) Arc melting: The raw materials are placed in the same crucible of the melting furnace. The Zr and V metals with higher melting temperatures are placed on the top layer of the water-cooled copper crucible, and the Ti, Fe, and Cu metals with lower melting temperatures are placed on the bottom layer of the crucible (the specific order from top to bottom is V, Zr, Ti, Fe, and Cu). The vacuum is pumped to 5 Pa by a mechanical pump, then filled with argon to 0.2 MPa, and then pumped to 5 Pa again. The vacuum is then pumped to 3×10 -3 Pa, the protective gas argon was introduced to 0.05MPa for arc melting. To ensure uniform distribution of alloy elements, the melting was repeated 5 times to finally obtain a button-shaped high-entropy alloy ingot.

[0049] (3) Polishing: The obtained high entropy alloy ingot was polished with 400-mesh sandpaper to remove surface stains and surface oxide scale, and then placed in acetone for ultrasonic cleaning.

[0050] (4) Mechanical crushing: The alloy ingots after grinding and cleaning are mechanically crushed into particles less than 2 mm.

[0051] (5) Ball milling: The mechanically crushed alloy particles are placed in the ball mill of a planetary ball mill with a ball-to-material ratio of 10:1. High-purity argon (purity 99.999%) is filled into the ball mill as a protective gas. The rotation speed is 200 rpm and the ball milling time is 2 hours. The alloy particles are crushed to less than 200 mesh to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 90 Cu 10 High entropy alloy ball milled powder.

[0052] pass Figure 2 (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 90 Cu 10 The microstructure picture shows that the alloy consists of three phases. Figure 4 It can be seen that (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 90 Cu 10 It is composed of C14 Laves phase, α-Ti phase and α-Zr phase. Figure 5 It can be seen that the alloy absorbs 1.33wt.% hydrogen within 100 minutes at room temperature. The C14 Laves phase has good hydrogen storage capacity at room temperature and low pressure. In summary, the high entropy alloy prepared by arc melting in this embodiment has novel microstructure characteristics, has the ability to quickly absorb hydrogen at room temperature, and the hydrogen storage capacity reaches 1.33wt.%.

[0053] Example 3: A (Ti) that can quickly absorb hydrogen at room temperature 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 80 Cu 20 High entropy alloy and preparation method thereof

[0054] (1) Raw material preparation: 20% Zr, 24% Ti, 16% V, 20% Fe and 20% Cu are mixed according to atomic percentage to obtain raw materials; considering the volatilization and burning loss during the smelting process, the ingredients should be weighed according to 102% of the components, and the mass should be accurate to two decimal places after the nominal composition, wherein the metal raw material Ti is sponge titanium, and Zr, V, Fe and Cu are all small columnar particles.

[0055] (2) Arc melting: The raw materials are placed in the same crucible of the melting furnace. The Zr and V metals with higher melting temperatures are placed on the top layer of the water-cooled copper crucible, and the Ti, Fe, and Cu metals with lower melting temperatures are placed on the bottom layer of the crucible (the specific order from top to bottom is V, Zr, Ti, Fe, and Cu). The vacuum is pumped to 5 Pa by a mechanical pump, then filled with argon to 0.2 MPa, and then pumped to 5 Pa again. The vacuum is then pumped to 3×10 -3 Pa, the protective gas argon was introduced to 0.05MPa for arc melting. To ensure uniform distribution of alloy elements, the melting was repeated 5 times to finally obtain a button-shaped high-entropy alloy ingot.

[0056] (3) Polishing: The obtained high entropy alloy ingot was polished with 400-mesh sandpaper to remove surface stains and surface oxide scale, and then placed in acetone for ultrasonic cleaning.

[0057] (4) Mechanical crushing: The alloy ingots after grinding and cleaning are mechanically crushed into particles less than 2 mm.

[0058] (5) Ball milling: The mechanically crushed alloy particles are placed in the ball mill of a planetary ball mill with a ball-to-material ratio of 10:1. High-purity argon (purity 99.999%) is filled into the ball mill as a protective gas. The rotation speed is 200 rpm and the ball milling time is 2 hours. The alloy particles are crushed to less than 200 mesh to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 80 Cu 20 High entropy alloy ball milled powder.

[0059] pass Figure 3 (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 80 Cu 20 The microstructure picture shows that the alloy is composed of three phases, among which there is a network-like second phase. Figure 4 It can be seen that (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 80 Cu 20 It is composed of C14 Laves phase, Cu8Zr3 phase and ZrTiCu2 phase. Figure 5 It can be seen that at room temperature and 1 MPa hydrogen pressure, the alloy absorbs 1.35 wt.% hydrogen in 20 minutes. The C14 Laves phase has good hydrogen storage capacity at room temperature and low pressure. The network ZrTiCu2 second phase (see Figure 3 ) provides diffusion channels to promote the diffusion of hydrogen atoms, so that the hydrogen absorption rate is greatly improved and the absorption time is greatly shortened. In summary, the high entropy alloy prepared by arc melting in this embodiment has novel microstructure characteristics, has the ability to quickly absorb hydrogen at room temperature, and has a hydrogen storage capacity of 1.35wt.%.

Claims

1. A high entropy alloy that can rapidly absorb hydrogen at room temperature, characterized in that: The high entropy alloy is composed of Zr, T, V, Fe, and Cu, and has the chemical formula (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x , where x ranges from 5 to 20.

2. A high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 1, characterized in that: The high entropy alloy is composed of 23.75% Zr, 28.50% Ti, 19% V, 23.75% Fe and 5% Cu in atomic percentage, and the chemical formula is (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 95 Cu5.

3. The high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 1, characterized in that: The high entropy alloy is composed of 22.5% Zr, 27.0% Ti, 18.0% V, 22.5% Fe and 10% Cu in atomic percentage, and the chemical formula is (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 90 Cu 10 .

4. A high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 1, characterized in that: The high entropy alloy is composed of 20% Zr, 24% Ti, 16% V, 20% Fe and 20% Cu in atomic percentage, and the chemical formula is (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 80 Cu 20 .

5. The method for preparing a high entropy alloy capable of rapidly absorbing hydrogen at room temperature as claimed in claim 1, characterized in that The preparation method is carried out according to the following steps:

1. Weighing Zr, Ti, V, Fe and Cu metal single substance particles according to the alloy atomic percentage to obtain raw materials; 2. Place the raw materials in a crucible of a melting furnace, evacuate and fill with argon, and then perform non-consumable vacuum arc melting to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x High entropy alloy ingots; 3. The obtained (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x The high entropy alloy ingot is polished to obtain a polished alloy ingot; 4. Mechanically crushing the polished alloy ingot to obtain alloy particles; 5. Ball mill the alloy particles to obtain (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x High entropy alloy ball milled powder.

6. The method for preparing a high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 5, characterized in that Step 2: Vacuum to 3×10 -3 Pa.

7. The method for preparing a high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 5, characterized in that Step 2: Introduce argon gas to 0.05 MPa.

8. The method for preparing a high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 5, characterized in that: Step 5: Use a planetary ball mill for ball milling. Fill the ball mill with high-purity argon gas, with a ball-to-material ratio of 10:1 and a rotation speed of 200 rpm.

9. The method for preparing a high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 5, characterized in that: The ball milling time in step 5 is 2 hours.

10. The method for preparing a high entropy alloy capable of rapidly absorbing hydrogen at room temperature according to claim 5, characterized in that: Step 5 (Ti 0.30 Zr 0.25 Fe 0.25 V 0.20 ) 100-x Cu x The mesh size of high entropy alloy ball-milled powder is less than 200 mesh.

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