A hydrogen storage alloy containing non-metallic elements and a preparation method thereof

Abstract

The present invention discloses a preparation method of a hydrogen storage alloy containing non-metallic elements. The preparation method provided by the present invention adds non-metallic elements during the melting process of the Ti-V hydrogen storage alloy, significantly improving the effective hydrogen release amount and activation performance of the alloy. The provided preparation method has a simple process and low cost, and is suitable for large-scale popularization and use.

Description

Technical Field

[0001] The present invention belongs to the field of hydrogen storage, and particularly relates to a hydrogen storage alloy containing non-metallic elements and a preparation method thereof. Background Art

[0002] Hydrogen energy is one of the advanced energies attracting much attention in the 21st century and is considered to play a key role in the global response to climate change and energy transformation. As a clean and efficient energy form, hydrogen energy has shown great potential in many fields. At present, the hydrogen energy industry chain can be divided into three aspects: hydrogen production, hydrogen storage, and hydrogen utilization. The hydrogen storage link, especially the hydrogen storage technology in the form of metal hydrides, is considered the key to solving the problem of hydrogen storage. The metal hydride hydrogen storage technology realizes the high-density storage of hydrogen by adsorbing hydrogen or reacting with metals to form hydrides. Compared with the traditional gaseous hydrogen storage and liquid hydrogen storage methods, the metal hydride hydrogen storage does not require a pressure-resistant container, has a higher storage density, and relatively simple operability. The development of this technology is expected to provide a more feasible hydrogen storage solution for the entire hydrogen energy industry chain.

[0003] Ti-V-based hydrogen storage alloys have the advantages of high hydrogen storage capacity, hydrogen absorption at normal temperature and pressure, and good cycle performance, and are one of the most widely studied hydrogen storage alloys at present. However, the dehydrogenation platform pressure of the existing Ti-V-based hydrogen storage alloys is generally less than 0.1 MPa, and they have disadvantages such as difficult dehydrogenation and low effective dehydrogenation amount in actual applications. At present, some methods for improving Ti-V-based hydrogen storage alloys have been disclosed in the prior art. For example, Patent CN116536559A discloses a Ti-V-Mn-based hydrogen storage alloy, its preparation method and application technology. The chemical general formula of the hydrogen storage alloy is Ti 23-x M x V 40 Mn 37-y Cr y , where M is one or two of Zr and Hf, and 0≤x≤6, 0≤y≤6. After adding the element Cr, the effective dehydrogenation amount of the hydrogen storage alloy can reach 2.09 wt%, but its hydrogen absorption and dehydrogenation platform region is short, severely inclined, and the dehydrogenation platform pressure is too small, which is not conducive to actual use. Patent CN116770145A discloses a vanadium-based hydrogen storage alloy with a high platform pressure and its preparation method. The composition of the hydrogen storage alloy is Ti a Cr b V c Mo x RE y, where Re is one of La, Ce or Y, 0.015 ≤ a ≤ 0.075, 0.01 ≤ y ≤ 0.255, 0.7 ≤ c ≤ 0.9, and a + b + c = 1, 0.01 ≤ x ≤ 0.005, 0.01 ≤ y ≤ 0.05. The effective hydrogen release amount of the alloy is greater than 2.28 wt%, and the hydrogen release kinetic time does not exceed 3 min. However, its vanadium content is relatively high, so the cost is relatively high, which is not conducive to practical use. Summary of the Invention

[0004] Aiming at the problems of difficult hydrogen release and high cost of existing Ti-V-based hydrogen storage alloys, the present invention provides a hydrogen storage alloy containing non-metallic elements and a preparation method thereof. The hydrogen storage alloy containing non-metallic elements provided by the present invention significantly improves the effective hydrogen storage amount of the alloy by adding non-metallic elements during the melting process of the Ti-V hydrogen storage alloy. The preparation method of the present invention has a simple process and low cost, and is suitable for large-scale popularization and use.

[0005] The hydrogen storage alloy containing non-metallic elements provided by the present invention has an element composition of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 R x , where R is a non-metallic element and is at least one of C, B and Si, and 0.01 ≤ x ≤ 0.03.

[0006] Furthermore, based on the Ti-V hydrogen storage alloy, the present invention controls the content of the non-metallic R element by adding it, so as to improve the effective hydrogen release amount, reduce the loss of hydrogen storage capacity and lower the preparation cost of the material while ensuring the hydrogen storage amount. Compared with the prior art which mostly has problems of difficult hydrogen release and high preparation cost, the hydrogen storage alloy of the present invention has a high effective hydrogen storage amount, a low platform inclination, a moderate hydrogen absorption and release platform pressure, and at the same time, it has a low cost and is easy to be popularized and used.

[0007] Furthermore, in the present invention, 0.01 ≤ x ≤ 0.03, for example, 0.01, 0.02 or 0.03, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0008] Furthermore, the raw material of the non-metallic element in the present invention is a manganese compound, specifically Mn3C, MnB2 or MnSi2.

[0009] Furthermore, the hydrogen storage alloy containing non-metallic elements is prepared by a method including the following steps:

[0010] (1) Weigh Ti, Zr, Mn, V and the raw material of the non-metallic element according to the element composition of the hydrogen storage alloy containing non-metallic elements, and mix them.

[0011] (2) Subject the mixture obtained in step (1) to multiple smeltings to obtain alloy ingots;

[0012] (3) Mechanically crush the alloy ingots obtained in step (2) and sieve to obtain hydrogen storage alloy powder containing non-metallic elements;

[0013] (4) Place the alloy powder obtained in step (3) in a tubular furnace for annealing to obtain a hydrogen storage alloy.

[0014] Furthermore, the purity of the metals Ti, Zr, Mn, and V in step (1) is ≥99.9%, and a 5wt% loss rate is considered for metal Mn;

[0015] The raw material of the non-metallic element is a manganese compound, specifically Mn3C, MnB2, or MnSi2;

[0016] Furthermore, the smelting in step (2) is carried out in a vacuum induction melting furnace; the smelting is carried out in a protective atmosphere; the protective gas can specifically be argon;

[0017] Furthermore, the number of smelting times in step (2) is 3 times, and the single smelting time is 100 - 300 s, such as 100 s, 200 s, 300 s, but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0018] Furthermore, the average particle size of the hydrogen storage alloy powder containing non-metallic elements obtained after sieving in step (3) is 50 - 150 μm, such as 50 μm, 100 μm, or 150 μm, but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0019] Furthermore, step (4) is carried out in an argon atmosphere.

[0020] Furthermore, the annealing temperature in step (4) is 1000 - 1200 °C, such as 1000 °C, 1050 °C, 1100 °C, 1150 °C, 1200 °C, but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0021] Furthermore, the annealing time in step (4) is 24 - 48 h, such as 24 h, 30 h, 36 h, 42 h, 48 h, but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0022] Furthermore, the testing process of the hydrogen storage alloy containing non-metallic elements of the present invention is carried out at a temperature of 25 °C.

[0023] The application of the above hydrogen storage alloy containing non-metallic elements in the field of hydrogen storage also belongs to the protection scope of the present invention.

[0024] The present invention has the following beneficial effects:

[0025] 1) The hydrogen storage alloy containing non-metallic elements of the present invention is based on the Ti-V hydrogen storage alloy. By adding non-metallic R and controlling its content, on the basis of ensuring the high hydrogen storage capacity of the Ti-V hydrogen storage alloy, the platform inclination can be reduced and the effective hydrogen storage capacity can be increased; the hydrogen storage alloy containing non-metallic elements provided by the present invention has the characteristics of high effective hydrogen storage capacity and a gentle hydrogen absorption and desorption platform.

[0026] 2) The hydrogen storage alloy of the present invention is formulated according to a specific atomic ratio, and the hydrogen storage alloy containing non-metallic elements can be obtained through simple melting, mechanical crushing, screening and annealing, effectively improving the hydrogen desorption performance of the Ti-V based hydrogen storage alloy, with the characteristics of simplicity and rapidity. At the same time, the preparation cost is low, which is suitable for large-scale popularization and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 It is the hydrogen absorption and desorption PCT curve of the hydrogen storage alloy prepared in Comparative Example 1 of the present invention.

[0028] Figure 2 It is the hydrogen absorption and desorption PCT curve of the hydrogen storage alloys containing non-metallic elements prepared in Example 1, Example 2 and Example 3 of the present invention.

[0029] Figure 3 It is the hydrogen absorption and desorption PCT curve of the hydrogen storage alloys containing non-metallic elements prepared in Example 4, Example 5 and Example 6 of the present invention.

[0030] Figure 4 It is the hydrogen absorption and desorption PCT curve of the hydrogen storage alloys containing non-metallic elements prepared in Example 7, Example 8 and Example 9 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0031] The present invention will be further described in detail below in conjunction with the specific embodiments. The embodiments given are only for clarifying the present invention, rather than limiting the scope of the present invention. The following provided embodiments can be used as a guide for those of ordinary skill in the art to make further improvements, and do not limit the present invention in any way.

[0032] The experimental methods in the following embodiments are all conventional methods unless otherwise specified, and are carried out according to the techniques or conditions described in the literature in this field or according to the product specifications. The materials, reagents, etc. used in the following embodiments can be obtained from commercial channels unless otherwise specified.

[0033] In the following embodiments, the raw materials of Ti, Zr, Mn, and V were purchased from Zhongnuo Technology Co., Ltd., and Mn3C, MnB2, and MnSi2 were purchased from Aladdin Reagent Co., Ltd.

[0034] Example 1

[0035] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 C 0.01 ;

[0036] It is prepared by the following method:

[0037] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 C 0.01 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixture;

[0038] (2) Put the mixture obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere. The single melting time is 200 s. After single melting, reverse the alloy for remelting. After repeated melting 3 times, an alloy ingot is obtained;

[0039] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a hydrogen storage alloy powder containing non-metallic elements with an average particle size of 150 μm;

[0040] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and carry out annealing under an argon protection atmosphere. The annealing temperature is 1100 °C, and the annealing time is 36 h;

[0041] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0042] Example 2

[0043] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 C 0.02 ;

[0044] It is prepared by the following method:

[0045] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 C 0.02 , use sandpaper to remove the surface oxide layer, and mix evenly to obtain a mixed material;

[0046] (2) Put the mixed material obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere, with a single melting time of 200 s. After each single melting, reverse the alloy for remelting. After repeating the melting 3 times, obtain an alloy ingot;

[0047] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with a 800-mesh sieve to obtain a hydrogen storage alloy powder containing non-metallic elements with an average particle size of 150 μm;

[0048] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and carry out annealing under an argon protection atmosphere. The annealing temperature is 1100 °C and the annealing time is 36 h;

[0049] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0050] Example 3

[0051] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 C 0.03 ;

[0052] It is prepared by the following method:

[0053] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 C 0.03 , use sandpaper to remove the surface oxide layer, and mix evenly to obtain a mixed material;

[0054] (2) Load the mixture obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere, with a single melting time of 200 s. After each single melting, invert the alloy for remelting. After repeating the melting 3 times, obtain an alloy ingot;

[0055] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a hydrogen storage alloy powder containing non-metallic elements with an average particle size of 150 μm;

[0056] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and carry out annealing under an argon protection atmosphere. The annealing temperature is 1100 °C and the annealing time is 36 h;

[0057] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0058] Example 4

[0059] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 B 0.01 ;

[0060] It is prepared by the following method:

[0061] (1) Weigh the corresponding raw materials with a purity ≥ 99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 B 0.01 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixture;

[0062] (2) Load the mixture obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere, with a single melting time of 200 s. After each single melting, invert the alloy for remelting. After repeating the melting 3 times, obtain an alloy ingot;

[0063] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a non-metal element-containing hydrogen storage alloy powder with an average particle size of 150 μm;

[0064] (4) Place the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, and then fill with argon to a gauge pressure of 0.05 MPa. Anneal under an argon protection atmosphere at an annealing temperature of 1100 °C for 36 h;

[0065] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0066] Example 5

[0067] This example provides a non-metal element-containing hydrogen storage alloy, and the element composition of the non-metal hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 B 0.02 ;

[0068] It is prepared by the following method:

[0069] (1) Weigh the corresponding raw materials with a purity ≥ 99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 B 0.02 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixture;

[0070] (2) Load the mixture obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere, with a single melting time of 200 s. After single melting, reverse the alloy for remelting, and repeat melting 3 times to obtain an alloy ingot;

[0071] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a non-metal element-containing hydrogen storage alloy powder with an average particle size of 150 μm;

[0072] (4) Place the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa. Anneal under an argon protection atmosphere at an annealing temperature of 1100 °C for 36 h;

[0073] (5) Repeatedly charge and discharge the hydrogen storage alloy obtained in step (4) 5 times under the conditions of 5 MPa and 25 °C.

[0074] Example 6

[0075] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 B 0.03 ;

[0076] It is prepared by the following method:

[0077] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 B 0.03 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixture;

[0078] (2) Put the mixture obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill it with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere. The single melting time is 200 s. After each single melting, reverse the alloy for remelting. After repeatedly melting 3 times, an alloy ingot is obtained;

[0079] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a hydrogen storage alloy powder containing non-metallic elements with an average particle size of 150 μm;

[0080] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tubular furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill it with argon to a gauge pressure of 0.05 MPa, and carry out annealing under an argon protection atmosphere. The annealing temperature is 1100 °C and the annealing time is 36 h;

[0081] (5) Repeatedly charge and discharge the hydrogen storage alloy obtained in step (4) 5 times under the conditions of 5 MPa and 25 °C.

[0082] Example 7

[0083] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 Si 0.01 ;

[0084] Prepared by the following method:

[0085] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 Si 0.01 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixed material;

[0086] (2) Put the mixed material obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere. The single melting time is 200 s. After single melting, reverse the alloy for remelting. After repeated melting 3 times, an alloy ingot is obtained;

[0087] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a hydrogen storage alloy powder containing non-metallic elements with an average particle size of 150 μm;

[0088] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and carry out annealing under an argon protection atmosphere. The annealing temperature is 1100 °C and the annealing time is 36 h;

[0089] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0090] Example 8

[0091] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 Si 0.02 ;

[0092] Prepared by the following method:

[0093] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 Si 0.02 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixed material;

[0094] (2) Load the mixture obtained in step (1) into the graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere, with a single melting time of 200 s. After each single melting, invert the alloy for remelting. After repeating the melting 3 times, an alloy ingot is obtained;

[0095] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a hydrogen storage alloy powder containing non-metallic elements with an average particle size of 150 μm;

[0096] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and carry out annealing under an argon protection atmosphere. The annealing temperature is 1100 °C and the annealing time is 36 h;

[0097] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0098] Example 9

[0099] This example provides a hydrogen storage alloy containing non-metallic elements. The element composition of the non-metallic hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 Si 0.03 ;

[0100] It is prepared by the following method:

[0101] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 Si 0.03 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixture;

[0102] (2) Load the mixture obtained in step (1) into the graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere, with a single melting time of 200 s. After each single melting, invert the alloy for remelting. After repeating the melting 3 times, an alloy ingot is obtained;

[0103] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a non-metal element-containing hydrogen storage alloy powder with an average particle size of 150 μm;

[0104] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, and then fill with argon to a gauge pressure of 0.05 MPa. Anneal under an argon protection atmosphere at an annealing temperature of 1100 °C for an annealing time of 36 h;

[0105] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0106] Comparative Example 1

[0107] This comparative example provides a non-metal element-containing hydrogen storage alloy, and the element composition of the non-metal hydrogen storage alloy is Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 ;

[0108] It is prepared by the following method:

[0109] (1) Weigh the corresponding raw materials with a purity of ≥99.9% according to the atomic ratio of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 , remove the surface oxide layer with sandpaper, and mix evenly to obtain a mixture;

[0110] (2) Put the mixture obtained in step (1) into a graphite crucible of a vacuum induction melting furnace, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa, and slowly increase the current until the raw materials are completely melted. Carry out melting under an argon protection atmosphere, with a single melting time of 200 s. After each single melting, reverse the alloy for remelting. After repeated melting 3 times, an alloy ingot is obtained;

[0111] (3) Mechanically crush the alloy ingot obtained in step (2), and sieve it with an 800-mesh sieve to obtain a non-metal element-containing hydrogen storage alloy with an average particle size of 150 μm;

[0112] (4) Put the alloy powder obtained in step (3) into a quartz tube in a tube furnace. First, evacuate to a gauge pressure of -0.05 MPa, then fill with argon to a gauge pressure of 0.05 MPa. Anneal under an argon protection atmosphere at an annealing temperature of 1100 °C for an annealing time of 36 h;

[0113] (5) Repeatedly charge and discharge hydrogen 5 times for the hydrogen storage alloy obtained in step (4) under the conditions of 5 MPa and 25 °C.

[0114] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 1 was evaluated. The test results are shown in Table 1. The hydrogen absorption amount of the alloy is 1.84 wt%, the effective hydrogen desorption amount is 1.70 wt%, the hydrogen absorption plateau slope factor is 0.44, and the hydrogen desorption plateau slope factor is 0.59.

[0115] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 2 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption amount of the alloy is 1.83 wt%, the effective hydrogen desorption amount is 1.71 wt%, the hydrogen absorption plateau slope factor is 0.37, and the hydrogen desorption plateau slope factor is 0.32.

[0116] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 3 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption amount of the alloy is 1.83 wt%, the effective hydrogen desorption amount is 1.69 wt%, the hydrogen absorption plateau slope factor is 0.22, and the hydrogen desorption plateau slope factor is 0.28.

[0117] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 4 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption amount of the alloy is 1.76 wt%, the effective hydrogen desorption amount is 1.65 wt%, the hydrogen absorption plateau slope factor is 0.50, and the hydrogen desorption plateau slope factor is 0.53.

[0118] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 5 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption amount of the alloy is 1.76 wt%, the effective hydrogen desorption amount is 1.66 wt%, the hydrogen absorption plateau slope factor is 0.41, and the hydrogen desorption plateau slope factor is 0.42.

[0119] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 6 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption amount of the alloy is 1.76 wt%, the effective hydrogen desorption amount is 1.62 wt%, the hydrogen absorption plateau slope factor is 0.31, and the hydrogen desorption plateau slope factor is 0.36.

[0120] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 7 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption amount of the alloy is 1.79 wt%, the effective hydrogen desorption amount is 1.64 wt%, the hydrogen absorption plateau slope factor is 0.47, and the hydrogen desorption plateau slope factor is 0.43.

[0121] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 8 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption amount of the alloy is 1.79 wt%, the effective hydrogen desorption amount is 1.69 wt%, the hydrogen absorption plateau slope factor is 0.35, and the hydrogen desorption plateau slope factor is 0.40.

[0122] The hydrogen storage performance of the non-metal element-containing hydrogen storage alloy prepared in Example 9 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption capacity of the alloy is 1.78 wt%, the effective hydrogen desorption capacity is 1.66 wt%, the hydrogen absorption plateau slope factor is 0.33, and the hydrogen desorption plateau slope factor is 0.33.

[0123] The hydrogen storage performance of the hydrogen storage alloy prepared in Comparative Example 1 was evaluated. The test results are shown in Table 1. The maximum hydrogen absorption capacity of the alloy is 1.78 wt%, the effective hydrogen desorption capacity is 1.62 wt%, the hydrogen absorption plateau slope factor is 0.71, and the hydrogen desorption plateau slope factor is 0.75.

[0124] Table 1 Hydrogen storage performance of the hydrogen storage alloys prepared in Examples 1-9 and Comparative Example 1

[0125]

[0126]

[0127] The calculation method of the hydrogen absorption and desorption plateau slope factor is ln(P H / M＝0.75 / P H / M＝0.25 ), that is, the ln value of the ratio of the pressure at 75% hydrogen storage capacity to the pressure at 25% hydrogen storage capacity.

[0128] It is well known in the art that the smaller the slope of the hydrogen absorption and desorption plateau, the better, that is, the flatter the plateau, which affects the actual use of the hydrogen storage alloy. The data listed in the present invention shows that the effective hydrogen storage capacity of Example 2 is the highest, and its improvement in the slope is also relatively high. It can be considered that the comprehensive performance of Example 3 is the best (the effective hydrogen storage capacity is not much different from that of Example 2, and the plateau is the flattest).

[0129] The above has described the present invention in detail. For those skilled in the art, without departing from the purpose and scope of the present invention and without unnecessary experiments, the present invention can be implemented within a relatively wide range under equivalent parameters, concentrations and conditions. Although the present invention gives special examples, it should be understood that the present invention can be further improved. In short, according to the principle of the present invention, this application intends to include any changes, uses or improvements to the present invention, including changes made by using conventional techniques known in the art that are outside the scope disclosed in this application.

Claims

1. Application of hydrogen storage alloy containing non-metallic elements in the field of hydrogen storage, characterized in that: The hydrogen storage alloy containing non-metallic elements has an element composition of Ti 0.8 Zr 0.2 Mn 1.5 V 0.2 R x , wherein R is a non-metallic element, which is at least one of C, B and Si, and 0.01≤x≤0.03; The non-metallic element-containing hydrogen storage alloy is prepared by a method comprising the following steps: (1) raw materials of Ti, Zr, Mn, V and non-metallic elements are prepared according to the element composition of the hydrogen storage alloy containing non-metallic elements, and mixed; (2) smelting the mixture obtained in step (1) multiple times to obtain alloy ingots; (3) mechanically crushing the alloy ingot obtained in step (2) and sieving to obtain a hydrogen storage alloy powder containing non-metallic elements; (4) placing the alloy powder obtained in step (3) in a tubular furnace for annealing to obtain a hydrogen storage alloy; The raw material of the non-metallic element is a manganese compound, specifically Mn3C, MnB2 or MnSi2; In step (4), the annealing temperature is 1000-1200° C. and the annealing time is 24-48 hours.

2. The use according to claim 1, characterized in that: The purity of the metal raw materials Ti, Zr, Mn and V in step (1) is ≥ 99.9%, and the loss rate of metal Mn is considered to be 5wt%.

3. The use according to claim 1, characterized in that: In step (2), the smelting is carried out in a vacuum induction melting furnace; the smelting is carried out in an argon protective atmosphere.

4. The use according to claim 1, characterized in that The smelting times are 3 times, and the single smelting time is 100-300s.

5. The use according to claim 1, characterized in that: The average particle size of the non-metallic element-containing hydrogen storage alloy obtained after screening in step (3) is 50-150 μm.

6. The use according to claim 1, characterized in that: Step (4) is carried out in an argon atmosphere.

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