Solid hydrogen storage material containing transition metal alloy additive as well as preparation method and application of solid hydrogen storage material

Abstract

The invention provides a solid hydrogen storage material containing a transition metal alloy additive as well as a preparation method and application of the solid hydrogen storage material, and relates to the technical field of solid hydrogen storage materials. The solid hydrogen storage material comprises magnesium hydride and a transition metal alloy additive, wherein the transition metal alloy additive is a magnesium-nickel-yttrium alloy. The magnesium-nickel-yttrium alloy is added into magnesium hydride (MgH2) to serve as an additive, the hydrogen absorption / hydrogen desorption dynamic performance of MgH2 is effectively improved, the hydrogen absorption performance and the hydrogen desorption performance of MgH2 are improved, the solid hydrogen storage material has the lower hydrogen absorption and hydrogen desorption temperature, and the high final hydrogen desorption amount is obtained within a short time.

Description

Technical Field

[0001] The present invention relates to the technical field of solid-state hydrogen storage, and in particular to a solid-state hydrogen storage material containing a transition metal alloy additive, and a preparation method and application thereof. Background Art

[0002] The impact of global warming is a hotly debated topic today. This impact is caused by the carbon dioxide produced by the burning of fossil fuels such as coal and oil. The ultimate solution to global warming is to develop carbon-neutral fuels. To achieve this goal, many options are available, such as wind power, solar power, tidal power, geothermal power, nuclear power, and hydrogen power. Hydrogen power seems to be the best choice for reducing global warming because it does not produce carbon dioxide during cold combustion in fuel cells and hot combustion in internal combustion engines or turbines (water is the only major combustion product). Magnesium hydride has a theoretical hydrogen storage capacity of up to 7.6%, making it a very promising hydrogen storage material for mobile applications. Moreover, magnesium-based hydrides are abundant and inexpensive. However, the extremely high dehydrogenation temperature and extremely poor dehydrogenation kinetics of magnesium hydride in practical applications still need to be improved.

[0003] Among hydrogen storage materials, magnesium hydride (MgH2) has a hydrogen storage capacity of 7.6wt% and good cyclic reversibility. However, due to the high thermal stability (ΔH=75kJ / mol H2) and reaction energy barrier (ΔE=161kJ / mol) of MgH2, it has a high dehydrogenation temperature (>300°C) and slow hydrogen absorption and dehydrogenation rate, which cannot meet application requirements.

[0004] CN113830729A discloses a MgH2 solid solution hydrogen storage material doped with Fe element and a preparation method thereof. The hydrogen storage material is composed of dopant nano Fe powder and MgH2 powder, and the doped Fe element comes from the nano Fe powder. The preparation method mainly comprises: mixing MgH2 powder and nano Fe powder evenly to obtain a mixture, placing the mixture in a ball mill, adding stainless steel balls as grinding balls, and ball milling under an inert gas atmosphere. Since the Fe catalyst itself does not have hydrogen storage performance and does not have the characteristics of enhancing hydrogen absorption and dissociation, more doping of components limits the further improvement of the hydrogen storage capacity of MgH2.

[0005] CN114507798A discloses a magnesium-based hydrogen storage alloy block and a preparation method thereof, belonging to the technical field of magnesium-based hydrogen storage materials. The method comprises the following steps: smelting and pouring a magnesium block, a magnesium-nickel master alloy and a magnesium-rare earth master alloy to obtain an alloy ingot; then hot-extruding the alloy ingot into an alloy rod and processing it into an alloy electrode; then atomizing and powdering the alloy electrode to obtain a magnesium-nickel-rare earth hydrogen storage alloy powder, and pressing the magnesium-nickel-rare earth hydrogen storage alloy powder into a mold. Although the magnesium-based hydrogen storage alloy block thus prepared can achieve a higher hydrogen absorption capacity in a shorter time and at a lower pressure, it requires smelting, pouring and other processes to obtain an alloy ingot, which then needs to be extruded into an alloy rod and processed into an alloy electrode. The preparation process is complicated and cumbersome, and the improvement of hydrogen storage capacity is limited.

[0006] In view of this, the present invention is proposed. Summary of the invention

[0007] The object of the present invention is to provide a solid hydrogen storage material containing a transition metal alloy additive, and a preparation method and application thereof. The solid hydrogen storage material of the present invention adds a magnesium-nickel-yttrium alloy as an additive to magnesium hydride (MgH2), has a lower hydrogen absorption and desorption temperature, obtains a high final hydrogen desorption amount in a shorter time, can effectively improve the hydrogen storage performance of MgH2, and enhances the hydrogen storage capacity of the prepared solid hydrogen storage material, and the hydrogen storage capacity has high stability.

[0008] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0009] In a first aspect, the present invention provides a solid hydrogen storage material containing a transition metal alloy additive, characterized in that the solid hydrogen storage material comprises magnesium hydride and a transition metal alloy additive; wherein the transition metal alloy additive is a magnesium-nickel-yttrium alloy.

[0010] Preferably, the mass ratio of the magnesium hydride to the transition metal alloy additive is (8-10):1.

[0011] Preferably, the chemical formula of the magnesium-nickel-yttrium alloy is Mg a Ni b Y c ;

[0012] Among them, 0.5≤a≤1.5, 1.5≤a≤2.5, 0.05≤c≤0.15.

[0013] In a second aspect, the present invention provides a method for preparing a solid hydrogen storage material containing a transition metal alloy additive as described in the first aspect, the preparation method comprising the following steps:

[0014] After magnesium hydride and a transition metal alloy additive are mixed, ball milling is performed to obtain the solid hydrogen storage material containing the transition metal alloy additive.

[0015] Preferably, the process parameters of the ball milling include:

[0016] The material of the grinding ball is stainless steel; the diameter of the grinding ball is 1-5 mm; the ball-to-material ratio is (20-40):1, the ball milling time is 10-20 min, with an interval of 5-10 min; the ball milling speed is 300-500 r / min.

[0017] Preferably, the transition metal alloy additive is prepared by the following steps:

[0018] (a) mixing magnesium powder, nickel powder and yttrium powder and grinding them to obtain a metal mixed powder;

[0019] (b) tableting the metal mixed powder obtained in step (a) to obtain metal tablets;

[0020] (c) sintering the metal pressed sheet obtained in step (b) to obtain the transition metal alloy additive.

[0021] Preferably, in step (a), the molar ratio of the magnesium powder, nickel powder and yttrium powder is (0.5-1.5):(1.5-2.5):(0.05-0.15).

[0022] Preferably, in step (a), the grinding is performed in an agate mortar.

[0023] Preferably, in step (a), the grinding time is 10 to 30 minutes.

[0024] Preferably, in step (b), the tabletting pressure is 1 to 3 MPa.

[0025] Preferably, in step (b), the thickness of the metal pressing sheet is 5 to 10 mm.

[0026] Preferably, in step (c), the sintering procedure is specifically as follows:

[0027] Raise the temperature to 550-650°C at 5-15°C / min, keep warm for 5-15 minutes, then raise the temperature to 750-850°C at 1-10°C / min, and keep warm for 4-6 hours.

[0028] In a third aspect, the present invention provides a use of the solid hydrogen storage material containing a transition metal alloy additive as described in the first aspect in the preparation of a hydrogen storage device.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The present invention adds magnesium-nickel-yttrium alloy as an additive to magnesium hydride (MgH2), thereby effectively improving the hydrogen absorption / desorption kinetics of MgH2, improving the hydrogen absorption and desorption properties of MgH2, and making the solid-state hydrogen storage material have a lower hydrogen absorption and desorption temperature, thereby obtaining a high final hydrogen desorption amount in a shorter time.

[0031] (2) The present invention adds magnesium-nickel-yttrium alloy as an additive to magnesium hydride (MgH2), which can effectively improve the hydrogen storage performance of MgH2, has a higher hydrogen storage capacity, and has high stability of hydrogen storage capacity.

[0032] (3) The preparation method of the solid hydrogen storage material containing transition metal alloy additives of the present invention has simple operation steps, low cost of raw materials, easy to obtain, conducive to large-scale mass production, and broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0034] Figure 1 This is a hydrogen charging curve of the composite material provided in Example 1 at 250°C and pure magnesium at 300°C within 0 to 180 minutes.

[0035] Figure 2 This is a hydrogen charging curve of the composite material provided in Example 1 at 250°C and pure magnesium at 300°C within 0 to 25 minutes.

[0036] Figure 3 This is a hydrogen release curve of the composite material provided in Example 1 at 250°C and pure magnesium at 300°C within 0 to 60 minutes. DETAILED DESCRIPTION

[0037] Unless otherwise defined herein, scientific and technological terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear, however, in the case of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, unless otherwise stated, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-limiting.

[0038] It should be noted that specific details are described in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in a variety of other ways different from those described herein, and those skilled in the art can make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0039] The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but it will be appreciated by those skilled in the art that the following embodiments and examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified, proceed according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0040] In a first aspect, the present invention provides a solid hydrogen storage material containing a transition metal alloy additive, wherein the solid hydrogen storage material comprises magnesium hydride and a transition metal alloy additive; wherein the transition metal alloy additive is a magnesium-nickel-yttrium alloy.

[0041] In the present invention, the transition metal alloy additive is transformed into Mg2NiH4 after reacting with Mg / MgH2, and Mg2NiH4 plays an important inducing role in the dehydrogenation process of MgH2; at the same time, the rare earth element Y promotes the formation of LPSO phase, and generates a YH2 nano-catalytic phase with a stable structure in situ after hydrogenation, and there are a large number of nano-interfaces, which have high energy and are conducive to the diffusion of H atoms. In addition, the additive magnesium-nickel-yttrium alloy can also supplement the Mg content in the main component, reducing the problem of the decrease in the final hydrogen storage capacity due to the addition of other elements.

[0042] As an optional embodiment, the mass ratio of the magnesium hydride to the transition metal alloy additive is (8-10):1, for example, it can be 8:1, 8.5:1, 9:1, 9.5:1, 10:1, etc.

[0043] As an optional embodiment, the chemical formula of the magnesium-nickel-yttrium alloy is Mg a Ni b Y c ; Among them, 0.5≤a≤1.5, 1.5≤a≤2.5, 0.05≤c≤0.15.

[0044] As an optional embodiment, a is 0.5 to 1.5, for example, it can be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc.

[0045] As an optional embodiment, b is 1.5 to 2.5, for example, it can be 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, etc.

[0046] As an optional embodiment, c is 0.05 to 0.15, for example, it can be 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, etc.

[0047] In a second aspect, the present invention provides a method for preparing a solid hydrogen storage material containing a transition metal alloy additive as described in the first aspect, the preparation method comprising the following steps:

[0048] After magnesium hydride and a transition metal alloy additive are mixed, ball milling is performed to obtain the solid hydrogen storage material containing the transition metal alloy additive.

[0049] As an optional embodiment, the process parameters of the ball milling include:

[0050] The material of the grinding ball is stainless steel; the diameter of the grinding ball is 1-5 mm; the ball-to-material ratio is (20-40):1, the ball milling time is 10-20 min, with an interval of 5-10 min; the ball milling speed is 300-500 r / min.

[0051] As an optional implementation, the diameter of the grinding balls is 1-5 mm, for example, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, etc.

[0052] As an optional embodiment, the ball-to-material ratio is (20-40):1, for example, it can be 20:1, 22:1, 24:1, 25:1, 26:1, 28:1, 30:1, 32:1, 34:1, 35:1, 36:1, 38:1, 40:1, etc.

[0053] As an optional embodiment, the ball milling time is 10 to 20 minutes, for example, it can be 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, 20 minutes, etc.

[0054] As an optional implementation manner, the intermittent time is 5 to 10 minutes, for example, it can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, etc.

[0055] As an optional embodiment, the ball mill has a rotation speed of 300 to 500 r / min, for example, 300 r / min, 320 r / min, 340 r / min, 350 r / min, 360 r / min, 380 r / min, 400 r / min, 420 r / min, 440 r / min, 450 r / min, 460 r / min, 480 r / min, 500 r / min, etc.

[0056] As an optional embodiment, the transition metal alloy additive is prepared by the following steps:

[0057] (a) mixing magnesium powder, nickel powder and yttrium powder and grinding them to obtain a metal mixed powder;

[0058] (b) tableting the metal mixed powder obtained in step (a) to obtain metal tablets;

[0059] (c) sintering the metal pressed sheet obtained in step (b) to obtain the transition metal alloy additive.

[0060] As an optional embodiment, in step (a), the molar ratio of the magnesium powder, the nickel powder and the yttrium powder is (0.5-1.5):(1.5-2.5):(0.05-0.15);

[0061] Here, “0.5-1.5” can be, for example, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc.

[0062] Here, “1.5-2.5” can be, for example, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, etc.

[0063] Here, “0.05-0.15” may be, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, etc.

[0064] As an optional embodiment, in step (a), the grinding is performed in an agate mortar.

[0065] As an optional embodiment, in step (a), the grinding time is 10 to 30 min, for example, it can be 10 min, 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, etc.

[0066] As an optional embodiment, in step (b), the tabletting pressure is 1 to 3 MPa, for example, it can be 1 MPa, 1.2 MPa, 1.4 MPa, 1.6 MPa, 1.8 MPa, 2 MPa, 2.2 MPa, 2.4 MPa, 2.6 MPa, 2.8 MPa, 3 MPa, etc.

[0067] As an optional implementation, in step (b), the thickness of the metal pressing sheet is 5 to 10 mm, for example, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, etc.

[0068] As an optional embodiment, in step (c), the sintering procedure specifically includes the following two stages:

[0069] The first stage: heating to 550-650℃ at 5-15℃ / min, keeping warm for 5-15min;

[0070] The second stage: heat up to 750-850℃ at 5-15℃ / min and keep warm for 4-6h.

[0071] As an optional embodiment, in step (c), the sintering procedure includes two stages, wherein the sintering temperature of the first stage is 550-650°C, for example, it can be 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, etc.; wherein the sintering temperature of the second stage is 750-850°C, for example, it can be 750°C, 760°C, 770°C, 780°C, 790°C, 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, etc.

[0072] As an optional embodiment, in step (c), the sintering procedure includes two stages, wherein the sintering time of the first stage is 5 to 15 min, for example, it can be 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min; wherein the sintering time of the second stage is 4 to 6 h, for example, it can be 4 h, 4.2 h, 4.4 h, 4.5 h, 4.6 h, 4.8 h, 5 h, 5.2 h, 5.4 h, 5.5 h, 5.6 h, 5.8 h, 6 h, etc.

[0073] As an optional embodiment, in step (c), the sintering procedure includes two stages, wherein the heating rate of the first stage is 5-15°C / min, for example, it can be 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min, 11°C / min, 12°C / min, 13°C / min, 14°C / min, 15°C / min, etc.; wherein the heating rate of the second stage is 1-10°C / min, for example, it can be 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min, etc.

[0074] As an optional embodiment, the method for preparing the solid hydrogen storage material containing a transition metal alloy additive specifically comprises the following steps:

[0075] S1, mixing magnesium powder, nickel powder and yttrium powder, and grinding them to obtain a metal mixed powder;

[0076] S2, tableting the metal mixed powder obtained in step S1 to obtain metal tablets;

[0077] S3, sintering the metal pressed sheet obtained in step S2 to obtain the transition metal alloy additive;

[0078] S4, mixing magnesium hydride and the transition metal alloy additive obtained in step S3, and then ball milling to obtain the solid hydrogen storage material containing the transition metal alloy additive.

[0079] As a preferred embodiment, the method for preparing the solid hydrogen storage material containing transition metal alloy additives specifically comprises the following steps:

[0080] S1. Mix magnesium powder, nickel powder and yttrium powder in a molar ratio of (0.5-1.5):(1.5-2.5):(0.05-0.15), and grind to obtain a metal mixed powder;

[0081] S2, using a pressure of 1 to 3 MPa to tablet the metal mixed powder obtained in step S1 to obtain a metal tablet;

[0082] S3, sintering the metal pressed sheet obtained in step S2 to obtain the transition metal alloy additive; wherein the sintering procedure is specifically as follows: heating to 550-650°C at 5-15°C / min, keeping the temperature for 5-15min, then heating to 750-850°C at 1-10°C / min, and keeping the temperature for 4-6h;

[0083] S4, mixing magnesium hydride with a mass ratio of (8-10):1 and the transition metal alloy additive obtained in step S3, and then ball milling to obtain the solid hydrogen storage material containing the transition metal alloy additive.

[0084] In a third aspect, the present invention provides a use of the solid hydrogen storage material containing a transition metal alloy additive as described in the first aspect in the preparation of a hydrogen storage device.

[0085] The present invention is further described below by means of specific examples and comparative examples. However, it should be understood that these examples are only used for more detailed description and should not be construed as limiting the present invention in any form.

[0086] Example 1

[0087] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive, and the solid hydrogen storage material containing a transition metal alloy additive is prepared by the following steps:

[0088] S1. Mixing of raw materials:

[0089] In a glove box, magnesium powder, nickel powder and yttrium powder were weighed in sequence with a molar ratio of 1:2:0.1. In order to mix the three powders evenly, the powders needed to be ground in an agate mortar for 20 min.

[0090] S2. Tableting of mixed powder:

[0091] The ground powder was loaded into the mold of a tablet press and pressed into a shape using a pressure of 2 MPa to obtain a metal tablet with a thickness of 6 mm.

[0092] S3. Sintering of tablets:

[0093] The metal pressed sheet is placed in a pre-prepared iron shell, sealed and taken out of the glove box, and transferred to a tubular furnace protected by argon atmosphere for sintering;

[0094] The specific sintering procedure is as follows: the temperature is raised from room temperature to 600°C at a rate of 10°C / min, and kept at 600°C for 10 min, then raised to 800°C at a rate of 5°C / min, and kept at 800°C for 5 h. After naturally cooling to room temperature, MgNi2Y 0.1 alloy powder.

[0095] S4. Preparation of solid hydrogen storage materials:

[0096] MgH2 and prepared MgNi2Y were mixed in a mass ratio of 9:1. 0.1 The alloy powder is compounded by ball milling to obtain the solid hydrogen storage material containing the transition metal alloy additive;

[0097] Among them, the ball milling parameters are set as follows: the material of the grinding ball is stainless steel; the diameter of the grinding ball is 3 mm; the ball-to-material ratio is 30:1, the ball milling time is 15 min, and the interval is 5 min; the ball milling speed is 400 r / min.

[0098] Example 2

[0099] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive, and the solid hydrogen storage material containing a transition metal alloy additive is prepared by the following steps:

[0100] S1. Mixing of raw materials:

[0101] In a glove box, magnesium powder, nickel powder and yttrium powder were weighed in sequence with a molar ratio of 1:2:0.1. In order to mix the three powders evenly, the powders needed to be ground in an agate mortar for 20 min.

[0102] S2. Tableting of mixed powder:

[0103] The ground powder was loaded into the mold of a tablet press and pressed into a shape using a pressure of 2 MPa to obtain a metal tablet with a thickness of 6 mm.

[0104] S3. Sintering of tablets:

[0105] The metal pressed sheet is placed in a pre-prepared iron shell, sealed and taken out of the glove box, and transferred to a tubular furnace protected by argon atmosphere for sintering;

[0106] The specific sintering procedure is as follows: the temperature is raised from room temperature to 550°C at 8°C / min, and kept at 550°C for 15 min, then raised to 750°C at 4°C / min, and kept at 750°C for 6 h, and then cooled naturally to room temperature to obtain MgNi2Y 0.1 alloy powder.

[0107] S4. Preparation of solid hydrogen storage materials:

[0108] MgH2 and prepared MgNi2Y were mixed in a mass ratio of 9:1. 0.1 The alloy powder is compounded by ball milling to obtain the solid hydrogen storage material containing the transition metal alloy additive;

[0109] Among them, the ball milling parameters are set as follows: the material of the grinding ball is stainless steel; the diameter of the grinding ball is 3 mm; the ball-to-material ratio is 30:1, the ball milling time is 15 min, and the interval is 5 min; the ball milling speed is 400 r / min.

[0110] Example 3

[0111] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive, and the solid hydrogen storage material containing a transition metal alloy additive is prepared by the following steps:

[0112] S1. Mixing of raw materials:

[0113] In a glove box, magnesium powder, nickel powder and yttrium powder were weighed in sequence with a molar ratio of 1:2:0.1. In order to mix the three powders evenly, the powders needed to be ground in an agate mortar for 20 min.

[0114] S2. Tableting of mixed powder:

[0115] The ground powder was loaded into the mold of a tablet press and pressed into a shape using a pressure of 2 MPa to obtain a metal tablet with a thickness of 6 mm.

[0116] S3. Sintering of tablets:

[0117] The metal pressed sheet is placed in a pre-prepared iron shell, sealed and taken out of the glove box, and transferred to a tubular furnace protected by argon atmosphere for sintering;

[0118] The specific sintering procedure is as follows: the temperature is raised from room temperature to 650°C at 12°C / min, and kept at 650°C for 5 minutes, then raised to 850°C at 6°C / min, and kept at 850°C for 4 hours, and then cooled naturally to room temperature to obtain MgNi2Y 0.1 alloy powder.

[0119] S4. Preparation of solid hydrogen storage materials:

[0120] MgH2 and prepared MgNi2Y were mixed in a mass ratio of 9:1. 0.1 The alloy powder is compounded by ball milling to obtain the solid hydrogen storage material containing the transition metal alloy additive;

[0121] Among them, the ball milling parameters are set as follows: the material of the grinding ball is stainless steel; the diameter of the grinding ball is 3 mm; the ball-to-material ratio is 30:1, the ball milling time is 15 min, and the interval is 5 min; the ball milling speed is 400 r / min.

[0122] Example 4

[0123] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive. The only difference from Embodiment 1 is that the molar ratio of magnesium powder, nickel powder and yttrium powder in S1 is 3:1:0.05, and the other steps are completely consistent with Embodiment 1.

[0124] Example 5

[0125] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive. The only difference from Embodiment 1 is that the molar ratio of magnesium powder, nickel powder and yttrium powder in S1 is 1:3:0.05, and the other steps are exactly the same as those in Embodiment 1.

[0126] Example 6

[0127] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive. The only difference from Embodiment 1 is that the molar ratio of magnesium powder, nickel powder and yttrium powder in S1 is 1:1:1, and the other steps are exactly the same as those in Embodiment 1.

[0128] Example 7

[0129] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive. The only difference from Embodiment 1 is that the sintering procedure described in S3 is as follows: heating to 520°C at 10°C / min, keeping warm for 1 hour, then heating to 720°C at 5°C / min, and keeping warm for 5 hours; the other steps are exactly the same as Embodiment 1.

[0130] Example 8

[0131] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive. The only difference from Embodiment 1 is that the sintering procedure described in S3 is as follows: heating to 720°C at 10°C / min, keeping warm for 5 minutes, then heating to 860°C at 5°C / min, and keeping warm for 4 hours; the other steps are exactly the same as Embodiment 1.

[0132] Example 9

[0133] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive, which is different from Embodiment 1 only in that the sintering procedure described in S3 is: directly heating to 750°C at 10°C / min and keeping the temperature for 6h; the other steps are exactly the same as Embodiment 1.

[0134] Example 10

[0135] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive, which is different from the embodiment 1 only in that MgH2 and MgNi2Y in S4 0.1 The mass ratio of the alloy powder is 12:1; the other steps are completely consistent with Example 1.

[0136] Embodiment 11

[0137] This embodiment provides a solid hydrogen storage material containing a transition metal alloy additive, which is different from the embodiment 1 only in that MgH2 and MgNi2Y in S4 0.1 The mass ratio of the alloy powder is 6:1; the other steps are completely consistent with Example 1.

[0138] Comparative Example 1

[0139] This comparative example provides a solid hydrogen storage material, wherein the solid hydrogen storage material is pure MgH2.

[0140] Comparative Example 2

[0141] This comparative example provides a solid hydrogen storage material containing a transition metal alloy additive, and the solid hydrogen storage material containing a transition metal alloy additive is prepared by the following steps:

[0142] S1. Mixing of raw materials:

[0143] Nickel powder and yttrium powder were weighed in a glove box in a molar ratio of 2:0.1. In order to mix the two powders evenly, the powders were ground in an agate mortar for 20 min.

[0144] S2. Tableting of mixed powder:

[0145] The ground powder was loaded into the mold of a tablet press and pressed into a shape using a pressure of 2 MPa to obtain a metal tablet with a thickness of 6 mm.

[0146] S3. Sintering of tablets:

[0147] The metal pressed sheet is placed in a pre-prepared iron shell, sealed and taken out of the glove box, and transferred to a tubular furnace protected by argon atmosphere for sintering;

[0148] The specific sintering procedure is as follows: the temperature is raised from room temperature to 600°C at a rate of 10°C / min, and kept at 600°C for 10 minutes, then raised to 800°C at a rate of 5°C / min, and kept at 800°C for 5 hours, and then cooled naturally to room temperature to obtain Ni2Y 0.1 alloy powder.

[0149] S4. Preparation of solid hydrogen storage materials:

[0150] MgH2 and prepared Ni2Y were mixed in a mass ratio of 9:1. 0.1 The alloy powder is compounded by ball milling to obtain the solid hydrogen storage material containing the transition metal alloy additive;

[0151] Among them, the ball milling parameters are set as follows: the material of the grinding ball is stainless steel; the diameter of the grinding ball is 3 mm; the ball-to-material ratio is 30:1, the ball milling time is 15 min, and the interval is 5 min; the ball milling speed is 400 r / min.

[0152] Comparative Example 3

[0153] This comparative example provides a solid hydrogen storage material containing a transition metal alloy additive, and the solid hydrogen storage material containing a transition metal alloy additive is prepared by the following steps:

[0154] S1. Mixing of raw materials:

[0155] Magnesium powder and yttrium powder were weighed in the glove box in sequence with a molar ratio of 1:0.1. In order to mix the two powders evenly, the powders needed to be ground in an agate mortar for 20 min.

[0156] S2. Tableting of mixed powder:

[0157] The ground powder was loaded into the mold of a tablet press and pressed into a shape using a pressure of 2 MPa to obtain a metal tablet with a thickness of 6 mm.

[0158] S3. Sintering of tablets:

[0159] The metal pressed sheet is placed in a pre-prepared iron shell, sealed and taken out of the glove box, and transferred to a tubular furnace protected by argon atmosphere for sintering;

[0160] The specific sintering procedure is as follows: the temperature is raised from room temperature to 600°C at a rate of 10°C / min, and kept at 600°C for 10 min, then raised to 800°C at a rate of 5°C / min, and kept at 800°C for 5 h, and then cooled naturally to room temperature to obtain MgY 0.1 alloy powder.

[0161] S4. Preparation of solid hydrogen storage materials:

[0162] MgH2 and prepared MgY were mixed in a mass ratio of 9:1. 0.1 The alloy powder is compounded by ball milling to obtain the solid hydrogen storage material containing the transition metal alloy additive;

[0163] Among them, the ball milling parameters are set as follows: the material of the grinding ball is stainless steel; the diameter of the grinding ball is 3 mm; the ball-to-material ratio is 30:1, the ball milling time is 15 min, and the interval is 5 min; the ball milling speed is 400 r / min.

[0164] Comparative Example 4

[0165] This comparative example provides a solid hydrogen storage material containing a transition metal alloy additive, and the solid hydrogen storage material containing a transition metal alloy additive is prepared by the following steps:

[0166] S1. Mixing of raw materials:

[0167] Magnesium powder and nickel powder were weighed in the glove box in a molar ratio of 2:1. In order to mix the two powders evenly, the powders were ground in an agate mortar for 20 min.

[0168] S2. Tableting of mixed powder:

[0169] The ground powder was loaded into the mold of a tablet press and pressed into a shape using a pressure of 2 MPa to obtain a metal tablet with a thickness of 6 mm.

[0170] S3. Sintering of tablets:

[0171] The metal pressed sheet is placed in a pre-prepared iron shell, sealed and taken out of the glove box, and transferred to a tubular furnace protected by argon atmosphere for sintering;

[0172] The specific sintering program is set as follows: first increase the temperature from room temperature to 600°C at 10°C / min, and keep it at 600°C for 10 minutes, then increase the temperature to 800°C at 5°C / min, and keep it at 800°C for 5 hours. After naturally cooling to room temperature, MgNi2 alloy powder is obtained.

[0173] S4. Preparation of solid hydrogen storage materials:

[0174] Compounding MgH2 and the prepared MgNi2 alloy powder by ball milling in a mass ratio of 9:1 to obtain the solid hydrogen storage material containing the transition metal alloy additive;

[0175] Among them, the ball milling parameters are set as follows: the material of the grinding ball is stainless steel; the diameter of the grinding ball is 3 mm; the ball-to-material ratio is 30:1, the ball milling time is 15 min, and the interval is 5 min; the ball milling speed is 400 r / min.

[0176] Test Example 1

[0177] Test samples: solid-state hydrogen storage materials containing transition metal alloy additives provided in Examples 1 to 11, and solid-state hydrogen storage materials provided in Comparative Examples 1 to 4.

[0178] Test method:

[0179] (1) Hydrogen charging test: the hydrogen absorption amount of each sample at different time was tested at 250°C; (2) Hydrogen desorption test: the hydrogen release amount of each sample at different time was tested at 250°C.

[0180] The specific test results are shown in Tables 1 and 2. Figure 1 , Figure 2 and Figure 3 As shown:

[0181] Table 1

[0182]

[0183]

[0184] Table 2

[0185]

[0186]

[0187] As shown in Table 1 and Table 2 above, the solid hydrogen storage material containing transition metal alloy additives of the present invention can absorb hydrogen of more than 5.0 wt% within 23 minutes at a low temperature of 250°C, and can release hydrogen of more than 5.0 wt% within 41 minutes at a low temperature of 250°C. This indicates that the present invention effectively improves the hydrogen absorption / desorption kinetics of MgH2 by adding magnesium-nickel-yttrium alloy as an additive to magnesium hydride (MgH2), improves the hydrogen absorption and desorption performance of MgH2, enables the solid hydrogen storage material to have a lower hydrogen absorption and desorption temperature, and obtains a high final desorption amount of hydrogen in a shorter time.

[0188] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A solid hydrogen storage material containing a transition metal alloy additive, characterized in that: The solid-state hydrogen storage material comprises magnesium hydride and a transition metal alloy additive; wherein the transition metal alloy additive is a magnesium-nickel-yttrium alloy.

2. The solid hydrogen storage material containing transition metal alloy additive according to claim 1, characterized in that: The mass ratio of the magnesium hydride to the transition metal alloy additive is (8-10):

1.

3. The solid hydrogen storage material containing transition metal alloy additive according to claim 1, characterized in that: The chemical formula of the magnesium-nickel-yttrium alloy is Mg a Ni b Y c ; Among them, 0.5≤a≤1.5, 1.5≤a≤2.5, 0.05≤c≤0.

15.

4. A method for preparing a solid hydrogen storage material containing a transition metal alloy additive according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: After magnesium hydride and a transition metal alloy additive are mixed, ball milling is performed to obtain the solid hydrogen storage material containing the transition metal alloy additive.

5. The method for preparing a solid hydrogen storage material containing a transition metal alloy additive according to claim 4, characterized in that: The process parameters of the ball milling include: The material of the grinding ball is stainless steel; the diameter of the grinding ball is 1-5 mm; the ball-to-material ratio is (20-40):1, the ball milling time is 10-20 min, with an interval of 5-10 min; the ball milling speed is 300-500 r / min.

6. The method for preparing a solid hydrogen storage material containing a transition metal alloy additive according to claim 4, characterized in that: The transition metal alloy additive is prepared by the following steps: (a) mixing magnesium powder, nickel powder and yttrium powder and grinding them to obtain a metal mixed powder; (b) tableting the metal mixed powder obtained in step (a) to obtain metal tablets; (c) sintering the metal pressed sheet obtained in step (b) to obtain the transition metal alloy additive.

7. The method for preparing a solid hydrogen storage material containing a transition metal alloy additive according to claim 6, characterized in that: In step (a), the molar ratio of the magnesium powder, the nickel powder and the yttrium powder is (0.5-1.5):(1.5-2.5):(0.05-0.15); Preferably, in step (a), the grinding is performed in an agate mortar; Preferably, in step (a), the grinding time is 10 to 30 minutes.

8. The method for preparing a solid hydrogen storage material containing a transition metal alloy additive according to claim 6, characterized in that: In step (b), the tabletting pressure is 1 to 3 MPa; Preferably, in step (b), the thickness of the metal pressing sheet is 5 to 10 mm.

9. The method for preparing a solid hydrogen storage material containing a transition metal alloy additive according to claim 6, characterized in that: In step (c), the sintering procedure is specifically as follows: Raise the temperature to 550-650°C at 5-15°C / min, keep warm for 5-15 minutes, then raise the temperature to 750-850°C at 1-10°C / min, and keep warm for 4-6 hours.

10. Use of the solid hydrogen storage material containing a transition metal alloy additive according to any one of claims 1 to 3 in the preparation of a hydrogen storage device.

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