An easily-activated TiFe-based solid hydrogen storage tank and a preparation method thereof

Abstract

This invention relates to the field of TiFe-based solid-state hydrogen storage technology, and particularly to an easily activated TiFe-based solid-state hydrogen storage tank and its preparation method. It includes a tank body and a total hydrogen storage alloy filled within the tank body. The total hydrogen storage alloy comprises a TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy. The easily activated hydrogen storage alloy has an activation temperature ≤80℃ and an activation cycle ≤5 times. This invention, by incorporating an easily activated hydrogen storage alloy into the TiFe-based hydrogen storage alloy, promotes the dissociation of hydrogen molecules into hydrogen atoms. The partially dissociated hydrogen atoms adsorb onto the surface of the TiFe-based hydrogen storage alloy, further promoting its activation. This effectively shortens the activation cycle of the TiFe-based solid-state hydrogen storage tank without altering the hydrogen absorption and desorption performance of the TiFe-based hydrogen storage alloy.

Description

Technical Field

[0001] This invention relates to the field of TiFe-based solid hydrogen storage technology, and in particular to an easily activated TiFe-based solid hydrogen storage tank and its preparation method. Background Technology

[0002] With the widespread application of hydrogen energy technology, efficient, safe, and low-cost hydrogen storage technology has become a key factor restricting its development. Among various hydrogen storage methods, solid-state hydrogen storage has attracted increasing attention due to its high volumetric hydrogen storage density and excellent safety (no need for high pressure or extremely low temperature conditions). Among various solid-state hydrogen storage materials, TiFe-based hydrogen storage alloys are considered a promising candidate material due to their relatively high mass hydrogen storage density (theoretical value of approximately 1.86 wt%), suitable thermodynamic plateau pressure for room temperature operation, and low cost (the main elements titanium and iron are abundant).

[0003] However, the commercial application of TiFe-based solid-state hydrogen storage tanks has long been limited by a key bottleneck: their demanding initial activation conditions. Newly prepared TiFe-based hydrogen storage alloys typically have a dense oxide layer (such as TiO2) on their surface. This oxide layer hinders the dissociation of hydrogen molecules and their penetration into the bulk alloy phase, making initial hydrogen absorption exceptionally difficult. Existing known technologies indicate that unmodified TiFe alloys usually require prolonged processing at high temperatures (350-450℃) and high vacuum, and undergo multiple low-temperature hydrogen absorption / high-temperature dehydrogenation cycles to complete activation. This process is energy-intensive and time-consuming, significantly increasing system complexity and cost.

[0004] Existing methods for improving the activation performance of TiFe-based solid hydrogen storage tanks mostly rely on enhancing the TiFe-based hydrogen storage alloy through methods such as elemental substitution and mechanical alloying, thereby promoting the activation process of the TiFe-based solid hydrogen storage tank. However, this method can lead to lower pressure on the hydrogen storage alloy platform or a more tilted platform region, thus affecting the hydrogen absorption and desorption performance of the TiFe-based solid hydrogen storage tank.

[0005] Therefore, there is an urgent need to provide an easily activated TiFe-based solid hydrogen storage tank to solve the above-mentioned technical problems. Summary of the Invention

[0006] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide an easily activated TiFe-based solid hydrogen storage tank and its preparation method, so as to solve the problem of poor activation in the prior art of TiFe-based solid hydrogen storage tanks.

[0007] To achieve the above and other related objectives, the present invention is obtained through the following technical solution.

[0008] The first aspect of the present invention is to provide an easily activated TiFe-based solid hydrogen storage tank, comprising a tank body and a total hydrogen storage alloy filled in the tank body, wherein the total hydrogen storage alloy comprises a TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy, wherein the easily activated hydrogen storage alloy has an activation temperature ≤80℃ and an activation cycle ≤5 times.

[0009] A second aspect of this invention provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0010] (1) A TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy are mixed to obtain a mixed powder; the easily activated hydrogen storage alloy has an activation temperature ≤80℃ and an activation cycle ≤5 times;

[0011] (2) The mixed powder obtained in step (1) is filled into the tank to obtain an easily activated TiFe-based solid hydrogen storage tank.

[0012] A third aspect of the present invention is to provide the application of the easily activated TiFe-based solid hydrogen storage tank described above in the field of solid hydrogen storage.

[0013] As described above, the easily activated TiFe-based solid hydrogen storage tank and its preparation method of the present invention have the following beneficial effects:

[0014] This invention improves the activation performance of the TiFe-based solid hydrogen storage tank by mixing and filling the tank with a TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy. During the activation process, the easily activated hydrogen storage alloy promotes the dissociation of hydrogen molecules into hydrogen atoms, thereby effectively improving the activation performance of the TiFe-based solid hydrogen storage tank without changing the hydrogen absorption and desorption performance of the TiFe-based hydrogen storage alloy. Attached Figure Description

[0015] Figure 1 The diagram shows the activation performance of the TiFe-based solid hydrogen storage tank of this invention. The horizontal axis represents the number of activations (unit: times), the left vertical axis represents the hydrogen storage capacity of the solid hydrogen storage tank (unit: NL), and the right vertical axis represents the activation rate (unit: %). The dotted line graph corresponds to the right vertical axis, representing the relationship between the activation rate and the number of activations; the bar graph corresponds to the left vertical axis, representing the relationship between the hydrogen storage capacity and the number of activations. Detailed Implementation

[0016] To make the inventive objectives, technical solutions, and beneficial effects of this invention clearer, the invention will be further described in detail below with reference to embodiments. Those skilled in the art can easily understand other advantages and effects of this invention from the content disclosed in this specification.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0018] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only,” “consisting of,” etc., is used, in which case another component may be added.

[0019] In this invention, the terms "preferredly," "more preferably," "better," and "even better" refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of the invention. That is, in this invention, "preferredly," "more preferably," "better," and "even better" are merely descriptions of more effective implementations or examples, but do not constitute a limitation on the scope of protection of the invention.

[0020] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0021] In this invention, "at least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layered" means at least two layers, such as two layers, three layers, etc., unless otherwise explicitly specified. In the description of this invention, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0022] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0023] Unless otherwise specified, all steps of this invention may be performed sequentially or randomly. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), indicating that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0024] Unless otherwise stated, a singular term may include a plural term and should not be understood as having a quantity of one.

[0025] In this invention, "above" or "below" both include the number itself. For example, "below 1" includes 1.

[0026] In this invention, room temperature refers to 0–40°C, including but not limited to 10–40°C, or further to 20–30°C.

[0027] In this invention, the AB5-type hydrogen storage alloy has a hexagonal crystal structure of the CaCu5 type. Here, A is typically a rare earth element (such as La, Ce, or mixed rare earth Mm) or calcium (Ca), and B is typically a transition metal (such as Ni, Co, Mn, or Al).

[0028] In this invention, the AB2-type hydrogen storage alloy has a Laves phase structure of MgZn2 or MgCu2 type. This is a topologically close-packed structure with more compact atomic stacking and more diverse interstitial sites. A is typically zirconium (Zr) or titanium (Ti), and B is typically chromium (Cr), manganese (Mn), vanadium (V), nickel (Ni), iron (Fe), etc.

[0029] In this invention, the BCC-type hydrogen storage alloy has a body-centered cubic crystal structure. It is typically not a single metallic element, but a solid solution alloy composed of elements such as vanadium (V), titanium (Ti), and chromium (Cr).

[0030] Traditional methods involve modifying the alloy by adding elements in different proportions to improve activation conditions. However, current technologies struggle to simultaneously achieve high maximum hydrogen storage capacity, high effective hydrogen release capacity, and low plateau tilt coefficient when improving the activation performance of TiFe-based hydrogen storage alloys. This leads to a decline in the overall performance of TiFe-based hydrogen storage alloys, hindering their widespread application.

[0031] The method described in this application does not alter the inherent properties of the TiFe hydrogen storage alloy but instead employs direct physical mixing with an easily activated alloy. Therefore, it completely avoids the problems of low plateau pressure and tilted plateau regions inherent in the original TiFe alloy.

[0032] The hydrogen absorption mechanism of hydrogen storage alloys consists of six steps: 1. Physical adsorption of H2 on the particle surface: H2 molecules are adsorbed onto the particle surface under the action of van der Waals forces; 2. Dissociation and chemical adsorption of H2 on the particle surface: H2 molecules dissociate into H atoms and adsorb onto the particle surface; 3. Surface permeation of hydrogen atoms: H atoms permeate into the alloy lattice through the surface; 4. α solid solution: Hydrogen atoms gradually diffuse into the interior of the lattice, forming an α solid solution; 5. α+β two-phase region: When the H concentration reaches a certain level, a phase transition occurs with the alloy, generating a hydride β phase; subsequently, hydrogen atoms diffuse inward through the β phase, and the β phase continuously forms and grows; 6. β phase solid solution: After the α phase is completely transformed into the β phase, hydrogen atoms dissolve into the β phase under higher pressure. Furthermore, the activation difficulty of TiFe hydrogen storage alloys is mainly due to the easy formation of a dense TiO2 oxide layer on the surface, which has a dense crystal structure and high chemical stability, thus blocking the contact between hydrogen and the alloy bulk. Therefore, this invention introduces an easily activated hydrogen storage alloy into a TiFe-based solid hydrogen storage tank, allowing H atoms dissociated through chemical adsorption to penetrate the dense TiO2 oxide layer. The generated hydrogen atoms diffuse from the surface into the TiFe-based hydrogen storage alloy lattice, thereby generating metal hydrides, promoting the activation of the TiFe-based hydrogen storage alloy, and improving the activation performance of the TiFe-based solid hydrogen storage tank.

[0033] The first aspect of the present invention is to provide an easily activated TiFe-based solid hydrogen storage tank, comprising a tank body and a total hydrogen storage alloy filled in the tank body, wherein the total hydrogen storage alloy comprises a TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy, wherein the easily activated hydrogen storage alloy has an activation temperature ≤80℃ and an activation cycle ≤5 times.

[0034] In some embodiments of the present invention, the activation method of the solid hydrogen storage tank is to perform a cyclic "vacuuming-filling-discharging" operation. The specific steps are as follows: 1. The solid hydrogen storage tank is evacuated at 60°C; 2. Hydrogen is filled at 10°C and 4.0 MPa H2; 3. Hydrogen is discharged at 60°C and 0.1 MPa outlet pressure.

[0035] In some embodiments of the present invention, the total hydrogen storage alloy is filled into the tank in the form of flakes or powder.

[0036] In some embodiments of the present invention, the total amount of hydrogen storage alloy is 40-80% of the tank volume.

[0037] In some embodiments of the present invention, based on the total hydrogen storage alloy, the amount of easily activated hydrogen storage alloy added is 0.5-50 wt.%. Specifically, it can be 0.5-5 wt.%, 5-10 wt.%, 10-20 wt.%, 20-40 wt.%, or 40-50 wt.%. The amount of easily activated hydrogen storage alloy added directly affects the activation performance of the easily activated TiFe-based solid hydrogen storage tank. As the amount of easily activated hydrogen storage alloy added increases, the activation cycle of the easily activated TiFe-based solid hydrogen storage tank is shortened. This is because a larger amount of easily activated hydrogen storage alloy added increases the concentration of dissociated H atoms during the activation process, thereby promoting the activation of the TiFe-based hydrogen storage alloy.

[0038] In some embodiments of the present invention, the TiFe-based hydrogen storage alloy powder has a particle size of 0.1-1 mm.

[0039] In some embodiments of the present invention, the particle size of the easily activated hydrogen storage alloy powder is 0.1-1 mm.

[0040] In some embodiments of the present invention, the readily activated hydrogen storage alloy is selected from one or more of AB2-type hydrogen storage alloys, AB5-type hydrogen storage alloys, and BCC-type hydrogen storage alloys. The AB2-type hydrogen storage alloy is a TiMn2-based hydrogen storage alloy; the AB5-type hydrogen storage alloy is a LaNi5-based hydrogen storage alloy; and the BCC-type hydrogen storage alloy is a V-based hydrogen storage alloy.

[0041] In some embodiments of the present invention, the readily activated hydrogen storage alloy is selected from one or more of titanium-based hydrogen storage alloys, vanadium-based hydrogen storage alloys, and rare earth-based hydrogen storage alloys. The titanium-based hydrogen storage alloy is a TiMn2-based hydrogen storage alloy, the vanadium-based hydrogen storage alloy is a V-based hydrogen storage alloy, and the rare earth-based hydrogen storage alloy is a LaNi5-based hydrogen storage alloy.

[0042] In some embodiments of the present invention, the tank body is further filled with heat transfer powder, preferably selected from one or more of expanded graphite powder or copper powder. The particle size of the heat transfer powder is 0.1-1 mm; based on the total hydrogen storage alloy, the amount of heat transfer powder added is 0.5-10 wt.%.

[0043] A second aspect of this invention provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0044] (1) A TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy are mixed to obtain a mixed powder; the easily activated hydrogen storage alloy has an activation temperature ≤80℃ and an activation cycle ≤5 times;

[0045] (2) The mixed powder obtained in step (1) is filled into the tank to obtain an easily activated TiFe-based solid hydrogen storage tank.

[0046] In some embodiments of the present invention, heat transfer powder is added in step (2), and the heat transfer powder is mixed with the mixed powder and filled into the tank.

[0047] In some embodiments of the present invention, the mixed powder in step (2) is pressed into a sheet and filled into a can. Preferably, the pressing pressure is 50-500 MPa. Specifically, it can be 50-150 MPa, 150-300 MPa, or 300-500 MPa.

[0048] In some embodiments of the present invention, the tank material is selected from one or more of aluminum alloy, 304 stainless steel, and 316L stainless steel.

[0049] A third aspect of the present invention is to provide the application of the easily activated TiFe-based solid hydrogen storage tank described above in the field of solid hydrogen storage.

[0050] The present invention will be further illustrated by the following examples, but these examples do not limit the scope of the invention.

[0051] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. All reagents or instruments whose manufacturers are not specified are conventional products that can be purchased commercially. In addition to the specific methods, equipment, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, equipment, and materials similar to or equivalent to those described, used, and materials in the embodiments of this invention may be used to implement this invention.

[0052] Example

[0053] Example 1

[0054] This embodiment provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0055] (1) Weigh 1995g of TiFe-based hydrogen storage alloy (TiFe) according to a mass ratio of 19:1. 0.86 Mn 0.1 ), 105g of V-series hydrogen storage alloy (V 80 Ti5Cr 12 Mn3), place the two alloys in a dry and clean mixing container and stir thoroughly until they are evenly mixed;

[0056] (2) The 2100g of uniformly mixed alloy powder was filled into an aluminum alloy bottle with a volume of 600ml to complete the filling operation and obtain an easily activated TiFe-based solid hydrogen storage tank. The theoretical hydrogen storage capacity of this solid hydrogen storage tank is 39.01g (i.e., 433.90NL).

[0057] The solid hydrogen storage tank was activated according to the predetermined activation conditions, and the total amount of hydrogen released each time was collected using a flow controller to determine the hydrogen storage capacity. When the measured hydrogen storage capacity reached the theoretical hydrogen storage capacity, and the fluctuation range of two consecutive measured hydrogen storage capacity values ​​was ≤ ±2%, the alloy was considered fully activated. The results of the number of activation cycles and hydrogen storage capacity tests are shown in Table 1 and... Figure 1 As shown. The activation method is to perform a cyclical "vacuuming-hydrogen charging-hydrogen discharging" operation. The specific steps are as follows: 1. Vacuum the solid hydrogen storage tank at 60℃ for 2 hours; 2. Charge the tank with hydrogen at 10℃ and 4.0MPa H2; 3. Discharge the tank with hydrogen at 60℃ and 0.1MPa outlet pressure at a flow rate of 10NL / min.

[0058] Example 2

[0059] This embodiment provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0060] (1) Weigh 1995g of TiFe-based hydrogen storage alloy (TiFe) according to a mass ratio of 19:1. 0.86 Mn 0.1 ), 105g of LaNi5-based hydrogen storage alloy (La 0.71 Ce 0.29 Ni 4.34 Co 0.53 Mn 0.13 Place the two alloys in a dry, clean mixing container and stir thoroughly until they are evenly mixed.

[0061] (2) The 2100g of uniformly mixed alloy powder is filled into an aluminum alloy bottle with a volume of 600ml to complete the filling operation and obtain an easily activated TiFe-based solid hydrogen storage tank. The theoretical hydrogen storage capacity of the solid hydrogen storage tank is 38.48g (i.e. 428.06NL).

[0062] The solid hydrogen storage tank was activated according to the predetermined activation conditions, and the total amount of hydrogen released each time was collected using a flow controller to determine the hydrogen storage capacity. When the measured hydrogen storage capacity reached the theoretical hydrogen storage capacity, and the fluctuation range of two consecutive measured hydrogen storage capacity values ​​was ≤ ±2%, the alloy was considered fully activated. The results of the number of activation cycles and hydrogen storage capacity tests are shown in Table 1 and... Figure 1As shown. The activation method is to perform a cyclical "vacuuming-hydrogen charging-hydrogen discharging" operation. The specific steps are as follows: 1. Vacuum the solid hydrogen storage tank at 60℃ for 2 hours; 2. Charge the tank with hydrogen at 10℃ and 4.0MPa H2; 3. Discharge the tank with hydrogen at 60℃ and 0.1MPa outlet pressure at a flow rate of 10NL / min.

[0063] Example 3

[0064] This embodiment provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0065] (1) Weigh 1995g of TiFe-based hydrogen storage alloy (TiFe) according to a mass ratio of 19:1. 0.86 Mn 0.1 ), 105g of TiMn2-based hydrogen storage alloy (Ti 0.84 Zr 0.16 Mn 0.9 Cr 0.7 Fe 0.1 Place the two alloys in a dry, clean mixing container and stir thoroughly until they are evenly mixed.

[0066] (2) Fill 2100g of uniformly mixed alloy powder into an aluminum alloy bottle with a volume of 600ml to complete the filling operation and obtain an easily activated TiFe-based solid hydrogen storage tank. The theoretical hydrogen storage capacity of the solid hydrogen storage tank is 38.85g (i.e. 432.15NL).

[0067] The solid hydrogen storage tank was activated according to the predetermined activation conditions, and the total amount of hydrogen released each time was collected using a flow controller to determine the hydrogen storage capacity. When the measured hydrogen storage capacity reached the theoretical hydrogen storage capacity, and the fluctuation range of two consecutive measured hydrogen storage capacity values ​​was ≤ ±2%, the alloy was considered fully activated. The results of the number of activation cycles and hydrogen storage capacity tests are shown in Table 1 and... Figure 1 As shown. The activation conditions are: vacuuming-filling with hydrogen-discharging with hydrogen. This process is repeated, with the activation method involving a cyclical "vacuuming-filling with hydrogen-discharging" operation. The specific steps are as follows: 1. Vacuum the solid hydrogen storage tank at 60℃ for 2 hours; 2. Fill with hydrogen at 10℃ and 4.0MPa H2; 3. Discharge hydrogen at 60℃ and 0.1MPa outlet pressure at a flow rate of 10NL / min.

[0068] Example 4

[0069] This embodiment provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0070] (1) Weigh 1890g of TiFe-based hydrogen storage alloy (TiFe) according to a mass ratio of 18:2. 0.86 Mn 0.1), 210g of TiMn2-based hydrogen storage alloy (Ti 0.84 Zr 0.16 Mn 0.9 Cr 0.7 Fe 0.1 Place the two alloys in a dry, clean mixing container and stir thoroughly until they are evenly mixed.

[0071] (2) The 2100g of uniformly mixed alloy powder was filled into an aluminum alloy bottle with a volume of 600ml to complete the filling operation and obtain an easily activated TiFe-based solid hydrogen storage tank. The theoretical hydrogen storage capacity of this solid hydrogen storage tank is 38.85g (i.e., 432.15NL).

[0072] The solid hydrogen storage tank was activated according to the predetermined activation conditions, and the total amount of hydrogen released each time was collected using a flow controller to determine the hydrogen storage capacity. When the measured hydrogen storage capacity reached the theoretical hydrogen storage capacity, and the fluctuation range of two consecutive measured hydrogen storage capacity values ​​was ≤ ±2%, the alloy was considered fully activated. The results of the number of activation cycles and hydrogen storage capacity tests are shown in Table 1 and... Figure 1 As shown. The activation method is to perform a cyclical "vacuuming-hydrogen charging-hydrogen discharging" operation. The specific steps are as follows: 1. Vacuum the solid hydrogen storage tank at 60℃ for 2 hours; 2. Charge the tank with hydrogen at 10℃ and 4.0MPa H2; 3. Discharge the tank with hydrogen at 60℃ and 0.1MPa outlet pressure at a flow rate of 10NL / min.

[0073] Example 5

[0074] This embodiment provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0075] (1) Weigh 1680g of TiFe-based hydrogen storage alloy (TiFe) according to a mass ratio of 16:4. 0.86 Mn 0.1 ), 420g TiMn2-based hydrogen storage alloy (Ti 0.84 Zr 0.16 Mn 0.9 Cr 0.7 Fe 0.1 Place the two alloys in a dry, clean mixing container and stir thoroughly until they are evenly mixed.

[0076] (2) Fill 2100g of uniformly mixed alloy powder into an aluminum alloy bottle with a volume of 600ml to complete the filling operation and obtain an easily activated TiFe-based solid hydrogen storage tank. The theoretical hydrogen storage capacity of the solid hydrogen storage tank is 38.85g (i.e. 432.15NL).

[0077] The solid hydrogen storage tank was activated according to the predetermined activation conditions, and the total amount of hydrogen released each time was collected using a flow controller to determine the hydrogen storage capacity. When the measured hydrogen storage capacity reached the theoretical hydrogen storage capacity, and the fluctuation range of two consecutive measured hydrogen storage capacity values ​​was ≤ ±2%, the alloy was considered fully activated. The results of the number of activation cycles and hydrogen storage capacity tests are shown in Table 1 and... Figure 1 As shown. The activation conditions are: vacuuming-filling with hydrogen-discharging with hydrogen. This process is repeated, with the activation method involving a cyclical "vacuuming-filling with hydrogen-discharging" operation. The specific steps are as follows: 1. Vacuum the solid hydrogen storage tank at 60℃ for 2 hours; 2. Fill with hydrogen at 10℃ and 4.0MPa H2; 3. Discharge hydrogen at 60℃ and 0.1MPa outlet pressure at a flow rate of 10NL / min.

[0078] Example 6

[0079] This embodiment provides a method for preparing an easily activated TiFe-based solid hydrogen storage tank, comprising the following steps:

[0080] (1) Weigh 1050g of TiFe-based hydrogen storage alloy (TiFe) according to a mass ratio of 10:10. 0.86 Mn 0.1 ), 1050g TiMn2-based hydrogen storage alloy (Ti 0.84 Zr 0.16 Mn 0.9 Cr 0.7 Fe 0.1 Place the two alloys in a dry, clean mixing container and stir thoroughly until they are evenly mixed.

[0081] (2) Fill 2100g of uniformly mixed alloy powder into an aluminum alloy bottle with a volume of 600ml to complete the filling operation and obtain an easily activated TiFe-based solid hydrogen storage tank. The theoretical hydrogen storage capacity of the solid hydrogen storage tank is 38.85g (i.e. 432.15NL).

[0082] The solid hydrogen storage tank was activated according to the predetermined activation conditions, and the total amount of hydrogen released each time was collected using a flow controller to determine the hydrogen storage capacity. When the measured hydrogen storage capacity reached the theoretical hydrogen storage capacity, and the fluctuation range of two consecutive measured hydrogen storage capacity values ​​was ≤ ±2%, the alloy was considered fully activated. The results of the number of activation cycles and hydrogen storage capacity tests are shown in Table 1 and... Figure 1 As shown. The activation conditions are: vacuuming-filling with hydrogen-discharging with hydrogen. This process is repeated, with the activation method involving a cyclical "vacuuming-filling with hydrogen-discharging" operation. The specific steps are as follows: 1. Vacuum the solid hydrogen storage tank at 60℃ for 2 hours; 2. Fill with hydrogen at 10℃ and 4.0MPa H2; 3. Discharge hydrogen at 60℃ and 0.1MPa outlet pressure at a flow rate of 10NL / min.

[0083] Comparative Example

[0084] Comparative Example 1

[0085] This comparative example provides a method for preparing a TiFe-based solid hydrogen storage tank, including the following steps: weighing 2100g of TiFe-based hydrogen storage alloy and filling it into an aluminum alloy bottle with a volume of 600ml to complete the filling operation.

[0086] The solid hydrogen storage tank was activated according to the predetermined activation conditions, and the total amount of hydrogen released each time was collected using a flow controller to determine the hydrogen storage capacity. When the measured hydrogen storage capacity reached the theoretical hydrogen storage capacity, and the fluctuation range of two consecutive measured hydrogen storage capacity values ​​was ≤ ±2%, the alloy was considered fully activated. The results of the number of activation cycles and hydrogen storage capacity tests are shown in Table 1 and... Figure 1 As shown. The activation conditions are: vacuuming-filling with hydrogen-discharging with hydrogen. This process is repeated, with the activation method involving a cyclical "vacuuming-filling with hydrogen-discharging" operation. The specific steps are as follows: 1. Vacuum the solid hydrogen storage tank at 60℃ for 2 hours; 2. Fill with hydrogen at 10℃ and 4.0MPa H2; 3. Discharge hydrogen at 60℃ and 0.1MPa outlet pressure at a flow rate of 10NL / min.

[0087] The performance test results are shown in Table 1.

[0088] Table 1. Number of activation cycles and hydrogen storage capacity of solid hydrogen storage tanks in Examples 1-6 and Comparative Example 1

[0089] Activation times / times 13 14 13 9 8 5 24 Hydrogen storage capacity / NL 440.10 428.04 434.29 441.69 441.82 455.46 438.95

[0090] In conjunction with Examples 1-6, and in conjunction with Table 1 and Figure 1 It can be seen that the TiFe-based solid hydrogen storage tanks prepared in Examples 1-6 have far fewer activation times than the TiFe-based solid hydrogen storage tanks obtained in Comparative Example 1. This indicates that by mixing TiFe-based hydrogen storage alloys with easily activated hydrogen storage alloys, the activation times of TiFe-based solid hydrogen storage tanks can be significantly reduced without changing the hydrogen absorption and desorption performance of the TiFe-based solid hydrogen storage tanks.

[0091] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. An easily-activatable TiFe-based solid-state hydrogen storage tank, characterized by: The device includes a tank body and a total hydrogen storage alloy filled within the tank body. The total hydrogen storage alloy comprises a TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy. The easily activated hydrogen storage alloy has an activation temperature ≤80℃ and an activation cycle ≤5 times. The easily activated hydrogen storage alloy is a TiMn2-based hydrogen storage alloy. Based on the total hydrogen storage alloy, the amount of the easily activated hydrogen storage alloy added is 40-50 wt.%. The tank body is also filled with heat transfer powder. The particle size of the heat transfer powder is 0.1-1 mm. Based on the total hydrogen storage alloy, the amount of the heat transfer powder added is 0.5-10 wt.%. The heat transfer powder is selected from one or more of expanded graphite and copper powder. The heat transfer powder, TiFe-based hydrogen storage alloy, and easily activated hydrogen storage alloy are mixed in powder form and filled into the tank body.

2. The solid hydrogen storage tank according to claim 1, characterized in that: The total amount of hydrogen storage alloy is 40-80% of the tank volume.

3. The solid hydrogen storage tank according to claim 1, characterized in that: The TiFe-based hydrogen storage alloy powder has a particle size of 0.1-1 mm; and / or, the easily activated hydrogen storage alloy powder has a particle size of 0.1-1 mm.

4. The solid hydrogen storage tank according to any one of claims 1-3, characterized in that: The activation method of the solid hydrogen storage tank is to perform a "vacuuming-filling-discharging" operation in a cycle.

5. A method for preparing an easily activated TiFe-based solid hydrogen storage tank as described in any one of claims 1-4, characterized in that, Includes the following steps: (1) A TiFe-based hydrogen storage alloy and an easily activated hydrogen storage alloy are mixed to obtain a mixed powder; the easily activated hydrogen storage alloy has an activation temperature ≤80℃ and an activation cycle ≤5 times; (2) The mixed powder obtained in step (1) is filled into the tank to obtain an easily activated TiFe-based solid hydrogen storage tank.

6. The application of the easily activated TiFe-based solid hydrogen storage tank as described in any one of claims 1-4 in the field of solid hydrogen storage.

Images