LU500786B1 - Ti-based High-capacity Solid-state Hydrogen Storage Alloy and Preparation Method and Hydrogen Storage System thereof - Google Patents

Ti-based High-capacity Solid-state Hydrogen Storage Alloy and Preparation Method and Hydrogen Storage System thereof Download PDF

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LU500786B1
LU500786B1 LU500786A LU500786A LU500786B1 LU 500786 B1 LU500786 B1 LU 500786B1 LU 500786 A LU500786 A LU 500786A LU 500786 A LU500786 A LU 500786A LU 500786 B1 LU500786 B1 LU 500786B1
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hydrogen storage
alloy
storage alloy
hydrogen
tank
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LU500786A
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Haiwen Li
Yongtao Li
Wenjing Li
Zhijie Gao
Qingan Zhang
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Univ Anhui Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C01B3/0052—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing titanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
    • C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a Ti-based high-capacity solid-state hydrogen storage alloy, preparation method and hydrogen storage system thereof. Chemical formula of hydrogen storage alloy is TiuZrxMnvMyVz, M is one of Cr, Ni and Cu, and u, x, v and z respectively represent the atomic numbers of Ti, Zr, Mn and V, as well as 0?x?0.2, 0.1?y?0.4, 0.1?z?0.5, u+x=1, v+y=1.5. The hydrogen storage alloy in the invention has good comprehensive properties such as large hydrogen storage capacity, small hysteresis, wide platform area, etc., and thus the developed hydrogen storage system with using this alloy has the advantages of high safety, convenient and safe operation, wide applicable temperature range and high hydrogen storage density.

Description

DESCRIPTION LU500786 Ti-based High-capacity Solid-state Hydrogen Storage Alloy and Preparation Method and Hydrogen Storage System thereof
TECHNICAL FIELD The invention relates to the technical field of hydrogen storage materials, in particular to a Ti-based high-capacity solid-state hydrogen storage alloy, preparation method and hydrogen storage system thereof.
BACKGROUND Faced with the increasingly serious energy shortage and environmental deterioration, many countries have carried out large-scale new energy exploration in recent years. Hydrogen energy, as a clean secondary energy, has attracted more attentions, but how to solve the problem of hydrogen storage and transportation is one of the key technologies in the application of hydrogen energy. Compared with traditional high-pressure gaseous hydrogen storage and liquid hydrogen storage, the metals and/or alloys for hydrogen storage have the advantages of high storage density, safety and portability, which is considered as an economical and effective hydrogen storage method. Therefore, it is urgent to find hydrogen storage alloys with advantages of high hydrogen storage capacity, appropriate equilibrium pressure, easy activation and fast hydrogen absorption and desorption.
Ti-Mn-based Laves phase hydrogen storage alloy has the characteristics of large hydrogen storage capacity, good cycle stability and excellent dynamic performance, so it has become the research hotspot of practical hydrogen storage alloy at present. However, the alloy also has some shortcomings, such as large hysteresis in hydrogen absorption and desorption platform, sloping platform, low hydrogen desorption pressure and so on. Gamo et al. first studied TiMng-H (a= 0.75-2.0) alloy system, and found that TiMnis alloy has the largest hydrogen storage capacity among Ti-Mn binary alloys. Semboshi et al. systematically studied the effect of chemical composition on hydrogen storage performance of TiMnx binary alloy, and the results show that the hydrogen storage capacity of the alloy 1s the highest when Mn content x=59.4at.%; furthermore, increasing Mn content not only greatly reduces the hydrogen storage capacity, but also deteriorates the cycle stability; the reasons of HUS00768 which may be as follows: the different occupancy of metal atoms caused by composition changes leads to lattice expansion and nonuniform strain. Therefore, in order to obtain an alloy with good comprehensive properties, it is necessary to strictly control the chemical composition of the alloy. In addition, Ming et al. uses multi-elements to substitute this series of alloys and optimized Tio.9Zr0.3Mn1 3Mo0.0sCuo.05Vo2Cro2 alloy with larger hydrogen storage capacity, but its platform characteristics were poor. Liu et al. selects the alloy with composition of Tio 85Cr0.15sMnCrosVo.1Cuo 1, although its hydrogen absorption and desorption curve is flat and its hysteresis is small, its platform area is too short. Therefore, it is of great significance to further develop Ti-Mn-based Laves phase hydrogen storage alloys with excellent comprehensive properties.
Hydrogen storage container is also important for hydrogen energy applications. For example, liquid hydrogen storage at low temperature is related to compressing hydrogen and cooling it to below -252°C for liquefying and storing it in an insulated vacuum storage. However, changing gaseous hydrogen into liquid hydrogen consumes a lot of energy, and a special container which is resistant to ultra-low temperature and keeps ultra-low temperature is also needed for frost resisting, compression resistance and strictly insulating. To overcome these drawbacks, a new hydrogen storage container with solid-state alloys is developed that can operate at low-pressure and room-temperature conditions, in addition to the easy manufacturing and, low cost and without potential safety hazards during operation.
SUMMARY The objective of the invention is to provide a Ti-based high-capacity solid-state hydrogen storage alloy, preparation method and hydrogen storage system thereof, so as to solve the problems existing in the prior art.
The invention provides a Ti-based high-capacity solid-state hydrogen storage alloy, and the chemical formula of hydrogen storage alloy is TiuZr<MnyMyV;,, M is one of Cr, Ni and Cu, and u, x, v and z respectively represent the atomic numbers of Ti, Zr, Mn and V, furthermore 0<x<0.2, 0.1<y<0.4, 0.1<z<0.5, u+x=1, v+y=1.5.
The hydrogen storage alloy is a single C14-Laves phase. HUS00768 Zr/Ti ratio x is adjusted to control the hydrogen desorption plateau of the hydrogen storage alloy to be 0.15-1.45 MPa.
The optimum additive amount of V is 0.1<z<0.3; M is the element Cr, and the optimal additive amount of its substitution is 0.1<y<0.2.
According to the preparation method of hydrogen storage alloy, selecting pure metals according to the alloy proportion, and smelting for 2-3 times in a magnetic suspension high-frequency induction furnace protected by argon, next annealing the melted as-cast alloy at 950-1050°C under the protection of inert gas, thus producing the Ti-based high-capacity solid-state hydrogen storage alloy according to claims 1-4.
The hydrogen storage system comprises a tank, hydrogen storage alloy plates, heat dissipation plates and a heat exchange tube; the hydrogen storage alloy plates are made of the Ti-based high-capacity solid-state hydrogen storage alloy described in claims 1-4; one end of that tank is connect with the hydrogen pipeline through a valve; the hydrogen storage alloy plates and the heat dissipation plates have the same shape and are arranged in the inner cavity of the tank, and a heat dissipation plate is tightly arranged between any two hydrogen storage alloy plates; the corresponding positions of the hydrogen storage alloy plates and the heat dissipation plates are both provided with through holes for accommodating the heat exchange tube; the heat exchange tube penetrates through the through hole, and one end of the heat exchange pipe is connected with the water inlet pipe and the other end is connected with the water outlet pipe; in addition, the water inlet pipe and the water outlet pipe are both arranged outside the other end of the tank.
The outside of tank wall is paved with an heat insulating layer, and between the heat insulating layer and the tank wall a plurality of thermocouples are also arranged.
In the tank, a hydrogen filter sheet is arranged between the hydrogen pipeline and the hydrogen storage alloy plate.
A sealing layer is arranged at the joint of the heat exchange tube, the water inlet pipe and the water outlet pipe, and an aluminum bushing is arranged outside the sealing layer to fix the water inlet pipe and the water outlet pipe.
The material of the tank (8) is stainless steel or aluminum alloy; the material of 7500796 heat dissipation plates (4) is aluminum or copper.
The invention disclose that following technical effect: the hydrogen storage alloy in the invention has good comprehensive properties such as large hydrogen storage capacity, small hysteresis, wide platform area, etc., so the hydrogen storage system with the alloy has the advantages of high safety, convenient and safe operation, wide applicable temperature range and high hydrogen storage density.
BRIEF DESCRIPTION OF THE FIGURES In order to explain the embodiment of the present invention or the technical scheme in the prior art more clearly, the following will briefly introduce the drawings used in the embodiment. Obviously, the drawings in the following description are only some embodiments of the present invention; for those skilled in the art, other drawings can be obtained according to these drawings without paying creative labor.
Fig. 1 is the hydrogen absorption/desorption curve of TiMn, sV, (z=0.1-0.5) alloy at 40°C.
Fig. 2 is the X-ray diffraction pattern of TiMni15Vo alloy.
Fig. 3 is the hydrogen absorption/desorption curve of TiuZr,Mn1sVo2 (x=0.05-0.20, u+x=1) alloy at 40°C.
Fig. 4 is the hydrogen absorption/desorption curve of TiogsZro.15Mm1 4Mo.1Vo2 (M=None, Cr, Ni, Cu) alloy at 40°C.
Fig. 5 is the X-ray diffraction pattern of Tio.ssZro.1sMnı.4Cro.ı Vo. alloy.
Fig. 6 is the hydrogen absorption/desorption curve of Tio.gsZro.15Mm1 4Cro.1Vo2 alloy at 25°C, 40°C and 60°C.
Fig. 7 is the X-ray diffraction pattern of Tio.ssZro.1sMnı.3Cro.2 Vo. alloy.
Fig. 8 is the hydrogen absorption/desorption curve of TiogsZro.15Mm1 3Cro2Vo2 alloy at 40°C.
Fig. 9 is a schematic diagram of the hydrogen storage system.
Among them, 1: heat exchange tube, 2: hydrogen pipeline, 3: hydrogen storage alloy plate, 4: heat dissipation plate, 5: hydrogen filter, 6: thermocouple, 7: heat insulating layer, 8: tank, 9: water inlet pipe, 10: water outlet pipe, 11: valve, 12: HUS00768 aluminum bushing and 13: sealing layer.
DESCRIPTION OF THE INVENTION The following will clearly and completely describe the technical scheme in the embodiment of the present invention with reference to the drawings in the embodiment of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative labor belong to the scope of protection of the present invention.
In order to make the above objects, features and advantages of the present invention more obvious and easy to understand, the present invention will be further explained in detail with reference to the drawings and specific embodiments.
In the further implementation process of the invention, adding V element on the basis of TiMnis alloy, and preferably, selecting an under-metered alloy TiMn1 sV,(0.1<z<0.5) with large hydrogen storage capacity; on this basis, using Zr, Cr, Ni and Cu for element substitution, and designing the chemical general formula of the new alloy as TiuZriMnyM,V,, where: 0<x<0.2, 0.1<y<0.4, 0.1<z<0.5, ut+x=1,v+y=1.5; the optimum range is 0.1<y<0.2, 0.1<z<0.3; and M is one of Cr, Ni and Cu. The preparation process of this series of alloys is as follows: smelting it for 2-3 times in a magnetic suspension high-frequency induction furnace protected by argon to ensure the uniformity of alloy components, wherein the heating power varies with the melting points of alloy components; and then annealing the as-cast alloy at 950°C -1050°C for 7 days under the protection of inert gas. The alloy prepared by the above method not only has high hydrogen storage capacity and small platform hysteresis of hydrogen absorption and desorption, but also is easy to activate under mild conditions. In addition, the hydrogen desorption platform pressure of the alloy can be controlled by adjusting the Zr/Ti ratio X, which is in the approximate range of 0.15-1.45 MPa.
The alloy compositions with good comprehensive properties, namely Tio 85Z10.15Mn1.4Cro.1 Vo.2 and Tio gsZro.1sMn13Cro2Vo.2, Were optimized.
Compared with the existing under-metered hydrogen storage alloy, the Ti-based HUS00768 high-capacity solid-state hydrogen storage alloy has a single C14-Laves phase.
The hydrogen desorption platform pressure of the obtained alloy can be controlled by changing the substitution amount of Zr within a specific range. The alloy obtained is easily activated under mild conditions (200°C, 3.5 MPaH»).
The alloy obtained has good comprehensive properties such as large hydrogen storage capacity, small hysteresis and wide platform area.
Furthermore, the reaction between metal and hydrogen is a reversible process. The forward reaction absorbs hydrogen and releases heat, while the reverse reaction releases hydrogen and absorbs heat. By changing the temperature and pressure conditions, the reaction can be repeated in the forward and reverse directions to dilute the hydrogen in the container. Whether the metal in the device absorbs hydrogen to generate metal hydride or metal hydride decomposes and releases hydrogen is controlled by temperature, pressure and alloy composition. The external hydrogen is connected with the hydrogen pipeline 2 under the control of the valve 11. The hydrogen enters the inside of the tank 8 and is filtered by the hydrogen filter 5, so that impurities and dirt are blocked at the front end of the tank 8, and the clean hydrogen enters the hydrogen storage alloy plate 3 for storage. When hydrogen is solidified into the alloy material, the volume of hydrogen absorbed is more than 1000 times that of the alloy material itself, which shows that the density of hydrogen stored and transported is high.
In the hydrogen absorption process, the heat exchange tube 1 of the device is connected with external circulating cold water through the water inlet pipe 9 and the water outlet pipe 10, the hydrogen storage alloy plate 3 absorbs hydrogen while releasing heat, and the circulating cold water in the heat exchange tube 1 exchanges heat with the hydrogen storage alloy plate 3. At the same time, the heat dissipation plates 4 and the hydrogen storage alloy plates 3 are closely arranged alternately and fully contacted, thus increasing the heat exchange efficiency. In this way, the heat released from the hydrogen storage alloy plates 3 is transferred from the inside of the tank to the water outlet pipe 10 by circulating cold water and released into the air, so that the hydrogen charging process can be continuously carried out. At this time, the HUS00768 heat insulating layer 7 made of insulation material outside the stainless steel shell 8 can ensure that the whole device is not affected by the external ambient temperature and will not affect the hydrogen charging process. In the hydrogen releasing process, the heat exchange tube 1 of the device is connected with external circulating warm water through the water inlet pipe 9 and the water outlet pipe 10, the hydrogen storage alloy plate 3 releases hydrogen while absorbing heat, and the circulating warm water in the heat exchange tube 1 inhibits the temperature drop of the hydrogen storage alloy plate 3.
At this time, the heat dissipation plate 4 will not dissipate heat to the outside environment due to the heat insulating layer 7, which will not affect the hydrogen desorption process, and the hydrogen desorption will continue. At the same time, the thermocouple 6 can be connected with a temperature measuring instrument to master the temperature of the shell in real time and monitor whether the state of the whole device is normal.
Furthermore, the number of hydrogen storage alloy plates 3 is two more than the number of heat dissipation plates 4, and the hydrogen storage alloy plates 3 are arranged in parallel with the hydrogen filter sheets 5 in the tank 8.
Preferably, the hydrogen storage system has a relatively flat and wide equilibrium platform nip (partial pressure at room temperature is 2-3 atm), alloy hydrogen storage materials with moderate partial pressure, and a hot water exchange pipe meeting the heat demand in the hydrogen charging and discharging process. The external temperature does not affect the process of charging and discharging hydrogen, and realizes the automatic charging and discharging of hydrogen, which is unique. The hydrogen storage system can work normally in the temperature range of -40°C -60°C, and has wide applicable temperature range and positive effect.
Example 1 According to the chemical composition of TiMn15V,(z=0.1-0.5) alloy, weighing g of Ti, Mn (considering the burning loss rate of 3wt.%) and V metal block with purity greater than 99% and smelting in a magnetic suspension high frequency induction furnace for 2-3 times; placing the as-cast alloy in a quartz tube, and keeping HUS00768 the temperature at 950°C for 7 days under argon protection; finally, cooling the furnace to room temperature, taking out the annealed alloy, polishing to remove the oxide scale on the alloy surface, mechanically crushing the alloy and then sieving through a 300-mesh sieve for later use. The alloy consists of single C14-Laves phase (Fig. 2 shows the X-ray diffraction pattern of TiMn1sVoz alloy). The hydrogen absorption/desorption curves of the alloy are measured by Sievert method, and the steps are as follows: firstly, weighing 2 g of the above alloy powder, putting into a sample chamber, and activating at 200°C and 3.5 MPaH>; then, when the temperature drops to 40°C, testing the hydrogen absorption/desorption curve, and the results are shown in Figure 1. With increasing V addition, the hydrogen storage capacity of the alloy increases at first and then decreases, wherein TiMn1 sVo2 alloy has the largest hydrogen storage capacity, reaching 1.54wt.%. Then, on the basis of TiMn1 5Vo alloy, Zr 1s used to partially replace Ti atom, and the hydrogen absorption/desorption curve of TiuZr<Mn1 5Vo.2(x=0.05-0.20, utx=1) alloy at 40°C is shown in fig. 3. It can be seen that the hydrogen storage capacity of the alloy increases with increasing Zr substitution, and the hydrogen desorption platform pressure of the alloy can be controlled within the range of 0.15-1.45 MPa by changing the Zr substitution (0<x<0.2). On the basis of the above, Cr, Ni and Cu are used to partially replace Mn, and the hydrogen absorption/desorption curve of Tio.ssZro.15Mnı 4Mo 1 Vo 2(M=Cr,Ni,Cu) alloy at 40°C is shown in fig. 4. It can be seen from the figure that all the three alternatives are beneficial to improve the hysteresis of the hydrogen absorption and desorption platform of the alloy, and the partial substitution of Cr for Mn also significantly increases the hydrogen storage capacity of the alloy.
Example 2 According to the chemical composition of TiosgsZro.15Mn1 4Cro 1 Vo alloy (Fig. 5 is the X-ray diffraction pattern of Tios8sZro.15Mn1 4Cro 1 Vo2 alloy), the lattice constant and unit cell volume are obviously larger than those of TiMn1 sVo2 alloy by Rietvield software fitting. The hydrogen absorption/desorption curves of the alloy are measured by Sievert method, and the steps are as follows: firstly, weighing 2 g of the above HUS00768 alloy powder, putting into a sample chamber, and activating for 2-3 times at 200°C and 3.5 MPaH;; then, when the alloy is cooled to different temperatures, the hydrogen absorption/desorption curves are tested, and the results are shown in Figure 6.
Compared with the existing Ti-Mn-based Laves phase alloy, the alloy has many advantages, such as high purity, large hydrogen storage capacity (the hydrogen storage capacity reaches more than 19wt.% at 25°C), easy activation, moderate platform pressure, long platform area, hydride generation enthalpy AH of -28.66 kJ/mol, simple preparation process and high practical value.
Example 3 According to the chemical composition of Tio.g5Zro.15Mm1 3Cro2Vo2 alloy (Fig. 7 is the X-ray diffraction pattern of TiossZro1sMn13Cro2Vo2 alloy), the hydrogen absorption/desorption curves of the alloy are measured by Sievert method, and the steps are as follows: firstly, weighing 2 g of the above alloy powder, putting into a sample chamber, and activating for 2 times at 200°C and 3.5 MPaH>; then, when the temperature drops to 40°C, testing the hydrogen absorption/desorption curve, and the results are shown in Figure 8. The alloy has the advantages of high hydrogen storage capacity, easy activation, moderate platform pressure, small hysteresis of hydrogen absorption and release platform, etc.
The above-mentioned embodiments only describe the preferred mode of the invention, and do not limit the scope of the invention. On the premise of not departing from the design spirit of the invention, various modifications and improvements made by ordinary technicians in the field to the technical scheme of the invention shall fall within the protection scope determined by the claims of the invention.

Claims (10)

CLAIMS LU500786
1. A Ti-based high-capacity solid-state hydrogen storage alloy 1s characterized in that chemical formula of hydrogen storage alloy is TiuZrMnyMyV,, M is one of Cr, Ni and Cu, and u, x, v and z respectively represent the atomic numbers of Ti, Zr, Mn and V, furthermore O<x<0 2, 0.1<y<0.4, 0.1<z<0.5, u+x=1, v+y=1.5.
2. The Ti-based high-capacity solid-state hydrogen storage alloy according to claim 1 is characterized in that the hydrogen storage alloy is a single C14-Zaves phase.
3. The Ti-based high-capacity solid-state hydrogen storage alloy according to claim 1 is characterized by adjusting the Zr/Ti ratio x to control the hydrogen desorption plateau of the hydrogen storage alloy to be 0.15-1.45 MPa.
4. The preparation method of the hydrogen storage alloy according to claim 1 is characterized in that the optimum additive amount of V is 0.1<z<0.3; M is the element Cr, and the optimal additive amount of its substitution is 0.1<y<0.2.
5. The preparation method of hydrogen storage alloy is characterized by selecting pure metals according to the alloy proportion, and smelting for 2-3 times in a magnetic suspension high-frequency induction furnace protected by argon, next annealing the melted as-cast alloy at 950-1050°C under the protection of inert gas, thus producing the Ti-based high-capacity solid-state hydrogen storage alloy according to claims 1-4.
6. A hydrogen storage system is characterized by comprising a tank (8), hydrogen storage alloy plates (3), heat dissipation plates (4) and a heat exchange tube (1); the hydrogen storage alloy plates (3) are made of the Ti-based high-capacity solid-state hydrogen storage alloy described in claims 1-4; one end of that tank (8) is connect with the hydrogen pipeline (2) through a valve (11); the hydrogen storage alloy plates (3) and the heat dissipation plates (4) have the same shape and are arranged in the inner cavity of the tank (8), and a heat dissipation plate (4) is tightly arranged between any two hydrogen storage alloy plates (3); the corresponding positions of the hydrogen storage alloy plates (3) and the heat dissipation plates (4) are both provided with through holes for accommodating the heat exchange tube (1); the heat exchange tube (1) penetrates through the through 7500786 hole, and one end of the heat exchange pipe (1) is connected with the water inlet pipe (9) and the other end is connected with the water outlet pipe (10); in addition, the water inlet pipe (9) and the water outlet pipe (10) are both arranged outside the other end of the tank (8).
7. The hydrogen storage system according to claim 6 is characterized in that the outside of tank wall is paved with an heat insulating layer (7), and between the heat insulating layer (7) and the tank wall a plurality of thermocouples (6) are also arranged.
8. The hydrogen storage system according to claim 6 is characterized in that in the tank (8), a hydrogen filter sheet (5) is arranged between the hydrogen pipeline (2) and the hydrogen storage alloy plate (3).
9. The hydrogen storage system according to claim 6 is characterized in that a sealing layer (13) is arranged at the joint of the heat exchange tube (1), the water inlet pipe (9) and the water outlet pipe (10), and an aluminum bushing (12) is arranged outside the sealing layer (13) to fix the water inlet pipe (9) and the water outlet pipe (10).
10. The hydrogen storage system according to claim 6 is characterized in that the material of the tank (8) is stainless steel or aluminum alloy; the material of heat dissipation plates (4) is aluminum or copper.
LU500786A 2021-10-26 2021-10-26 Ti-based High-capacity Solid-state Hydrogen Storage Alloy and Preparation Method and Hydrogen Storage System thereof LU500786B1 (en)

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