CN116516229A - Under-stoichiometric magnesium-containing C15 structure Laves phase room temperature reversible hydrogen storage high-entropy alloy and preparation method thereof - Google Patents
Under-stoichiometric magnesium-containing C15 structure Laves phase room temperature reversible hydrogen storage high-entropy alloy and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 159
- 239000000956 alloy Substances 0.000 title claims abstract description 159
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 118
- 239000001257 hydrogen Substances 0.000 title claims abstract description 118
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000011777 magnesium Substances 0.000 title claims abstract description 91
- 238000003860 storage Methods 0.000 title claims abstract description 89
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001068 laves phase Inorganic materials 0.000 title claims abstract description 32
- 230000002441 reversible effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- 239000011572 manganese Substances 0.000 claims description 45
- 239000010936 titanium Substances 0.000 claims description 45
- 230000000694 effects Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- 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
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/04—Hydrogen absorbing
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a low-stoichiometry magnesium-containing C15 structure Laves phase room-temperature reversible hydrogen storage high-entropy alloy and a preparation method thereof, wherein the chemical formula of the material is Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 (x=0.2 to 0.4). The preparation process of the hydrogen storage high entropy alloy comprises the steps of smelting Zr by arc melting 0.85 Ti 0.15 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 And (3) mixing the precursor after crushing with Mg powder, and sintering the mixed sample to obtain the high-entropy alloy. The preparation method is simple and easy to control, can accurately control the components of the magnesium-containing high-entropy alloy, does not contain rare earth elements, contains only a small amount of V elements, and has the added Mg content of 12%, so that the cost and density of the alloy are greatly reduced. The under-stoichiometric hydrogen storage high-entropy alloy prepared by the invention has a C15Laves single-phase structure, has a hydrogen storage capacity of 0.3-1.0 wt.% at room temperature, and has the characteristics of rapid and reversible hydrogen storage at room temperature and easy activation.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a low-stoichiometry magnesium-containing C15 structure Laves phase room-temperature reversible hydrogen storage high-entropy alloy and a preparation method thereof.
Background
Today, energy crisis and environmental crisis force people to develop clean energy. Among them, hydrogen energy is considered as an ideal carrier of renewable energy sources due to advantages of cleanliness, high efficiency, environmental protection, sustainable utilization, etc., but the development of the hydrogen energy industry is still limited by the lack of efficient and safe hydrogen storage methods. Compared with liquid hydrogen storage and gaseous hydrogen storage, solid hydrogen storage is widely studied due to the advantages of higher energy density and safety, lower cost, convenience in transportation and the like. Currently, the hydrogen storage alloys are mainly of rare earth type, ferrotitanium type, zirconium type, vanadium type and magnesium type. Wherein, the rare earth hydrogen storage alloy has lower hydrogen storage capacity, high cost and poor cycle performance; the ferrotitanium hydrogen storage alloy has a Laves phase crystal structure, so that the alloy has the advantages of high hydrogen storage capacity, long cycle life and the like, but is difficult to activate; the hydrogen release temperature of the zirconium hydrogen storage alloy is higher; although both vanadium-based and magnesium-based hydrogen storage alloys have high hydrogen storage capacity, the problems of too high hydrogen release temperature, poor dynamic performance and the like exist, so that a novel hydrogen storage alloy still needs to be explored at present, and the appearance of high-entropy alloy possibly provides a novel thought for researching novel hydrogen storage materials.
The high-entropy alloy consists of five or more elements including a high-entropy effect, a cocktail effect, a lattice distortion effect and a delayed diffusion effect, and the four effects have a certain effect on obtaining a hydrogen storage alloy excellent in hydrogen storage performance. The high entropy effect provides a certain condition for the high entropy alloy to form a single-phase solid solution; the difference in atomic radii causes severe lattice distortion, which results in the alloy having more lattice gaps, defects, and strains, providing more vacancies and channels, which facilitate diffusion, dissociation, and recombination of hydrogen atoms; the hysteresis diffusion effect provides a basis for the high-entropy alloy to have good hydrogen storage capacity; meanwhile, under the influence of cocktail effect, all principal elements affect alloy performance together, and due to the diversity of element selection, the adjustability of element proportion provides possibility for preparing high-entropy alloy with comprehensive performance meeting the requirement of hydrogen storage application.
In recent years, researchers at home and abroad are increasingly researching the hydrogen storage performance of high-entropy alloy. Among them, intermetallic high entropy alloys have been widely studied for their high hydrogen storage capacity, good low temperature hydrogen release performance, and good kinetics of hydrogen absorption and release, such as AB 2 The TiZrCrMnFeNi high entropy alloy has a room temperature reversible hydrogen storage capacity of 1.6wt.% [ P Edalati, R Floriano, A Mohammadi, et al, script a materials, 2020,178:387-390.]；AB 2 The TiZrFeMnCrV high entropy alloy still has a hydrogen storage capacity of about 1.76wt.% after 50 cycles [ J Chen, Z Li, H Huang, et al script a materials, 2022,212:114548.]. In addition, studies have shown that designing different A/B intermetallic high entropy alloys has the potential to improve the hydrogen storage properties of the alloys, such as A with the C14 Laves phase as the major phase at 473K temperature 3 B 2 The TiZrNbCrFe high entropy alloy even has a reversible hydrogen storage capacity of 1.9wt.% [ R Floriano, G Zepon, K Edalati, et al International Journal of Hydrogen Energy,2021,46 (46): 23757-23766.]. However, the intermetallic high entropy alloys studied so far all have a C14 Laves phase as the main phase, but the C15Laves phase crystal structure has a specific C14 Laves phase with higher stacking fault density and this defect structure allows the alloy to exhibit better hydrogen storage properties, e.g. Young et al [ K.Young, T.Ouchi, B.Huang, et al journal of Alloys and composites 2010,506 (2): 841-848]It was found that an alloy having a C15Laves phase as a main phase exhibits better performance in terms of hydrogen storage amount, reversible hydrogen storage amount, high-power discharge performance, hydrogen diffusion, and low-temperature performance than an alloy having a C14 Laves phase as a main phase. Therefore, designing intermetallic high-entropy alloys with the C15Laves phase as the main phase may exhibit more excellent hydrogen storage properties.
In addition, the non-stoichiometric composition design is also one of the means to improve the hydrogen storage properties of intermetallic compounds due to the following aspects: on the one hand because non-stoichiometric alloys generally possess higher defect densities relative to alloys of strictly stoichiometric composition; on the other hand, the non-stoichiometric method is adopted to change the proportion of each atom and the atomic occupation in the unit cell, so as to achieve the effect of regulating the chemical environment of tetrahedral gaps and the unit cell volume, and the change of the microstructure can bring great change to the hydrogen storage performance of the alloy. For example: YFe relative to stoichiometry 1.5 Al 0.5 Under-stoichiometric YFe for alloys 1.5 Al 0.5-x The (x=0.1, 0.2) alloy has improved hydrogenation capacity and hydrogen absorption rate and has a larger reversible capacity [ Z Li, H Wang, L Ouyang, et al journal of Alloys and Compounds,2017,704:491-498.]. In addition, because metal Mg has the advantages of high hydrogen storage capacity, low density, wide sources, low cost and the like, the addition of Mg into Laves-phase intermetallic high-entropy alloy can better reduce the density of the alloy and has the possibility of further improving the hydrogen storage capacity, but at present, the research on magnesium-containing Laves-phase hydrogen storage high-entropy alloy in domestic and foreign literature is not available, which is possibly related to the preparation of the magnesium-containing Laves-phase hydrogen storage high-entropy alloy: the traditional smelting method cannot accurately prepare the magnesium-containing Laves-phase hydrogen storage high-entropy alloy because of the low smelting boiling point of Mg, and the mechanical alloying is also difficult to prepare the high-purity Laves-phase magnesium-containing hydrogen storage high-entropy alloy, so that the material performance is deteriorated.
In view of the above, how to design and prepare a Laves phase room temperature reversible hydrogen storage high entropy alloy with a hypostoichiometric magnesium-containing C15 structure, which has important practical application value.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, designs a Laves-phase room-temperature reversible hydrogen storage high-entropy alloy with a hypostoichiometric magnesium-containing C15 structure, and simultaneously develops a corresponding preparation method. Firstly pressing Zr 0.85 Ti 0.15 Ni 1. 2 Mn 0.56 V 0.12 Fe 0.12 Preparing raw materials of an alloy molecular formula, and preparing an alloy precursor through arc melting; according to Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 (x=0.2-0.4) the molecular formula of the alloy is that the precursor after mechanical crushing is weighed and mixed with Mg powder manually; and then sintering the mixed sample to obtain the Laves phase room-temperature reversible hydrogen storage high-entropy alloy with the understoichiometric magnesium-containing C15 structure. The invention prepares the understoichiometric magnesium-containing hydrogen storage high-entropy alloy which has a C15Laves single-phase structure, wherein B/A=1.4-1.7, the alloy does not contain rare earth elements, and the content of added Mg can reach 12 percent, so that the cost and density of the alloy are greatly reduced; in addition, the Laves phase hydrogen storage high entropy alloy with the understoichiometric magnesium-containing C15 structure has the hydrogen storage capacity of 0.3 to 1.0wt.% at room temperature, and has the characteristics of rapid and reversible hydrogen storage at room temperature and easy activation.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the invention provides a Laves phase room temperature reversible hydrogen storage high entropy alloy with a hypostoichiometric magnesium-containing C15 structure, which is characterized in that the chemical formula of the material is Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Wherein x=0.2 to 0.4, B/a=1.4 to 1.7, the a-type elements include Zr, ti and Mg, and the B-type elements include Ni, mn, V and Fe.
The invention also provides a preparation method of the under-stoichiometric magnesium-containing C15 structure Laves phase room temperature reversible hydrogen storage high-entropy alloy, which comprises the following steps:
1) Firstly pressing Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Weighing a certain amount of zirconium blocks, titanium blocks, vanadium blocks, iron blocks, nickel sheets and manganese sheets according to the molecular formula of the alloy; under argon atmosphere, the metal raw material is laid in a crucible from bottom to top according to the melting point from low to high, and then is mixed in a ratio of (0.3-1) x 10 -2 Arc vacuum smelting is carried out under Pa vacuum degree, alloy is completely melted and cooled to form an alloy cast ingot, the alloy cast ingot is turned over, and smelting is repeated for 3-4 times, so that a precursor sample of the hydrogen storage high-entropy alloy can be obtained;
2) Mechanically crushing the obtained precursor sample into precursor powder of 100-300 meshes by using a stainless steel mortar in a glove box;
3) According to Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Weighing precursor powder and Mg powder according to the molecular formula of the alloy, and mixing the precursor powder and the Mg powder in a glove box by hand uniformly;
4) Weighing a certain amount of mixed samples by using an analytical balance in a glove box, and pressing the mixed samples into tablets with the diameter of 10-15 mm by adopting a powder tablet press;
5) Putting the pressed sheet into a stainless steel closed container in a glove box, and filling argon with the pressure of 0.2-0.4 MPa; and then placing the alloy into an annealing furnace for sintering, cooling the alloy to room temperature along with the furnace after the sintering is completed, and taking out the alloy to finally obtain the low-stoichiometric magnesium-containing C15 structure Laves phase room-temperature reversible hydrogen storage high-entropy alloy.
Further, in the step 1), the purity of the zirconium block is more than or equal to 99.7%, the purity of the titanium block is more than or equal to 99.9%, the purity of the vanadium block is more than or equal to 99.9%, the purity of the iron block is more than or equal to 99.9%, the purity of the nickel sheet is more than or equal to 99.5%, and the purity of the manganese sheet is more than or equal to 99.5%.
Further, in step 1), considering that there is burning loss of the titanium blocks and manganese flakes during arc melting, 2wt.% of titanium blocks and 5wt.% of manganese flakes are additionally added.
Further, in the step 3), the purity of the Mg powder is more than or equal to 99.5 percent.
Further, in step 3), 20wt.% Mg powder is additionally added for compensating for the burn-out of Mg powder during the subsequent sintering process.
Further, in the step 5), the sintering temperature of the sintering process is 750-850 ℃ and the sintering time is 12-48 h.
The invention also provides application of the under-stoichiometric magnesium-containing C15 structure Laves phase room temperature reversible hydrogen storage high-entropy alloy in hydrogen storage, and the hydrogen storage high-entropy alloy can be used for hydrogen storage after the activity of the hydrogen storage high-entropy alloy is obtained by carrying out hydrogen absorption and desorption circulation for 1-2 times at the temperature of 250 ℃ and the pressure of 3.5MPa before the hydrogen storage function of the high-entropy alloy is utilized.
The principle of the invention is as follows: in Zr (Zr) 0.85 Ti 0.15 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The hydrogen storage performance of the alloy is further improved by adding light element Mg on the basis of the high-entropy alloy, which is attributable to the following two aspects: on one hand, the addition of light element Mg obviously reduces the density of the alloy, thereby improving the hydrogen storage capacity of the alloy; on the other hand, the addition of Mg changes the stoichiometric ratio of the alloy, so that the hydrogen storage high-entropy alloy with understoichiometery is formed, and a vacancy is formed at the position occupied by the B side atom in the alloy and occupied by part of the A side atom, so that the alloy has a dislocation, twin crystal, stacking fault and other defect structures which are favorable for improving the hydrogen storage performance of the alloy. In addition, there is a large difference in atomic radius and electronegativity in the hydrogen storage high-entropy alloy, which results in the alloy having more lattice gaps, defects and strains, while weakening bond energy in the alloy, thereby promoting diffusion, dissociation and recombination of hydrogen atoms.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention designs a low-stoichiometry magnesium-containing C15 structure Laves phase room-temperature reversible hydrogen storage high-entropy alloy, and develops a corresponding preparation method. The preparation method is simple and easy to control, and can overcome the problems that the components of the magnesium-containing high-entropy alloy are not easy to control, the alloy is composed of multiple phases and the like in the preparation process, so that the components and the phase purity of the magnesium-containing high-entropy alloy can be accurately controlled, and finally the under-stoichiometric magnesium-containing hydrogen storage high-entropy alloy with a C15Laves single-phase structure can be accurately prepared.
2. The invention successfully prepares the Laves phase room temperature reversible hydrogen storage high entropy alloy with the understoichiometric magnesium-containing C15 structure, zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The (x=0.2-0.4) alloy contains no rare earth elements, and the content of added Mg can reach 12%, so that the cost and density of the alloy are greatly reduced.
3. Zr prepared by the invention 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The high-entropy alloy is easy to activate, and can be completely activated only by absorbing and releasing hydrogen for 1-2 times at 250 ℃.
4. Zr prepared by the invention 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The high-entropy alloy has the characteristic of rapid and reversible hydrogen storage at room temperature, can fully absorb hydrogen within 4min under 303K, and can fully release hydrogen within 5min under 303K. Compared with other high-entropy alloys, the invention has the outstanding effects of taking a high-purity C15Laves phase as a main phase and reversibly absorbing and releasing hydrogen at room temperature.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is Zr 0.85 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 (x= 0.2,0.3) high entropy alloy X-ray diffraction (XRD) test patterns;
FIG. 2 is Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 (x= 0.2,0.3) highConstant temperature hydrogen absorption kinetics curve graph of the entropy alloy at 303K;
FIG. 3 is Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 (x= 0.2,0.3) constant temperature hydrogen desorption kinetics plot of high entropy alloy at 303K temperature.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a low-stoichiometry magnesium-containing C15 structure Laves phase room temperature reversible hydrogen storage high-entropy alloy, the chemical formula of which is Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Wherein x=0.2 to 0.4 and b/a=1.4 to 1.7. The preparation process of the hydrogen storage high entropy alloy comprises the steps of smelting Zr by arc melting 0.85 Ti 0.15 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 And (3) crushing the precursor, mixing the crushed precursor with Mg powder, and sintering the mixed sample to obtain the Laves-phase room-temperature reversible hydrogen storage high-entropy alloy with the understoichiometric magnesium-containing C15 structure. The preparation method is simple and easy to control, can accurately control the components of the magnesium-containing high-entropy alloy, does not contain rare earth elements, contains only a small amount of V elements, and has the added Mg content of 12%, so that the cost and density of the alloy are greatly reduced. The under-stoichiometric hydrogen storage high-entropy alloy prepared by the invention has a C15Laves single-phase structure, has a hydrogen storage capacity of 0.3-1.0 wt% (mass percent) at room temperature, and has the characteristics of rapid and reversible hydrogen storage at room temperature and easy activation, and compared with other high-entropy alloys, the alloy provided by the invention has the outstanding effects of the C15Laves single-phase structure and rapid and reversible hydrogen absorption and desorption at room temperature.
The related embodiments of the invention are:
example 1
Zr 0.85 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The preparation method of the high-entropy alloy comprises the following specific steps:
(1) Firstly pressing Zr 0.85 Ti 0.15 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The molecular formula of the alloy is that a certain amount of zirconium blocks (the purity is more than or equal to 99.7 percent), titanium blocks (the purity is more than or equal to 99.9 percent), vanadium blocks (the purity is more than or equal to 99.9 percent), iron blocks (the purity is more than or equal to 99.9 percent), nickel sheets (the purity is more than or equal to 99.5 percent) and manganese sheets (the purity is more than or equal to 99.5 percent) are weighed, and the total mass of the alloy is 30g; under argon atmosphere, the metal raw material is laid in a crucible from bottom to top according to the melting point from low to high, and then arc vacuum melting (vacuum degree is 3×10) -3 Pa), forming an alloy cast ingot after the alloy is completely melted and cooled, turning over the alloy cast ingot, and repeatedly smelting for 4 times to obtain Zr 0.85 Ti 0.15 Ni 1. 2 Mn 0.56 V 0.12 Fe 0.12 A precursor;
(2) Mechanically crushing the precursor into 200-mesh powder by using a stainless steel mortar in a glove box;
(3) According to Zr 0.85 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The preparation method comprises the steps of weighing precursor powder and Mg powder (purity is more than or equal to 99.5%) according to the molecular formula of the alloy, mixing the precursor powder and the Mg powder uniformly by hand in a glove box, weighing 20g of mixed sample by using an analytical balance, and pressing the mixed sample into tablets with the diameter of 13mm by using a powder tablet press;
(4) Putting the pressed sheet into a stainless steel closed container in a glove box, and filling argon with the pressure of 0.4 MPa; and then sintering the alloy in an annealing furnace for one day, wherein the sintering temperature is 800 ℃, cooling the alloy to room temperature along with the furnace after sintering is completed, and removing the alloy to finally obtain the under-stoichiometric magnesium-containing C15 structure Laves phase room temperature reversible hydrogen storage high entropy alloy.
Zr 0.85 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The high entropy alloy consists of a C15Laves single phase (see FIG. 1: zr) 0.8 5 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 High entropy alloy X-ray diffraction (XRD) test pattern). Zr (Zr) 0.85 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The high entropy alloy is capable of absorbing 0.3wt.% hydrogen at 303K temperature (see fig. 2: zr 0.85 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Constant temperature hydrogen absorption kinetics plot of the high entropy alloy at 303K temperature) and complete hydrogen release at 303K temperature (see fig. 3: zr (Zr) 0.85 Ti 0.15 Mg 0.2 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Constant temperature hydrogen desorption kinetics curve graph of the high-entropy alloy at the temperature of 303K, which shows that the alloy has reversible hydrogen storage performance.
Example 2
Zr 0.85 Ti 0.15 Mg 0.3 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The preparation method of the high-entropy alloy comprises the following specific steps:
(1) Firstly pressing Zr 0.85 Ti 0.15 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The molecular formula of the alloy is that a certain amount of zirconium blocks (the purity is more than or equal to 99.7 percent), titanium blocks (the purity is more than or equal to 99.9 percent), vanadium blocks (the purity is more than or equal to 99.9 percent), iron blocks (the purity is more than or equal to 99.9 percent), nickel sheets (the purity is more than or equal to 99.5 percent) and manganese sheets (the purity is more than or equal to 99.5 percent) are weighed, and the total mass of the alloy is 30g; under argon atmosphere, the metal raw material is laid in a crucible from bottom to top according to the melting point from low to high, and then arc vacuum melting (vacuum degree is 3×10) -3 Pa), forming an alloy cast ingot after the alloy is completely melted and cooled, turning over the alloy cast ingot, and repeatedly smelting for 4 times to obtain Zr 0.85 Ti 0.15 Ni 1. 2 Mn 0.56 V 0.12 Fe 0.12 A precursor;
(2) Mechanically crushing the precursor into 200-mesh powder by using a stainless steel mortar in a glove box;
(3) According to Zr 0.85 Ti 0.15 Mg 0.3 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The preparation method comprises the steps of weighing precursor powder and Mg powder (purity is more than or equal to 99.5%) according to the molecular formula of the alloy, mixing the precursor powder and the Mg powder uniformly by hand in a glove box, weighing 20g of mixed sample by using an analytical balance, and pressing the mixed sample into tablets with the diameter of 13mm by using a powder tablet press;
(4) Putting the pressed sheet into a stainless steel closed container in a glove box, and filling argon with the pressure of 0.4 MPa; and then sintering the alloy in an annealing furnace for one day, wherein the sintering temperature is 800 ℃, cooling the alloy to room temperature along with the furnace after sintering is completed, and removing the alloy to finally obtain the under-stoichiometric magnesium-containing C15 structure Laves phase room temperature reversible hydrogen storage high entropy alloy.
Zr 0.85 Ti 0.15 Mg 0.3 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The high entropy alloy consists of a C15Laves single phase (see FIG. 1: zr) 0.8 5 Ti 0.15 Mg 0.3 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 High entropy alloy X-ray diffraction (XRD) test pattern). Zr (Zr) 0.85 Ti 0.15 Mg 0.3 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 The high entropy alloy is capable of absorbing 1.0wt.% hydrogen at 303K temperature (see fig. 2: zr 0.85 Ti 0.15 Mg 0.3 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Constant temperature hydrogen absorption kinetics plot of the high entropy alloy at 303K temperature) and complete hydrogen release at 303K temperature (see fig. 3: zr (Zr) 0.85 Ti 0.15 Mg 0.3 Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Constant temperature hydrogen desorption kinetics curve graph of the high-entropy alloy at the temperature of 303K, which shows that the alloy has reversible hydrogen storage performance.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. A low-stoichiometric magnesium-containing C15-structure Laves-phase room-temperature reversible hydrogen storage high-entropy alloy is characterized in that the chemical formula of the material is Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Wherein x=0.2 to 0.4, B/a=1.4 to 1.7, the a-type elements include Zr, ti and Mg, and the B-type elements include Ni, mn, V and Fe.
2. The method for preparing the low-stoichiometric magnesium-containing C15 structural Laves phase room temperature reversible hydrogen storage high-entropy alloy according to claim 1, which is characterized by comprising the following steps:
1) Firstly pressing Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Weighing a certain amount of zirconium blocks, titanium blocks, vanadium blocks, iron blocks, nickel sheets and manganese sheets according to the molecular formula of the alloy; under argon atmosphere, the metal raw material is laid in a crucible from bottom to top according to the melting point from low to high, and then is mixed in a ratio of (0.3-1) x 10 -2 Arc vacuum smelting is carried out under Pa vacuum degree, alloy is completely melted and cooled to form an alloy cast ingot, the alloy cast ingot is turned over, and smelting is repeated for 3-4 times, so that a precursor sample of the hydrogen storage high-entropy alloy can be obtained;
2) Mechanically crushing the obtained precursor sample into precursor powder of 100-300 meshes by using a stainless steel mortar in a glove box;
3) According to Zr 0.85 Ti 0.15 Mg x Ni 1.2 Mn 0.56 V 0.12 Fe 0.12 Weighing precursor powder and Mg powder according to the molecular formula of the alloy, and mixing the precursor powder and the Mg powder in a glove box by hand uniformly;
4) Weighing a certain amount of mixed samples by using an analytical balance in a glove box, and pressing the mixed samples into tablets with the diameter of 10-15 mm by adopting a powder tablet press;
5) Putting the pressed sheet into a stainless steel closed container in a glove box, and filling argon with the pressure of 0.2-0.4 MPa; and then placing the alloy into an annealing furnace for sintering, cooling the alloy to room temperature along with the furnace after the sintering is completed, and taking out the alloy to finally obtain the low-stoichiometric magnesium-containing C15 structure Laves phase room-temperature reversible hydrogen storage high-entropy alloy.
3. The method according to claim 2, wherein in step 1), the purity of the zirconium piece is not less than 99.7%, the purity of the titanium piece is not less than 99.9%, the purity of the vanadium piece is not less than 99.9%, the purity of the iron piece is not less than 99.9%, the purity of the nickel piece is not less than 99.5%, and the purity of the manganese piece is not less than 99.5%.
4. The method according to claim 2, wherein in step 1), 2wt.% of titanium pieces and 5wt.% of manganese pieces are additionally added, taking into account the burning loss of the titanium pieces and manganese pieces during arc melting.
5. The method according to claim 2, wherein in step 3), the purity of the Mg powder is not less than 99.5%.
6. The method of claim 2, wherein in step 3), 20wt.% Mg powder is additionally added to compensate for the burn-out of Mg powder during subsequent sintering.
7. The method according to claim 2, wherein in step 5), the sintering temperature of the sintering process is 750 to 850 ℃ and the time is 12 to 48 hours.
8. The use of a low-stoichiometry mg-containing C15 structured Laves phase room temperature reversible hydrogen storage high entropy alloy according to claim 1 for hydrogen storage, characterized in that: before utilizing the hydrogen storage function of the high-entropy alloy, hydrogen is absorbed and released for 1-2 times at the temperature of 250 ℃ and the pressure of 3.5MPa, so that the activity of the hydrogen storage high-entropy alloy is obtained, and then the hydrogen storage high-entropy alloy can be used for hydrogen storage.
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