CN116607061A - Ti-Cr-Mn-based hydrogen storage alloy and preparation method thereof - Google Patents
Ti-Cr-Mn-based hydrogen storage alloy and preparation method thereof Download PDFInfo
- Publication number
- CN116607061A CN116607061A CN202310691261.1A CN202310691261A CN116607061A CN 116607061 A CN116607061 A CN 116607061A CN 202310691261 A CN202310691261 A CN 202310691261A CN 116607061 A CN116607061 A CN 116607061A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- alloy
- hydrogen storage
- storage alloy
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 289
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 289
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 164
- 239000000956 alloy Substances 0.000 title claims abstract description 164
- 238000003860 storage Methods 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 50
- 229910008651 TiZr Inorganic materials 0.000 claims abstract description 17
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 12
- 238000003723 Smelting Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000003578 releasing effect Effects 0.000 claims description 4
- 238000009841 combustion method Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 239000011232 storage material Substances 0.000 abstract description 19
- 238000007906 compression Methods 0.000 abstract description 18
- 230000006835 compression Effects 0.000 abstract description 18
- 238000003795 desorption Methods 0.000 abstract description 18
- 239000011572 manganese Substances 0.000 description 85
- 239000010936 titanium Substances 0.000 description 40
- 239000000463 material Substances 0.000 description 19
- 230000008859 change Effects 0.000 description 11
- 230000008901 benefit Effects 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000004576 sand Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910010169 TiCr Inorganic materials 0.000 description 2
- 229910010340 TiFe Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- FEPMHVLSLDOMQC-UHFFFAOYSA-N virginiamycin-S1 Natural products CC1OC(=O)C(C=2C=CC=CC=2)NC(=O)C2CC(=O)CCN2C(=O)C(CC=2C=CC=CC=2)N(C)C(=O)C2CCCN2C(=O)C(CC)NC(=O)C1NC(=O)C1=NC=CC=C1O FEPMHVLSLDOMQC-UHFFFAOYSA-N 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
-
- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- 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
-
- 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 discloses a Ti-Cr-Mn based hydrogen storage alloy and a preparation method thereof, wherein the general formula of the Ti-Cr-Mn based hydrogen storage alloy is (TiZr) 1+k Cr 2‑x‑y Mn x Fe y Wherein k represents the stoichiometric number of TiZr side, x and y respectively represent the atomic numbers of Mn and Fe, and the value range satisfies the following conditions: k is 0.01-0.05, x is 0.1-0.9, and y is 0.1-0.9. The platform pressure of the hydrogen storage alloy is controllable, and the hydrogen absorption and release pressure is less than or equal to 8MPa at room temperature; pressure of hydrogen absorption and desorption at above 90deg.C and below 100deg.C>25Ma; the pressure of the hydrogen discharge platform can be increased from 5MPa to about 27MPa in the temperature range of 298-363K, and the temperature range and the pressure range are particularly suitable for the primary hydrogen compression hydrogen storage material of the hydrogen compressor.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a Ti-Cr-Mn-based hydrogen storage alloy and a preparation method thereof.
Background
The high-density hydrogen storage material and the hydrogen compression material based on the resource advantages of China are created to meet the high-density safety hydrogen storage demand, and the high-density hydrogen storage material and the hydrogen compression material are the basis of a high-safety solid hydrogen storage and supply system for a hydrogen station. And a three-stage hydrogen compressor is adopted, the primary hydrogen compression hydrogen storage material is supplied with pressure of 25MPa, the middle-stage hydrogen compression hydrogen storage material is supplied with pressure of 35MPa, and the final-stage hydrogen compression hydrogen storage material is supplied with pressure of 85MPa. Mainly meets the filling pressure requirements of 35MPa and 70MPa of the hydrogenation station. The primary compression hydrogen storage material is required to be boosted from low pressure to 25MPa, and the material is critical in shape selection and preparation, and is the first link. The development platform hydrogen pressure highly matched high compression ratio static hydrogen compression material realizes that the equilibrium pressure of hydrogen release of the hydrogen compression material is 25, 45 and 85MPa respectively at the temperature lower than 100 ℃ is an important support for realizing large-scale utilization of hydrogen energy. Wherein, the hydrogen storage alloy for the primary hydrogen compressor of 25MPa and the preparation method are key links.
AB 2 The binary alloy has the advantages of large hydrogen storage amount, easy activation and good dynamic performance, and is concerned by the scientific and industrial circles. Zirconium is used as one of novel mineral resources of national strategy, and the external dependence is over 90 percent for a long time. In 2017, the yield of China is less than 1 ten thousand tons, the demand reaches 62.3 ten thousand tons, and the imported demand exceeds 100 ten thousand tons in 2020. The reserve of the Chinese zirconium resources is 50 ten thousand t and is less than 1% of the global reserve, and the zircon sand is mainly concentrated in southeast coastal areas represented by Wenchang in Hainan, wherein the reserve of the zircon sand in Hainan is 67% of the total reserve of the national sand, and 19% of the reserve of the national zirconium resources, and is the only coastal sand which can be exploited at present in China. Titanium resources in China are the first place in the world, and the total reserve of titanium resources is found to be about 20 hundred million tons at home and abroad, and the total reserve of titanium resources in China accounts for about 48 percent. There are 20 provincial municipalities in China with titanium ore 98.9% being ilmenite and only about 1% being rutile. Vanadium titano-magnetite is the largest reserve in China, accounts for 90% of national titanium resources, and is mainly distributed in Panzhihua and Maillard. Therefore, based on the resource advantage of China, the innovative preparation of the high-density hydrogen storage material and the hydrogen compression material should take priority of titanium-based AB 2 Hydrogen storage materials.
In addition, the hydrogen absorbing and releasing material requirement of the metal hydride hydrogen booster suitable for high pressure gradeIs obviously different from the working temperature range and the corresponding hydrogen absorption and desorption rate required by the hydrogen absorption and desorption materials of the metal hydride hydrogen booster with low pressure level. The compressed material adopts rare earth system AB at present 5 AB-type and ilmenite-type materials, e.g. LaNi 5 ，LaNi 4.63 Al 0.37 ，TiFe，TiFe 0.9 Mn0.1, etc. These materials generally have the lowest capacity (1.5 to 1.8 mass%) and require temperatures above 150 ℃ to reach 20MPa, and are therefore not suitable for use as chemical hydrogen compression materials to achieve greater than 20 MPa. Wang Xinhua A Ti-Mn/Ti-Cr multi-element hydrogen storage alloy for metal hydride hydrogen compressor was studied, and a pair of hydrogen storage alloys (Ti) 0.95 Zr 0.15 )(Mn 1.1 Cr 0.7 V 0.2 ) And (Ti) 0.95 Zr 0.07 )(Cr 1.4 Mn 0.4 Fe 0.1 Cu 0.1 ) The alloy is used as low-pressure level alloy and high-pressure level alloy of a two-stage heat driven chemical hydrogen compressor, and hydrogen with the pressure of 2.5MPa can be compressed to more than 40MPa by taking water as heat exchange stop. Research shows that at 30 ℃, ti 0.83 V 0.08 Nb 0.25 Mn 1.17 Ni 0.60 Al 0.07 The compound absorbs hydrogen at 24.2MPa and the hydride is heated to 124 c, which will release hydrogen at a rate of 80 MPa. Therefore, three different hydrogen storage materials for hydrogen compressors cannot be used in common. For example, medium-grade hydrogen compressed (i.e., medium-grade hydrogen compressed) hydrogen storage materials cannot be applied to primary hydrogen compression.
At present, the problems of the primary hydrogen compression hydrogen storage machine are focused on the problems of high cost, low hydrogen absorption and desorption capacity, lag in hydrogen absorption and desorption, difficulty in activation and the like under the pressure of 25MPa of a hydrogen desorption platform at the temperature lower than 100 ℃.
Disclosure of Invention
Based on the resource advantages of China and the actual application demands of hydrogen compression materials, the invention provides a Ti-Cr-Mn-based hydrogen storage alloy and a preparation method thereof, zr and Fe elements with higher abundance in crust are added into the Ti-Cr-Mn alloy, and the content of each metal is adjusted, so that the prepared hydrogen storage alloy has low cost, controllable platform pressure, easy activation and high hydrogen storage capacity, and meets the actual application demands of high-density hydrogen storage materials and hydrogen compression materials based on the resource advantages of China. The hydrogen storage alloy has the characteristics of low cost and controllable platform pressure, and is a nickel-free hydrogen storage material suitable for large-scale engineering application.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a Ti-Cr-Mn-based hydrogen storage alloy has a general formula (TiZr) 1+k Cr 2-x-y Mn x Fe y Wherein k represents an A-side superstoichiometric number, x, y and z represent the atomic numbers of Mn and Fe respectively, and the value range satisfies the following conditions: k is 0.01-0.05 (e.g., 0.02, 0.03, 0.04), x is 0.1-0.9 (e.g., 0.2, 0.3,0.4, 0.5, 0.6, 0.7, 0.8), y is 0.1-0.9 (e.g., 0.2, 0.3,0.4, 0.5, 0.6, 0.7, 0.8), wherein side A refers to TiCr 2 The Ti side in the hydrogen storage alloy corresponds to the general formula (TiZr) 1+k Cr 2-x-y Mn x Fe y In (TiZr) 1+k Side, B side is TiCr 2 Cr side in the hydrogen storage alloy corresponds to the general formula (TiZr) 1+k Cr 2-x-y Mn x Fe y Cr in (B) 2-x-y Mn x Fe y And (3) sides.
As a preferable implementation mode, the Ti-Cr-Mn-based hydrogen storage alloy consists of a C14 type hexagonal Laves type structure, zr and Fe are doped in a Ti-Cr-Mn matrix according to a proportion, and the doping mole number of Fe can be smaller than, equal to or larger than Mn, so that the alloy can be effectively regulated and controlled to regulate the hydrogen storage capacity and the plateau pressure.
At the (TiZr) 1+k Cr 2-x-y Mn x Fe y In the alloy, zr is selected to replace part of Ti on the side A, the side A is subjected to stoichiometric quantity, and the range of the stoichiometric quantity k is 0.01-0.05; mn and Fe are selected to replace Cr on the B side.
In the invention, because Zr and Ti belong to the same transition element of the subgroup and have the same outer layer electronic structure,atomic radius of greater than->Zr replaces part of Ti atoms in the alloy, thereby increasing the unit cell volume and increasing the hydrogen absorption capacity. The over-stoichiometric amount of the A-side element has obvious effect on improving the hydrogen absorption and activation performance of the alloy. With the increase of Ti over-stoichiometry, the alloy activation performance is obviously improved, meanwhile, the unit cell volume of the alloy is increased, the hydrogen absorption amount of the alloy is increased, and the platform pressure is reduced.
The above Ti-Cr-Mn-based hydrogen occluding alloy as a preferred embodiment, is described in the (TiZr) 1+k Cr 2-x- y Mn x Fe y In the hydrogen storage alloy, mn and Fe are selected for the B side to replace part of Cr element; wherein the range x of Mn to Cr is selected to be 0.1-0.9, i.e., the atomic number of Mn in the hydrogen storage alloy is in the range of 0.1-0.9. Since part of Cr is replaced by Mn, the properties of the main phase intermetallic compound and the corresponding hydride change. The addition of Mn easily forms defects in the phase transition process, namely active sites in the hydrogenation reaction, and the existence of the active sites improves the activation performance and the kinetic performance. Meanwhile, since the electronegativity of Mn is lower than that of Cr, the alloy plateau pressure is reduced. Preferably, x is 0.15-0.6 (e.g., 0.15,0.3,0.45, 0.6).
The above Ti-Cr-Mn-based hydrogen occluding alloy as a preferred embodiment, is described in the (TiZr) 1+k Cr 2-x- y Mn x Fe y The range y of the Fe substituting part Cr in the alloy is selected to be 0.1-0.9, namely, the atomic number of Fe in the hydrogen storage alloy is 0.1-0.9.Fe is a transition metal, is an important component element of the hydrogen storage alloy, is commonly used for adjusting the acting force between metals of the alloy, and can not directly react with hydrogen, but can adjust the acting force between the alloy and the hydrogen, thereby improving the dynamic performance of hydrogen absorption and hydrogen release. Preferably, y is 0.3-0.5 (e.g., 0.35, 0.4, 0.45).
In a preferred embodiment, the atomic number ratio (or molar ratio) of the Ti element to the Zr element in the above-mentioned Ti-Cr-Mn-based hydrogen storage alloy is (0.90-0.95): (0.07-0.12), for example, 0.90:0.12, 0.91:0.11, 0.92:0.10, 0.93:0.09, 0.94:0.08, 0.95:0.07.
In a preferred embodiment of the above-described Ti-Cr-Mn-based hydrogen occluding alloy, the atomic number ratio (or molar ratio) of the Ti element to the Zr element is 0.92:0.1.
The above Ti-Cr-Mn-based hydrogen occluding alloy having the general formula Ti as a preferred embodiment 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 Wherein x is 0.15-0.6 (e.g., 0.15,0.3,0.45, 0.6).
As a preferred embodiment, the Ti-Cr-Mn-based hydrogen storage alloy is at 298K, (TiZr) 1+k Cr 2-x- y Mn x Fe y The hydrogen absorption platform pressure of the alloy is 4.3-8 MPa, preferably 5-8 MPa (for example, 5.5MPa, 6MPa, 7MPa, 7.5MPa, 7.82 MPa), and the hydrogen release platform pressure is 3.2-7 MPa, preferably 5-7 MPa (for example, 5.5MPa, 6MPa, 6.5MPa, 6.8 MPa); the hydrogen absorption platform pressure is 26-29.5 MPa under 363K, and the hydrogen release platform pressure is 25-28 MPa (for example, 25.5MPa, 26MPa, 27MPa, 27.21MPa and 27.5 MPa).
The Ti-Cr-Mn-based hydrogen storage alloy adopts the component formulation and the engineering preparation technology of the invention as a preferable implementation mode, (TiZr) under 298K 1+k Cr 2-x-y Mn x Fe y The alloy has a mass hydrogen storage density of 1.6-1.8 wt.% and a volume hydrogen storage density of 100-120 kg/m 3 The slope of the platform is 0.3-0.31, the pressure of 363K hydrogen release platform is 26.5-27.4 MPa, the hydrogen storage capacity deviation between batches of hundred kilogram-level hydrogen storage and supply materials prepared in batches is 2.6-2.62%, and the cost is lower than 45 yuan/kg.
The above Ti-Cr-Mn-based hydrogen occluding alloy having the general formula Ti as a preferred embodiment 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 At 298K, ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The alloy hydrogen absorption platform pressure is 7.82MPa, and the volume hydrogen storage density is 115.53kg/m 3 The hydrogen absorption platform pressure is 29.19MPa when the platform slope is 0.31 and 363K, the hydrogen release platform pressure is 27.21MPa, the hydrogen storage capacity deviation among batches of hundred kilogram-level hydrogen storage and supply materials prepared in batches is 2.62%, and the cost is lower than 45 yuan/kg.
The invention also provides a preparation method of the Ti-Cr-Mn-based hydrogen storage alloy, which comprises the following steps:
alloy preparation: weighing the metal element elements according to the alloy component formula, and preparing the alloy by an arc melting method, a vacuum melting method, a magnetic suspension melting method or a hydrogenation combustion method.
In the above-mentioned preparation method of Ti-Cr-Mn-based hydrogen storage alloy, as a preferred embodiment, the ingot raw materials of the elemental metal elements are weighed according to a proportion and put into arc melting, the melting furnace chamber is cleaned three times with inert gas (for example, high purity argon (99.99%)), then vacuum is pumped (for example, vacuum pumping is carried out for 2 hours), inert gas is again filled for protection, and the hydrogen storage alloy is obtained through turning over and melting, preferably, 4 to 5 times of turning over and melting are carried out to ensure the uniformity of the components of the hydrogen storage alloy.
In the above method for producing a Ti-Cr-Mn-based hydrogen storage alloy, as a preferred embodiment, the temperature of the turnover smelting is 1500 to 1800 ℃ (for example, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃, 1750 ℃), and the single turnover smelting time is 2 to 5 minutes (for example, 3 minutes, 4 minutes).
In the above-described method for producing a Ti-Cr-Mn-based hydrogen storage alloy, as a preferred embodiment, the purity of all elemental substances is 99.5% or more.
In the above-mentioned preparation method of Ti-Cr-Mn-based hydrogen storage alloy, as a preferred embodiment, since the saturated vapor pressure of Mn is high, component deviation is easily caused by volatilization in the smelting process, and a proper amount of excessive Mn is added into the raw material to compensate for the loss in the smelting process.
In the above-mentioned method for producing a Ti-Cr-Mn-based hydrogen storage alloy, as a preferred embodiment, the method further comprises an alloy activation step of:
heating the alloy to an activation temperature, vacuumizing to remove water attached to the surface of the alloy and residual hydrogen in the alloy after hydrogen release, then filling 9MPa hydrogen (purity is 99.999%) into a system at normal temperature to perform hydrogen absorption activation, enabling an alloy sample to react with the hydrogen, vacuumizing the system for 30min after the sample is saturated by hydrogen absorption, enabling the alloy to release hydrogen completely, and completing a hydrogen absorption-hydrogen release process, wherein the hydrogen absorption-hydrogen release process is repeated for more than 2 times to ensure the alloy to be activated completely, and the alloy is activated completely.
In the above method for producing a Ti-Cr-Mn-based hydrogen storage alloy, in the alloy activation step, the activation temperature is 25 to 500 ℃ (e.g., 50 ℃, 100 ℃, 200 ℃, 300 ℃, 400 ℃, 450 ℃, 480 ℃), and the evacuation time is 0.5 to 5 hours (e.g., 1 hour, 2 hours, 3 hours, 4 hours, 4.5 hours).
In the preparation method of the Ti-Cr-Mn-based hydrogen storage alloy, as a preferred implementation manner, in the alloy activation step, the alloy is heated to 400 ℃ and vacuumized for 4 hours to remove moisture attached to the surface of the alloy and residual hydrogen in the alloy after hydrogen release, then 9MPa hydrogen (purity 99.999%) is filled into a system at normal temperature to perform hydrogen absorption activation, so that an alloy sample reacts with the hydrogen, after the sample is saturated by hydrogen absorption, the system is vacuumized for 30 minutes to enable the alloy to release hydrogen completely, and a hydrogen absorption-hydrogen release process is completed, and in order to ensure complete activation of the alloy, the hydrogen absorption-hydrogen release process is repeated for more than 2 times, and the alloy is completely activated.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the Ti-Cr-Mn-based hydrogen storage alloy has no rare earth element, no noble metal such as metallic cobalt, nickel and the like, so the alloy elements are all elements with abundant mineral resources, the cost is low, the price cost is lower than 45 yuan/kg, the cost is far lower than the high cost of more than 100 yuan/kg of the rare earth hydrogen storage alloy, and the price advantage is obvious;
2. according to the Ti-Cr-Mn-based hydrogen storage alloy, the platform pressure is controllable (namely, the platform pressure can be controlled to be equal to or less than 8MPa, the hydrogen absorption and desorption pressure is more than 90 ℃ and less than 100 ℃, and the hydrogen absorption and desorption pressure is more than 25 Ma) at the room temperature, the hydrogen desorption platform pressure can be increased to about 27MPa from 5MPa in the temperature range of 298-363K, and the temperature range and the pressure range are particularly suitable for primary hydrogen compression hydrogen storage materials of a hydrogen compressor;
3. the invention develops a series of Ti 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 (x=0.15, 0.3,0.45, 0.6) hydrogen storage material, obtaining optimal component formulation and engineering preparation technique; for exampleAt 298K, ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The alloy hydrogen absorption platform pressure is 7.82MPa, the mass hydrogen storage density is 1.79wt.%, and the volume hydrogen storage density is 115.53kg/m 3 The platform slope is 0.31, 363K hydrogen release platform pressure is 27.21MPa, the hydrogen storage capacity deviation between batches of hundred kilogram-level hydrogen storage and supply materials prepared in batches is 2.62%, and the cost is 40.42 yuan/kg; meets the requirements of the demonstration engineering and practical application of the hydrogen storage material for the primary compressor.
Drawings
FIG. 1 shows Ti as in examples 1-4 of the invention 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 PCT hydrogen absorption/desorption profiles of the alloys at temperatures of 298K,308K and 318K, where x is 0.15 (fig. 1 a), 0.3 (fig. 1 b), 0.45 (fig. 1 c) and 0.6 (fig. 1 d), respectively.
FIG. 2 is Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 A graph of (a) PCT hydrogen absorption/desorption curves and (b) plateau pressure versus temperature for alloys at temperatures between 298 and 363K.
FIG. 3 is Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 Van't Hoff plot of hydrogen storage alloy, wherein, (a) hydrogen is absorbed and (b) hydrogen is released.
FIG. 4 is Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 RMC plot of alloy.
FIG. 5 is a diagram of different batches of Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 PCT hydrogen absorption/desorption profile of the alloy.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art without making any inventive effort, are intended to be within the scope of the present invention, based on the examples herein.
Example 1
Example 1 provides a Ti-Cr-Mn-based hydrogen storage alloy of the general formula (TiZr) 1+k Cr 2-x-y Mn x Fe y Where k=0.02 and y=0.4, i.e. the hydrogen storage alloy has the general formula Ti 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 When x is 0.15,0.3,0.45 and 0.6, respectively.
The preparation method, activation and hydrogen absorption-desorption performance of the Ti-Cr-Mn-based hydrogen storage alloy are tested as follows.
(1) Alloy preparation
Raw materials with the purity higher than 99.5 weight percent are weighed according to the proportion and put into arc melting, a melting furnace chamber is washed three times by high-purity argon (99.99 percent), then the furnace chamber is vacuumized for 2 hours, a certain amount of high-purity argon (99.99 percent) is filled for protection, and the alloy is melted for 4 to 5 times through turning over to ensure the uniformity of components; the surface oxide layer of the obtained as-cast alloy is removed by sand paper polishing, and the as-cast alloy is put into a glove box (H) protected by argon atmosphere after being cleaned by absolute alcohol 2 O<3ppm，O 2 <5 ppm) was crushed into powder and sieved through a 200 mesh sieve, and the undersize was taken.
(2) Activation and hydrogen absorption-desorption performance test of hydrogen storage alloy
The above hydrogen absorbing alloy samples were activated and tested for hydrogen absorbing-releasing properties using a PCT tester manufactured by Suzuki shakang corporation, japan. Before the alloy is activated, the block sample is mechanically crushed into fine particles with 200 meshes or more, so that the alloy exposes a larger fresh surface to facilitate the reaction of the hydrogen storage alloy and hydrogen, and 2g of hydrogen storage alloy powder is filled into a sample chamber of a PCT tester.
The sample activation is to heat the crushed hydrogen storage alloy powder to 400 Jin Gaowen and vacuumize for 4 hours to remove water attached to the surface of the hydrogen storage alloy and residual hydrogen in the hydrogen storage alloy after hydrogen release, then to charge 9MPa hydrogen (purity 99.999%) into the system at normal temperature for hydrogen absorption activation to enable the hydrogen storage alloy sample to react with the hydrogen, and vacuumize the system for 30 minutes after the sample is saturated in hydrogen absorption to enable the hydrogen storage alloy to completely release hydrogen, so that a hydrogen absorption-hydrogen release process is completed, and in order to ensure the hydrogen storage alloy to be completely activated, the hydrogen absorption-hydrogen release process is repeated for more than 2 times to enable the hydrogen storage alloy to be completely activated, and pressure-concentration-temperature (P-C-T) curve test is carried out on the hydrogen storage alloy at different temperatures to study the heat absorption-heat release mechanical and dynamic properties of the hydrogen storage alloy.
FIG. 1 shows Ti in example 1 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 (x=0.15, 0.3,0.45, 0.6) hydrogen absorption and desorption PCT curve test results of hydrogen storage alloy at 298K,308K and 318K temperatures.
As can be seen from FIG. 1, in the hydrogen storage alloy, mn partially replaces Cr, and as the Mn atomic number (content) increases, the hydrogen absorption/desorption plateau pressure of the hydrogen storage alloy increases, and when the Mn atomic number increases from 0.15 (FIG. 1 a) to 0.6 (FIG. 1 d), the hydrogen storage alloy increases significantly from 4.32MPa to 7.82MPa at 298K while the hydrogen absorption plateau pressure increases from 3.21MPa to 6.67MPa due to Mn (atomic radius: 127pm, covalent radius: 117 pm) being smaller than Cr (atomic radius: 128pm, covalent radius: 118 pm) radius, with a related reduction in unit cell volume. When the Mn atomic number is 0.6, the hydrogen absorption temperature is increased from 298K to 318K, the hydrogen absorption pressure is increased from 7.82MPa to 12.59MPa, and the hydrogen release platform pressure is increased from 6.67MPa to 10.57MPa. In the temperature range 298K-318K, mn stoichiometry increases from 0.15 to 0.6, with no significant change in maximum hydrogen storage capacity (hydrogen storage capacity, i.e., mass hydrogen storage density) and reversible hydrogen storage capacity. 298K, the maximum hydrogen storage capacity at Mn stoichiometry of 0.6 is 1.79wt.%. Therefore, the Mn content has no obvious effect on the hydrogen storage capacity, and mainly regulates and controls the platform pressure and the activation performance of the material. .
Table 1 lists Ti 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 (x=0.15, 0.3,0.45, 0.6) kinetic performance parameters of the alloy. H f As a hysteresis factor, H f ＝ln(P a /P d )，P a P is the pressure of the hydrogen absorption platform d For the pressure of the hydrogen discharge platform, a larger hysteresis factor causes energy loss, and the lost energy is used for overcoming micro-strain in the process of hydrogen absorption and desorption; s is S f Is the slope factor S f ＝ln(P 2 /P 1 )，P 1 For the left end pressure of the platform, P 2 The right end point pressure of the platform; h Max To maximum hydrogen absorption amount, H Re Can be made intoReverse hydrogen absorption amount.
TABLE 1Ti 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 (x= 0.15,0.3,0.45,0.6) kinetic performance parameters of hydrogen occluding alloy
As can be seen from Table 1, at 298K, the slope factors S of the four alloys f The Mn content in the alloy is gradually reduced from 0.48, and the slope factor S f Are all less than 0.5.Ti (Ti) 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The hysteresis factor and the slope factor of the alloy are 0.16 and 0.31, respectively. The smaller the slope factor, the smaller the difference in hydrogen bonding ability of these gap sites (gap sites refer to interatomic gaps between metal chemicals), facilitating the release of hydrogen. As can be seen from a combination of the PCT curve (FIG. 1) and Table 1, the hysteresis (H f ) Are very small, and the platform hysteresis factor is increased from 0.11 in the Ti-Zr-Cr-Mn-Fe alloy along with the increase of Mn content, but the platform hysteresis factor is H f Are all less than 0.2. Thus Ti is 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The alloy has excellent comprehensive performance.
FIG. 2 shows Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 Alloy (a) PCT curve of alloy at 298-363K temperature and (b) plateau pressure curve with temperature.
As can be seen from FIG. 2, as the operating temperature increases, ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The platform pressure of the alloy increases monotonically and the hydrogen storage capacity decreases gradually. Ti (Ti) 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The corresponding hydrogen discharge platform pressures of the alloy at 298, 308, 318, 353 and 363K are 6.67MPa, 8.27MPa, 10.57MPa, 22.05MPa and 27.21MPa respectively; the hydrogen storage capacities (mass hydrogen storage densities) are respectively: 1.77 wt.%, 1.74 wt.%, 1.69wt.%, 1.61 wt.% and 1.54wt.%. At 298, 308, 318, 353 andthe corresponding hydrogen absorption platform pressures at 363K are 7.82MPa, 10.20MPa, 12.59MPa, 23.09MPa and 29.19MPa, respectively.
FIG. 3 shows Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 A Van't Hoff plot of a hydrogen storage alloy, wherein (a) is hydrogen absorption; (b) is hydrogen release.
In the invention, the relationship between the equilibrium pressure of hydrogen absorption and hydrogen release and the temperature of the hydrogen storage material accords with Van't Hoff equation: RLnPH 2 ＝ΔH 0 /T-ΔS 0 Wherein the pH is 2 Represents the hydrogen equilibrium pressure, deltaS 0 Represents entropy change, R is molar gas constant 8.314J/(mol.K), and ΔH 0 Enthalpy of hydride formation is an important parameter characterizing hydride stability; the van't Hoff curve of the alloy is obtained according to the hydrogen absorption platform pressure of the alloy at different temperatures, and the enthalpy change value and the entropy change value of the hydrogen absorption and desorption reaction are shown in table 2.
As can be seen from table 2, as the manganese content increases, both the enthalpy change and the entropy change of the hydride monotonically decrease, indicating that the hydride stability decreases. The number of manganese atoms is increased from 0.15 to 0.6, the hydrogen release enthalpy change delta Hd is reduced from 25.06kJ/mol to 19.50kJ/mol, and the entropy change delta Sd is reduced from 112.8kJ/mol to 100.12kJ/mol. Ti (Ti) 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The alloy has an enthalpy change and entropy change of hydride absorption of 17.30kJ/mol and 94.64J.mol, respectively -1 .K -1 The formation of an ordered hydride phase structure is shown to meet practical application requirements from the standpoint of energy efficiency.
TABLE 2Ti 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 Thermodynamic properties of (x= 0.15,0.3,0.45,0.6) hydrogen storage alloy
FIGS. 4 and 5 show Ti, respectively 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 RMC curve of Hydrogen storage alloy and different batches of Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 PCT yeast of hydrogen storage alloyA wire. As can be seen from FIG. 4, the alloy has very high hydrogen absorption speed, can absorb hydrogen for saturation at 298K for 168s, has excellent hydrogen absorption kinetic performance, and has a hydrogen storage capacity of 1.794wt%. As can be seen from FIG. 5, 5 batches of Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The maximum hydrogen storage capacity of the hydrogen storage alloy is 1.750wt%, 1.794wt%, 1.778wt%, 1.797wt% and 1.762wt%, and the maximum deviation of the hydrogen storage capacities of different batches is 2.62% and less than 3% of the assessment index. Accounting is carried out according to the price of the raw materials in 2019, and Ti is further known by further calculating the unit price of Ti, zr, cr, mn and Fe raw materials 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The price of the alloy is 40.42 yuan/kg, and the alloy has obvious price advantage.
In conclusion, the Ti-Cr-Mn-based hydrogen storage alloy developed by the invention has the characteristics of low cost and controllable platform pressure, and meets the actual application requirements of high-density hydrogen storage materials and hydrogen compression materials based on the advantages of resources in China, namely, the requirements of primary hydrogen compressors for hydrogenation stations.
Claims (10)
1. A Ti-Cr-Mn-based hydrogen storage alloy is characterized in that the general formula of the hydrogen storage alloy is (TiZr) 1+k Cr 2-x- y Mn x Fe y Wherein k represents the stoichiometric number of TiZr side, x and y respectively represent the atomic numbers of Mn and Fe, and the value range satisfies the following conditions: k is 0.01-0.05, x is 0.1-0.9, and y is 0.1-0.9.
2. The Ti-Cr-Mn-based hydrogen storage alloy of claim 1, wherein the Ti-Cr-Mn-based hydrogen storage alloy consists of a C14 type hexagonal Laves type structure with Zr and Fe doped in proportion in a Ti-Cr-Mn matrix.
3. The Ti-Cr-Mn-based hydrogen storage alloy according to claim 1 or 2, wherein in the (TiZr) 1+k Cr 2-x- y Mn x Fe y In the hydrogen storage alloy, mn and Fe are selected to replace part of Cr element; wherein the atomic number range x of Mn is 0.1 to 0.9, preferably 0.15 to 0.6; and/or the number of the groups of groups,
the atomic number y of Fe is in the range of 0.1 to 0.9, preferably 0.3 to 0.5; and/or the number of the groups of groups,
in the hydrogen storage alloy, the atomic number ratio of Ti element to Zr element is (0.90-0.95): 0.07-0.12; preferably, the atomic number ratio of the Ti element to the Zr element is 0.92:0.1.
4. A Ti-Cr-Mn-based hydrogen storage alloy according to claim 3, wherein the hydrogen storage alloy has the general formula Ti 0.92 Zr 0.1 Cr 1.6-x Mn x Fe 0.4 Wherein x is 0.15-0.6.
5. The Ti-Cr-Mn-based hydrogen storage alloy according to any one of claims 1 to 4, wherein at 298K temperature, (TiZr 1+k Cr 2-x-y Mn x Fe y The hydrogen absorption platform pressure of the hydrogen storage alloy is 4.3-8 MPa, preferably 5-8 MPa, and the hydrogen release platform pressure is 3.2-7 MPa, preferably 5-7 MPa; the pressure of the hydrogen discharging platform is 25-28 MPa at 363K;
preferably, at 298K temperature, (TiZr) 1+k Cr 2-x-y Mn x Fe y The alloy has a mass hydrogen storage density of 1.6-1.8 wt.% and a volume hydrogen storage density of 100-120 kg/m 3 The platform slope is 0.3-0.31, 363K hydrogen releasing platform pressure is 26.5-27.4 MPa.
6. The Ti-Cr-Mn-based hydrogen storage alloy according to claim 4, wherein the hydrogen storage alloy has a general formula of Ti 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The Ti is 0.92 Zr 0.1 Cr 1.0 Mn 0.6 Fe 0.4 The hydrogen absorption platform pressure of the alloy is 7.82MPa at 298K, the hydrogen release platform pressure is 6.67MPa, and the volume hydrogen storage density is 115.53kg/m 3 The hydrogen absorption platform pressure is 29.19MPa and the hydrogen release platform pressure is 27.21MPa when the platform slope is 0.31 and 363K.
7. A method for producing a Ti-Cr-Mn-based hydrogen storage alloy according to any one of claims 1 to 6, comprising:
and an alloy preparation step, namely weighing the elementary substances of each metal element according to the alloy component formula, and preparing the alloy by an arc melting method, a vacuum melting method, a magnetic suspension melting method or a hydrogenation combustion method.
8. The method for producing a Ti-Cr-Mn-based hydrogen storage alloy according to claim 7, wherein in the alloy production step, the ingot raw materials of the elemental metal elements are weighed in proportion and put into arc melting, the melting furnace chamber is cleaned three times with inert gas, then vacuumized, then again filled with inert gas for protection, and the hydrogen storage alloy is obtained through turning-over melting, preferably 4 to 5 times of turning-over melting;
preferably, in the alloy preparation step, the smelting temperature of the turning smelting is 1500-1800 ℃ and the single-time turning smelting time is 2-5 min;
preferably, the purity of all elemental substances is above 99.5%;
preferably, during smelting, an excess of Mn is added to the raw materials to compensate for losses during smelting.
9. The method for producing a Ti-Cr-Mn-based hydrogen storage alloy according to claim 7 or 8, further comprising:
an alloy activation step, namely heating the alloy to an activation temperature, vacuumizing, then filling 9MPa hydrogen into a system at normal temperature for hydrogen absorption activation, vacuumizing the system for 30min after a sample is saturated in hydrogen absorption, and completely releasing hydrogen from the alloy to complete a hydrogen absorption-hydrogen release process;
preferably, in the alloy activation step, the activation temperature is 25-500 ℃, and the vacuumizing time is 0.5-5 h.
10. The method for producing a Ti-Cr-Mn-based hydrogen storage alloy according to claim 9, wherein in the alloy activation step, the alloy is heated to 400 ℃ and evacuated for 4 hours, then hydrogen of 9MPa is filled into the system at normal temperature for hydrogen absorption activation, and after the sample is saturated by hydrogen absorption, the system is evacuated for 30 minutes to allow the alloy to be completely released, thereby completing a hydrogen absorption-hydrogen release process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310691261.1A CN116607061A (en) | 2023-06-12 | 2023-06-12 | Ti-Cr-Mn-based hydrogen storage alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310691261.1A CN116607061A (en) | 2023-06-12 | 2023-06-12 | Ti-Cr-Mn-based hydrogen storage alloy and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116607061A true CN116607061A (en) | 2023-08-18 |
Family
ID=87674609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310691261.1A Pending CN116607061A (en) | 2023-06-12 | 2023-06-12 | Ti-Cr-Mn-based hydrogen storage alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116607061A (en) |
-
2023
- 2023-06-12 CN CN202310691261.1A patent/CN116607061A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Dehydriding properties of ternary Mg2Ni1− xZrx hydrides synthesized by ball milling and annealing | |
| CN113215467B (en) | Solid hydrogen storage material for hydrogen filling station and preparation method and application thereof | |
| CN111636012B (en) | La-Mg-Ni series hydrogen storage material and preparation method thereof | |
| EP1243041B1 (en) | Modified magnesium based hydrogen storage alloys | |
| CN112877567B (en) | Hydrogen storage alloy suitable for low-pressure solid hydrogen storage and preparation method thereof | |
| CN112899548A (en) | Yttrium-zirconium-iron-aluminum alloy material, preparation method and application | |
| JP6367477B2 (en) | CaMg2 alloy hydride as a hydrogen generating material, its preparation method, and its application | |
| CN116607061A (en) | Ti-Cr-Mn-based hydrogen storage alloy and preparation method thereof | |
| CN111485165A (en) | Yttrium-scandium-iron alloy material, yttrium-titanium-scandium-iron alloy material, preparation method and application | |
| CN114293046B (en) | Preparation method of porous titanium/zirconium-based hydrogen storage alloy for powder metallurgy with low oxygen content | |
| CN114645179B (en) | Hydrogen storage alloy for 25MPa primary hydrogen compressor and preparation method thereof | |
| CN111074127B (en) | Ce-Mg-Ni low-pressure hydrogen storage alloy material and preparation method thereof | |
| JPS626739B2 (en) | ||
| CN108796326B (en) | A kind of MgAl based hydrogen storage material of catalyst enhancing | |
| CN109097612B (en) | High-pressure hydrogen storage alloy for hydrogen storage and preparation method thereof | |
| CN114671403B (en) | Ti-Mn-Fe hydrogen storage material and preparation method thereof | |
| JP3752987B2 (en) | Hydrogen storage alloy | |
| JPH055137A (en) | Hydrogen storing alloy member and its production | |
| Ivey et al. | Hydriding properties of Zr (FexCr1− x) 2 intermetallic compounds | |
| CN116162836A (en) | Hydrogen storage alloy and preparation method thereof | |
| EP4129535A1 (en) | Ab2 type-based hydrogen storage alloys, methods of preparation and uses thereof | |
| EP4129534A1 (en) | Ab5-type based hydrogen storage alloys, methods of preparation and uses thereof | |
| JPH0570693B2 (en) | ||
| CN115838882A (en) | Hydrogen compression rare earth hydrogen storage material and preparation method thereof | |
| CN117943548A (en) | TiFe hydrogen storage alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |