CN107099724B - The preparation method of nanometer titanium trifluoride catalysis Mg-RE-Ni-Al-Ti-Co base hydrogen-storing alloy - Google Patents
The preparation method of nanometer titanium trifluoride catalysis Mg-RE-Ni-Al-Ti-Co base hydrogen-storing alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 142
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- NLPMQGKZYAYAFE-UHFFFAOYSA-K titanium(iii) fluoride Chemical compound F[Ti](F)F NLPMQGKZYAYAFE-UHFFFAOYSA-K 0.000 title abstract description 3
- 238000006555 catalytic reaction Methods 0.000 title abstract 2
- 239000001257 hydrogen Substances 0.000 claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 95
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000003860 storage Methods 0.000 claims abstract description 57
- 229910010348 TiF3 Inorganic materials 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 238000005275 alloying Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000010936 titanium Substances 0.000 abstract description 54
- 238000003795 desorption Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000011777 magnesium Substances 0.000 description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 238000010521 absorption reaction Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010791 quenching Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 150000002910 rare earth metals Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000713 high-energy ball milling Methods 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- B22F1/0003—
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention relates to the preparation method of the Mg-RE-Ni-Al-Ti-Co base hydrogen-storing alloy of a kind of nanometer of titanium trifluoride catalysis, chemical compositions are as follows: Mg18‑x‑yLaxREyNi2‑z‑mAlzTim+ 50 (wt) %Co+n (wt) %TiF3；Wherein, x, y, z, m are atomic ratio, 1 < x < 3,0.2 < y < 1,0 < z < 1,0 < m < 1, n TiF3Account for Mg18‑x‑ yLaxREyNi2‑z‑mAlzTimMass percent, 3 < n < 8；RE includes at least one of rare earth element ce, Nd, Y, Sm and Gd.Hydrogen-storage alloy provided by the invention has high hydrogen storage capacity and excellent dynamic performance, not only has high suction hydrogen release ability at a lower temperature, but also inhales hydrogen desorption kinetics performance and also increase substantially.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a nano TiF3A preparation method of a catalytic Mg-RE-Ni-Al-Ti-Co based hydrogen storage alloy.
Background
Metal hydrides are considered as ideal hydrogen fuel carriers for fuel cells due to efficient and safe hydrogen storage properties, but none of the currently commercialized hydrogen storage materials can meet the requirements of fuel cells in terms of hydrogen storage capacity. Magnesium-based alloys are known as the most potential hydrogen storage materials due to their high hydrogen storage density and abundant resources. Wherein Mg17La2The hydrogen storage capacity of the type alloy is about 6 wt%, and as for its hydrogen storage capacity, it completely satisfies the capacity requirement of the fuel cell. However, crystalline Mg17La2The alloy has almost no hydrogen releasing capacity at room temperature, and the hydrogen absorbing and releasing kinetics of the alloy prepared by the conventional casting process is extremely poor. Therefore, how to reduce the thermal stability of alloy hydride and improve the hydrogen absorption and desorption kinetics of alloy becomes a serious challenge for researchers.
Based on this, it is important to research a new hydrogen storage alloy having high hydrogen absorption and desorption capacity and excellent hydrogen absorption and desorption kinetic properties.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nano TiF3A preparation method of a catalytic Mg-RE-Ni-Al-Ti-Co based hydrogen storage alloy. The hydrogen storage alloy provided by the invention adopts multi-element rare earth, adds a certain amount of nickel, aluminum and titanium, is mixed with cobalt powder for ball milling, and a small amount of nano TiF is added in the ball milling process3As catalyst, nanocrystalline-amorphous Mg with high hydrogen storage capacity and excellent kinetic properties is obtained17La2The hydrogen storing alloy has high hydrogen absorbing and releasing capacity at relatively low temperature and greatly raised hydrogen absorbing and releasing dynamic performance.
Therefore, the invention provides the following technical scheme:
in a first aspect, the present invention provides a hydrogen storage alloy comprising a first component: the first component has the chemical formula of Mg18-x-yLaxREyNi2-z-mAlzTim(ii) a Wherein x, y, z and m are atomic ratios of 1<x<3，0.2<y<1，0<z<1，0<m<1; RE comprises at least one of rare earth elements Ce, Nd, Y, Sm and Gd.
In a further embodiment of the invention, the hydrogen storage alloy further comprises a second component, the chemical formula of the second component being Co, i.e. metallic cobalt powder; mass of Co in Mg18-x-yLaxREyNi2-z-mAlzTim50% by mass, i.e. the chemical formula of the hydrogen-storage alloy is Mg18-x-yLaxREyNi2-z-mAlzTim+50(wt)％Co。
In a further embodiment of the invention, the hydrogen storage alloy further comprises a third component having the chemical formula TiF3；TiF3Is Mg18-x-yLaxREyNi2-z-mAlzTim3 to 8 percent of the mass, namely the chemical formula of the hydrogen storage alloy is Mg18-x-yLaxREyNi2-z-mAlzTim+50(wt)％Co+n(wt)％TiF3N is TiF3Occupy Mg18-x-yLaxREyNi2-z-mAlzTimIn percentage by mass.
In a further embodiment of the present invention, in the hydrogen absorbing alloy, x is 2, y is 0.5, z is 0.5, m is 0.5, and n is 4.
In a further embodiment of the invention, cobalt powder with a particle size of 150-200 mesh is selected for the Co.
In a second aspect, the present invention provides a method for preparing a hydrogen storage alloy, comprising the steps of: s101: according to the formula Mg18-x-yLaxREyNi2-z-mAlzTimCompounding, heating and obtaining molten Mg18-x-yLaxREyNi2-z-mAlzTimAlloying; s102: pouring the molten alloy into a water-cooled copper mold to obtain an as-cast master alloy ingot; s103: placing a master alloy cast ingot in a quartz tube with a slit at the bottom, heating the master alloy cast ingot to a molten state, spraying the master alloy cast ingot out of the slit of the quartz tube by using the pressure of protective gas, and dropping the master alloy cast ingot on the surface of a copper roller rotating at a linear speed of 25-35 m/s to obtain a rapid-quenched alloy thin strip Mg18-x-yLaxREyNi2-z-mAlzTim(ii) a S104: mechanically crushing the quick-quenched alloy thin strip, sieving the crushed strip with a 180-200-mesh sieve, and mixing the crushed strip with cobalt powder in a ratio of 2: 1, putting the mixture into a stainless steel ball-milling tank, vacuumizing the ball-milling tank, introducing high-purity argon, and carrying out ball milling in an all-dimensional planetary high-energy ball mill; s105: the product obtained in S104 is mixed with TiF3Mixing, and ball milling to obtain the hydrogen storage alloy. Specifically, in the batching process of step S101, the burning loss of magnesium, lanthanum and rare earth in the chemical formula composition is increased by 5% -10% in the proportioning, and the metal purity of the raw material is more than or equal to 99.5%.
In a further embodiment of the present invention, in S101, the heating conditions are: vacuum-pumping to 1 × 10-2Pa～5×10-4Pa, introducing inert gas of 0.01MPa to 1MPa as protective gas, heating to 1300 ℃ to 1500 ℃, and preserving heat for 5min to 10 min; and the heating mode is induction heating, of course, other heating modes such as arc melting and the like can be selected. Specifically, the inclusion gas may be pure helium or a mixed gas of helium and argon at a volume ratio of 1: 1.
In a further embodiment of the present invention, in S104 and S105, the ball milling conditions are both: the ball material ratio is 1: 40, the rotating speed is 300 rpm-400 rpm, and the ball milling is carried out in a ball milling tank; the ball milling time in the S104 is 20-50 h, and the ball milling time in the S105 is 2.5-3.5 h.
In a further embodiment of the present invention, in S104, the ball milling is performed with a stop of 1 hour for 3 hours per ball milling.
In a third aspect, the invention provides the application of the hydrogen storage alloy in the preparation of fuel cells.
The technical scheme provided by the invention has the following advantages:
(1) the applicant has found through a great deal of research that: the hydrogen storage alloy provided by the invention adopts multi-element rare earth, adds a certain amount of nickel, aluminum and titanium, is mixed with cobalt powder for ball milling, and a small amount of nano TiF is added in the ball milling process3As catalyst, nanocrystalline-amorphous Mg with high hydrogen storage capacity and excellent kinetic properties is obtained17La2The hydrogen storing alloy has high hydrogen absorbing and releasing capacity at relatively low temperature and greatly raised hydrogen absorbing and releasing dynamic performance.
(2) The invention has the advantages that: in the presence of Mg17La2The multi-element rare earth, Ni, Al and Ti are added into the alloy, the thermal stability of the alloy is reduced on the premise of ensuring that the hydrogen absorption amount of the alloy is not reduced, the hydrogen release thermodynamics and kinetics of the alloy are improved, and the alloy is obtained by a rapid quenching processThe rapid quenching alloy thin strip with the nanocrystalline-amorphous structure further enables the prepared hydrogen storage alloy to show higher stability; and then mixing the crushed quick-quenched alloy thin strip with the mass ratio of 2: 1, performing high-energy ball milling on the cobalt powder to generate a large amount of crystal defects on the surfaces of alloy particles, and reducing the hydrogen absorption and desorption activation energy of the alloy; during the ball milling process, a trace amount of nano TiF is added3The catalyst further increases the surface activity of the alloy, reduces the thermal stability of hydride, and greatly improves the hydrogen absorption and desorption capacity and dynamics of the alloy.
(3) In the preparation method provided by the invention, the rapid quenching treatment is firstly carried out on the master alloy so as to obtain a nanocrystalline-amorphous structure and form rapid quenching crystal defects in the alloy. The research shows that: the crystal defects formed by rapid quenching have higher stability than the ball milling defects, and are beneficial to improving the hydrogen absorption and desorption circulation stability of the alloy. The ball milling of the alloy in the rapid quenching state can improve the surface characteristics of the alloy, increase the defects of the alloy surface and be beneficial to improving the hydrogen absorption and desorption performance of the alloy.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic view of a rapidly quenched alloy ribbon according to example 1 of the present invention;
FIG. 2 is a view showing the morphology of a hydrogen storage alloy in example 1 of the present invention;
FIG. 3 is an XRD diffraction pattern of a hydrogen storage alloy according to various embodiments of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
The experimental procedures in the following examples are conventional unless otherwise specified.
The test materials used in the following examples were purchased from a conventional reagent store unless otherwise specified.
In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
The invention provides a hydrogen storage alloy, which comprises a first component: the first component has the chemical formula of Mg18-x- yLaxREyNi2-z-mAlzTim(ii) a Wherein x, y, z and m are atomic ratios of 1<x<3，0.2<y<1，0<z<1，0<m<1; RE comprises at least one of rare earth elements Ce, Nd, Y, Sm and Gd.
Preferably, the material also comprises a second component, wherein the chemical formula of the second component is Co; mass of Co in Mg18-x- yLaxREyNi2-z-mAlzTim50% of the mass.
Preferably, the paint also comprises a third component, and the chemical formula of the third component is TiF3；TiF3Is Mg18-x- yLaxREyNi2-z-mAlzTim3 to 8 percent of the mass.
In addition, the invention specially designs a method for preparing the hydrogen storage alloy, which comprises the following steps:
s101: according to the formula Mg18-x-yLaxREyNi2-z-mAlzTimCompounding, heating and obtaining molten Mg18-x-yLaxREyNi2-z-mAlzTimAnd (3) alloying. Wherein, the heating conditions are as follows: vacuuming to 110-2Pa～5×10-4Pa, introducing inert gas of 0.01MPa to 1MPa as protective gas, heating to 1300 ℃ to 1500 ℃, and preserving heat for 5min to 10 min; and the heating method is an induction heating method.
S102: and pouring the molten alloy into a copper mold to obtain an as-cast master alloy ingot.
S103: placing a master alloy cast ingot in a quartz tube with a slit at the bottom, heating the master alloy cast ingot to a molten state, spraying the master alloy cast ingot out of the slit of the quartz tube by using the pressure of protective gas, and dropping the master alloy cast ingot on the surface of a copper roller rotating at a linear speed of 25-35 m/s to obtain a rapid-quenched alloy thin strip Mg18-x-yLaxREyNi2-z-mAlzTim。
S104: mechanically crushing the quick-quenched alloy thin strip, sieving the crushed strip with a 180-200-mesh sieve, and mixing the crushed strip with cobalt powder in a ratio of 2: 1, and ball milling in an argon atmosphere. Wherein, the ball milling conditions are as follows: the ball material ratio is 1: 40, the rotating speed is 300-400 rpm, the ball milling is carried out in a ball milling tank, the ball milling is stopped for 1h every 3h, and the ball milling time of S104 is 20-50 h after the stop time is removed.
S105: the product obtained in S104 is mixed with TiF3Mixing, and ball milling to obtain the hydrogen storage alloy. Wherein, the ball milling conditions are as follows: the ball material ratio is 1: 40, the rotating speed is 300 rpm-400 rpm, the ball milling is carried out in a ball milling tank, and the ball milling time of S105 is 2.5 h-3.5 h.
The following description is made with reference to specific embodiments:
example one
The invention provides a hydrogen storage alloy with a chemical formula of Mg16La1.5Y0.5NiAl0.5Ti0.5+50(wt)％Co+4(wt)％TiF3(ii) a Wherein, cobalt powder with the granularity of 200 meshes is selected, and the mass of Co accounts for Mg16La1.5Y0.5NiAl0.5Ti0.550% of the mass of the alloy; TiF3Is Mg16La1.5Y0.5NiAl0.5Ti0.54 percent of the mass of the alloy.
The preparation method for preparing the hydrogen storage alloy comprises the following steps:
s101: selecting bulk magnesium metal, rare earth lanthanum and yttrium metal, metallic nickel, metallic aluminum and titanium; the purity of each metal is more than or equal to 99.5 percent, and the metal-based intermediate alloy is weighed according to the chemical dosage ratio after being polished to remove the surface oxide layer. 1054.1g of metal magnesium, 564.8g of metal lanthanum, 120.5g of metal yttrium, 159.1g of metal nickel, 36.5g of metal aluminum and 64.8g of metal titanium are weighed, (the metal magnesium increases 8% of burning loss amount in proportioning, and the rare earth elements increase 5% of burning loss amount) the weighed metal is placed in a magnesium oxide crucible of a medium-frequency induction furnace, then a furnace cover is covered, and in the adding process, except that the magnesium is placed at the top layer of the crucible, other materials are added into the crucible in no sequence; then vacuumizing for about 40 minutes to the vacuum degree of 5X 10-2Pa above, introducing protective gas (argon and helium in a volume ratio of 1: 1) until the air pressure reaches-0.04 MPa negative pressure, adjusting the power to 5kW and the temperature to 650 ℃ to melt the metal magnesium; then adjusting the power to 25kW, controlling the temperature to 1600 ℃, melting all metals, and keeping for 5 minutes after the metals are melted to obtain molten Mg16La1.5Y0.5NiAl0.5Ti0.5And (3) alloying.
S102: the molten alloy was poured into a copper mold and the power was adjusted to 8.2kW when pouring into the ingot mold. And cooling for 20min under the helium protective atmosphere, and discharging to obtain the as-cast master alloy ingot.
S103: placing about 100g of a master alloy ingot into a quartz tube with the diameter of 30mm and a slit at the bottom, wherein the size of the slit is 0.05mm multiplied by 20mm (the length of the slit can be increased or decreased according to needs); heating to be molten by 245kHz radio frequency, wherein the heating power is 1kW under the protection of helium atmosphere; spraying the molten alloy on the surface of a water-cooled copper roller with the surface linear velocity of 30m/s through a slit nozzle at the bottom of a quartz tube under the pressure of 1.05atm heliumTo obtain the fast quenched alloy thin strip Mg16La1.5Y0.5NiAl0.5Ti0.5As shown in fig. 1.
S104: mixing fast quenched alloy thin strip Mg16La1.5Y0.5NiAl0.5Ti0.5Mechanically crushing and sieving by a 200-mesh sieve, weighing 50 g of sieved alloy powder and 25 g of cobalt powder with the granularity of 200 meshes, mixing, putting into a stainless steel ball milling tank, vacuumizing, filling high-purity argon, sealing, and performing full-direction planetary high-energy ball milling in a ball-material ratio of 1: 40 at 350rpm for 30 hours (eliminating down time) and 1 hour for 3 hours per ball mill.
S105: mixing the product obtained in S104 with nano TiF32g (4 wt%) were mixed and then continued at a pellet to pellet ratio of 1: and 40, ball milling for 3 hours at the rotating speed of 350rpm to obtain the hydrogen storage alloy. The morphology and crystalline state of the ball-milled powder was observed by High Resolution Transmission Electron Microscopy (HRTEM) and Selected Area Electron Diffraction (SAED), as shown in fig. 2.
Example two
The invention provides a hydrogen storage alloy with a chemical formula of Mg16LaSmNiAl0.5Ti0.5+50(wt)％Co+6(wt)％TiF3(ii) a Wherein, cobalt powder with the granularity of 200 meshes is selected, and the mass of Co accounts for Mg16LaSmNiAl0.5Ti0.550% of the mass of the alloy; TiF3Is Mg16LaSmNiAl0.5Ti0.56 percent of the mass of the alloy. In addition, according to Mg16LaSmNiAl0.5Ti0.5+50(wt)％Co+6(wt)％TiF3The raw materials were weighed and the alloy powder of this example was prepared by the method of example one.
EXAMPLE III
The invention provides a hydrogen storage alloy with a chemical formula of Mg16La1.5Gd0.5NiAl0.2Ti0.8+50(wt)％Co+3(wt)％TiF3(ii) a Wherein, cobalt powder with the granularity of 200 meshes is selected, and the mass of Co accounts for Mg16La1.5Gd0.5NiAl0.2Ti0.850% of the mass of the alloy; TiF3Is Mg16La1.5Gd0.5NiAl0.2Ti0.83 percent of the mass of the alloy. In addition, according to Mg16La1.5Gd0.5NiAl0.2Ti0.8+50(wt)％Co+3(wt)％TiF3The raw materials were weighed and the alloy powder of this example was prepared by the method of example one.
Example four
The invention provides a hydrogen storage alloy with a chemical formula of Mg16La1.5Ce0.5NiAl0.8Ti0.2+50(wt)％Co+5(wt)％TiF3(ii) a Wherein, cobalt powder with the granularity of 200 meshes is selected, and the mass of Co accounts for Mg16La1.5Ce0.5NiAl0.8Ti0.250% of the mass of the alloy; TiF3Is Mg16La1.5Ce0.5NiAl0.8Ti0.25 percent of the mass of the alloy. In addition, according to Mg16La1.5Ce0.5NiAl0.8Ti0.2+50(wt)％Co+5(wt)％TiF3The raw materials were weighed and the alloy powder of this example was prepared by the method of example one.
EXAMPLE five
The invention provides a hydrogen storage alloy with a chemical formula of Mg16La1.5Pr0.5Ni1.4Al0.3Ti0.3+50(wt)％Co+7(wt)％TiF3(ii) a Wherein, cobalt powder with the granularity of 200 meshes is selected, and the mass of Co accounts for Mg16La1.5Pr0.5Ni1.4Al0.3Ti0.350% of the mass of the alloy; TiF3Is Mg16La1.5Pr0.5Ni1.4Al0.3Ti0.37 percent of the mass of the alloy. In addition, according to Mg16La1.5Pr0.5Ni1.4Al0.3Ti0.3+50(wt)％Co+7(wt)％TiF3The raw materials were weighed and the alloy powder of this example was prepared by the method of example one.
EXAMPLE six
The invention provides a hydrogen storage alloy with a chemical formula of Mg16La1.0Y0.5Sm0.5NiAl0.5Ti0.5+50(wt)％Co+4(wt)％TiF3(ii) a Wherein, cobalt powder with the granularity of 200 meshes is selected, and the mass of Co accounts for Mg16La1.0Y0.5Sm0.5NiAl0.5Ti0.550% of the mass of the alloy; TiF3Is Mg16La1.0Y0.5Sm0.5NiAl0.5Ti0.54 percent of the mass of the alloy. In addition, according to Mg16La1.0Y0.5Sm0.5NiAl0.5Ti0.5+50(wt)％Co+4(wt)％TiF3The raw materials were weighed and the alloy powder of this example was prepared by the method of example one.
EXAMPLE seven
The invention provides a hydrogen storage alloy with a chemical formula of Mg16La1.0Ce0.5Pr0.5NiAl0.5Ti0.5+50(wt)％Co+4(wt)％TiF3(ii) a Wherein, cobalt powder with the granularity of 200 meshes is selected, and the mass of Co accounts for Mg16La1.0Ce0.5Pr0.5NiAl0.5Ti0.550% of the mass of the alloy; TiF3Is Mg16La1.0Ce0.5Pr0.5NiAl0.5Ti0.54 percent of the mass of the alloy. In addition, according to Mg16La1.0Ce0.5Pr0.5NiAl0.5Ti0.5+50(wt)％Co+4(wt)％TiF3The raw materials were weighed and the alloy powder of this example was prepared by the method of example one.
In addition, in order to further illustrate the properties of the hydrogen storage alloys prepared in the examples of the present invention, the following tests were performed:
the structure of the hydrogen storage alloy obtained in each example was measured by XRD method, and the results are shown in fig. 3. In addition, the electrochemical cycling stability of the gaseous hydrogen storage capacity and the hydrogen absorption and desorption dynamics of the hydrogen storage alloy powder of each embodiment is tested by adopting a full-automatic Sieverts device, the hydrogen absorption and desorption temperature is 250 ℃, the initial hydrogen pressure of hydrogen absorption is 3MPa, and the hydrogen desorption is carried out at 250 ℃ and 1 × 10- 4The test is carried out under MPa pressure, and the specific test results are shown in Table 1. In addition, the performance of the hydrogen storage alloy of each embodiment of the invention is compared with that of the conventional hydrogen storage alloy Mg17La2The properties of (i.e. the comparative examples in table 1) were compared and prepared by: formulation of Mg according to chemical composition17La2And then ball-milling for 30 h.
TABLE 1 electrochemical hydrogen storage capacity and cycle stability of hydrogen storage alloys of alloy powders of different compositions
Wherein,hydrogen uptake (wt.%) at an initial hydrogen pressure of 3MPa and 250 ℃ in 5 minutes,- -at an initial pressure of 1X 10-4MPa and hydrogen evolution (wt.%) at 250 ℃ in 10 minutes. Capacity retention rate S100＝C100/CmaxX 100%, wherein CmaxIs the saturated hydrogen absorption of the alloy, C100Cycle 100Hydrogen uptake behind the ring.
As can be seen from the data in table 1: the hydrogen storage alloy has high hydrogen absorption and desorption capacity and excellent dynamic performance. Compared with similar alloys at home and abroad, the hydrogen storage performance of the alloy is obviously improved.
The hydrogen storage alloy provided by the invention adopts multi-element rare earth, adds a certain amount of nickel, aluminum and titanium, is mixed with cobalt powder for ball milling, and a small amount of nano TiF is added in the ball milling process3As catalyst, nanocrystalline-amorphous Mg with high hydrogen storage capacity and excellent kinetic properties is obtained17La2The hydrogen storing alloy has high hydrogen absorbing and releasing capacity at relatively low temperature and greatly raised hydrogen absorbing and releasing dynamic performance. In the presence of Mg17La2The multielement rare earth, Ni, Al and Ti are added into the alloy, so that on the premise of ensuring that the hydrogen absorption amount of the alloy is not reduced, the thermal stability of the alloy is reduced, the hydrogen discharge thermodynamics and kinetics of the alloy are improved, a rapid quenching alloy thin strip with a nanocrystalline-amorphous structure is obtained through a rapid quenching process, and the prepared hydrogen storage alloy shows higher stability; and then mixing the crushed quick-quenched alloy thin strip with the mass ratio of 2: 1, performing high-energy ball milling on the cobalt powder to generate a large amount of crystal defects on the surfaces of alloy particles, and reducing the hydrogen absorption and desorption activation energy of the alloy; during the ball milling process, a trace amount of nano TiF is added3The catalyst further increases the surface activity of the alloy, reduces the thermal stability of hydride, and greatly improves the hydrogen absorption and desorption capacity and dynamics of the alloy.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. A preparation method of hydrogen storage alloy is characterized in that the chemical formula of the hydrogen storage alloy is Mg18-x- yLaxREyNi2-z-mAlzTim+50(wt)％Co+n(wt)％TiF3；
Wherein x, y, z and m are atomic ratios of 1<x<3，0.2<y<1，0<z<1，0<m<1; RE comprises at least one of rare earth elements Ce, Nd, Y, Sm and Gd; the mass of the Co accounts for the mass of the Mg18-x-yLaxREyNi2-z-mAlzTim50% of the mass; n is TiF3Occupy Mg18-x-yLaxREyNi2-z-mAlzTimIn mass percent of (1), and TiF3In mass of said Mg18-x-yLaxREyNi2-z-mAlzTim3-8% of the mass;
the preparation method comprises the following steps:
s101: according to the formula Mg18-x-yLaxREyNi2-z-mAlzTimCompounding, heating and obtaining molten Mg18-x- yLaxREyNi2-z-mAlzTimAlloying; wherein the heating conditions are as follows: vacuum-pumping to 1 × 10-2Pa～5×10-4Pa, introducing inert gas of 0.01MPa to 1MPa as protective gas, heating to 1300 ℃ to 1500 ℃, and preserving heat for 5min to 10 min; the heating mode is an induction heating method;
s102: pouring the molten alloy into a copper mold to obtain an as-cast master alloy ingot;
s103: placing the master alloy cast ingot in a quartz tube with a slit at the bottom, heating the master alloy cast ingot to a molten state, spraying the master alloy cast ingot out of the slit of the quartz tube by using the pressure of protective gas, and dropping the master alloy cast ingot on the surface of a copper roller rotating at a linear speed of 25-35 m/s to obtain a rapid-quenched alloy thin strip Mg18-x-yLaxREyNi2-z-mAlzTim；
S104: mechanically crushing the rapidly quenched alloy thin strip, sieving the crushed strip with a 180-200-mesh sieve, and mixing the crushed strip with cobalt powder in a ratio of 2: 1, ball milling in an argon atmosphere; wherein, the ball-milling is carried out in a ball-milling tank, and the ball-material ratio is 1: 40, the rotating speed is 300-400 rpm, the ball milling time is 20-50 h, and the ball milling is stopped for 1h after 3 h;
s105: reacting the product obtained in S104 with TiF3Mixing, and then ball-milling to obtain a hydrogen storage alloy; wherein, the ball-milling is carried out in a ball-milling tank, and the ball-material ratio is 1: 40, the rotating speed is 300rpm to 400rpm, and the ball milling time is 2.5h to 3.5 h.
2. The method for producing a hydrogen storage alloy according to claim 1, characterized in that:
in the hydrogen storage alloy, x is 2, y is 0.5, z is 0.5, m is 0.5, and n is 4.
3. The method for producing a hydrogen storage alloy according to claim 2, characterized in that:
the Co is selected from cobalt powder with the granularity of 150-200 meshes.
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