CN1281775C - Magnesium base hydrogen storage material and its mechanical-alloying preparation method - Google Patents
Magnesium base hydrogen storage material and its mechanical-alloying preparation method Download PDFInfo
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- CN1281775C CN1281775C CNB031496520A CN03149652A CN1281775C CN 1281775 C CN1281775 C CN 1281775C CN B031496520 A CNB031496520 A CN B031496520A CN 03149652 A CN03149652 A CN 03149652A CN 1281775 C CN1281775 C CN 1281775C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a magnesium based hydrogen storage material and a method for preparing magnesium based hydrogen storage materials by a mechanical-alloying method. The magnesium based hydrogen storage materials have the chemical component of La<2-x>M<x>Mg<17>, wherein M is selected from Cu, Al, Ni, Fe, Co, Mn, V, Cr, Zn, Ca, Sn, etc., and the x is less than 2 but more than 0. The method for preparing magnesium based hydrogen storage materials by a mechanical-alloying method comprises the following steps: (1) alloy La<2-x>M<x> is prepared by a traditional smelting method; (2) La<2-x>M<x> alloy and Mg metal powder are processed by ball milling by a high-energy ball mill under the atmosphere of hydrogen gas or argon gas. The ball milling procedure is carried out under the protection of hydrogen gas of 0.3MPa to 20.0MPa; a material preparation procedure and a hydrogenization procedure are merged and finished once. The magnesium based hydrogen storage alloy has the advantages of large hydrogen storage amount (5.23 to 7.01 wt%), no need of activation, high speed of sucking and discharging hydrogen, stable performance, etc. The present invention can be used for the recovery, purification, refining, storage and transportation of hydrogen, hydrogen fuel vehicles, electric vehicles, hydrogen energy power generating systems, rechargeable batteries, fuel batteries, etc.
Description
Technical field
Originally relate to invention and relate to method and the magnesium-base hydrogen storage material thereof that a kind of mechanical alloying method prepares magnesium-base hydrogen storage material.
Background technology
At present, hydrogen is a kind of high-energy-density, clean energy efficiently, is one of the most attractive energy form, is considered to replace effective selection of fossil fuel.Since the seventies, many in the world countries promptly begin broad research, predict according to energy experts, and hydrogen is expected to become in the latter stage of petroleum times a kind of main secondary energy.Utilize hydrogen storage material storing hydrogen, compact construction, safe and reliable does not only have the danger of blast, and highly purified hydrogen can be provided.The standard of the following novel hydrogen storage material that International Energy Agency (1EA) is definite be hydrogen storage capability greater than 5wt.%, and can under mild conditions, inhale and put hydrogen.Because magnesium resource is abundant, cheap, and the big (MgH of Magnuminium hydrogen storage capability
2Can reach 7.6wt%), therefore be considered to one of hydrogen source such as most promising fuel cell, hydrogen-burning automobile, in addition, good application prospects is arranged also in secondary alkaline batteries, thereby attracted numerous scientists to be devoted to the development of new Magnuminium.
In addition, preparation method's difference also can make the performance of Mg base hydrogen storage alloy produce very big-difference.Chang Yong preparation method adopted high melt method, sintering synthesis method, combustion synthesis method, solid phase diffusion method, vapour deposition synthesis method, chemical synthesis, the decrystallized method of chilling etc. in the past.The magnesium-base hydrogen storage material that adopts these methods to obtain exists working temperature too high to some extent, cyclical stability difference or be difficult to shortcomings such as activation.
Summary of the invention
The purpose of this invention is to provide a kind of good magnesium-base hydrogen storage material that stores the hydrogen performance that has.
Another object of the present invention provides the method that a kind of mechanical alloying method prepares magnesium-base hydrogen storage material.Adopt method of the present invention can synthetic La-M-Mg the series hydrogen storage alloy, the sample of preparation is active high, need not activate, and shows good suction in gas-solid phase reaction, puts the hydrogen characteristic.The present invention prepares the mild condition of material, and equipment is simple and convenient, easily operation.
For achieving the above object, the present invention takes following technical scheme:
A kind of mechanical alloying method prepares the method for magnesium-base hydrogen storage material, and this method comprises the steps:
(1) adopt traditional smelting process with La and M according to La
2-xM
x, (M is Cu, Al, Ni, Fe, Co, Mn, V, Cr, Zn or Sn etc., 0＜x＜2) proportioning, preparation alloy La
2-xM
x
(2) according to La
2-xM
xMg
17(0＜x＜2) stoichiometric equation takes by weighing La
2-xM
xAlloy and Mg metal-powder; under hydrogen atmosphere, adopt high energy ball mill to carry out ball milling; ratio of grinding media to material is 5-20: 1; the ball milling time is between 10～100 hours; mechanical milling process carries out under the hydrogen shield of 0.3-20.0MPa, material preparation and hydrogenation process is merged once finish, and simultaneously it is carried out wind cooling temperature lowering; with gained material vacuum sealed package, promptly make magnesium-base hydrogen storage material at last.
Or,
(2) ' according to La
2-xM
xMg
17(0＜x＜2) stoichiometric equation takes by weighing La
2-xM
xAlloy and Mg metal-powder, under vacuum or argon gas, adopt high energy ball mill to carry out ball milling, ratio of grinding media to material is 5-20: 1, and the ball milling time is between 10～100 hours, then, extract argon gas out, charge into hydrogen, the pressure of hydrogen is 1.0-15.0MPa, carries out hydrogenation process, simultaneously it is carried out wind cooling temperature lowering, with gained material vacuum sealed package, promptly make magnesium-base hydrogen storage material at last.
Method of the present invention is to unite two into one in conjunction with mechanical alloying method on employing smelting process basis, because the easy oxidation of simple substance La is difficult to make metal-powder (wherein oxygen level is restive), so at first adopt traditional smelting process that La and M are made La
2-xM
xAlloy adopts mechanical alloying method with La again
2-xM
xAlloy and Mg metal-powder are made magnesium-base hydrogen storage material.Adopt this method to prepare magnesium-base hydrogen storage material, avoided the low composition that brings of easy oxidation of La and magnesium vapour pressure height and fusing point to be difficult to problems such as control well, and ordinary method is difficult to synthesize and the corresponding to alloy material of design mix.
In the method for the invention, can under hydrogen atmosphere, adopt high energy ball mill to carry out reaction ball milling, and material preparation and hydrogenation process merging are once finished, as step (2); Also can under vacuum or argon gas, adopt high energy ball mill to carry out ball milling, and then carry out hydrogenation process, as step (2) '.
The process of described step (1) is; described La and M are adopted electric arc furnace or induction melting furnace melting in argon shield atmosphere; in non-consumable arc furnace during melting; its melting number of times is no less than 6 times; be composition analysis and XRD after melting finishes and detect testimonial material for after designing composition and structure; under argon shield, smashed the alloy of melting to pieces 400 mesh sieve, vacuum sealed package again.
In described step (2) or (2) ' in, institute's employing ball mill is Spex-8000 type or Zoz ball mill.
A kind of magnesium-base hydrogen storage material that adopts method preparation of the present invention, the chemical composition of this magnesium-base hydrogen storage material is La
2-xM
xMg
17, wherein, M is selected from Cu, Al, Ni, Fe, Co, Mn, V, Cr, Zn and Sn etc., 0＜x＜2.
Prepare magnesium-base hydrogen storage material of the present invention and be not limited to above-mentioned method, also can adopt other method to be prepared.
Magnesium-base hydrogen storage material of the present invention is near the standard of the definite following novel hydrogen storage material of International Energy Agency, for the application of Mg base hydrogen bearing alloy at aspects such as fuel cell and hydrogen-burning automobiles lays the first stone.
Advantage of the present invention is: Mg base hydrogen bearing alloy of the present invention have hydrogen-storage amount big (5.23～7.01wt%), need not activate, speed for hydrogen absorbing and releasing is fast, steady performance is expected to be used for recovery, the purification, refining of hydrogen; The storage of hydrogen and transportation; The recycling of waste heat or used heat; Heat reservoir, heat pump or air-conditioning, refrigeration; Hydrogen powered vehicle, electromobile, hydrogen power generation system; Rechargeable battery and fuel cell etc.
The invention will be further described in conjunction with the accompanying drawings below by embodiment.
Description of drawings
Fig. 1 is combined to La for mechanical alloy
2-xMg
17Ni
xP-C-T curve under differing temps
Wherein, Fig. 1-a is that mechanical alloy is combined to La
2-xMg
17Ni
x(x=1) the P-C-T curve under differing temps; Fig. 1-b is that mechanical alloy is combined to La
2-xMg
17Ni
x(x=0.5) the P-C-T curve under differing temps
Fig. 2 is La
1.5Ni
0.5Mg
17Hydrogen-absorption speed curve under differing temps
Fig. 3 is La
1.5Ni
0.5Mg
17The XRD result (MA) of different ball milling times
Fig. 4 is La
1.5Ni
0.5La
17TEM dark field image behind the alloy ball milling 60h and polycrystalline diffraction ring
Fig. 5 is combined to LaMg for mechanical alloy
17The X diffractogram of Ni
Embodiment
Embodiment 1
At first adopt traditional smelting process with La and Ni according to RE
2-xM
x(x=0.5) proportioning; in argon shield atmosphere, adopt the electric arc furnace melt back to guarantee that the material alloys composition is even for 6 times; after melting finishes; do composition and structure detection; testimonial material is for after designing composition and structure; under argon shield, smashed the alloy of melting to pieces 400 mesh sieve, vacuum sealed package.
With La
1.5Ni
0.5With the Mg metal-powder according to La
1.5Ni
0.5Mg
17The ratio uniform mixing, be placed on the sealing stainless steel jar mill in, ratio of grinding media to material is 15: 1, ball matter is stainless steel, is evacuated to 10 earlier
-3Pa, the hydrogen that charges into 5MPa is then made protective atmosphere.Adopt Spex-8000 type ball mill to carry out ball milling, drum's speed of rotation is 1750 commentaries on classics/min, and the ball milling time is 20～80 hours, carries out wind cooling temperature lowering simultaneously.The magnesium-base hydrogen storage material that obtains is at last carried out the mensuration of XRD, SEM, TEM, hydrogen storage capability and suction hydrogen discharging rate.Display material is at 300 ℃ as a result for PCT, and hydrogen storage capability is 7.01wt% (shown in Fig. 1-b) under the 1MPa hydrogen, also can inhale hydrogen at 100 ℃ and reach 4.03wt%.When temperature is between 150～300 ℃ the time, material can be inhaled hydrogen and reach 4.55～7.01wt% under the suction hydrogen pressure condition of 1MPa in 600 seconds,
As shown in Figure 2, in identical time and temperature, under the 0.0133MPa, material can discharge 4.40～6.90wt%.The obvious broadening of the bright material of XRD figure stave diffraction peak in mechanical milling process, along with the ball milling time increases, broadening obvious more (as shown in Figure 3), TEM result also shows identical analytical results (as shown in Figure 4), the crystal formation that shows this product is a nanocrystalline structure, and alloying pellet is of a size of 20～30nm.
Adopt smelting process that La and Ni are made the LaNi alloy, remove La and Ni according to RE
2-xM
x(x=1) outside proportioning and embodiment 1 were different, remaining fusion process was all identical with embodiment 1.
Then with LaNi and Mg metal-powder according to LaNiMg
17The ratio uniform mixing, place Spex-8000 type ball mill to carry out ball milling, drum's speed of rotation is 1750 commentaries on classics/min; ratio of grinding media to material is 15: 1; the ball milling time is 80 hours, and mechanical milling process carries out under the hydrogen shield of 5MPa, and material preparation and hydrogenation process merging are once finished.Material is carried out the mensuration of PCT, XRD and suction hydrogen discharging rate.The PCT curve is shown in Fig. 1-a, and material can be inhaled hydrogen 5.23wt% at 280 ℃ under the 1MPa hydrogen.Also can inhale hydrogen at 100 ℃ and reach 2.31wt%.
When temperature between 150～300 ℃, material is inhaled under the condition of hydrogen pressure at 1Mpa in 600 seconds, can inhale hydrogen and reach 4.20～5.55wt%; In identical time and temperature, under the 0.0133MPa, material can discharge 4.01～5.28wt%.The obvious broadening of the bright material of XRD figure stave diffraction peak in mechanical milling process, along with the ball milling time increases, broadening obvious more (as shown in Figure 5), the crystal formation that shows this product is indefiniteness structure or nanocrystalline structure.
Claims (4)
1, a kind of mechanical alloying method prepares the method for magnesium-base hydrogen storage material, it is characterized in that: this method comprises the steps:
(1) with traditional smelting process with La and M according to La
2-xM
x, M be Cu, Al, Ni, Fe,
Co, Mn, V, Cr, Zn or Sn, 0＜x＜2 proportionings, preparation alloy La
2-xM
x
(2) according to La
2-xM
xMg
17, 0＜x＜2 stoichiometric equations take by weighing La
2-xM
xAlloy and Mg metal-powder, under hydrogen atmosphere, adopt high energy ball mill to carry out ball milling, ratio of grinding media to material is 5-20: 1, the ball milling time is between 10～100 hours, mechanical milling process carries out under the hydrogen shield of 0.3-20.0MPa, material preparation and hydrogenation process is merged once finish, and simultaneously it is carried out wind cooling temperature lowering, with gained material vacuum sealed package, promptly make magnesium-base hydrogen storage material at last;
Or,
(2) ' according to La
2-xM
xMg
17, 0＜x＜2 stoichiometric equations take by weighing La
2-xM
xAlloy and Mg metal-powder, under vacuum or argon gas, adopt high energy ball mill to carry out ball milling, ratio of grinding media to material is 5-20: 1, and the ball milling time is between 10～100 hours, then, extract argon gas out, charge into hydrogen, the pressure of hydrogen is 1.0-15.0MPa, carries out hydrogenation process, simultaneously it is carried out wind cooling temperature lowering, with gained material vacuum sealed package, promptly make magnesium-base hydrogen storage material at last.
2, mechanical alloying method according to claim 1 prepares the method for magnesium-base hydrogen storage material; it is characterized in that: the process of described step (1) is; described La and M are adopted electric arc furnace or induction melting furnace melting in argon shield atmosphere; be composition and XRD after melting finishes and detect testimonial material for after designing composition and structure; under argon shield, smashed the alloy of melting to pieces 400 mesh sieve, vacuum sealed package again.
3, mechanical alloying method according to claim 1 prepares the method for magnesium-base hydrogen storage material, it is characterized in that: in described step (2) or (2) ' in, institute's employing ball mill is Spex-8000 type or Zoz ball mill.
4, a kind of magnesium-base hydrogen storage material that adopts the method preparation of claim 1, it is characterized in that: the chemical composition of this magnesium-base hydrogen storage material is La
2-xM
xMg
17, wherein M is selected from Cu, Al, Ni, Fe, Co, Mn, V, Cr, Zn and Sn, 0＜x＜2.
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|---|---|---|---|
| CNB031496520A CN1281775C (en) | 2003-08-04 | 2003-08-04 | Magnesium base hydrogen storage material and its mechanical-alloying preparation method |
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| CNB031496520A CN1281775C (en) | 2003-08-04 | 2003-08-04 | Magnesium base hydrogen storage material and its mechanical-alloying preparation method |
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| CN1281775C true CN1281775C (en) | 2006-10-25 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634714A (en) * | 2012-04-19 | 2012-08-15 | 重庆大学 | Copper-added magnesium-aluminum hydrogen storage alloy and preparation method thereof |
| CN104831138B (en) * | 2015-05-11 | 2017-03-29 | 北京科技大学 | Solar energy heating generates electricity with mischmetal magnesium metal hydride high-temperature heat-storage material |
| CN105132770B (en) * | 2015-09-11 | 2017-01-25 | 安徽工业大学 | Mg2Ni-based ternary Mg-Ni-Cu reversible hydrogen storage material and preparation method thereof |
| CN105271113A (en) * | 2015-10-16 | 2016-01-27 | 安徽工业大学 | Composite hydrogen storage material and preparation method thereof |
| CN107190193A (en) * | 2017-06-11 | 2017-09-22 | 烟台大学 | A kind of nano-amorphous Mg M Y hydrogen bearing alloys and its production and use |
| CN108374100B (en) * | 2018-04-18 | 2020-01-03 | 北京矿冶科技集团有限公司 | Efficient preparation method of hydrogen storage material |
| CN108687355A (en) * | 2018-06-28 | 2018-10-23 | 西京学院 | A kind of Mg-based hydrogen storage alloy preparation method based on mechanical ball mill technology |
| CN114438386A (en) * | 2022-03-15 | 2022-05-06 | 北京氢冉新能源科技有限公司 | Magnesium-based hydrogen storage material doped with single metal element and preparation method thereof |
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Effective date of registration: 20190625 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: YOUYAN ENGINEERING TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |
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Granted publication date: 20061025 |