CN106756369A - A kind of Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period and preparation method thereof - Google Patents

A kind of Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period and preparation method thereof Download PDF

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CN106756369A
CN106756369A CN201611075580.6A CN201611075580A CN106756369A CN 106756369 A CN106756369 A CN 106756369A CN 201611075580 A CN201611075580 A CN 201611075580A CN 106756369 A CN106756369 A CN 106756369A
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bearing alloy
hydrogen bearing
base hydrogen
long period
containing long
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CN106756369B (en
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彭秋明
王栋彬
葛炳成
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Yanshan University
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Yanshan University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball 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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Abstract

A kind of Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period, its chemical molecular formula represents the one kind in V or Co, a, b, c representation quality percentage, 3%≤a≤8%, 17%≤b≤19%, 0.5%≤c≤1%, balance of Mg for Mg aX bY cLi, X；The preparation method of above-mentioned Mg base hydrogen bearing alloy is mainly by the alloying pellet loading ball grinder of mentioned component, by 15：1~20:1 ratio of grinding media to material adds the stainless steel abrading-ball of 4~6mm, rotating speed is 300~400r/min, 10min is stalled after operating 30min, the powder that average grain diameter is 50~90nm is obtained after 30~50h of ball milling, it is put into high-temperature vacuum furnace, 200 DEG C are heated under an argon atmosphere and 24 hours are incubated, and the Mg base hydrogen bearing alloy containing long period orderly accumulation structure is obtained.Present invention process equipment is simple and easy to control, low cost, and obtained Mg base hydrogen bearing alloy suction hydrogen discharging temperature is moderate, inhales hydrogen desorption kineticses performance good.

Description

A kind of Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period and preparation method thereof
Technical field
Contain the present invention relates to a kind of Mg base hydrogen bearing alloy of long period orderly accumulation structure and preparation method thereof.
Background technology
With fossil fuel reduction and environmental pollution it is increasingly serious, people in the urgent need to find it is a kind of it is new, do not have There is the energy of environmental pollution.Hydrogen Energy has that clean, energy is high, will not produce the lot of advantages such as secondary pollution, therefore hydrogen energy source Exploitation causes the great interest of people.Hydrogen energy system includes hydrogen source exploitation, hydrogen producing technology, hydrogen storage technology, the utilization technology of hydrogen Deng.In whole hydrogen energy system, hydrogen storage is the link of most critical.
Mg base hydrogenous alloys are because its hydrogen storage content is big, density is low, aboundresources and lower-price characteristic and make it One of most promising hydrogen storage material.But hydrogen condition (hydrogen discharging temperature is high, speed is slow) obstruction is put in the harsh suction of Mg based hydrogen storage materials Its application in practice, therefore how to reduce its suction hydrogen discharging temperature (300 DEG C) and improve and inhale hydrogen desorption kineticses performance one It is directly the emphasis of people's research.At present, the method for improving magnesium-base hydrogen storage material hydrogen storage property mainly has：Element doping with substitute, Mechanical alloying, addition catalyst, surface treatment and improvement synthetic method.For example, being studied with regard to someone early in the eighties in last century LaMg12、CeMg12、MmMg12、La2Mg17And La2Mg16The hydrogen storage property of Ni, although find this kind of Mg based alloys can compared with Hydrogen is inhaled at low temperature, but hydrogen absorption capacity is relatively low, and less than 4wt%, and hydrogen discharging temperature is still very high, more than 300 DEG C.And And, the Mg of the research such as nearest Ou Yangliu chapters3Pr and Mg3PrNi0.1Hydrogen can be at room temperature inhaled, and it is non-to inhale hydrogen desorption kineticses performance Chang Hao, reversible hydrogen storage capacity is respectively 2.58wt% and 3.23wt%, but desorption temperature is still very high, about 300 DEG C.
The content of the invention：
It is an object of the invention to provide a kind of process equipment it is simple, with low cost, magnesium-base hydrogen storage material can be reduced Inhale hydrogen discharging temperature improves the Mg base hydrogen bearing alloy and its system of the structure of orderly accumulation containing long period for inhaling hydrogen desorption kineticses performance simultaneously Preparation Method.
The chemical molecular formula of the Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period of the invention is Mg-aX-bY-cLi, X represents the one kind in V or Co, a, b, c representation quality percentage, 3%≤a≤8%, 17%≤b≤19%, and 0.5%≤c≤ 1%, balance of Mg.
Above-mentioned element is simple metal powder.
The preparation method of above-mentioned Mg base hydrogen bearing alloy：
The alloying pellet of mentioned component chemical raw material is loaded into ball grinder, by 15~20:1 ratio of grinding media to material adds a diameter of 4 The stainless steel abrading-ball of~6mm, rotating speed is 300~400r/min, and 10min is stalled after operating 30min, is obtained after 30~50h of ball milling Average grain diameter is the powder of 50~90nm, is then placed in high-temperature vacuum furnace, and 200 DEG C and insulation 24 are heated under an argon atmosphere Hour, the Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period is obtained.
The present invention has the following advantages that compared with prior art：
1st, process equipment is simple, using ball-milling method so that metallic particles is constantly refined, until reaching Nano grade, produces Substantial amounts of unsalted surface and lattice defect, so as to effectively reduce activation energy.
2nd, on traditional ball-milling technology, with the addition of the operation of heat treatment so that evaporated lithium be hydrogen in the sample Transport provide passage, so as to greatly reinforce hydrogen storage property.
3rd, the obtained Mg base hydrogen bearing alloy containing long period orderly accumulation structure have that hydrogen storage content is big, hydrogen discharging temperature is low, Inhale the good advantage of hydrogen desorption kineticses performance.
4th, it is cheap, can be suitably used for producing in enormous quantities.
Brief description of the drawings
Fig. 1 is Mg obtained in the embodiment of the present invention 191V3Y5PCT curve maps of the Li under the conditions of 200 DEG C, 1Mpa.
Fig. 2 is Mg obtained in the embodiment of the present invention 291Co3Y5Suction of the Li alloys in 25min under the conditions of 200 DEG C, 1Mpa is moved Force diagram figure.
Fig. 3 is Mg obtained in the embodiment of the present invention 393Co2Y4Li alloys put hydrogen in 25min under the conditions of 200 DEG C, 1Mpa Dynamic curve diagram.
Specific embodiment：
Embodiment 1
The pure magnesium powders of 7.79g, 0.45g vanadium powders, 1.71g yttrium powders and 0.05g lithium powder are weighed, after being selected with 200 mesh sieves, loads ball milling In tank, placing into the stainless steel abrading-ball of a diameter of 4mm of 150g carries out ball milling, and rotating speed is 300r/min, is stalled after operating 30min 10min, so circulation ball milling 30h, obtain the magnesium alloy powder that average grain diameter is 90nm, and magnesium alloy powder then is put into vacuum In high temperature furnace, 200 DEG C being heated under an argon atmosphere and 24 hours are incubated, the magnesium-based containing long period orderly accumulation structure is obtained Hydrogen bearing alloy.
Take the above-mentioned Mg base hydrogen bearing alloys of 1g to be fitted into PCT testers sample room, vacuumized after sealing, use temperature control heating by electric cooker To 200 DEG C of H2 for being filled with 2MPa afterwards, the measure of alloy hydrogen storage property is started after activation 3 times.As shown in Figure 1, it can be seen that 200 DEG C of alloy hydrogen absorption and desorption total amounts reach 4.4% or so, and it is 0.2/0.15MPa to inhale/put hydrogen platform pressure, and hydrogen storage total amount is big, Platform pressure is small, and hysteresis quality is small.
Embodiment 2
The pure magnesium powders of 7.68g, 0.51g cobalt powders, 1.71g yttrium powders and 0.1g lithium powder are weighed, after being selected with 200 mesh sieves, loads ball milling In tank, placing into the stainless steel abrading-ball of a diameter of 6mm of 200g carries out ball milling, and rotating speed is 400r/min, is stalled after operating 30min 10min, so circulation ball milling 50h, obtain the magnesium alloy powder that average grain diameter is 50nm, and magnesium alloy powder then is put into vacuum In high temperature furnace, 200 DEG C being heated under an argon atmosphere and 24 hours are incubated, the magnesium-based containing long period orderly accumulation structure is obtained Hydrogen bearing alloy.
Take the above-mentioned Mg base hydrogen bearing alloys of 1g to be fitted into PCT testers sample room, vacuumized after sealing, use temperature control heating by electric cooker To 200 DEG C of H2 for being filled with 2MPa afterwards, the measure of alloy hydrogen storage property is started after activation 3 times.As shown in Figure 2, it can be seen that 200 DEG C, under the conditions of 1Mpa, the alloy has been basically completed suction hydrogen in 7min.
Embodiment 3
The pure magnesium powders of 8.41g, 0.33g cobalt powders, 1.16g yttrium powders and 0.1g lithium powder are weighed, after being selected with 200 mesh sieves, loads ball milling In tank, placing into the stainless steel abrading-ball of a diameter of 6mm of 200g carries out ball milling, and rotating speed is 400r/min, is stalled after operating 30min 10min, so circulation ball milling 50h, obtain the magnesium alloy powder that average grain diameter is 50nm, and magnesium alloy powder then is put into vacuum In high temperature furnace, 200 DEG C being heated under an argon atmosphere and 24 hours are incubated, the magnesium-based containing long period orderly accumulation structure is obtained Hydrogen bearing alloy.
Take the above-mentioned Mg base hydrogen bearing alloys of 1g to be fitted into PCT testers sample room, vacuumized after sealing, use temperature control heating by electric cooker To 200 DEG C of H2 for being filled with 2MPa afterwards, the measure of alloy hydrogen storage property is started after activation 3 times.As shown in Figure 3, it can be seen that 200 DEG C, the alloy has been basically completed in 7min and has put hydrogen under the conditions of 1Mpa.

Claims (3)

1. a kind of Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period, it is characterised in that：Its chemical molecular formula is Mg- AX-bY-cLi, X represent the one kind in V or Co, a, b, c representation quality percentage, 3%≤a≤8%, 17%≤b≤19%, 0.5%≤c≤1%, balance of Mg.
2. the preparation method of the Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period of claim 1, it is characterised in that：Will be upper The alloying pellet for stating Components Chemical raw material loads ball grinder, by 15~20:1 ratio of grinding media to material adds the stainless steel of a diameter of 4~6mm Abrading-ball, rotating speed is 300~400r/min, and 10min is stalled after operating 30min, obtained after 30~50h of ball milling average grain diameter for 50~ The powder of 90nm, is then placed in high-temperature vacuum furnace, and 200 DEG C are heated under an argon atmosphere and 24 hours are incubated, and is obtained containing length The Mg base hydrogen bearing alloy of cycle orderly accumulation structure.
3. the preparation method of the Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period according to claim 2, its feature It is：The chemical raw material is simple metal powder.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06316740A (en) * 1992-11-13 1994-11-15 Toyota Motor Corp High strength magnesium-base alloy and its production
CN1271025A (en) * 2000-05-31 2000-10-25 南开大学 Magnesium-base hydrogen storing alloy material
CN101405417A (en) * 2006-03-20 2009-04-08 国立大学法人熊本大学 High-strength high-toughness magnesium alloy and method for producing the same
CN102337438A (en) * 2011-09-26 2012-02-01 华南理工大学 Magnesium-based hydrogen storage alloy with long period structure and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06316740A (en) * 1992-11-13 1994-11-15 Toyota Motor Corp High strength magnesium-base alloy and its production
CN1271025A (en) * 2000-05-31 2000-10-25 南开大学 Magnesium-base hydrogen storing alloy material
CN101405417A (en) * 2006-03-20 2009-04-08 国立大学法人熊本大学 High-strength high-toughness magnesium alloy and method for producing the same
CN102337438A (en) * 2011-09-26 2012-02-01 华南理工大学 Magnesium-based hydrogen storage alloy with long period structure and preparation method thereof

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