CN106756369B - A kind of Mg base hydrogen bearing alloy and preparation method thereof of the structure of orderly accumulation containing long period - Google Patents

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

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CN106756369B
CN106756369B CN201611075580.6A CN201611075580A CN106756369B CN 106756369 B CN106756369 B CN 106756369B CN 201611075580 A CN201611075580 A CN 201611075580A CN 106756369 B CN106756369 B CN 106756369B
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bearing alloy
hydrogen bearing
long period
base hydrogen
containing long
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CN106756369A (en
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彭秋明
王栋彬
葛炳成
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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 are that Mg aX bY cLi, X represent one kind in V or Co, a, b, c representation quality percentage, 3%≤a≤8%, 17%≤b≤19%, 0.5%≤c≤1%, surplus Mg；The preparation method of above-mentioned Mg base hydrogen bearing alloy is mainly that the alloying pellet of mentioned component is packed into ball grinder, by 15：1~20:The stainless steel abrading-ball of 4~6mm is added in 1 ratio of grinding media to material, 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, it is heated to 200 DEG C under an argon atmosphere and keeps the temperature 24 hours, the Mg base hydrogen bearing alloy containing long period orderly accumulation structure is made.Present invention process equipment is simple and easy to control, at low cost, and Mg base hydrogen bearing alloy suction hydrogen discharging temperature obtained is moderate, and it is good to inhale hydrogen desorption kinetics performance.

Description

A kind of Mg base hydrogen bearing alloy and preparation method thereof of the structure of orderly accumulation containing long period
Inventor：Peng Qiuming；Wang Dongbin；Ge Ping Cheng.
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 the getting worse of reduction and the environmental pollution of fossil fuel, people there is an urgent need to find it is a kind of it is novel, do not have There is the energy of environmental pollution.Hydrogen Energy has clean, energy height, not will produce the lot of advantages such as secondary pollution, therefore hydrogen energy source Exploitation causes the great interest of people.Hydrogen energy system include hydrogen source exploitation, hydrogen producing technology, hydrogen storage technology, hydrogen utilization technology Deng.In entire hydrogen energy system, hydrogen storage is the link of most critical.
Mg base hydrogenous alloys due to its hydrogen storage content is big, density is low, resourceful and lower-price characteristic and make it One of most promising hydrogen storage material.But the suction hydrogen release condition (hydrogen discharging temperature is high, speed is slow) of Mg based hydrogen storage material harshnesses hinders Its application in practice, therefore how to reduce its suction hydrogen discharging temperature (300 DEG C) and improve and inhale hydrogen desorption kinetics performance one It is directly the emphasis of people's research.Currently, 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, is less than 4wt%, and hydrogen discharging temperature is still very high, is more than 300 DEG C.And And the Mg of the researchs such as nearest Ou Yangliu chapters3Pr and Mg3PrNi0.1Hydrogen can be inhaled at room temperature, and it is non-to inhale hydrogen desorption kinetics 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.
Invention content：
That the purpose of the present invention is to provide a kind of process equipments is simple, of low cost, can reduce magnesium-base hydrogen storage material 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 kinetics 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 present invention is Mg-aX-bY-cLi, X represents one kind in V or Co, a, b, c representation quality percentages, 3%≤a≤8%, 17%≤b≤19%, and 0.5%≤c≤ 1%, surplus Mg.
Above-mentioned element is simple metal powder.
The preparation method of above-mentioned Mg base hydrogen bearing alloy：
The simple metal powder of mentioned component chemical raw material is packed into ball grinder, by 15~20:1 ratio of grinding media to material is added a diameter of 4 The stainless steel abrading-ball of~6mm, rotating speed are 300~400r/min, stall 10min after operating 30min, are obtained after 30~50h of ball milling Average grain diameter is the powder of 50~90nm, is then placed in high-temperature vacuum furnace, is heated to 200 DEG C under an argon atmosphere and keeps the temperature 24 Hour, the Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period is made.
The present invention has the following advantages that compared with prior art：
1, process equipment is simple, using ball-milling method so that metallic particles constantly refines, until reaching Nano grade, generates A large amount of fresh surface and lattice defect, to effectively reduce activation energy.
2, on traditional ball-milling technology, be added to the operation of heat treatment so that evaporated lithium be hydrogen in the sample Transport provide channel, to greatly reinforce hydrogen storage property.
3, the Mg base hydrogen bearing alloy obtained containing long period orderly accumulation structure have hydrogen storage content is big, hydrogen discharging temperature is low, Inhale the good advantage of hydrogen desorption kinetics performance.
4, cheap, it can be suitably used for producing in enormous quantities.
Description of the drawings
Fig. 1 is Mg made from the embodiment of the present invention 191V3Y5PCT curve graphs of Li under the conditions of 200 DEG C, 1Mpa.
Fig. 2 is Mg made from the embodiment of the present invention 291Co3Y5Suction of Li alloys under the conditions of 200 DEG C, 1Mpa in 25min is dynamic Force diagram figure.
Fig. 3 is Mg made from the embodiment of the present invention 393Co2Y4Hydrogen release of Li alloys under the conditions of 200 DEG C, 1Mpa in 25min Dynamic curve diagram.
Specific implementation mode：
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 screened with 200 mesh, is packed into ball milling In tank, the stainless steel abrading-ball for placing into a diameter of 4mm of 150g carries out ball milling, and rotating speed 300r/min is stalled after operating 30min 10min so recycles ball milling 30h, obtains the magnesium alloy powder that average grain diameter is 90nm, magnesium alloy powder is then put into vacuum In high temperature furnace, it is heated to 200 DEG C under an argon atmosphere and keeps the temperature 24 hours, the magnesium-based containing long period orderly accumulation structure is made Hydrogen bearing alloy.
It takes the above-mentioned Mg base hydrogen bearing alloys of 1g to be fitted into PCT testers sample room, is vacuumized after sealing, heated with temperature control electric furnace It is filled with the H2 of 2MPa after to 200 DEG C, starts the measurement of alloy hydrogen storage property after activating 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 suction/hydrogen release platform pressure is 0.2/0.15MPa, 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 screened with 200 mesh, is packed into ball milling In tank, the stainless steel abrading-ball for placing into a diameter of 6mm of 200g carries out ball milling, and rotating speed 400r/min is stalled after operating 30min 10min so recycles ball milling 50h, obtains the magnesium alloy powder that average grain diameter is 50nm, magnesium alloy powder is then put into vacuum In high temperature furnace, it is heated to 200 DEG C under an argon atmosphere and keeps the temperature 24 hours, the magnesium-based containing long period orderly accumulation structure is made Hydrogen bearing alloy.
It takes the above-mentioned Mg base hydrogen bearing alloys of 1g to be fitted into PCT testers sample room, is vacuumized after sealing, heated with temperature control electric furnace It is filled with the H2 of 2MPa after to 200 DEG C, starts the measurement of alloy hydrogen storage property after activating 3 times.As shown in Figure 2, it can be seen that 200 DEG C, under the conditions of 1Mpa, which 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 screened with 200 mesh, is packed into ball milling In tank, the stainless steel abrading-ball for placing into a diameter of 6mm of 200g carries out ball milling, and rotating speed 400r/min is stalled after operating 30min 10min so recycles ball milling 50h, obtains the magnesium alloy powder that average grain diameter is 50nm, magnesium alloy powder is then put into vacuum In high temperature furnace, it is heated to 200 DEG C under an argon atmosphere and keeps the temperature 24 hours, the magnesium-based containing long period orderly accumulation structure is made Hydrogen bearing alloy.
It takes the above-mentioned Mg base hydrogen bearing alloys of 1g to be fitted into PCT testers sample room, is vacuumized after sealing, heated with temperature control electric furnace It is filled with the H2 of 2MPa after to 200 DEG C, starts the measurement of alloy hydrogen storage property after activating 3 times.As shown in Figure 3, it can be seen that 200 DEG C, the alloy has been basically completed hydrogen release in 7min under the conditions of 1Mpa.

Claims (1)

1. a kind of preparation method of the Mg base hydrogen bearing alloy of the structure of orderly accumulation containing long period, the knot of orderly accumulation containing long period The chemical molecular formula of the Mg base hydrogen bearing alloy of structure is Mg-aX-bY-cLi, and X represents one kind in V or Co, a, b, c representation quality hundred Score, 3%≤a≤8%, 17%≤b≤19%, 0.5%≤c≤1%, surplus Mg, it is characterised in that：By mentioned component The simple metal powder for learning raw material is packed into ball grinder, by 15~20:The stainless steel abrading-ball of a diameter of 4~6mm is added in 1 ratio of grinding media to material, turns Speed is 300~400r/min, and 10min is stalled after operating 30min, and it is 50~90nm's that average grain diameter is obtained after 30~50h of ball milling Powder is then placed in high-temperature vacuum furnace, is heated to 200 DEG C under an argon atmosphere and is kept the temperature 24 hours, being made has containing long period The Mg base hydrogen bearing alloy of sequence packed structures.
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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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