CN106756361A - A kind of Nanocrystalline Magnesium aluminium base hydrogen storage material and preparation method - Google Patents
A kind of Nanocrystalline Magnesium aluminium base hydrogen storage material and preparation method Download PDFInfo
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- CN106756361A CN106756361A CN201611120717.5A CN201611120717A CN106756361A CN 106756361 A CN106756361 A CN 106756361A CN 201611120717 A CN201611120717 A CN 201611120717A CN 106756361 A CN106756361 A CN 106756361A
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- 239000011777 magnesium Substances 0.000 title claims abstract description 95
- 239000001257 hydrogen Substances 0.000 title claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 49
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 41
- 239000004411 aluminium Substances 0.000 title claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011232 storage material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 70
- 239000000956 alloy Substances 0.000 claims abstract description 70
- 238000003860 storage Methods 0.000 claims abstract description 43
- 238000000498 ball milling Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 14
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 235000012054 meals Nutrition 0.000 claims description 2
- 238000013461 design Methods 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910001339 C alloy Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005338 heat storage Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910002335 LaNi5 Inorganic materials 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 240000001624 Espostoa lanata Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- -1 magnesium metals Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Classifications
-
- 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
- C22C23/02—Alloys based on magnesium with aluminium as the next major 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic 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
- 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
-
- 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
- B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet 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)
- Nanotechnology (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a kind of Nanocrystalline Magnesium aluminium base hydrogen storage material and preparation method, its chemical formula composition is：Mg100‑xAlx+ y (wt.%) C.X is atomic ratio in formula, and y is mass percent, and 10≤x≤30,1≤y≤8.Preferred alloy compositions are Mg90Al10+ 5wt.%C.The preparation method is obtained by by magnesium grain, aluminium powder and the Nano graphite powder mixing and ball milling in planetary ball mill under high-purity argon gas protection.It is component that the present invention is mainly characterized by being used in composition design rich reserves in nature, cheap Mg, Al, while a small amount of Nano graphite powder of addition carries out mixing and ball milling.Said components material prepared by the technique is nanocrystalline structure, and principal phase is Mg phases, also comprising a small amount of Al phases.Material possesses quick hydrogen storage property, broken, and maximum hydrogen storage amount reaches 6.41wt.%, and hydrogen is put in saturation suction most only needs 600s soon, it is adaptable to vehicle-mounted storage hydrogen system or hydrogenation stations.
Description
Technical field
The invention belongs to hydrogen-storage alloy technical field, more particularly to a kind of Nanocrystalline Magnesium aluminium base hydrogen storage material and preparation side
Method.
Background technology
The advantage such as hydrogen cell automobile (HFCV) is because pipeline time is short, non-secondary pollution, course continuation mileage are remote, easy-maintaining
It is considered as the ultimate form of future automobile.Japan, Britain, the U.S., South Korea maintain the leading position in terms of the research and development of HFCV.But
Compared to the fast development of electric automobile (EV, HEV), HFCV is also not up to the level of large-scale application.Limit the master of its development
Factor is wanted in addition to price higher, the safe and efficient storage hydrogen methods of shortage are also resided in.Existing high-pressure gaseous storage hydrogen, low temperature
Liquefaction hydrogen storage technology cannot meet user and require at aspects such as safety, costs.Another has the storage hydrogen methods of practical prospect
To store hydrogen using metal hydride, hydrogen is stored in structure cell with atom form, safe, can Reusability, easily reclaim, it is comprehensive
Low cost.It is disadvantageous in that the LaNi of unique large-scale production5The theoretical hydrogen storage amount of type hydrogen-storage alloy only has 1.36wt.%,
Far from meeting vehicle-mounted storage requirement to energy storage density of hydrogen system and hydrogenation stations.
Metal magnesium base hydrogen-storing alloy possesses hydrogen storage amount high, and the hydrogen storage amount of pure magnesium is up to 7.6wt.%, Mg2NiH4Reach
3.6wt.%, Mg2CoH5Up to 4.5wt.%, Mg2FeH6Up to 5.4wt.%.In addition, magnesium base hydrogen-storing alloy also has heat accumulation high close
Degree, is 10-20 times of fuse salt quantity of heat storage up to 2800kJ/kg, is 4-7 times of phase-change heat-storage material.With reference to the light that China is huge
Volt industry and the steel mill for spreading all over the country, hydrogen is made in magnesium base hydrogen-storing alloy middle-high density using solar-powered heating or steel mill's used heat
Storage be to realize the applicable key of hydrogen.But above-mentioned hydrogen-storage alloy inhales hydrogen desorption kineticses poor performance, Mg2Fe、Mg2Co alloy systems
Standby efficiency is low, Mg2The price of Co alloys is also higher, does not possess practical application foreground.Therefore, improve and inhale hydrogen desorption kineticses performance, drop
The technology of preparing that the low cost of raw material and research and development are easy to large-scale production is to realize the emphasis of magnesium base hydrogen-storing alloy application.Metal
The compound that magnesium is formed with metallic aluminium, possesses hydrogen storage amount higher, but the alloy hydrogen absorption and desorption dynamics prepared by traditional fusion casting
Poor performance, while good toughness, difficult broken.Nanometer by prepared by magnesium grain, aluminium powder and Nano graphite powder mixing and ball milling of the invention
Brilliant magnalium base hydrogen-storing alloy possesses quick charge and discharge Hydrogen Energy power, for hydrogen cell automobile hydrogen source and hydrogenation stations are provided with real
Hydrogen-storage alloy with value and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of Nanocrystalline Magnesium aluminium base hydrogen storage material, hydrogen-storage alloy is set to inhale hydrogen desorption kineticses
Can substantially improve, possess quick charge and discharge Hydrogen Energy power.
Another object of the present invention is to provide a kind of preparation method of Nanocrystalline Magnesium aluminium base hydrogen storage material.
To achieve the above object, technical scheme is as follows：
A kind of Nanocrystalline Magnesium aluminium base hydrogen storage material, it is characterised in that：
The Nanocrystalline Magnesium aluminium base hydrogen storage material is the powder being made up of Mg-Al hydrogen-storage alloys and graphite, and it is into being grouped into：
Mg100-xAlx+ y (wt.%) C, wherein：Mg100-xAlxIt is Mg-Al hydrogen-storage alloys, x is atomic ratio, 10≤x≤30；C is nanometer stone
Ink powder, y is the mass percent for adding graphite as radix with Mg-Al hydrogen-storage alloys quality, 1≤y≤8.
The Nanocrystalline Magnesium aluminium base hydrogen storage material into being grouped into：Mg90Al10+ 5wt.%C.
The magnesium-aluminum-based hydrogen storage material is nanocrystalline structure, and material granule pattern is sheet.
There is principal phase Mg phases and a small amount of Al phases in Mg-Al hydrogen storage materials.
The Nanocrystalline Magnesium aluminium base hydrogen storage material is flakey or particulate powder, and powder size scope is D10=5-14 μm,
D50=65-80 μm, D90=100-120 μm.
The magnesium-aluminum-based hydrogen storage material is made by the steps：Dispensing → and Nano graphite powder mixing and ball milling → impact grinding
Powder processed.
A kind of preparation method of the hydrogen storage material of magnesium-aluminum-based as mentioned, methods described comprises the following steps：
A. dispensing：According to chemical composition constitute：Mg100-xAlx+ y (wt.%) C weighs raw material meal, and x is atomic ratio in formula,
Y is the mass percent for adding graphite as radix with Mg-Al hydrogen-storage alloys quality, and 10≤x≤30,1≤y≤8；
B. mixing and ball milling：By magnesium grain and aluminium powder weighing by mass percentage mix, the mixture again with the stone of 1~8wt.%
Ball milling after ink powder is well mixed, ratio of grinding media to material is 20:1, high-purity argon gas are filled with as protection gas, setting speed 350r/min is used
The ball milling pattern of ball milling 0.5h, rest 0.5h starts ball milling, and total Ball-milling Time is in 9~11h；
C. impact grinding：After mechanical ball mill, gained alloy is flakey or powdered, without Mechanical Crushing directly in impact grinding
Middle crushing, powder size is controlled in D10=5-14 μm, D50=65-80 μm, D90In=100-120 μ ms.
In step a, raw material is from 80 mesh magnesium grain, 200 mesh aluminium powders, metal purity ＞ 99% used.
In step b, the graphite powder is Nano graphite powder.
In step b, the mixture mixes with the graphite powder of 1-8wt.% and is put into stainless steel jar mill, adds stainless steel
Abrading-ball carries out ball milling in planetary ball mill.
The beneficial effects of the present invention are：
(1) compared to traditional LaNi5Type hydrogen-storage alloy, uses cheap Mg, Al metal, two in composition design
Element rich reserves in nature are planted, it is cheap, be conducive to large-scale promotion application.
(2) the Nanocrystalline Magnesium reversible hydrogen storage amount of aluminium base hydrogen-storage alloy prepared by has brought up to 6.41wt.%, is LaNi5Type
4.7 times of hydrogen-storage alloy theory hydrogen storage amount, are also generally higher than other magnesium base hydrogen-storing alloys, and hydrogen storage amount has reached USDOE pair
The requirement of vehicle-mounted storage hydrogen system energy storage density.
(3) the Nanocrystalline Magnesium aluminium base hydrogen storage material prepared by possesses quick suction and puts Hydrogen Energy power.The addition of Nano graphite powder shows
The dynamic performance that increased alloy for writing.At 380 DEG C, the pressure of 3MPa hydrogen only needs 600s to can reach the 90% of saturation hydrogen-sucking amount
More than, hydrogen is put completely only needs 600-2000s, hence it is evident that better than other types of magnesium base hydrogen-storing alloy.
(4) technique with Nano graphite powder mixing and ball milling for being used, prepared alloy is flakey or powdery.Phase
Than traditional melting casting ingot process, Mechanical Crushing process is eliminated, solve the problems, such as the broken hardly possible of as cast condition magnadure.Gained is closed
Golden scale or powder can the direct powder processed in impact grinding.Compared to melting+fast quenching+flouring technology, save the production time, reduced
Energy consumption, while can improve the automaticity of production, labour needed for reducing.
(5) compared to other ball-milling technologies, the technique with Nano graphite powder mixing and ball milling for being used, prepared alloy
In, during graphite is with layer structure insertion alloy, the passage that hydrogen atom spreads in alloy body is increased, it has been obviously improved magnesium-based
The dynamic performance of hydrogen-storage alloy.
Brief description of the drawings
Fig. 1 is Mg90Al10The XRD spectrum of+y (wt.%) C alloy.
Fig. 2 is Mg90Al10The Dynamic isotherms of hydrogen absorption of+y (wt.%) C alloy.
Fig. 3 is Mg90Al10The hydrogen desorption kineticses curve of+y (wt.%) C alloy.
Fig. 4 is Mg90Al10The TEM photos of+5 (wt.%) C alloys.
Fig. 5 is Mg90Al10+ 5 (wt.%) C alloys inhale the SEM patterns before hydrogen.
Fig. 6 is Mg90Al10SEM patterns after the activation of+5 (wt.%) C alloys.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiment of the invention is described in further detail.
Mentality of designing of the invention is as follows：
Composition design aspect, first, from cheap, rich reserves magnesium metals and metallic aluminium as main former material
Material, while adding a small amount of Nano graphite powder, chemical composition composition is：
Mg100-xAlx+ y (wt.%) C.X is atomic ratio in formula, and y is mass percent, and 10≤x≤30,0≤y≤8.It is excellent
The alloy compositions of choosing are Mg90Al10+ 5 (wt.%) C.
The preparation method of magnalium base hydrogen-storing alloy of the invention, comprises the following steps：
A. according to chemical composition constitute：Mg100-xAlx+ y (wt.%) C weighs raw material.X is atomic ratio in formula, and y is quality hundred
Divide ratio, and 10≤x≤30,0≤y≤8.From 80 mesh magnesium grain, 200 mesh aluminium powders, metal purity ＞ 99% used.
B. magnesium grain and aluminium powder weighing by mass percentage are mixed, the mixture mixes with the Nano graphite powder of 1-8wt.%
It is put into stainless steel jar mill.Add certain mass than stainless steel quench abrading-ball, ratio of grinding media to material is 20:1, it is filled with high-purity argon gas work
It is protection gas.Setting speed is 350r/min, and using ball milling 0.5h, the ball milling pattern of rest 0.5h starts ball milling, during total ball milling
Between in 10h.After ball milling, take out powder sieving and weigh, whole operation process is carried out all in the vacuum glove box full of argon gas, is kept away
Exempt to be aoxidized with air contact, and sealed with vacuum packing machine.
C. ball milling gained alloy is flakey or powdered, directly can be crushed in impact grinding without Mechanical Crushing, control
Powder size processed is in D10=5-14 μm, D50=65-80 μm, D90=100-120 μm.
Alloy to above-mentioned preparation carries out structural characterization and performance test, and alloy phase group is observed using X-ray diffraction (XRD)
Into；The change of alloying pellet pattern before and after hydrogen is inhaled using ESEM (SEM) observation；Alloy is observed using transmission electron microscope (TEM)
Heterogeneous microstructure；Hydrogen desorption kineticses performance and PCT curves are inhaled using the gaseous state of semi-automatic Seviet testers beta alloy,
It is 3MPa to inhale hydrogen test condition, and 380 DEG C, it is 0.1 × 10 to put hydrogen test condition-3MPa, 380 DEG C.
Below in conjunction with accompanying drawing and representative embodiment, describe in further detail design philosophy of the invention and
Formation mechenism, so that technical solution of the invention is clearer.
With reference to embodiment, the present invention is described in detail.
The chemical formula composition of embodiment of the present invention 1-9 is as follows：
The Mg of embodiment 190Al10
The Mg of embodiment 290Al10+ 1 (wt.%) C
The Mg of embodiment 390Al10+ 3 (wt.%) C
The Mg of embodiment 490Al10+ 5 (wt.%) C
The Mg of embodiment 590Al10+ 8 (wt.%) C
The Mg of embodiment 685Al15+ 5 (wt.%) C
The Mg of embodiment 780Al20+ 5 (wt.%) C
The Mg of embodiment 875Al25+ 5 (wt.%) C
The Mg of embodiment 970Al30+ 5 (wt.%) C
Embodiment 1
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg90Al10Raw metal 10g is weighed by mass percentage, tests used gold
The purity of category simple substance is more than 99%.Above-mentioned powder in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.
3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount is 4.01wt.%, and reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely to be needed
Want 2000s.The phase composition of gained alloy is as shown in figure 1, hydrogen-absorption speed curve is as shown in Fig. 2 hydrogen discharging rate curve is as shown in Figure 3.
Embodiment 2
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg90Al10+ 1 (wt.%) C weighs raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.1g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 5.92wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 1200s.The phase composition of gained alloy as shown in figure 1,
Hydrogen-absorption speed curve is as shown in Fig. 2 hydrogen discharging rate curve is as shown in Figure 3.
Embodiment 3
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg90Al10+ 3 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.3g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 6.21wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 1000s.The phase composition of gained alloy as shown in figure 1,
Hydrogen-absorption speed curve is as shown in Fig. 2 hydrogen discharging rate curve is as shown in Figure 3.
Embodiment 4
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg90Al10+ 5 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.5g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 6.41wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 600s.The phase composition of gained alloy as shown in figure 1,
Hydrogen-absorption speed curve is as shown in Fig. 2 hydrogen discharging rate curve is as shown in Figure 3.Alloy is nanocrystalline structure, the Nano graphite powder of addition
With laminar structured embedded alloy, as shown in figure 4, increased diffusion admittance of the hydrogen in alloy body, greatly improve suction and put hydrogen
Dynamic performance.Material granule pattern is laminated structure after ball milling, as shown in Figure 5.The structure not only improves increase alloy and hydrogen
Contact area, while shorten diffusion path of the hydrogen in alloy body, be conducive to inhaling the improvement of hydrogen desorption kineticses performance.Alloy
It is lax porous structure after activation, as shown in fig. 6, specific surface area further increases, so that the suction hydrogen desorption kineticses of alloy
Performance reaches most preferably.
Embodiment 5
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg90Al10+ 8 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.8g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 5.61wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 900s.The phase composition of gained alloy as shown in figure 1,
Hydrogen-absorption speed curve is as shown in Fig. 2 hydrogen discharging rate curve is as shown in Figure 3.
Embodiment 6
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg85Al15+ 5 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.5g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 6.13wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 500s.
Embodiment 7
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg80Al20+ 5 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.5g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 5.77wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 500s.
Embodiment 8
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg75Al25+ 5 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.5g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 4.21wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 500s.
Embodiment 9
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg70Al30+ 5 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of the metal simple-substance for being used is more than 99%.The Nano graphite powder of 0.5g is well mixed with raw material metal powder
Afterwards in planetary ball mill, the ball milling 10h under 350r/min rotating speeds.In 3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount
It is 3.66wt.%, reaching saturation hydrogen-sucking amount needs 600s, and hydrogen is put completely needs 500s.
Above-described embodiment 1-9 hydrogen storage properties are as shown in table 2.
The gaseous state performance of the embodiment alloy of table 2
Claims (10)
1. a kind of Nanocrystalline Magnesium aluminium base hydrogen storage material, it is characterised in that：
The Nanocrystalline Magnesium aluminium base hydrogen storage material is the powder being made up of Mg-Al hydrogen-storage alloys and graphite, and it is into being grouped into：
Mg100-xAlx+ y (wt.%) C, wherein：Mg100-xAlxIt is Mg-Al hydrogen-storage alloys, x is atomic ratio, 10≤x≤30；C is nanometer stone
Ink powder, y is the mass percent for adding graphite as radix with Mg-Al hydrogen-storage alloys quality, 1≤y≤8.
2. Nanocrystalline Magnesium aluminium base hydrogen storage material according to claim 1, it is characterised in that：
The Nanocrystalline Magnesium aluminium base hydrogen storage material into being grouped into：Mg90Al10+ 5wt.%C.
3. Nanocrystalline Magnesium aluminium base hydrogen storage material according to claim 1, it is characterised in that：
The magnesium-aluminum-based hydrogen storage material is nanocrystalline structure, and material granule pattern is sheet.
4. Nanocrystalline Magnesium aluminium base hydrogen storage material according to claim 1, it is characterised in that：
There is principal phase Mg phases and a small amount of Al phases in Mg-Al hydrogen storage materials.
5. Nanocrystalline Magnesium aluminium base hydrogen storage material according to claim 1, it is characterised in that：
The Nanocrystalline Magnesium aluminium base hydrogen storage material is flakey or particulate powder, and powder size scope is D10=5-14 μm, D50=
65-80 μm, D90=100-120 μm.
6. magnesium-aluminum-based hydrogen storage material according to claim 1, it is characterised in that：
The magnesium-aluminum-based hydrogen storage material is made by the steps：Dispensing → ground with Nano graphite powder mixing and ball milling → impact
Powder.
7. a kind of preparation method of magnesium-aluminum-based hydrogen storage material as claimed in claim 1, it is characterised in that：
Methods described comprises the following steps：
A. dispensing：According to chemical composition constitute：Mg100-xAlx+ y (wt.%) C weighs raw material meal, and x is atomic ratio in formula, and y is
The mass percent of graphite, and 10≤x≤30,1≤y≤8 are added as radix with Mg-Al hydrogen-storage alloys quality；
B. mixing and ball milling：By magnesium grain and aluminium powder weighing by mass percentage mix, the mixture again with the graphite powder of 1~8wt.%
Ball milling after well mixed, ratio of grinding media to material is 20:1, high-purity argon gas are filled with as protection gas, setting speed 350r/min, using ball milling
The ball milling pattern of 0.5h, rest 0.5h starts ball milling, and total Ball-milling Time is in 9~11h；
C. impact grinding：After mechanical ball mill, gained alloy is flakey or powdered, without the direct powder in impact grinding of Mechanical Crushing
Broken, powder size is controlled in D10=5-14 μm, D50=65-80 μm, D90In=100-120 μ ms.
8. preparation method according to claim 7, it is characterised in that：
In step a, raw material is from 80 mesh magnesium grain, 200 mesh aluminium powders, metal purity ＞ 99% used.
9. preparation method according to claim 7, it is characterised in that：
In step b, the graphite powder is Nano graphite powder.
10. preparation method according to claim 7, it is characterised in that：
In step b, the mixture mixes with the graphite powder of 1-8wt.% and is put into stainless steel jar mill, adds stainless steel abrading-ball
Ball milling is carried out in planetary ball mill.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107760947A (en) * | 2017-09-18 | 2018-03-06 | 西北工业大学 | Mg Al Ni system's hydrogen storage particles and its catalytic modification preparation method |
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| CN113862536A (en) * | 2021-09-14 | 2021-12-31 | 钢铁研究总院 | Mg-Al-Y-based hydrogen storage material and preparation method thereof |
| CN113862536B (en) * | 2021-09-14 | 2022-07-08 | 钢铁研究总院 | Mg-Al-Y-based hydrogen storage material and preparation method thereof |
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