CN106756361B - 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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- CN106756361B CN106756361B CN201611120717.5A CN201611120717A CN106756361B CN 106756361 B CN106756361 B CN 106756361B CN 201611120717 A CN201611120717 A CN 201611120717A CN 106756361 B CN106756361 B CN 106756361B
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- 239000011777 magnesium Substances 0.000 title claims abstract description 95
- 239000001257 hydrogen Substances 0.000 title claims abstract description 87
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 87
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 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 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 42
- 238000000498 ball milling Methods 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 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
- 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 5
- 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
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 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 4
- 238000005338 heat storage Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 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
- 238000012827 research and development Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 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
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 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
- -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
- 238000010791 quenching 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
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 239000002918 waste heat Substances 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, chemical formula compositions are as follows: 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 under high-purity argon gas protection by the way that by magnesium grain, aluminium powder and nano graphite powder, mixing and ball milling is made in a planetary ball mill.The present invention is mainly characterized by using rich reserves in nature, cheap Mg, Al for component in terms of composition design, while adding a small amount of nano graphite powder and carrying out mixing and ball milling.The said components material of technique preparation is nanocrystalline structure, and it also includes a small amount of Al phase that main phase, which is Mg phase,.Material has quick hydrogen storage property, easily broken, and maximum hydrogen storage amount reaches 6.41wt.%, and saturation, which inhales hydrogen release, most only needs 600s fastly, is suitable for vehicle-mounted storage hydrogen system or hydrogenation stations.
Description
Technical field
The invention belongs to hydrogen-storage alloy technical field, in particular to a kind of Nanocrystalline Magnesium aluminium base hydrogen storage material and preparation side
Method.
Background technique
Hydrogen cell automobile (HFCV) is since pipeline time is short, without secondary pollution, course continuation mileage is remote, the advantages such as 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 car (EV, HEV), HFCV is also not up to the level of large-scale application.Limit the master of its development
It wants factor other than higher price, also resides in and lack safe and efficient storage hydrogen methods.Existing high-pressure gaseous stores hydrogen, low temperature
Liquefaction hydrogen storage technology safety, in terms of be unable to satisfy user require.Another storage hydrogen methods with practical prospect
To store hydrogen using metal hydride, hydrogen is stored in structure cell in the form of atom, highly-safe, can Reusability, easily recycle, it is comprehensive
It is at 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 requirement to energy storage density of storage hydrogen system and hydrogenation stations.
Metal magnesium base hydrogen-storing alloy has high hydrogen storage amount, and the hydrogen storage amount of pure magnesium is up to 7.6wt.%, Mg2NiH4It reaches
3.6wt.%, Mg2CoH5Up to 4.5wt.%, Mg2FeH6Up to 5.4wt.%.In addition, magnesium base hydrogen-storing alloy also has high heat accumulation close
Degree reaches 2800kJ/kg, is 10-20 times of fuse salt quantity of heat storage, is 4-7 times of phase-change heat-storage material.In conjunction with the light that China is huge
Volt industry and steel mill throughout the country make hydrogen in magnesium base hydrogen-storing alloy middle-high density using solar-powered heating or steel mill's waste heat
Storage be realize the applicable key of hydrogen.But above-mentioned hydrogen-storage alloy suction hydrogen desorption kinetics performance is poor, Mg2Fe、Mg2Co alloy system
Standby low efficiency, Mg2The price of Co alloy is also higher, does not have practical application foreground.Therefore, it improves and inhales hydrogen desorption kinetics 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 and metallic aluminium are formed has higher hydrogen storage amount, but alloy hydrogen absorption and desorption dynamics prepared by traditional fusion casting
Performance is poor, while good toughness, and hardly possible is broken.The present invention passes through the nanometer for preparing magnesium grain, aluminium powder and nano graphite powder mixing and ball milling
Brilliant magnalium base hydrogen-storing alloy has quick charge and discharge Hydrogen Energy power, provides for hydrogen cell automobile hydrogen source and hydrogenation stations with real
With the hydrogen-storage alloy and preparation method thereof of value.
Summary of the invention
The purpose of the present invention is to provide a kind of Nanocrystalline Magnesium aluminium base hydrogen storage materials, and hydrogen-storage alloy is made to inhale hydrogen desorption kinetics
It can substantially improve, have quick charge and discharge Hydrogen Energy power.
Another object of the present invention is to provide a kind of preparation methods 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 of Mg-Al hydrogen-storage alloy and graphite, at being grouped as are as follows:
Mg100-xAlx+ y (wt.%) C, in which: Mg100-xAlxFor Mg-Al hydrogen-storage alloy, x is atomic ratio, 10≤x≤30；C is nanometer stone
Ink powder, y are the mass percent that graphite is added by radix of Mg-Al hydrogen-storage alloy quality, 1≤y≤8.
The Nanocrystalline Magnesium aluminium base hydrogen storage material at being grouped as are as follows: Mg90Al10+ 5wt.%C.
The magnesium-aluminum-based hydrogen storage material is nanocrystalline structure, and material granule pattern is sheet.
There is main phase Mg phase and a small amount of Al phase in Mg-Al hydrogen storage material.
The Nanocrystalline Magnesium aluminium base hydrogen storage material is flakey or particulate powder, and powder size range 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: ingredient → and nano graphite powder mixing and ball milling → impact grinding
Powder processed.
A kind of preparation method of magnesium-aluminum-based hydrogen storage material as mentioned, described method includes following steps:
A. it ingredient: according to chemical composition forms: Mg100-xAlx+ y (wt.%) C weighs raw material coarse powder, and x is atomic ratio in formula,
Y is the mass percent that graphite is added by radix of Mg-Al hydrogen-storage alloy quality, and 10≤x≤30,1≤y≤8；
B. mixing and ball milling: the weighing by mass percentage of magnesium grain and aluminium powder is mixed, the mixture again with the stone of 1~8wt.%
Ink powder ball milling, ratio of grinding media to material 20:1 after mixing are filled with high-purity argon gas as protection gas, and setting speed 350r/min is used
The ball milling mode of ball milling 0.5h, rest 0.5h start 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 are controlled in D10=5-14 μm, D50=65-80 μm, D90In=100-120 μ m.
In step a, raw material selects 80 mesh magnesium grains, 200 mesh aluminium powders, metal purity > 99% used.
In step b, the graphite powder is nano graphite powder.
In step b, the mixture is mixed with the graphite powder of 1-8wt.% and is put into stainless steel jar mill, and stainless steel is added
Abrading-ball carries out ball milling in a planetary ball mill.
The beneficial effects of the present invention are:
(1) compared to traditional LaNi5Type hydrogen-storage alloy, in terms of composition design use cheap Mg, Al metal, two
Element rich reserves in nature are planted, it is cheap, be conducive to large-scale promotion application.
(2) the reversible hydrogen storage amount of Nanocrystalline Magnesium aluminium base hydrogen-storage alloy prepared by has been increased 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 U.S. Department of Energy pair
The requirement of vehicle-mounted storage hydrogen system energy storage density.
(3) the Nanocrystalline Magnesium aluminium base hydrogen storage material prepared by, which has, quickly inhales hydrogen release ability.The addition of nano graphite powder is aobvious
The dynamic performance for increasing alloy write.At 380 DEG C, the pressure of 3MPa hydrogen only needs 600s i.e. and can reach the 90% of saturation hydrogen-sucking amount
More than, complete hydrogen release only needs 600-2000s, hence it is evident that is better than other types of magnesium base hydrogen-storing alloy.
(4) with the technique of nano graphite powder mixing and ball milling used by, prepared alloy is flakey or powdery.Phase
Than traditional melting casting ingot process, Mechanical Crushing process is omitted, solves the problems, such as the broken hardly possible of as cast condition magnesium alloy.Gained closes
Golden scale or powder can directly in impact grinding powder processed.It compared to melting+fast quenching+flouring technology, has saved the production time, has reduced
Energy consumption, while can be improved the degree of automation of production, labour needed for reducing.
(5) compared to other ball-milling technologies, the used technique with nano graphite powder mixing and ball milling, prepared alloy
In, graphite is to increase the channel that hydrogen atom is spread in alloy body, be obviously improved magnesium-based in layer structure insertion alloy
The dynamic performance of hydrogen-storage alloy.
Detailed description of the invention
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 kinetics curve of+y (wt.%) C alloy.
Fig. 4 is Mg90Al10The TEM photo of+5 (wt.%) C alloys.
Fig. 5 is Mg90Al10+ 5 (wt.%) C alloys inhale the SEM pattern before hydrogen.
Fig. 6 is Mg90Al10SEM pattern after the activation of+5 (wt.%) C alloys.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.
Mentality of designing of the invention is as follows:
Ingredient design aspect, firstly, selecting cheap, rich reserves magnesium metals and metallic aluminium as main former material
Material, while a small amount of nano graphite powder is added, chemical component composition are as follows:
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, comprising the following steps:
A. it according to chemical composition forms: 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.Select 80 mesh magnesium grains, 200 mesh aluminium powders, metal purity > 99% used.
B. the weighing by mass percentage of magnesium grain and aluminium powder is mixed, which mixes with the nano graphite powder of 1-8wt.%
It is put into stainless steel jar mill.The stainless steel that certain mass ratio is added quenches abrading-ball, and ratio of grinding media to material 20:1 is filled with high-purity argon gas work
To protect gas.Setting speed is 350r/min, and using ball milling 0.5h, the ball milling mode of rest 0.5h starts ball milling, when total ball milling
Between in 10h.After ball milling, powder sieving weighing is taken out, whole operation process is all carried out in the vacuum glove box full of argon gas, kept away
Exempt to contact with air and aoxidize, and is sealed with vacuum packing machine.
C. alloy obtained by ball milling is flakey or powdered, can directly be crushed in impact grinding without Mechanical Crushing, is controlled
Powder size processed is in D10=5-14 μm, D50=65-80 μm, D90=100-120 μm.
Structural characterization and performance test are carried out to the alloy of above-mentioned preparation, alloy phase group is observed using X-ray diffraction (XRD)
At；The variation of alloying pellet pattern before and after inhaling hydrogen is observed using scanning electron microscope (SEM)；Alloy is observed using transmission electron microscope (TEM)
Heterogeneous microstructure；Hydrogen desorption kinetics performance and PCT curve are inhaled using the gaseous state of semi-automatic Seviet tester beta alloy,
Suction hydrogen test condition is 3MPa, and 380 DEG C, hydrogen release test condition is 0.1 × 10-3MPa, 380 DEG C.
Below in conjunction with attached drawing and representative embodiment, be described in further detail design philosophy of the invention and
Formation mechenism, so that technical solution of the invention is clearer.
Below with reference to embodiment, the present invention is described in detail.
The chemical formula composition of 1-9 of the embodiment of the present invention is as follows:
1 Mg of embodiment90Al10
2 Mg of embodiment90Al10+ 1 (wt.%) C
3 Mg of embodiment90Al10+ 3 (wt.%) C
4 Mg of embodiment90Al10+ 5 (wt.%) C
5 Mg of embodiment90Al10+ 8 (wt.%) C
6 Mg of embodiment85Al15+ 5 (wt.%) C
7 Mg of embodiment80Al20+ 5 (wt.%) C
8 Mg of embodiment75Al25+ 5 (wt.%) C
9 Mg of embodiment70Al30+ 5 (wt.%) C
Embodiment 1
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg90Al10Raw metal 10g is weighed by mass percentage, tests used gold
Belong to the purity of simple substance 99% or more.Above-mentioned powder in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.?
3MPa, at 380 DEG C, gained alloy maximum hydrogen-sucking amount is 4.01wt.%, reaches saturation hydrogen-sucking amount and needs 600s, complete hydrogen release needs
Want 2000s.The phase composition of gained alloy as shown in Figure 1, hydrogen-absorption speed curve 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 used metal simple-substance is 99% or more.The nano graphite powder of 0.1g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 5.92wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release 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 used metal simple-substance is 99% or more.The nano graphite powder of 0.3g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 6.21wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release 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 used metal simple-substance is 99% or more.The nano graphite powder of 0.5g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 6.41wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release 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 insertion alloy, as shown in figure 4, increasing hydrogen in the intracorporal diffusion admittance of alloy, suction hydrogen release is greatly improved
Dynamic performance.Material granule pattern is laminated structure after ball milling, as shown in Figure 5.The structure, which not only improves, increases alloy and hydrogen
Contact area, while shortening hydrogen in the intracorporal diffusion path of alloy, be conducive to the improvement for inhaling hydrogen desorption kinetics performance.Alloy
It is lax porous structure, as shown in fig. 6, specific surface area further increases, to make the suction hydrogen desorption kinetics of alloy after activation
Performance reaches best.
Embodiment 5
Nanocrystalline Magnesium aluminium base hydrogen-storage alloy Mg90Al10+ 8 (wt.%) C weigh raw metal 10g by mass percentage, experiment
The purity of used metal simple-substance is 99% or more.The nano graphite powder of 0.8g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 5.61wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release 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 used metal simple-substance is 99% or more.The nano graphite powder of 0.5g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 6.13wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release 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 used metal simple-substance is 99% or more.The nano graphite powder of 0.5g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 5.77wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release 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 used metal simple-substance is 99% or more.The nano graphite powder of 0.5g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 4.21wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release 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 used metal simple-substance is 99% or more.The nano graphite powder of 0.5g is uniformly mixed with raw material metal powder
Afterwards in a planetary ball mill, the ball milling 10h under 350r/min revolving speed.At 3MPa, 380 DEG C, gained alloy maximum hydrogen-sucking amount
For 3.66wt.%, reaches saturation hydrogen-sucking amount and need 600s, complete hydrogen release needs 500s.
Above-described embodiment 1-9 hydrogen storage property is as shown in table 2.
The gaseous state performance of 2 embodiment alloy of table
Claims (8)
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 of Mg-Al hydrogen-storage alloy and graphite, at being grouped as are as follows:
Mg100-xAlx+ y (wt.%) C, in which: Mg100-xAlxFor Mg-Al hydrogen-storage alloy, x is atomic ratio, 10≤x≤30；C is nanometer stone
Ink powder, y are the mass percent that graphite is added by radix of Mg-Al hydrogen-storage alloy quality, 1≤y≤8；
There is main phase Mg phase and a small amount of Al phase in Mg-Al hydrogen storage material；
The magnesium-aluminum-based hydrogen storage material is made by the steps: ingredient → grind with nano graphite powder mixing and ball milling → impact
Powder；Mixing and ball milling step therein are as follows: the weighing by mass percentage of magnesium grain and aluminium powder is mixed, the mixture again with 1~
The graphite powder of 8wt.% ball milling after mixing, total Ball-milling Time is in 9~11h.
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 at being grouped as are as follows: 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:
The Nanocrystalline Magnesium aluminium base hydrogen storage material is flakey or particulate powder, and powder size range is D10=5-14 μm, D50=
65-80 μm, D90=100-120 μm.
5. a kind of preparation method of magnesium-aluminum-based hydrogen storage material as described in claim 1, it is characterised in that:
Described method includes following steps:
A. it ingredient: according to chemical composition forms: Mg100-xAlx+ y (wt.%) C weighs raw material coarse powder, and x is atomic ratio in formula, and y is
The mass percent of graphite, and 10≤x≤30,1≤y≤8 are added using Mg-Al hydrogen-storage alloy quality as radix；
B. mixing and ball milling: the weighing by mass percentage of magnesium grain and aluminium powder is mixed, the mixture again with the graphite powder of 1~8wt.%
Ball milling after mixing, ratio of grinding media to material 20:1 are filled with high-purity argon gas as protection gas, setting speed 350r/min, using ball milling
The ball milling mode of 0.5h, rest 0.5h start ball milling, and total Ball-milling Time is in 9~11h；
C. impact grinding: after mechanical ball mill, gained alloy is flakey or powdered, is not necessarily to Mechanical Crushing powder directly in impact grinding
Broken, powder size is controlled in D10=5-14 μm, D50=65-80 μm, D90In=100-120 μ m.
6. preparation method according to claim 5, it is characterised in that:
In step a, raw material selects 80 mesh magnesium grains, 200 mesh aluminium powders, metal purity > 99% used.
7. preparation method according to claim 5, it is characterised in that:
In step b, the graphite powder is nano graphite powder.
8. preparation method according to claim 5, it is characterised in that:
In step b, the mixture is mixed with the graphite powder of 1-8wt.% and is put into stainless steel jar mill, and stainless steel abrading-ball is added
Ball milling is carried out in a planetary ball mill.
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