CN106566965B - A kind of nano-magnesium-based hydrogen storage material of polymer overmold and preparation method thereof - Google Patents
A kind of nano-magnesium-based hydrogen storage material of polymer overmold and preparation method thereof Download PDFInfo
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- CN106566965B CN106566965B CN201610931895.XA CN201610931895A CN106566965B CN 106566965 B CN106566965 B CN 106566965B CN 201610931895 A CN201610931895 A CN 201610931895A CN 106566965 B CN106566965 B CN 106566965B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- 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
Abstract
The present invention relates to nano-magnesium-based hydrogen storage materials of a kind of polymer overmold and preparation method thereof, belong to hydrogen storage material preparation technical field.The nano-magnesium-based hydrogen storage material of the polymer overmold is made of following component by mass percentage: magnesium-nickel alloy: 80-98%, polymer: 2-20%；Pretreatment, hydriding combustion synthesis are mixed with nickel powder as raw material using magnesium powder and then are prepared with polymer by strength mechanical ball mill.There is the nano-magnesium-based hydrogen storage material of polymer overmold provided by the invention excellent low temperature to inhale hydrogen desorption kinetics performance: at 473K, in 60min, hydrogen-sucking amount reaches 3.73wt.%, and in 120min, hydrogen desorption capacity reaches 1.02wt.%；At 523K, in 60min, hydrogen-sucking amount is up to 4.04wt.%, and in 120min, hydrogen desorption capacity is up to 2.18wt.%, can be used for storage and transportation and the hydrogen fuel cell of hydrogen.
Description
Technical field
The present invention relates to a kind of high performance nano-magnesium-based hydrogen storage materials and preparation method thereof, and in particular to a kind of polymer
Nano-magnesium-based hydrogen storage material of cladding and preparation method thereof belongs to hydrogen storage material preparation technical field.
Background technique
Fossil energy exhaustion and environmental pollution crisis force human development renewable and clean energy resource.Hydrogen is the secondary energy of cleaning
Source, even more renewable non-renewable energy ideal carrier.Hydrogen storage is that Hydrogen Energy development and utilization are crucial, and current many developed countries are all by hydrogen storage
Technical research is classified as major scientific and technological program project.Magnesium-base hydrogen storage material, because of the big (MgH of resourceful, cheap and hydrogen storage content2
Theoretical hydrogen storage 7.6wt.%, meets the requirement of DOE), it is occupied an important position in hydrogen storage material.But Mg base hydrogen bearing alloy is practical
It is higher (Thermodynamically stable) to face main problem suction hydrogen discharging temperature, usual 573K or more.Application-oriented reduction Mg base hydrogen bearing alloy
Inhaling hydrogen discharging temperature is always the research hotspot gone together for many years both at home and abroad.
Magnesium-base hydrogen storage material inhales hydrogen discharging temperature height, and Thermodynamically stable is the intrinsic problem of material structure, it is necessary to from material knot
Structure is started with solution, and alloying and nanosizing are main means of going together both at home and abroad；Magnesium-base hydrogen storage material inhales hydrogen release poor circulation, removes
With alloy with high activity surface is oxidizable has outside the Pass, also and inhale hydrogen release process expansion-contraction effect cause dusting repeatedly, and inhale
It is related that hydrogen release process fuel factor causes crystal grain to be grown up.In recent years, nano Mg base is prepared by metallo-organic compound in-situ reducing
Alloy and saturating hydrogen antioxygen polymer composites, can improve thermodynamic property simultaneously and improve oxidation resistance becomes research heat
Point.The application is based on HCS (synthesis of hydriding combustion synthesis method)+MM (ball milling) technology and prepares Mg base hydrogen bearing alloy high activity high capacity
Low temperature hydrogen storage unique advantage, 1, hydrogen bearing alloy-polymer composites as MM auxiliary agent are prepared using polymer, strengthen hydrogen storage and closes
Gold nano grain structure and its nano effect further improve thermodynamics of alloys stability；2, saturating hydrogen antioxygen polymer film is realized
Cladding improves hydrogen bearing alloy oxidation resistance, and low temperature is kept to inhale hydrogen high activity, meanwhile, confinement mechanism is coated by polymer film,
Hydrogen bearing alloy nano particle anti-recrystallizing ability is improved, alloy hydrogen absorption and desorption cycle performance is further improved.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of high performance nano Mg base hydrogen storage materials
Material, the hydrogen storage material are the nano-magnesium-based hydrogen storage material of polymer overmold.
It is a further object to provide a kind of preparation sides of the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold
Method.
To achieve the above object, the invention adopts the following technical scheme:
A kind of nano-magnesium-based hydrogen storage material of polymer overmold, is made of following component by mass percentage: magnesium-nickel alloy:
80-98%, polymer: 2-20%.
In the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold, the magnesium-nickel alloy as a preferred implementation manner,
It is made by mass percentage of following component, magnesium: 90-98%, nickel: 2%-10%；Preferably, the magnesium-nickel alloy presses quality hundred
Divide than being made of following component, magnesium: 95%, nickel: 5%.
In the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold, the polymer is as a preferred implementation manner,
Polymer with saturating hydrogen antioxidant capacity, can film stop oxygen contact alloy surface, but do not influence hydrogen reach alloy surface
And to spreading inside alloy.The above-mentioned polymer for cladding has and alleviates in hydrogen bearing alloy suction hydrogen release cyclic process due to de-
Volume contraction when hydrogen, when inhaling hydrogen blind crack caused by volume expansion and its alloy pulverization ability, reduce hydrogen bearing alloy due to
It inhales crystal boundary migration caused by hydrogen release fuel factor and crystal grain is grown up.Preferably, the polymer is thermoplastic resin or thermosetting property tree
Rouge；It is highly preferred that the thermoplastic resin be polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate,
Polyester, polyformaldehyde, polyamide, polyimides, polypyrrole etc., the thermosetting resin are phenolic resin, epoxy resin, amino tree
Rouge, unsaturated polyester resin and silicon ether resin etc.；Further, the polymer be saturating hydrogen antioxygen ability preferably, price
Cheap, easily prepared thermoplastic resin polymethyl methacrylate (PMMA), weight average molecular weight are 6000 to 10000, and/
Or epoxy resin (EP), weight average molecular weight are 600 to 1000.
In the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold, the polymer packet as a preferred implementation manner,
The average particle size of the nano-magnesium-based hydrogen storage material covered be 100~500nm (such as 110nm, 120nm, 150nm, 200nm, 300nm,
400nm、450nm、480nm)。
The preparation method of the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold, includes the following steps:
Step 1 weighs magnesium powder and nickel powder according to above-mentioned mass percent, dispersing agent is added, with ultrasonic method or ball-milling method into
Row mixing pretreatment, obtains magnesium nickel mixed-powder after drying；
The magnesium nickel mixed-powder is carried out hydriding combustion synthesis, obtains powdered magnesium-nickel alloy by step 2；
Step 3, the magnesium-nickel alloy of step 2 preparation is more molten than the macromolecule containing polymer is added by certain mass
In liquid, strength mechanical ball mill is then carried out, obtained product is filtered, dried under an inert atmosphere until solvent and small molecule
Volatilization completely, finally obtains the nano-magnesium-based hydrogen storage material of the polymer overmold.
In above-mentioned preparation method, as a preferred implementation manner, in step 1, mixing pretreatment is carried out using ultrasonic method
When, the mixed time is 1-2h, ultrasonic power 1-2kW.
In above-mentioned preparation method, as a preferred implementation manner, in step 1, the dispersing agent is organic solvent, excellent
It is selected as acetone or alcohol.Dispersing agent of the acetone as ultrasonic disperse, low boiling point are easy to dry and remove；Ethyl alcohol as dispersing agent,
Boiling point is somewhat higher.The mixing pretreatment is carried out by ultrasonic cell disruptor.
In above-mentioned preparation method, as a preferred implementation manner, the purity of magnesium powder described in step 1 be 98.55% with
On, grain graininess is 44 μm or less (such as 43 μm, 40 μm, 35 μm, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm)；The nickel powder
Purity is 99.9% or more, and grain graininess is 2-3 μm.
In above-mentioned preparation method, the specific work of hydriding combustion synthesis described in step 2 as a preferred implementation manner,
Skill is as follows: it is 2-2.5MPa (such as 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa) that the magnesium nickel mixed-powder, which is placed in pressure,
Hydrogen atmosphere reactor in, be warming up to 550-600 DEG C (such as 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C) and keep the temperature 1-2h (ratio
Such as 1.1h, 1.3h, 1.5h, 1.8h), it is then cooled to 330-350 DEG C (such as 335 DEG C, 340 DEG C, 345 DEG C) and keeps the temperature 3-5h
(such as 3.1h, 3.5h, 4h, 4.5h), last cooled to room temperature obtain powdered magnesium-nickel alloy.
In above-mentioned preparation method, as a preferred implementation manner, in step 3, the polymer is dissolved in corresponding benign
Solvent in form the Polymer Solution, wherein the solvent is acetone, tetrahydrofuran, ethyl alcohol, ethylene glycol etc., described poly-
Conjunction object is the polymer with saturating hydrogen antioxidant capacity；It is highly preferred that the polymer is the poly- first that molecular weight is 6000 to 10000
Base methyl acrylate (PMMA), the solvent are tetrahydrofuran；PMMA is preferable, cheap for saturating hydrogen antioxidant capacity, is easy to make
Standby polymer, and tetrahydrofuran is the good solvent of PMMA, thus prepares and forms Polymer Solution.
In above-mentioned preparation method, as a preferred implementation manner, in step 3, polymer is that molecular weight arrives for 600
1000 epoxy resin (EP), the Polymer Solution are made by epoxy resin A, B glue hybrid reaction.
In above-mentioned preparation method, magnesium-nickel alloy described in step 3 and the polymer as a preferred implementation manner,
Mass ratio be 4-49:1 (such as 6:1,8:1,10:1,15:1,25:1,30:1,35:1,40:1,45:1,48:1).
In above-mentioned preparation method, strength mechanical ball mill described in step 3 is in planet as a preferred implementation manner,
It is carried out under hydrogen atmosphere protection in formula high energy ball mill；The Ball-milling Time of the strength mechanical ball mill be 10-20h (such as
10.5h, 12h, 15h, 17h, 19h), ratio of grinding media to material is 25-35:1 (such as 26:1,28:1,30:1,32:1,34:1), and revolving speed is
300-500r/min (such as 305r/min, 320r/min, 350r/min, 400r/min, 450r/min, 470r/min, 490r/
min)。
In above-mentioned preparation method, strength mechanical ball mill described in step 3 uses liquid phase as a preferred implementation manner,
Ball milling method, Polymer Solution effectively improve the grinding efficiency to magnesium-nickel alloy as grinding aid, dispersing agent, reduce its particle
Size, polymer add more, and solution is more sticky, and grinding efficiency height causes becoming smaller in size after ball milling.According to addition solvent
The difference of volume, forms the Polymer Solution of different sliminess, and the sliminess of solution has grinding efficiency a degree of
It influences, it is preferable that in step 3, in the Polymer Solution, the concentration of the polymer is 4-20g/L, it is highly preferred that institute
The concentration for stating polymer is 8-15g/L.
In above-mentioned preparation method, temperature dry described in step 3 is 70-90 DEG C as a preferred implementation manner,
(such as 72 DEG C, 75 DEG C, 78 DEG C, 82 DEG C, 85 DEG C, 88 DEG C), time are 7-10h (such as 7.5h, 8h, 8.5h, 9h, 9.5h)；It is excellent
Selection of land, the suction filtration and the drying carry out under an argon atmosphere.
Application of the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold in the storage and transportation of hydrogen or hydrogen fuel cell.
Compared with prior art, the beneficial effects of the present invention are:
1) using the nano-magnesium-based hydrogen storage material of the method for the present invention preparation polymer overmold with anti-oxidant resistance to dusting, and/
Or the feature excellent with low temperature hydrogen storage property.The present invention is to be prepared for the first time using different polymer to hydriding combustion synthesis method
Obtained Mg base hydrogen bearing alloy is coated, and effectively improves grinding efficiency using liquid phase ball milling method, drops low-alloyed particle
Size；Simultaneously polymer alloy is effectively coated, can film stop oxygen contact alloy surface, but do not influence hydrogen reach
Alloy surface, and to spreading inside alloy, and hydrogen bearing alloy can be alleviated and inhale in hydrogen release cyclic process volume contraction when due to dehydrogenation,
The ability of blind crack caused by volume expansion and its alloy pulverization when inhaling hydrogen reduces hydrogen bearing alloy and leads due to inhaling hydrogen release fuel factor
The crystal boundary migration and crystal grain of cause are grown up, so as to improve the hydrogen discharging performance of material.
2) there is the nano-magnesium-based hydrogen storage material of polymer overmold provided by the invention excellent low temperature to inhale hydrogen desorption kinetics
Performance: at 473K, in 60min, hydrogen-sucking amount reaches 3.73wt.%, and in 120min, hydrogen desorption capacity reaches 1.02wt.%；In 523K
Under, in 60min, hydrogen-sucking amount is up to 4.04wt.%, and in 120min, hydrogen desorption capacity is up to 2.18wt.%.
3) nano-magnesium-based hydrogen storage material of polymer overmold prepared by the present invention can be used for storage and transportation and the hydrogen fuel of hydrogen
Battery.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is PMMA, HCS product Mg95Ni5, HCS+MM combination product Mg95Ni5- 5%PMMA and Mg95Ni5- 10%PMMA
X-ray diffraction (XRD) figure；Wherein: (a) being PMMA；It (b) is 2) the step hydriding combustion conjunction in embodiment 1-4 and comparative example 1
The powdered magnesium-nickel alloy Mg prepared at method95Ni5；(c) Mg prepared for embodiment 195Ni5- 5%PMMA；It (d) is embodiment 2
The Mg of preparation95Ni5- 10%PMMA；
Fig. 2 is HCS+MM combination product Mg95Ni5- 5%PMMA and Mg95Ni5The SEM spectrum of -10%PMMA；Wherein: (a)
The Mg prepared for embodiment 195Ni5- 5%PMMA；(b) Mg prepared for embodiment 295Ni5- 10%PMMA；
Fig. 3 is HCS+MM combination product Mg95Ni5- 5%PMMA, Mg95Ni5The XRD spectra of -10%PMMA；Wherein, (A) is
Mg prepared by embodiment 195Ni5- 5%PMMA, (B) are Mg prepared by embodiment 295Ni5- 10%PMMA, in figure, (a) is original
The sample of argon gas protection；(b) sample to expose one day in air；(c) sample to expose one week in air；
Fig. 4 is HCS+MM combination product Mg prepared by embodiment 295Ni5- 10%PMMA schemes in the TEM of different amplification
Spectrum；
Fig. 5 is HCS product Mg95Ni5, the HCS+MM combination product Mg of the preparation of embodiment 295Ni5- 10%PMMA in 473K,
The Dynamic isotherms of hydrogen absorption of 3.0MPa hydrogen pressure；
Fig. 6 is HCS product Mg95Ni5, the HCS+MM combination product Mg of the preparation of embodiment 295Ni5- 10%PMMA in 523K,
The Dynamic isotherms of hydrogen absorption of 3.0MPa hydrogen pressure；
Fig. 7 is HCS product Mg95Ni5, the HCS+MM combination product Mg of the preparation of embodiment 295Ni5- 10%PMMA in 473K,
Hydrogen desorption kinetics curve under vacuum condition；
Fig. 8 is HCS product Mg95Ni5, the HCS+MM combination product Mg of the preparation of embodiment 295Ni5- 10%PMMA in 523K,
Hydrogen desorption kinetics curve under vacuum condition.
Specific embodiment
Following embodiment is described in further detail the contents of the present invention, and protection scope of the present invention includes but unlimited
In following each embodiments.
The purity of raw material magnesium powder used in following embodiment and comparative example be 98.55%, grain graininess be 44 μm with
Under；The purity of the nickel powder material is 99.9%, and grain graininess is 2-3 μm；Polymethyl methacrylate (PMMA's) divides equally again
Son amount is 8000；The weight average molecular weight of epoxy resin (EP) is 600.Various reagents used in following embodiment and comparative example and
Raw material is commercial product.
Heretofore described Mg95Ni5- 5%PMMA, Mg95Ni5- 10%PMMA, Mg95Ni5- 20%PMMA and Mg95Ni5-
5%, 10%, 20% in 10%EP refers to that corresponding polymer P MMA or EP accounts for the percentage of nano-magnesium-based hydrogen storage material gross mass
Number.
1 Mg of embodiment95Ni5The preparation of -5%PMMA nano-magnesium-based hydrogen storage material
(1) it takes 9.5g magnesium powder and 0.5g nickel powder to be put into beaker and carries out mixing pretreatment, 40mL acetone is added as dispersion
Agent after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder using the uniform 1h of ultrasonic mixing, ultrasonic power 1kW
End；
(2) magnesium nickel mixed-powder is subjected to hydrogenation combustion method synthesis, in the synthesis process, magnesium nickel mixed-powder is in 2MPa hydrogen
It is warming up to 580 DEG C of heat preservation 2h under gas atmosphere, is then cooled to 340 DEG C of heat preservation 4h, is finally cooled to room temperature, obtains powdered magnesium
Nickel alloy.
(3) it takes 0.1gPMMA to be put into beaker, 20mL tetrahydrofuran is added, stir 1h, be configured to Polymer Solution, take
The powdered magnesium-nickel alloy that 1.9g step (2) obtains is put into ball grinder, and ball grinder is added in configured Polymer Solution
In, the ball milling 10h under 0.1Mpa argon atmosphere, revolving speed 400rpm, ratio of grinding media to material 30:1, obtained product is put into argon atmosphere
It in glove box, is filtered, dry 8h finally obtains polymer overmold until solvent and small molecule are volatilized completely at 80 DEG C
Nano-magnesium-based hydrogen storage material.
(c) in Fig. 1 is Mg manufactured in the present embodiment95Ni5The XRD diagram of -5%PMMA nano-magnesium-based hydrogen storage material, from this
Figure is as can be seen that it coordinates and is divided into PMMA, Mg, MgH2And Mg2NiH4, with Mg95Ni5It compares, combination product Mg95Ni5- 5%PMMA
High wide and relative peak intensities reduce very much, while widthization phenomenon occurs, this shows that magnesium base alloy particle becomes smaller, crystal grain refinement,
Crystal structure changes.
(a) in Fig. 2 is that the present embodiment prepares Mg95Ni5The SEM spectrum of -5%PMMA nano-magnesium-based hydrogen storage material, from this
Figure is as can be seen that its particle size is about 400-500nm.(a), (b) and (c) in Fig. 3 its (1) are Mg95Ni5- 5%PMMA
It is exposed to the XRD spectra of exposure after a week in one day and air under protection of argon gas, in air respectively, from this figure, it can be seen that
Exposing one day in air sample has apparent Mg (OH)2With the diffraction maximum of MgO, one week sample of exposure air, two kinds of diffraction
Peak further increases, this shows that the composite material of the mass fraction 5%PMMA only added cannot play effectively magnesium base alloy
Protective effect, sample oxidation and hydrolysis phenomena are serious.
The Mg that the present embodiment is prepared95Ni5- 5%PMMA nano-magnesium-based hydrogen storage material, in 60min at 473K and 523K
Interior hydrogen-sucking amount respectively reaches 3.37wt.% and 4.52wt%；At low temperature 473K can hydrogen release, hydrogen desorption capacity is up to
1.42wt.%, temperature are increased under 523K, and hydrogen release can reach 2.46wt.% in 120min.
2 Mg of embodiment95Ni5The preparation of -10%PMMA nano-magnesium-based hydrogen storage material
(1) it takes 9.5g magnesium powder and 0.5g nickel powder to be put into beaker and carries out mixing pretreatment, 40mL acetone is added as dispersion
Agent after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed-powder using the uniform 1h of ultrasonic mixing, ultrasonic power 1kW；
(2) magnesium nickel mixed-powder is subjected to hydrogenation combustion method synthesis, in the synthesis process, magnesium nickel mixed-powder is in 2MPa hydrogen
It is warming up to 580 DEG C of heat preservation 2h under gas atmosphere, is then cooled to 340 DEG C of heat preservation 4h, is finally cooled to room temperature, obtains powdered magnesium
Nickel alloy.
(3) it takes 0.2gPMMA to be put into beaker, 20mL tetrahydrofuran is added, stir 1h, be configured to Polymer Solution, take
The powdered magnesium-nickel alloy that 1.8g step (2) obtains is put into ball grinder, and ball grinder is added in configured Polymer Solution
In, the ball milling 10h under 0.1Mpa argon atmosphere, revolving speed 400rpm, ratio of grinding media to material 30:1, obtained product is put into argon atmosphere
It in glove box, is filtered, dry 8h finally obtains polymer overmold until solvent and small molecule are volatilized completely at 80 DEG C
Nano-magnesium-based hydrogen storage material.
(d) in Fig. 1 is that the present embodiment prepares Mg95Ni5The XRD diagram of -10%PMMA nano-magnesium-based hydrogen storage material, from the figure
It can be seen that it, which coordinates, is divided into PMMA, Mg, MgH2And Mg2NiH4, with Mg95Ni5It compares, combination product Mg95Ni5- 10%PMMA half
High wide and relative peak intensities equally reduce very much, while widthization phenomenon occurs, this shows that magnesium base alloy particle becomes smaller, and crystal grain is thin
Change, crystal structure changes.
(b) in Fig. 2 is that the present embodiment prepares Mg95Ni5The SEM spectrum of -10%PMMA nano-magnesium-based hydrogen storage material, from this
Figure is as can be seen that its particle size is about 200-300nm.(a), (b) and (c) in Fig. 3 its (2) are Mg95Ni5- 10%
PMMA is exposed to the XRD spectra of exposure after a week in one day and air under protection of argon gas, in air, from this figure, it can be seen that
Sample expose one day in air after there is no apparent oxidation and hydrolysis phenomena occurs, until sample places in air one
Just there is Mg (OH) in week2With the diffraction maximum of MgO, and the relative intensity of the diffraction maximum of two kinds of substances shows all well below the former
The PMMA of addition 10wt.% can relatively efficiently protect combination product, and the resistance to oxidation and hydrolysis ability of product substantially enhance.
Referring to figure 5-8, Mg that the present embodiment is prepared95Ni5- 10%PMMA nano-magnesium-based hydrogen storage material, in 473K and
Hydrogen-sucking amount under 523K in 60min respectively reaches 3.37wt.% and 4.04wt%；At low temperature 473K can hydrogen release, hydrogen release
Amount is up to 1.02wt.%, and temperature is increased under 523K, and hydrogen release can reach 2.18wt.% in 120min.
3 Mg of embodiment95Ni5The preparation of -20%PMMA nano-magnesium-based hydrogen storage material
(1) it takes 9.5g magnesium powder and 0.5g nickel powder to be put into beaker and carries out mixing pretreatment, 40mL acetone is added as dispersion
Agent after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder using the uniform 1h of ultrasonic mixing, ultrasonic power 1KW
End；
(2) magnesium nickel mixed-powder is subjected to hydrogenation combustion method synthesis, in the synthesis process, magnesium nickel mixed-powder is in 2MPa hydrogen
It is warming up to 580 DEG C of heat preservation 2h under gas atmosphere, is then cooled to 340 DEG C of heat preservation 4h, is finally cooled to room temperature, obtains powdered magnesium
Nickel alloy.
(3) it takes 0.4gPMMA to be put into beaker, 20mL tetrahydrofuran is added, stir 1h, be configured to Polymer Solution, take
The powdered magnesium-nickel alloy that 1.6g step (2) obtains is put into ball grinder, and ball grinder is added in configured Polymer Solution
In, the ball milling 10h under 0.1Mpa argon atmosphere, revolving speed 400rpm, ratio of grinding media to material 30:1, obtained product is put into argon atmosphere
It in glove box, is filtered, dry 8h finally obtains polymer overmold until solvent and small molecule are volatilized completely at 80 DEG C
Nano-magnesium-based hydrogen storage material
Mg manufactured in the present embodiment95Ni5The phase constituent of -20%PMMA nano-magnesium-based hydrogen storage material be similarly PMMA, Mg,
MgH2And Mg2NiH4, but the polymer content coated is higher, and the diffraction peak intensity of metal alloy therein is caused to be greatly reduced.
The present embodiment prepares Mg95Ni5- 20%PMMA nano-magnesium-based hydrogen storage material thicker, particle due to polymer overmold
Size is about 300-400nm.The PMMA of addition 20wt.% can be effectively protected combination product, the resistance to oxidation of product and water-fast
Solution ability substantially enhances.
The Mg that the present embodiment is prepared95Ni5The content mistake of -20%PMMA nano-magnesium-based hydrogen storage material due to polymer overmold
Height causes the suction hydrogen desorption kinetics of material to be decreased obviously, and the hydrogen-sucking amount at 473K and 523K in 60min respectively reaches
1.23wt.% and 2.56wt%；Hardly seen hydrogen release, temperature are increased under 523K at low temperature 473K, the hydrogen release in 120min
1.22wt.% can be reached.
4 Mg of embodiment95Ni5The preparation of -10%EP nano-magnesium-based hydrogen storage material
(1) it takes 9.5g magnesium powder and 0.5g nickel powder to be put into beaker and carries out mixing pretreatment, 40mL acetone is added as dispersion
Agent after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder using the uniform 1h of ultrasonic mixing, ultrasonic power 1kW
End；
(2) magnesium nickel mixed-powder is subjected to hydrogenation combustion method synthesis, in the synthesis process, magnesium nickel mixed-powder is in 2MPa hydrogen
It is warming up to 580 DEG C of heat preservation 2h under gas atmosphere, is then cooled to 340 DEG C of heat preservation 4h, is finally cooled to room temperature, obtains powdered magnesium
Nickel alloy.
(3) raw material uses two kinds of solution of epoxy resin A and B, and the powdered magnesium-nickel alloy for taking 1.8g step (2) to obtain is put
Enter in ball grinder, be separately added into two kinds of each 0.1g of solution of A, B and mix 1h to two kinds of solution and be mixed thoroughly to form EP, in 0.1Mpa
Ball milling 10h under argon atmosphere, revolving speed 400rpm, ratio of grinding media to material 30:1, obtained product are put into argon atmosphere glove box, into
Row filters, the dry 8h at 80 DEG C, until solvent and small molecule are volatilized completely, finally obtains the nano Mg base storage of polymer overmold
Hydrogen material.
Mg manufactured in the present embodiment95Ni5Coordinating for -10%EP nano-magnesium-based hydrogen storage material is divided into EP, Mg, MgH2With
Mg2NiH4, with Mg95Ni5It compares, finds combination product Mg95Ni5- 10%PMMA halfwidth and relative peak intensities equally reduce very
It is more, while widthization phenomenon occurs, which results in magnesium base alloy particles to become smaller, and crystal grain refinement, crystal structure changes.
Mg manufactured in the present embodiment95Ni5The particle size of -10%EP nano-magnesium-based hydrogen storage material is about 200-300nm.
The EP of addition 10wt.% can relatively efficiently protect combination product, and the resistance to oxidation and hydrolysis ability of product substantially enhance.
The Mg that the present embodiment is prepared95Ni5- 10%EP nano-magnesium-based hydrogen storage material and the saturating hydrogen effect of polymer P MMA are slightly
The suction hydrogen desorption kinetics of difference, material have certain decline, but still have good hydrogen storage property, at 473K and 523K
Hydrogen-sucking amount in 60min respectively reaches 1.89wt.% and 2.94wt%；Hydrogen desorption capacity is 0.78wt.%, temperature at low temperature 473K
It is increased under 523K, hydrogen release can reach 1.98wt.% in 120min.
5 Mg of embodiment95Ni5The preparation of -2%PMMA nano-magnesium-based hydrogen storage material
(1) it takes 9.5g magnesium powder and 0.5g nickel powder to be put into beaker and carries out mixing pretreatment, 40mL acetone is added as dispersion
Agent after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder using the uniform 1h of ultrasonic mixing, ultrasonic power 1KW
End；
(2) magnesium nickel mixed-powder is subjected to hydrogenation combustion method synthesis, in the synthesis process, magnesium nickel mixed-powder is in 2MPa hydrogen
It is warming up to 580 DEG C of heat preservation 2h under gas atmosphere, is then cooled to 340 DEG C of heat preservation 4h, is finally cooled to room temperature, obtains powdered magnesium
Nickel alloy.
(3) it takes 0.04gPMMA to be put into beaker, 20mL tetrahydrofuran is added, stir 1h, be configured to Polymer Solution, take
The powdered magnesium-nickel alloy that 1.96g step (2) obtains is put into ball grinder, and ball grinder is added in configured Polymer Solution
In, the ball milling 10h under 0.1Mpa argon atmosphere, revolving speed 400rpm, ratio of grinding media to material 30:1, obtained product is put into argon atmosphere
It in glove box, is filtered, dry 8h finally obtains polymer overmold until solvent and small molecule are volatilized completely at 80 DEG C
Nano-magnesium-based hydrogen storage material.
Mg manufactured in the present embodiment95Ni5The phase constituent of -2%PMMA nano-magnesium-based hydrogen storage material be similarly PMMA, Mg,
MgH2And Mg2NiH4, but the polymer content coated is less, and sample oxidation and hydrolysis phenomena are serious.
The Mg that the present embodiment is prepared95Ni5- 2%PMMA nano-magnesium-based hydrogen storage material, in 60min at 473K and 523K
Interior hydrogen-sucking amount respectively reaches 3.98wt.% and 5.12wt%；At low temperature 473K can hydrogen release, hydrogen desorption capacity reaches
1.01wt.%, temperature are increased under 523K, and hydrogen release can reach 2.84wt.% in 120min.
Comparative example l Mg95Ni5The preparation of nano-magnesium-based hydrogen storage material
(1) it takes 9.5g magnesium powder and 0.5g nickel powder to be put into beaker and carries out mixing pretreatment, 40ml acetone is added as dispersion
Agent after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder using the uniform 1h of ultrasonic mixing, ultrasonic power 1kW
End；
(2) magnesium nickel mixed-powder is subjected to hydrogenation combustion method synthesis, in the synthesis process, magnesium nickel mixed-powder is in 2MPa hydrogen
It is warming up to 580 DEG C of heat preservation 2h under gas atmosphere, is then cooled to 340 DEG C of heat preservation 4h, is finally cooled to room temperature, obtains powdered magnesium
Nickel alloy.
(3) the powdered magnesium-nickel alloy for taking 2g step (2) to obtain is put into ball grinder, the ball under 0.1Mpa argon atmosphere
10h is ground, Mg can be obtained in revolving speed 400rpm, ratio of grinding media to material 30:195Ni5Nano-magnesium-based hydrogen storage material.
(b) in Fig. 1 is that this comparative example prepares Mg95Ni5The XRD diagram of nano-magnesium-based hydrogen storage material, therefrom it can be seen that its
It coordinates and is divided into Mg, MgH2And Mg2NiH4。Mg95Ni5Its particle size is about 600-800nm, in air without any protection,
It can be oxidized quickly.
Referring to figure 5-8, Mg that this comparative example is prepared95Ni5Nano-magnesium-based hydrogen storage material, at 473K and 523K
Hydrogen-sucking amount in 60min respectively reaches 2.08wt.%, 2.48wt.%；Hardly hydrogen release, temperature are increased to 523K at 473K
Under, hydrogen release 0.24wt% is only capable of in 120min.
Technological parameter (such as temperature, time) section bound value of the invention and interval value can realize this law,
Embodiment numerous to list herein.
Claims (13)
1. a kind of nano-magnesium-based hydrogen storage material of polymer overmold, which is characterized in that be made by mass percentage of following component:
Magnesium-nickel alloy: 80-98%, polymer: 2-20%；
The magnesium-nickel alloy is made of following component by mass percentage, magnesium: 90-98%, nickel: 2%-10%；
The preparation method of the nano-magnesium-based hydrogen storage material of the polymer overmold includes the following steps:
Step 1 weighs magnesium powder and nickel powder according to the mass percent, dispersing agent is added, is mixed with ultrasonic method or ball-milling method
Pretreatment is closed, magnesium nickel mixed-powder is obtained after drying；The purity of the magnesium powder be 98.55% or more, grain graininess be 44 μm with
Under；The purity of the nickel powder is 99.9% or more, and grain graininess is 2-3 μm；
The magnesium nickel mixed-powder is carried out hydriding combustion synthesis, obtains powdered magnesium-nickel alloy by step 2；
Step 3, by the magnesium-nickel alloy of step 2 preparation by certain mass than the Polymer Solution containing polymer is added
In, strength mechanical ball mill is then carried out, obtained product is filtered under an inert atmosphere, dried until solvent and small molecule are complete
Full volatilization, finally obtains the nano-magnesium-based hydrogen storage material of the polymer overmold；The strength mechanical ball mill is in planetary height
It is carried out under hydrogen atmosphere protection in energy ball mill；The Ball-milling Time of the strength mechanical ball mill is 10-20h, and ratio of grinding media to material is
25-35:1, revolving speed 300-500r/min；The polymer is the polymethylacrylic acid that weight average molecular weight is 6000 to 10000
The epoxy resin that methyl esters or weight average molecular weight are 600 to 1000.
2. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 1, which is characterized in that the magnesium-nickel alloy is pressed
Mass percent is made of following component, magnesium: 95%, nickel: 5%.
3. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 1 or claim 2, which is characterized in that the polymer
The average particle size of the nano-magnesium-based hydrogen storage material of cladding is 100~500nm.
4. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 1, which is characterized in that in step 1, use
When ultrasonic method carries out mixing pretreatment, the mixed time is 1-2h, ultrasonic power 1-2kW.
5. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 4, which is characterized in that described in step 1
Dispersing agent is organic solvent.
6. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 5, which is characterized in that described in step 1
Dispersing agent is acetone or alcohol.
7. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 1, which is characterized in that in step 3, by institute
State polymer and be dissolved in corresponding benign solvent and form the Polymer Solution, wherein the solvent be acetone, tetrahydrofuran,
Ethyl alcohol or ethylene glycol.
8. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 7, which is characterized in that in step 3, in institute
It states in Polymer Solution, the concentration of the polymer is 4-20g/L.
9. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 8, which is characterized in that in step 3, in institute
It states in Polymer Solution, the concentration of the polymer is 8-15g/L.
10. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 7, which is characterized in that in step 3, when poly-
When conjunction object is the epoxy resin that molecular weight is 600 to 1000, the Polymer Solution is by epoxy resin A, B glue hybrid reaction system
?.
11. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 1, which is characterized in that described in step 3
The mass ratio of magnesium-nickel alloy and the polymer is 4-49:1.
12. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 11, which is characterized in that in step 3, institute
State dry temperature be 70-90 DEG C, time 7-10h.
13. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 11, which is characterized in that in step 3, institute
It states suction filtration and the drying carries out under an argon atmosphere.
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