CN106566965A - Polymer wrapped nano magnesium based hydrogen storage material and preparation method thereof - Google Patents
Polymer wrapped nano magnesium based hydrogen storage material and preparation method thereof Download PDFInfo
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- CN106566965A CN106566965A CN201610931895.XA CN201610931895A CN106566965A CN 106566965 A CN106566965 A CN 106566965A CN 201610931895 A CN201610931895 A CN 201610931895A CN 106566965 A CN106566965 A CN 106566965A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C23/00—Alloys based on magnesium
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- 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
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Abstract
The invention relates to a polymer wrapped nano magnesium based hydrogen storage material and a preparation method thereof, and belongs to the technical field of hydrogen storage material preparation. The hydrogen storage material is prepared from the following components in percentage by weight: 80 to 98% of magnesium-nickel alloy, and 2 to 20% of polymer. Magnesium powder and nickel powder are taken as the raw materials and then are mixed and preprocessed; the mixture is hydrogenated, burned, and synthesized, and finally the product and polymers are fiercely and mechanically ball-milled to prepare the hydrogen storage material. The hydrogen storage material has excellent low temperature hydrogen absorption/desorption dynamics performances: at a temperature of 473K, the hydrogen absorption amount can reach 3.73 wt.% with 60 minutes; the hydrogen desorption amount can reach 1.02 wt.% within 120 minutes; at a temperature of 523 K, the hydrogen absorption amount is as high as 4.04 wt.% within 60 minutes, and the hydrogen desorption amount can reach 2.18 wt.% within 120 minutes. The hydrogen storage material can be used to store/transport hydrogen and prepare hydrogen fuel battery.
Description
Technical field
The present invention relates to a kind of high performance nano-magnesium-based hydrogen storage material 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 preparing technical field.
Background technology
Fossil energy is exhausted and environmental pollution crisis forces human development renewable and clean energy resource.Hydrogen is the secondary energy of cleaning
Source, even more renewable primary energy ideal carrier.Hydrogen storage is that Hydrogen Energy develops key, and at present 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 aboundresources, the big (MgH of cheap and hydrogen storage content2
Theoretical hydrogen storage 7.6wt.%, meets the requirement of DOE), critical role is occupied in hydrogen storage material.But Mg base hydrogen bearing alloy is practical
Face subject matter suction hydrogen discharging temperature higher (Thermodynamically stable), usual more than 573K.Application-oriented reduction Mg base hydrogen bearing alloy
Inhale the study hotspot that hydrogen discharging temperature is always 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 sex chromosome mosaicism of material structure, it is necessary to from material knot
Structure is started with solution, and alloying and nanorize are Main Means of going together both at home and abroad；Magnesium-base hydrogen storage material inhales that to put hydrogen cycle performance poor, removes
It is oxidizable with alloy with high activity surface to have outside the Pass, also put hydrogen process repeatedly expansion-contraction effect causes efflorescence with suction, and inhale
Putting hydrogen process heat effect, to cause crystal grain to grow up relevant.In recent years, nano Mg base is prepared by metallo-organic compound in-situ reducing
Alloy and saturating hydrogen antioxygen polymer composites, can simultaneously improve thermodynamic property and improve oxidation resistance becomes research heat
Point.The application prepares Mg base hydrogen bearing alloy high activity high power capacity based on HCS (synthesis of hydriding combustion synthesis method)+MM (ball milling) technology
Low temperature hydrogen storage unique advantage, 1, hydrogen bearing alloy-polymer composites are prepared as MM auxiliary agents using polymer, reinforcing hydrogen storage is closed
Gold nano grain structure and its nano effect, further improve thermodynamics of alloys stability；2nd, hydrogen antioxygen polymeric film is realized
Cladding, improves hydrogen bearing alloy oxidation resistance, keeps low temperature to inhale hydrogen high activity, meanwhile, confinement mechanism is coated by polymeric film,
Hydrogen bearing alloy nano-particle anti-recrystallizing ability is improved, further improves alloy hydrogen absorption and desorption cycle performance.
The content of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of high performance nano Mg base hydrogen storage material
Material, the hydrogen storage material is the nano-magnesium-based hydrogen storage material of polymer overmold.
It is a further object to provide a kind of preparation side of the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold
Method.
For achieving the above object, the present invention is employed the following technical solutions：
A kind of nano-magnesium-based hydrogen storage material of polymer overmold, is made up by mass percentage of following component：Magnesium-nickel alloy：
80-98%, polymer：2-20%.
In the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold, as a kind of preferred implementation, the magnesium-nickel alloy
It is made up of following component by mass percentage, magnesium：90-98%, nickel：2%-10%；Preferably, the magnesium-nickel alloy presses quality hundred
Divide than being made up of following component, magnesium：95%, nickel：5%.
In the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold, used as a kind of preferred implementation, the polymer is
Polymer with saturating hydrogen antioxidant capacity, can film stop oxygen contact alloy surface, but do not affect hydrogen to reach alloy surface
And to alloy diffusion inside.The above-mentioned polymer for cladding, puts in hydrogen cyclic process due to de- with hydrogen bearing alloy suction is alleviated
Volume contraction during hydrogen, when inhaling hydrogen caused by volumetric expansion blind crack and its alloy pulverization ability, reduce hydrogen bearing alloy due to
Suction is put crystal boundary migration and crystal grain caused by hydrogen heat effect and is grown up.Preferably, the polymer is thermoplastic resin or thermosetting tree
Fat；It is highly preferred that the thermoplastic resin be polyethylene, polypropylene, polrvinyl chloride, polystyrene, polymethyl methacrylate,
Polyester, polyformaldehyde, polyamide, polyimides, polypyrrole etc., the thermosetting resin is phenolic resin, epoxy resin, amino tree
Fat, unsaturated polyester resin and silicon ether resin etc.；Further, the polymer be hydrogen antioxygen ability preferably, price
Cheap, easily prepared thermoplastic resin polymethyl methacrylate (PMMA), its weight average molecular weight is 6000 to 10000, and/
Or epoxy resin (EP), its weight average molecular weight is 600 to 1000.
In the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold, as a kind of preferred implementation, the polymer bag
The particle mean size of the nano-magnesium-based hydrogen storage material for covering 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, comprises the steps：
Step one, according to above-mentioned mass percent magnesium powder and nikel powder are weighed, and add dispersant, are entered with ultrasonic method or ball-milling method
Row mixing pretreatment, obtains magnesium nickel mixed-powder after drying；
Step 2, by the magnesium nickel mixed-powder hydriding combustion synthesis are carried out, and obtain the magnesium-nickel alloy of powder；
Step 3, certain mass is pressed than adding the macromolecule containing polymer molten by the magnesium-nickel alloy prepared by step 2
In liquid, strength mechanical ball milling is then carried out, the product for obtaining carries out under an inert atmosphere sucking filtration, drying until solvent and small molecule
Volatilize completely, finally give the nano-magnesium-based hydrogen storage material of the polymer overmold.
In above-mentioned preparation method, as a kind of preferred implementation, in step one, mixing pretreatment is carried out using ultrasonic method
When, the time of the mixing is 1-2h, and ultrasonic power is 1-2kW.
In above-mentioned preparation method, used as a kind of preferred implementation, in step one, the dispersant is organic solvent, excellent
Elect acetone or alcohol as.Used as the dispersant of ultrasonic disperse, low boiling point is easily dry to be removed acetone；Ethanol as dispersant, its
Boiling point is somewhat higher.The mixing pretreatment is carried out by ultrasonic cell disruptor.
In above-mentioned preparation method, as a kind of preferred implementation, the purity of magnesium powder described in step one be 98.55% with
On, grain graininess is less than 44 μm (such as 43 μm, 40 μm, 35 μm, 30 μm, 25 μm, 20 μm, 15 μm, 10 μm)；The nikel powder
Purity is more than 99.9%, and grain graininess is 2-3 μm.
In above-mentioned preparation method, as a kind of preferred implementation, the concrete work of hydriding combustion synthesis described in step 2
Skill is as follows：The magnesium nickel mixed-powder is placed in into pressure for 2-2.5MPa (such as 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa)
Hydrogen atmosphere reactor in, be warmed up to 550-600 DEG C (such as 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C) and be incubated 1-2h (ratio
Such as 1.1h, 1.3h, 1.5h, 1.8h), then it is cooled to 330-350 DEG C (such as 335 DEG C, 340 DEG C, 345 DEG C) and is incubated 3-5h
(such as 3.1h, 3.5h, 4h, 4.5h), finally naturally cools to room temperature, obtains the magnesium-nickel alloy of powder.
In above-mentioned preparation method, as a kind of preferred implementation, in step 3, the polymer is dissolved in corresponding benign
Solvent in form the macromolecular solution, wherein, the solvent is acetone, tetrahydrofuran, ethanol, ethylene glycol etc., described poly-
Compound is the polymer with saturating hydrogen antioxidant capacity；It is highly preferred that the polymer is poly- first that molecular weight is 6000 to 10000
Base acrylic acid methyl ester. (PMMA), the solvent is tetrahydrofuran；PMMA is for saturating hydrogen antioxidant capacity is preferable, cheap, be easy to system
Standby polymer, and tetrahydrofuran is the good solvent of PMMA, thus prepares and forms macromolecular solution.
In above-mentioned preparation method, used as a kind of preferred implementation, in step 3, polymer is that molecular weight is arrived for 600
1000 epoxy resin (EP), the macromolecular solution is obtained by epoxy resin A, B glue hybrid reaction.
In above-mentioned preparation method, as a kind of preferred implementation, magnesium-nickel alloy described in step 3 and the polymer
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, used as a kind of preferred implementation, strength mechanical ball milling described in step 3 is in planet
Carry out under hydrogen atmosphere protection in formula high energy ball mill；The Ball-milling Time of the strength mechanical ball milling 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), rotating 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, used as a kind of preferred implementation, strength mechanical ball milling described in step 3 adopts liquid phase
Ball milling method, macromolecular solution effectively improves the grinding efficiency to magnesium-nickel alloy as grinding aid, dispersant, reduces its granule
Size, it is many that polymer adds, 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 macromolecular solution of different sliminesses, and the sliminess of solution has a certain degree of to grinding efficiency
Affect, it is preferable that in step 3, in the macromolecular 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, used as a kind of preferred implementation, the temperature being dried described in step 3 is 70-90 DEG C
(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 sucking filtration and the drying are carried out under an argon atmosphere.
Application of the nano-magnesium-based hydrogen storage material of above-mentioned polymer overmold in the accumulating of hydrogen or hydrogen fuel cell.
Compared with prior art, the invention has the beneficial effects as follows：
1) nano-magnesium-based hydrogen storage material for preparing polymer overmold using the inventive method has a resistance to efflorescence of antioxidation, and/
Or with the excellent feature of low temperature hydrogen storage property.The present invention is for first using different polymer to the preparation of hydriding combustion synthesis method
The Mg base hydrogen bearing alloy for obtaining is coated, and effectively improves grinding efficiency using liquid phase ball milling method, drops low-alloyed granule
Size；Simultaneously polymer is effectively coated to alloy, can film stop oxygen contact alloy surface, but do not affect hydrogen to reach
Alloy surface, and to alloy diffusion inside, hydrogen bearing alloy suction can be alleviated again and is put due to volume contraction during dehydrogenation in hydrogen cyclic process,
When inhaling hydrogen caused by volumetric expansion blind crack and its alloy pulverization ability, reduce hydrogen bearing alloy and put hydrogen heat effect and lead due to inhaling
The crystal boundary migration and crystal grain of cause is grown up, so as to improve the hydrogen discharging performance of material.
2) there is the nano-magnesium-based hydrogen storage material of the polymer overmold that the present invention is provided excellent low temperature to inhale hydrogen desorption kineticses
Performance：Under 473K, in 60min, hydrogen-sucking amount reaches 3.73wt.%, and in 120min, hydrogen desorption capacity reaches 1.02wt.%；In 523K
Under, in 60min, its 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 accumulating and the hydrogen fuel of hydrogen
Battery.
Description of the drawings
In order that present disclosure is more likely to be clearly understood, the specific embodiment below according to the present invention is simultaneously combined
Accompanying drawing, the present invention is further detailed explanation, 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 () is PMMA；B () is 2) the step hydriding combustion conjunction in embodiment 1-4 and comparative example 1
Into powder magnesium-nickel alloy Mg prepared by method95Ni5；C () is Mg prepared by embodiment 195Ni5- 5%PMMA；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)
For Mg prepared by embodiment 195Ni5- 5%PMMA；B () is Mg prepared by embodiment 295Ni5- 10%PMMA；
Fig. 3 is HCS+MM combination product Mg95Ni5- 5%PMMA, Mg95Ni5The XRD spectra of -10%PMMA；Wherein, (A) it is
Mg prepared by embodiment 195Ni5- 5%PMMA, (B) Mg prepared for embodiment 295Ni5- 10%PMMA, is (a) original in figure
The sample of argon protection；B () is the exposure sample of a day in atmosphere；C () is the exposure sample of a week in atmosphere；
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, HCS+MM combination product Mg prepared by embodiment 295Ni5- 10%PMMA in 473K,
The Dynamic isotherms of hydrogen absorption of 3.0MPa hydrogen pressure；
Fig. 6 is HCS product Mg95Ni5, HCS+MM combination product Mg prepared by embodiment 295Ni5- 10%PMMA in 523K,
The Dynamic isotherms of hydrogen absorption of 3.0MPa hydrogen pressure；
Fig. 7 is HCS product Mg95Ni5, HCS+MM combination product Mg prepared by embodiment 295Ni5- 10%PMMA in 473K,
Hydrogen desorption kineticses curve under vacuum condition；
Fig. 8 is HCS product Mg95Ni5, HCS+MM combination product Mg prepared by embodiment 295Ni5- 10%PMMA in 523K,
Hydrogen desorption kineticses curve under vacuum condition.
Specific embodiment
Following examples are described in further detail to present disclosure, and protection scope of the present invention is included but do not limited
In following each embodiments.
The purity of the 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 examples and comparative example and
Raw material is commercially available prod.
Heretofore described Mg95Ni5- 5%PMMA, Mg95Ni5- 10%PMMA, Mg95Ni5- 20%PMMA and Mg95Ni5-
In 10%EP 5%, 10%, 20% refers to that corresponding polymer P MMA or EP accounts for the percentage of nano-magnesium-based hydrogen storage material gross mass
Number.
The Mg of embodiment 195Ni5The preparation of -5%PMMA nano-magnesium-based hydrogen storage materials
(1) take 9.5g magnesium powder and 0.5g nikel powders are put in beaker and carry out mixing pretreatment, add 40mL acetone as dispersion
Agent, using the uniform 1h of ultrasonic mixing, ultrasonic power is 1kW, after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder
End；
(2) magnesium nickel mixed-powder is carried out into hydrogenation combustion method synthesis, in building-up process, magnesium nickel mixed-powder is in 2MPa hydrogen
580 DEG C of insulation 2h are warmed up under gas atmosphere, 340 DEG C of insulation 4h are then cooled to, room temperature is finally cooled to, the magnesium of powder is obtained
Nickel alloy.
(3) take 0.1gPMMA to be put in beaker, add 20mL tetrahydrofurans, stir 1h, be configured to macromolecular solution, take
The magnesium-nickel alloy of the powder that 1.9g steps (2) are obtained is put in ball grinder, and the macromolecular solution for having configured is added into ball grinder
In, the ball milling 10h under 0.1Mpa argon gas atmospheres, rotating speed is 400rpm, and ratio of grinding media to material is 30:1, the product for obtaining is put into argon gas atmosphere
In glove box, sucking filtration is carried out, at 80 DEG C 8h is dried, until solvent and small molecule are volatilized completely, finally give polymer overmold
Nano-magnesium-based hydrogen storage material.
(c) in Fig. 1 is Mg manufactured in the present embodiment95Ni5The XRD figure of -5%PMMA nano-magnesium-based hydrogen storage materials, from this
Figure is as can be seen that it coordinates and is divided into PMMA, Mg, MgH2And Mg2NiH4, with Mg95Ni5Compare, combination product Mg95Ni5- 5%PMMA
High wide and relative peak intensities are reduced a lot, while there is widthization phenomenon, this shows that magnesium base alloy granule diminishes, 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 materials, 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) is Mg95Ni5- 5%PMMA
Respectively under argon protection, the XRD spectra that is exposed in air after exposing one week in one day and air, from this figure, it can be seen that
Exposing the sample of a day in atmosphere has obvious Mg (OH)2With the diffraction maximum of MgO, two kinds of diffraction of the exposure air sample of a week
Peak is further raised, and this shows that the composite of the only mass fraction 5%PMMA of addition can not be played effectively to magnesium base alloy
Protective effect, sample oxidation and hydrolysis phenomena it is serious.
The Mg that the present embodiment is prepared95Ni5- 5%PMMA nano-magnesium-based hydrogen storage materials, in 60min under 473K and 523K
Interior hydrogen-sucking amount respectively reaches 3.37wt.% and 4.52wt%；Hydrogen can be put under low temperature 473K, hydrogen desorption capacity is up to
1.42wt.%, temperature is increased under 523K, and hydrogen is put in 120min can reach 2.46wt.%.
The Mg of embodiment 295Ni5The preparation of -10%PMMA nano-magnesium-based hydrogen storage materials
(1) take 9.5g magnesium powder and 0.5g nikel powders are put in beaker and carry out mixing pretreatment, add 40mL acetone as dispersion
Agent, using the uniform 1h of ultrasonic mixing, ultrasonic power is 1kW, is then dried after 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed-powder；
(2) magnesium nickel mixed-powder is carried out into hydrogenation combustion method synthesis, in building-up process, magnesium nickel mixed-powder is in 2MPa hydrogen
580 DEG C of insulation 2h are warmed up under gas atmosphere, 340 DEG C of insulation 4h are then cooled to, room temperature is finally cooled to, the magnesium of powder is obtained
Nickel alloy.
(3) take 0.2gPMMA to be put in beaker, add 20mL tetrahydrofurans, stir 1h, be configured to macromolecular solution, take
The magnesium-nickel alloy of the powder that 1.8g steps (2) are obtained is put in ball grinder, and the macromolecular solution for having configured is added into ball grinder
In, the ball milling 10h under 0.1Mpa argon gas atmospheres, rotating speed is 400rpm, and ratio of grinding media to material is 30:1, the product for obtaining is put into argon gas atmosphere
In glove box, sucking filtration is carried out, at 80 DEG C 8h is dried, until solvent and small molecule are volatilized completely, finally give polymer overmold
Nano-magnesium-based hydrogen storage material.
(d) in Fig. 1 is that the present embodiment prepares Mg95Ni5The XRD figure of -10%PMMA nano-magnesium-based hydrogen storage materials, from the figure
Can see that it coordinates and be divided into PMMA, Mg, MgH2And Mg2NiH4, with Mg95Ni5Compare, combination product Mg95Ni5- 10%PMMA half
High wide and relative peak intensities are equally reduced a lot, while there is widthization phenomenon, this shows that magnesium base alloy granule diminishes, 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 materials, 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) is Mg95Ni5- 10%
PMMA is exposed to the XRD spectra after exposing a week in a day and air under argon protection, in air, from this figure, it can be seen that
There is no significantly oxidation and hydrolysis phenomena in sample, after exposing in atmosphere one day until sample places in atmosphere one
In week, just there is Mg (OH)2Show all well below the former with the diffraction maximum of MgO, and the relative intensity of the diffraction maximum of two kinds of materials
The PMMA of addition 10wt.% can relatively efficiently protect the resistance to oxidation and hydrolysis ability of combination product, product significantly to strengthen.
Referring to Fig. 5-Fig. 8, the Mg that the present embodiment is prepared95Ni5- 10%PMMA nano-magnesium-based hydrogen storage materials, in 473K and
Hydrogen-sucking amount under 523K in 60min respectively reaches 3.37wt.% and 4.04wt%；Hydrogen can be put under low temperature 473K, hydrogen is put
Amount is up to 1.02wt.%, and temperature is increased under 523K, and hydrogen is put in 120min can reach 2.18wt.%.
The Mg of embodiment 395Ni5The preparation of -20%PMMA nano-magnesium-based hydrogen storage materials
(1) take 9.5g magnesium powder and 0.5g nikel powders are put in beaker and carry out mixing pretreatment, add 40mL acetone as dispersion
Agent, using the uniform 1h of ultrasonic mixing, ultrasonic power is 1KW, after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder
End；
(2) magnesium nickel mixed-powder is carried out into hydrogenation combustion method synthesis, in building-up process, magnesium nickel mixed-powder is in 2MPa hydrogen
580 DEG C of insulation 2h are warmed up under gas atmosphere, 340 DEG C of insulation 4h are then cooled to, room temperature is finally cooled to, the magnesium of powder is obtained
Nickel alloy.
(3) take 0.4gPMMA to be put in beaker, add 20mL tetrahydrofurans, stir 1h, be configured to macromolecular solution, take
The magnesium-nickel alloy of the powder that 1.6g steps (2) are obtained is put in ball grinder, and the macromolecular solution for having configured is added into ball grinder
In, the ball milling 10h under 0.1Mpa argon gas atmospheres, rotating speed is 400rpm, and ratio of grinding media to material is 30:1, the product for obtaining is put into argon gas atmosphere
In glove box, sucking filtration is carried out, at 80 DEG C 8h is dried, until solvent and small molecule are volatilized completely, finally give polymer overmold
Nano-magnesium-based hydrogen storage material
Mg manufactured in the present embodiment95Ni5The phase constituent of -20%PMMA nano-magnesium-based hydrogen storage materials be similarly PMMA, Mg,
MgH2And Mg2NiH4, but the polymer content for coating is higher, and the diffraction peak intensity for causing metal alloy therein is greatly reduced.
The present embodiment prepares Mg95Ni5- 20%PMMA nano-magnesium-based hydrogen storage materials thicker, granule due to polymer overmold
Size is about 300-400nm.The PMMA of addition 20wt.% can effectively protect combination product, the resistance to oxidation of product and water-fast
Solution ability significantly strengthens.
The Mg that the present embodiment is prepared95Ni5- 20%PMMA nano-magnesium-based hydrogen storage materials are due to the content mistake of polymer overmold
Height, the suction hydrogen desorption kineticses for causing material are decreased obviously, and the hydrogen-sucking amount under 473K and 523K in 60min is respectively reached
1.23wt.% and 2.56wt%；Nearly no under low temperature 473K to put hydrogen, temperature is increased under 523K, and hydrogen is put in 120min
1.22wt.% can be reached.
The Mg of embodiment 495Ni5The preparation of -10%EP nano-magnesium-based hydrogen storage materials
(1) take 9.5g magnesium powder and 0.5g nikel powders are put in beaker and carry out mixing pretreatment, add 40mL acetone as dispersion
Agent, using the uniform 1h of ultrasonic mixing, ultrasonic power is 1kW, after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder
End；
(2) magnesium nickel mixed-powder is carried out into hydrogenation combustion method synthesis, in building-up process, magnesium nickel mixed-powder is in 2MPa hydrogen
580 DEG C of insulation 2h are warmed up under gas atmosphere, 340 DEG C of insulation 4h are then cooled to, room temperature is finally cooled to, the magnesium of powder is obtained
Nickel alloy.
(3) raw material adopts two kinds of solution of epoxy resin A and B, the magnesium-nickel alloy for taking the powder that 1.8g steps (2) are obtained to put
In entering ball grinder, it is separately added into each 0.1g of two kinds of solution of A, B and mixes 1h to two kind of solution and be mixed thoroughly to form EP, in 0.1Mpa
Ball milling 10h under argon gas atmosphere, rotating speed is 400rpm, and ratio of grinding media to material is 30:1, the product for obtaining is put in argon gas atmosphere glove box, is entered
Row sucking filtration, at 80 DEG C 8h is dried, until solvent and small molecule are volatilized completely, finally gives the nano Mg base storage of polymer overmold
Hydrogen material.
Mg manufactured in the present embodiment95Ni5Coordinating for -10%EP nano-magnesium-based hydrogen storage materials is divided into EP, Mg, MgH2With
Mg2NiH4, with Mg95Ni5Compare, find combination product Mg95Ni5- 10%PMMA halfwidths and relative peak intensities are equally reduced very
It is many, while there is widthization phenomenon, which results in magnesium base alloy granule and diminish, crystal grain refinement, crystal structure changes.
Mg manufactured in the present embodiment95Ni5The particle size of -10%EP nano-magnesium-based hydrogen storage materials is about 200-300nm.
The EP of addition 10wt.% can relatively efficiently protect the resistance to oxidation and hydrolysis ability of combination product, product significantly to strengthen.
The Mg that the present embodiment is prepared95Ni5- 10%EP nano-magnesium-based hydrogen storage materials are with the saturating hydrogen effects of polymer P MMA slightly
Difference, the suction hydrogen desorption kineticses of material have certain decline, but still have good hydrogen storage property, under 473K and 523K
Hydrogen-sucking amount in 60min respectively reaches 1.89wt.% and 2.94wt%；Under low temperature 473K hydrogen desorption capacity be 0.78wt.%, temperature
Under being increased to 523K, hydrogen is put in 120min can reach 1.98wt.%.
The Mg of embodiment 595Ni5The preparation of -2%PMMA nano-magnesium-based hydrogen storage materials
(1) take 9.5g magnesium powder and 0.5g nikel powders are put in beaker and carry out mixing pretreatment, add 40mL acetone as dispersion
Agent, using the uniform 1h of ultrasonic mixing, ultrasonic power is 1KW, after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder
End；
(2) magnesium nickel mixed-powder is carried out into hydrogenation combustion method synthesis, in building-up process, magnesium nickel mixed-powder is in 2MPa hydrogen
580 DEG C of insulation 2h are warmed up under gas atmosphere, 340 DEG C of insulation 4h are then cooled to, room temperature is finally cooled to, the magnesium of powder is obtained
Nickel alloy.
(3) take 0.04gPMMA to be put in beaker, add 20mL tetrahydrofurans, stir 1h, be configured to macromolecular solution, take
The magnesium-nickel alloy of the powder that 1.96g steps (2) are obtained is put in ball grinder, and the macromolecular solution for having configured is added into ball grinder
In, the ball milling 10h under 0.1Mpa argon gas atmospheres, rotating speed is 400rpm, and ratio of grinding media to material is 30:1, the product for obtaining is put into argon gas atmosphere
In glove box, sucking filtration is carried out, at 80 DEG C 8h is dried, until solvent and small molecule are volatilized completely, finally give polymer overmold
Nano-magnesium-based hydrogen storage material.
Mg manufactured in the present embodiment95Ni5The phase constituent of -2%PMMA nano-magnesium-based hydrogen storage materials be similarly PMMA, Mg,
MgH2And Mg2NiH4, but the polymer content for coating 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 materials, in 60min under 473K and 523K
Interior hydrogen-sucking amount respectively reaches 3.98wt.% and 5.12wt%；Hydrogen can be put under low temperature 473K, hydrogen desorption capacity reaches
1.01wt.%, temperature is increased under 523K, and hydrogen is put in 120min can reach 2.84wt.%.
Comparative example l Mg95Ni5The preparation of nano-magnesium-based hydrogen storage material
(1) take 9.5g magnesium powder and 0.5g nikel powders are put in beaker and carry out mixing pretreatment, add 40ml acetone as dispersion
Agent, using the uniform 1h of ultrasonic mixing, ultrasonic power is 1kW, after then drying 8h at a temperature of 80 DEG C, obtains magnesium nickel mixed powder
End；
(2) magnesium nickel mixed-powder is carried out into hydrogenation combustion method synthesis, in building-up process, magnesium nickel mixed-powder is in 2MPa hydrogen
580 DEG C of insulation 2h are warmed up under gas atmosphere, 340 DEG C of insulation 4h are then cooled to, room temperature is finally cooled to, the magnesium of powder is obtained
Nickel alloy.
(3) magnesium-nickel alloy for taking the powder that 2g steps (2) are obtained is put in ball grinder, the ball under 0.1Mpa argon gas atmospheres
Mill 10h, rotating speed is 400rpm, and ratio of grinding media to material is 30:1, you can obtain Mg95Ni5Nano-magnesium-based hydrogen storage material.
(b) in Fig. 1 is that this comparative example prepares Mg95Ni5The XRD figure of nano-magnesium-based hydrogen storage material, can therefrom see it
Coordinate and be divided into Mg, MgH2And Mg2NiH4。Mg95Ni5Its particle size is about 600-800nm, in atmosphere without any protection,
Can be oxidized quickly.
Referring to Fig. 5-Fig. 8, the Mg that this comparative example is prepared95Ni5Nano-magnesium-based hydrogen storage material, under 473K and 523K
Hydrogen-sucking amount in 60min respectively reaches 2.08wt.%, 2.48wt.%；Hydrogen is hardly put under 473K, temperature is increased to 523K
Under, it is only capable of putting hydrogen 0.24wt% in 120min.
Technological parameter (such as temperature, time) the interval bound value of the present invention and interval value can realize this law,
Embodiment numerous to list herein.
Claims (10)
1. a kind of nano-magnesium-based hydrogen storage material of polymer overmold, it is characterised in that be made up of following component by mass percentage：
Magnesium-nickel alloy：80-98%, polymer：2-20%.
2. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 1, it is characterised in that the magnesium-nickel alloy is pressed
Mass percent is made up of following component, magnesium：90-98%, nickel：2%-10%；Preferably, the magnesium-nickel alloy presses quality percentage
Than being made up of following component, magnesium：95%, nickel：5%.
3. the nano-magnesium-based hydrogen storage material of polymer overmold according to claim 1, it is characterised in that the polymer is tool
There is the polymer of hydrogen antioxidant capacity；Preferably, the polymer is thermoplastic resin or thermosetting resin；It is highly preferred that institute
Thermoplastic resin is stated for polyethylene, polypropylene, polrvinyl chloride, polystyrene, polymethyl methacrylate, polyester, polyformaldehyde, poly-
Amide, polyimides or polypyrrole, the thermosetting resin is phenolic resin, epoxy resin, amino resins, unsaturated polyester (UP) tree
Fat or silicon ether resin；Further, the polymer be polymethyl methacrylate that weight average molecular weight is 6000 to 10000 or
Weight average molecular weight is 600 to 1000 epoxy resin.
4. according to any one of claim 1-3 polymer overmold nano-magnesium-based hydrogen storage material, it is characterised in that it is described
The particle mean size of the nano-magnesium-based hydrogen storage material of polymer overmold is 100～500nm.
5. the preparation method of the nano-magnesium-based hydrogen storage material of polymer overmold any one of a kind of claim 1-4, it is special
Levy and be, comprise the steps：
Step one, according to mass percent any one of claim 1-4 magnesium powder and nikel powder are weighed, and add dispersant, are used
Ultrasonic method or ball-milling method carry out mixing pretreatment, and magnesium nickel mixed-powder is obtained after drying；
Step 2, by the magnesium nickel mixed-powder hydriding combustion synthesis are carried out, and obtain the magnesium-nickel alloy of powder；
Step 3, certain mass is pressed than adding the macromolecular solution containing polymer by the magnesium-nickel alloy prepared by step 2
In, strength mechanical ball milling is then carried out, the product for obtaining carries out under an inert atmosphere sucking filtration, drying until solvent and small molecule are complete
Full volatilization, finally gives the nano-magnesium-based hydrogen storage material of the polymer overmold.
6. preparation method according to claim 5, it is characterised in that in step one, mixing pretreatment is carried out using ultrasonic method
When, the time of the mixing is 1-2h, and ultrasonic power is 1-2kW；
Preferably, the dispersant is organic solvent, more preferably acetone or alcohol；
Preferably, the purity of the magnesium powder is more than 98.55%, and grain graininess is less than 44 μm；The purity of the nikel powder is
More than 99.9%, grain graininess is 2-3 μm.
7. preparation method according to claim 5, it is characterised in that the concrete technology of hydriding combustion synthesis described in step 2
It is as follows：The magnesium nickel mixed-powder is placed in the hydrogen atmosphere reactor that pressure is 2-2.5MPa, 550-600 DEG C is warmed up to simultaneously
Insulation 1-2h, is then cooled to 330-350 DEG C and is incubated 3-5h, finally naturally cools to room temperature, and the magnesium nickel for obtaining powder is closed
Gold.
8. preparation method according to claim 5, it is characterised in that in step 3, the polymer is dissolved in corresponding benign
Solvent in form the macromolecular solution, wherein, the solvent be acetone, tetrahydrofuran, ethanol or ethylene glycol, the polymerization
Thing is the polymer with saturating hydrogen antioxidant capacity；Preferably, the polymer is the poly- first that weight average molecular weight is 6000 to 10000
Base acrylic acid methyl ester., the solvent is tetrahydrofuran；
Preferably, in the macromolecular solution, the concentration of the polymer is 4-20g/L, it is highly preferred that the polymer
Concentration is 8-15g/L.
9. preparation method according to claim 5, it is characterised in that in step 3, it is 600 to 1000 that polymer is molecular weight
Epoxy resin, the macromolecular solution is obtained by epoxy resin A, B glue hybrid reaction.
10. preparation method according to claim 5, it is characterised in that magnesium-nickel alloy described in step 3 and the polymer
Mass ratio be 4-49:1；
Preferably, the strength mechanical ball milling is carried out in planetary high-energy ball mill under hydrogen atmosphere protection；It is described
The Ball-milling Time of strength mechanical ball milling is 10-20h, and ratio of grinding media to material is 25-35:1, rotating speed is 300-500r/min；
Preferably, the temperature of the drying be 70-90 DEG C, the time be 7-10h；
Preferably, the sucking filtration and the drying is carried out under an argon atmosphere.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108193107A (en) * | 2017-12-21 | 2018-06-22 | 陕西科技大学 | A kind of novel organic coating core-shell structure copolymer nanocomposite hydrogen storage material and preparation method thereof |
| CN108439330A (en) * | 2018-04-20 | 2018-08-24 | 常州达奥新材料科技有限公司 | A kind of preparation method of compound magnalium based hydrogen storage material |
| CN110804705A (en) * | 2019-11-28 | 2020-02-18 | 晚叶保旺 | Oxidation-resistant polyimide-Mg-based composite hydrogen storage material and preparation method thereof |
| CN112390224A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院大连化学物理研究所 | Polymer-coated hydrogen storage material and preparation method and application thereof |
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| CN115321476A (en) * | 2022-08-29 | 2022-11-11 | 湖南水素新能源科技有限公司 | Air-stable hydrogen storage material and preparation method thereof |
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| CN116101974A (en) * | 2023-03-07 | 2023-05-12 | 大连大学 | Aluminum hydride hydrogen storage material doped with polymer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050074612A1 (en) * | 2003-03-14 | 2005-04-07 | Eklund Peter C. | Hydrogen storage material based on platelets and/or a multilayered core/shell structure |
| US20120195823A1 (en) * | 2011-01-28 | 2012-08-02 | The Regents Of The University Of California | Novel Hydrogen Storage Materials |
| CN104884382A (en) * | 2012-12-21 | 2015-09-02 | 赛勒收购有限公司 | Hydrogen storage pellet |
| CN105731378A (en) * | 2016-01-26 | 2016-07-06 | 北京科技大学 | Organic polymer/AB5 or AB2 composite hydrogen storage material and preparation method thereof |
-
2016
- 2016-10-31 CN CN201610931895.XA patent/CN106566965B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050074612A1 (en) * | 2003-03-14 | 2005-04-07 | Eklund Peter C. | Hydrogen storage material based on platelets and/or a multilayered core/shell structure |
| US20120195823A1 (en) * | 2011-01-28 | 2012-08-02 | The Regents Of The University Of California | Novel Hydrogen Storage Materials |
| CN104884382A (en) * | 2012-12-21 | 2015-09-02 | 赛勒收购有限公司 | Hydrogen storage pellet |
| CN105731378A (en) * | 2016-01-26 | 2016-07-06 | 北京科技大学 | Organic polymer/AB5 or AB2 composite hydrogen storage material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAOFENG LIU等: "Hydrogen storage properties of Mg100-xNix (x = 5,11.3,20,25) composites prepared by hydriding combustion synthesis followed by mechanical milling (HCS+MM)", 《INTERMETALLICS》 * |
| 汪洋: "《高校便捷的氢能》", 30 September 2014, 甘肃科学技术出版社 * |
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| CN112390224A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院大连化学物理研究所 | Polymer-coated hydrogen storage material and preparation method and application thereof |
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| CN113735057A (en) * | 2021-08-31 | 2021-12-03 | 苏州睿分电子科技有限公司 | Activation-free hydrogen storage material and preparation method and device thereof |
| CN114411028A (en) * | 2022-01-21 | 2022-04-29 | 徐州工程学院 | Trace nickel composite layered magnesium composite material and preparation method and application thereof |
| US11878907B2 (en) | 2022-01-21 | 2024-01-23 | Xuzhou University Of Technology | Trace nickel-compounded layered magnesium composite material and preparation method and use thereof |
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