CN1743066A - A kind of nanocomposite hydrogen storage material and preparation method thereof - Google Patents
A kind of nanocomposite hydrogen storage material and preparation method thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 144
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 144
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 36
- 239000011232 storage material Substances 0.000 title claims abstract description 36
- 238000000498 ball milling Methods 0.000 claims abstract description 64
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910012375 magnesium hydride Inorganic materials 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003795 desorption Methods 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 5
- 239000001996 bearing alloy Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000011056 performance test Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000000227 grinding Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000713 high-energy ball milling Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- -1 magnesium hydride form compound Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention provides a kind of nanocomposite hydrogen storage material, is the mixture of magnesium hydride 90wt%～99wt% and nano-sized carbon 1wt%～10wt%.Its preparation method: nano-sized carbon is blended in the magnesium hydride in required ratio, and mechanical ball milling is 30 minutes～100 hours under argon gas or hydrogen atmosphere, and carries out desorption subsequently; Perhaps with magnesium hydride ball milling 1 hour～100 hours, add nano-sized carbon ball milling 30 minutes～10 hours more then, and carry out desorption subsequently.The invention has the advantages that: preparation technology is simple, and the composite of preparation gained does not need activation, can directly carry out the dynamic performance test; Preparation gained composite hydrogen storage material has the excellent comprehensive hydrogen storage property, also has excellent dynamic performance when keeping higher hydrogen storage capability, and hydrogen storage capability is 4.5wt%～6.7wt%.
Description
Technical field:
The present invention relates to a kind of hydrogen storage material, particularly contain the novel hydrogen storage material of the collaborative storage hydrogen of having of magnesium and nano-sized carbon effect, also relate to the preparation method of novel hydrogen storage material.
Background technology:
Environment, the energy and sustainable development are the three big themes that our times faces, and Hydrogen Energy is one of desirable clean energy resource.In recent years, the fast development of fuel cell car and business-like propelling have swept across All Around The World, and it is energy-efficient, and zero-emission or near the good environment performance of zero-emission, make it to become world today's energy and field of traffic hot of research and development.But the technical bottleneck that solves fuel cell car at present is still the storage problem of hydrogen.
As everyone knows, in the various metal hydrides of research at present, Mg is because its high weight hydrogen-storage density (the theoretical weight hydrogen-storage density is 7.6wt%) has caused people's very big interest, and it is in light weight, cost is low, and the content in the earth's crust is extremely abundant again.But Mg storage hydrogen has shortcoming clearly again, be exactly its storage, hydrogen discharging temperature height (～673K), dynamics is poor.In order to improve the dynamic performance of Mg storage hydrogen, people add catalyst and adopt the method for ball milling to prepare nano hydrogen-storage material in Mg, but from present result, add the thermodynamic problems that these catalyst also fundamentally do not solve the Mg storage, put hydrogen.
1-dimention nano such as nano carbon fiber, CNT material with carbon element is the hollow form carbon structural nano that is curled and formed by graphene film, because its special structure, CNT at room temperature also has good storage hydrogen effect.The hydrogen storage capability of report SWNTs such as U.S. Dillon in 1997 is approximately 5～10wt%; SWNT can be inhaled hydrogen 4.2wt% (ZL991122902.4) after Metal Inst., Chinese Academy of Sciences's report was purified in 1999 under room temperature 12MPa hydrogen pressure.Nankai University adopts several different preparation methods to prepare hydrogen bearing alloy/CNT composite hydrogen storage material, and its hydrogen storage capability is 2.5wt%～4.5wt% (CN1259584A).Wuhan University of Technology adopts the unidimensional nanocarbon surface of microwave plasma etching to mix or deposition hydrogen storage metal or the prepared hydrogen storage material of hydrogen bearing alloy, and its hydrogen storage capability is 3.8wt%～5.5wt% (CN1398664A).
Summary of the invention:
The present invention aims to provide a kind of nanocomposite hydrogen storage material and preparation method thereof, to have obtained the good hydrogen dynamic performance that stores.
The invention provides a kind of nanocomposite hydrogen storage material, it is characterized in that: hydrogen storage material is the mixture of magnesium hydride 90wt%～99wt% and nano-sized carbon 1wt%～10wt%.Because the special nanostructured of nano-sized carbon, in mechanical milling process can and magnesium hydride form compound even and the composite of ultra-fine microstructure arranged, in mechanical milling process, not only increased specific area by short nano-sized carbon of cutting, and the structure of hollow can provide passage for the diffusion of hydrogen, improves and stores the hydrogen performance.The X ray diffracting spectrum of CNT composite after the ball milling preparation as shown in Figure 1 behind magnesium hydride+purifying; The X ray diffracting spectrum of CNT composite after desorption is also for the first time inhaled hydrogen as shown in Figure 2 behind magnesium hydride+purifying; Scanning electron microscopy sheet behind magnesium hydride+purifying behind the CNT composite ball milling as shown in Figure 3.
Nanocomposite hydrogen storage material provided by the invention can also contain catalyst, its weight ratio is 70wt%～99wt% for magnesium hydride content, nano-sized carbon content is 1wt%～10wt%, catalyst content is 0.1～29wt%, catalyst can be magnesium-yttrium-transition metal such as Fe, Co, Ni, Ti, V, Zr, Mn, Nb, Li, Ca, Cr, Cu, Zn, Al, Y, Mo, Sn, B, compound such as Nb such as metal oxide
2O
5, V
2O
5, Fe
3O
4, TiO
2, Cr
2O
3, ZrO, can or be lower than the hydrogen bearing alloy such as lanthanum nickel system, ferrotitanium system of reversible hydrogen adsorption and desorption under the normal temperature, the combination of wherein one or more at normal temperature.Catalyst promotes hydrogen molecule to dissociate into hydrogen atom, then is expected to make the polynary hydrogen storage system of magnesium+nano-sized carbon+catalyst keeping under the prerequisite of high hydrogen-storage density, obtains the good hydrogen dynamic performance that stores.
Nano-sized carbon in the nanocomposite hydrogen storage material provided by the invention can be CNT or nano carbon fiber, or the mixture of the two, and wherein, CNT is the SWNT or the multiple-wall carbon nanotube of purifying or not purifying.
In addition, the invention provides a kind of preparation method of nanocomposite hydrogen storage material, it is characterized in that: nano-sized carbon is blended in the magnesium hydride in required ratio, mechanical ball milling is 30 minutes～100 hours under argon gas or hydrogen atmosphere, and carry out desorption subsequently, the adding of sample and taking-up are all carried out in glove box, and wherein water, oxygen content all are lower than 1ppm.
The invention provides the preparation method of another kind of nanocomposite hydrogen storage material, it is characterized in that: with magnesium hydride ball milling 1 hour～100 hours; Add nano-sized carbon ball milling 30 minutes～10 hours and carry out desorption subsequently more then.
Among the preparation method of nanocomposite hydrogen storage material provided by the invention, can be earlier with pure magnesium ball milling under hydrogen atmosphere, Hydrogen Vapor Pressure is 0.5～1MPa, the ball milling time is 1h～20h, makes magnesium hydride.
The present invention provides a kind of preparation method of nanocomposite hydrogen storage material again, earlier with magnesium hydride+catalyst ball milling 10 hours～100 hours, adds nano-sized carbon ball milling 30 minutes～10 hours more then.
The present invention also provides a kind of preparation method of nanocomposite hydrogen storage material, and earlier with magnesium+catalyst ball milling 10 hours～100 hours under hydrogen atmosphere, Hydrogen Vapor Pressure is 0.5～1MPa, adds nano-sized carbon ball milling 30 minutes～10 hours more then.
The present invention also provides a kind of preparation method of nanocomposite hydrogen storage material, earlier the catalyst ball milling is mixed 10 minutes～2 hours, and repeated hydrogenation magnesium ball milling 10 hours～100 hours adds nano-sized carbon ball milling 30 minutes～10 hours more then.
Among the preparation method of nanocomposite hydrogen storage material provided by the invention, magnesium hydride obtains pure magnesium ball milling under hydrogen atmosphere, and Hydrogen Vapor Pressure is 0.5～1MPa, and the ball milling time is 1h～20h.
The nanocomposite hydrogen storage material of the present invention's preparation, observe confirmation through X-ray diffraction, ESEM and high-resolution-ration transmission electric-lens, the crystallite dimension of composite has reached nanoscale, nano-sized carbon or catalysis are uniformly distributed in the Mg matrix mutually, and nano-sized carbon or catalysis all generate intermetallic compound with Mg mutually.Sample of the present invention need not activation, directly carries out the dynamic performance test, temperature range: 100 ℃～350 ℃, and pressure limit: 0.5～2.0MPa.
The invention has the advantages that:
1, preparation technology is simple, and the composite of preparation gained does not need activation, can directly carry out the dynamic performance test;
2, preparation gained composite hydrogen storage material has the excellent comprehensive hydrogen storage property, also has excellent dynamic performance when keeping higher hydrogen storage capability, and hydrogen storage capability is 4.5wt%～6.7wt%.
Description of drawings:
Fig. 1 is the X ray diffracting spectrum of CNT composite after the ball milling preparation behind magnesium hydride+purifying;
Fig. 2 is the X ray diffracting spectrum of CNT composite behind magnesium hydride+purifying after desorption is also for the first time inhaled hydrogen;
Fig. 3 is the scanning electron microscopy sheet behind the CNT composite ball milling behind magnesium hydride+purifying;
Fig. 4 is CNT composite and the first time hydrogen sucking function test comparison of pure magnesium hydride sample behind desorption behind magnesium hydride+purifying, and temperature is 573K;
Fig. 5 is CNT composite and the first time hydrogen sucking function test comparison of pure magnesium hydride sample behind desorption behind magnesium hydride+purifying, and temperature is 473K;
Fig. 6 is the first time hydrogen sucking function test curve of purifying nano carbon pipe sample behind desorption of magnesium hydride+not;
Fig. 7 is CNT+catalyst sample and the first time hydrogen sucking function test comparison of magnesium hydride+catalyst sample behind desorption behind magnesium hydride+purifying;
Fig. 8 is the hydrogen discharging performance test comparison after desorption is also for the first time inhaled hydrogen for CNT sample behind magnesium hydride+purifying and pure magnesium hydride sample, and temperature is 623K.
The specific embodiment:
The purification SWNT, its purity is about 90%, and caliber is 1～2nm.Then the SWNT behind the purifying is sneaked into and adopt the reaction ball milling legal system to be equipped with in the magnesium hydride powder and mix (SWNT: MgH
2=5: 95, percentage by weight), under argon shield, carry out high-energy ball milling then, ratio of grinding media to material is 20: 1, the ball milling time is 10 hours.Nano composite material to the preparation gained is carried out hydrogen storage property test (shown in Figure 4 and 5) with volumetric method behind desorption, hydrogen pressure is 2MPa.Under 573K, hydrogen storage capability is 6.67wt% in 600 seconds; Can inhale hydrogen 5.47wt% under 473K, in one hour, maximum can be inhaled hydrogen 6.35wt%; Even when temperature is 423K, can inhale hydrogen 2.5wt% in one hour, and maximum hydrogen can reach 4.8wt%.Under 623K, the hydrogen desorption capacity of nanocomposite hydrogen storage material in 30 minutes of preparation gained is 6.23wt% (as shown in Figure 8), is about 93% of maximum hydrogen.
The purification SWNT, its purity is about 90%, and caliber is 1～2nm.Then the SWNT behind the purifying is sneaked into and adopt the reaction ball milling legal system to be equipped with in the magnesium hydride powder and mix (SWNT: MgH
2=10: 90, percentage by weight), under argon shield, carry out high-energy ball milling then, ratio of grinding media to material is 20: 1, the ball milling time is 30 hours.Nano composite material to the preparation gained is carried out hydrogen storage property test (shown in Figure 4 and 5) with volumetric method behind desorption, hydrogen pressure is 2MPa.Under 573K, hydrogen storage capability is 6.5wt%; Under 473K, hydrogen storage capability is 6.0wt%.
The SWNT (wherein containing Fe, Co, Ni catalyst) of will not purifying is sneaked in the magnesium hydride powder that adopts the preparation of reaction ball milling method and is mixed (SWNT: MgH
2=1: 99, percentage by weight), under argon shield, carry out high-energy ball milling then, ratio of grinding media to material is 20: 1, the ball milling time is 20 hours.Nano composite material to the preparation gained is carried out hydrogen storage property test (as shown in Figure 6) with volumetric method behind desorption, hydrogen pressure is 2MPa.Under 573K, hydrogen storage capability is 5.5wt%; Under 473K, hydrogen storage capability reaches 4.6wt% in 10 minutes, and maximum hydrogen storage capability reaches 5.3wt%.
Embodiment 4
The purification multiple-wall carbon nanotube, its purity is about 90%, and caliber is 20～30nm.Then the multiple-wall carbon nanotube behind the purifying is sneaked into and adopt the reaction ball milling legal system to be equipped with in the magnesium hydride powder and mix (multiple-wall carbon nanotube: MgH
2=5: 95, percentage by weight), under argon shield, carry out high-energy ball milling then, ratio of grinding media to material is 20: 1, the ball milling time is 10 hours.Nano composite material to the preparation gained is carried out the hydrogen storage property test with volumetric method behind desorption, hydrogen pressure is 2MPa.Under 573K, hydrogen storage capability is 6.3wt%; Under 473K, hydrogen storage capability is 5.5wt%.
Fe, Ti powder are mixed with 2: 1 ratio of atomic percent, sneak in the magnesium hydride powder that adopts the preparation of reaction ball milling method then and mix Fe when sneaking into
2The percentage by weight of Ti and magnesium hydride powder is 5: 95.Mixed sample is carried out high-energy ball milling under the argon gas atmosphere protection, ratio of grinding media to material is 20: 1, and the ball milling time is 60 hours.And then added 5wt% SWNT and ball milling therein 10 hours.Nano composite material to the preparation gained is carried out hydrogen storage property test (as shown in Figure 7) with volumetric method behind desorption, hydrogen pressure is 2MPa.When 473K, hydrogen reaches 4.7wt% in 10 minutes, and maximum hydrogen can reach 5.6wt%.When not adding the carbon pipe, hydrogen storage capability increases about 1.5wt%.
Zr, Mn powder are mixed with 1: 1 ratio of atomic percent, sneak in the magnesium hydride powder that adopts the preparation of reaction ball milling method then and mix, the percentage by weight of ZrMn and magnesium hydride powder is 4: 96 when sneaking into.Mixed sample is carried out high-energy ball milling under the argon gas atmosphere protection, ratio of grinding media to material is 20: 1, and the ball milling time is 30 hours.And then added 5wt% SWNT and ball milling therein 10 hours.Nano composite material to the preparation gained is carried out the hydrogen storage property test with volumetric method behind desorption, hydrogen pressure is 2MPa.When 473K, hydrogen reaches 5.2wt% in 10 minutes, and maximum hydrogen can reach 6.3wt%; When 423K, hydrogen can reach 3.8wt% in 10 minutes.When not adding the carbon pipe respectively, hydrogen storage capability increases about 0.8wt% and 1.0wt%.
With Mg, LaNi
5With V be that 85: 10: 5 ratio is mixed and to be placed on ball milling under the hydrogen atmosphere with percentage by weight, Hydrogen Vapor Pressure is 1MPa, ratio of grinding media to material is 20: 1, the ball milling time is 30 hours, and every 10 hours in the ball grinder hydrogen make-up once arrive 1MPa.And then toward the carbon pipe ball milling that wherein adds 5wt% and placed under the argon gas atmosphere ball milling 10 hours.Nano composite material to the preparation gained is carried out the hydrogen storage property test with volumetric method behind desorption, hydrogen pressure is 2MPa.Under 473K, hydrogen reaches 4.1wt% in 10 minutes, and maximum hydrogen can reach 5.2wt%; When 423K, hydrogen can reach 3.5wt% in 10 minutes, and hydrogen can reach 4.5wt% in 60 minutes.When not adding the carbon pipe respectively, hydrogen storage capability increases about 1.0wt% and 1.2wt%.
Embodiment 8
With Nb
2O
5In powder and the magnesium hydride powder that adopts the preparation of reaction ball milling method and mix Nb when sneaking into
2O
5With the mol ratio of magnesium hydride powder be 0.2: 98.8.Mixed sample is carried out high-energy ball milling under the argon gas atmosphere protection, ratio of grinding media to material is 20: 1, and the ball milling time is 40 hours.And then added 5wt% SWNT and ball milling therein 10 hours.Nano composite material to the preparation gained is carried out the hydrogen storage property test with volumetric method behind desorption, hydrogen pressure is 2MPa.Recording hydrogen storage capability under 473K in 10 minutes is 4.2wt%, and maximum hydrogen is 5.2wt%.
Embodiment 9
With magnesium hydride powder ball milling under argon gas atmosphere of catalytic reacting ball milling method preparation, ratio of grinding media to material is 20:1, and the ball milling time is 80 hours.And then added 10wt% SWNT and ball milling therein 30 minutes.Nano composite material to the preparation gained is carried out the hydrogen storage property test with volumetric method behind desorption, hydrogen pressure is 2MPa.Recording hydrogen storage capability under 473K in 10 minutes is 5.2wt%, and maximum hydrogen is 5.9wt%.
Embodiment 10
With metal V, Zr and Mn by atomic percent V: Zr: Mn=5: mix at 4: 4 and mechanical ball milling 1 hour, then with magnesium hydride and above-mentioned metal mixture mixes and in argon gas atmosphere mechanical ball milling, its percentage by weight is MgH
2: VZrMn=95: 5, ratio of grinding media to material is 20: 1.And then added the carbon nano-fiber of 1wt% and ball milling 1 hour, and the nano composite material of preparation gained is carried out the hydrogen storage property test with volumetric method behind desorption, hydrogen pressure is 2Mpa.Recording hydrogen storage capability under 473K in 5 minutes is 5.0wt%, and maximum hydrogen is 5.8wt%.
Claims (10)
1, a kind of nanocomposite hydrogen storage material is characterized in that: hydrogen storage material is the mixture of magnesium hydride 90wt%～99wt% and nano-sized carbon 1wt%～10wt%.
2, according to the described nanocomposite hydrogen storage material of claim 1, it is characterized in that: described mixture also contains catalyst, and its weight ratio is: magnesium hydride 70wt%～99wt%, nano-sized carbon 1wt%～10wt%, catalyst 0.1～29wt%; Catalyst is magnesium-yttrium-transition metal such as Fe, Co, Ni, Ti, V, Zr, Mn, Nb, Li, Ca, Cr, Cu, Zn, Al, Y, Mo, Sn, B, compound such as Nb such as metal oxide
2O
5, V
2O
5, Fe
3O
4, TiO
2, Cr
2O
3, ZrO, can or be lower than the hydrogen bearing alloy such as lanthanum nickel system, ferrotitanium system of reversible hydrogen adsorption and desorption under the normal temperature, the combination of wherein one or more at normal temperature.
3, according to claim 1 or 2 described nanocomposite hydrogen storage materials, it is characterized in that: described nano-sized carbon is CNT or nano carbon fiber, or the mixture of the two, wherein, CNT is the SWNT or the multiple-wall carbon nanotube of purifying or not purifying.
4, the preparation method of nanocomposite hydrogen storage material as claimed in claim 1 is characterized in that: nano-sized carbon is blended in the magnesium hydride in required ratio, and mechanical ball milling is 30 minutes～100 hours under argon gas or hydrogen atmosphere, and carries out desorption subsequently.
5, the preparation method of nanocomposite hydrogen storage material as claimed in claim 1 is characterized in that: with magnesium hydride ball milling 1 hour～100 hours; Add nano-sized carbon ball milling 30 minutes～10 hours and carry out desorption subsequently more then.
6, according to the preparation method of claim 4 or 5 described nanocomposite hydrogen storage materials, it is characterized in that: described magnesium hydride obtains pure magnesium ball milling under hydrogen atmosphere, and Hydrogen Vapor Pressure is 0.5～1MPa, and the ball milling time is 1h～20h.
7, the preparation method of nanocomposite hydrogen storage material as claimed in claim 2 is characterized in that: earlier with magnesium hydride+catalyst ball milling 10 hours～100 hours, add nano-sized carbon ball milling 30 minutes～10 hours more then.
8, the preparation method of nanocomposite hydrogen storage material as claimed in claim 2, it is characterized in that: earlier with magnesium+catalyst ball milling 10 hours～100 hours under hydrogen atmosphere, Hydrogen Vapor Pressure is 0.5～1MPa, adds nano-sized carbon ball milling 30 minutes～10 hours more then.
9, the preparation method of nanocomposite hydrogen storage material as claimed in claim 2 is characterized in that: earlier the catalyst ball milling was mixed 10 minutes～2 hours, repeated hydrogenation magnesium ball milling 10 hours～100 hours adds nano-sized carbon ball milling 30 minutes～10 hours more then.
10, according to the preparation method of claim 7 or 9 described nanocomposite hydrogen storage materials, it is characterized in that: described magnesium hydride makes pure magnesium ball milling under hydrogen atmosphere, and Hydrogen Vapor Pressure is 0.5～1MPa, and the ball milling time is 1h～20h.
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100421781C (en) * | 2006-09-20 | 2008-10-01 | 太原理工大学 | Production of porous molecular-sieve hydrogen-storage material |
| SG159438A1 (en) * | 2008-08-25 | 2010-03-30 | Ind Tech Res Inst | Nanotization of magnesium-based hydrogen storage material |
| CN102060266A (en) * | 2010-11-25 | 2011-05-18 | 张文丛 | Magnesium hydride based composite powder |
| CN102491265A (en) * | 2011-12-06 | 2012-06-13 | 南京工业大学 | Method for preparing hydrogen by hydrolysis of magnesium-based material |
| CN101671788B (en) * | 2008-09-12 | 2013-06-19 | 财团法人工业技术研究院 | Method for nanocrystallization of magnesium-based hydrogen storage material |
| CN103663369A (en) * | 2012-09-12 | 2014-03-26 | 财团法人工业技术研究院 | Hydrogen storage composite and method of forming same |
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