CN101260492A - Magnesium-base nano hydrogen-storage material and preparing method thereof - Google Patents
Magnesium-base nano hydrogen-storage material and preparing method thereof Download PDFInfo
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- CN101260492A CN101260492A CNA2008100955892A CN200810095589A CN101260492A CN 101260492 A CN101260492 A CN 101260492A CN A2008100955892 A CNA2008100955892 A CN A2008100955892A CN 200810095589 A CN200810095589 A CN 200810095589A CN 101260492 A CN101260492 A CN 101260492A
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- 239000011232 storage material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 111
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 111
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000463 material Substances 0.000 claims abstract description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011777 magnesium Substances 0.000 claims abstract description 65
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 39
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 35
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 73
- 239000000956 alloy Substances 0.000 claims description 73
- 238000002360 preparation method Methods 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 15
- 238000007712 rapid solidification Methods 0.000 description 15
- 238000003860 storage Methods 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 239000001996 bearing alloy Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000003795 desorption Methods 0.000 description 8
- 230000006698 induction Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012876 topography Methods 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 239000002707 nanocrystalline material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001339 C alloy Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910005438 FeTi Inorganic materials 0.000 description 1
- -1 Hydride Chemical compound 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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Abstract
The invention relates to an mg-based hydrogen storage material, which comprises15 to 25 weight percent of nickel, and 5 to 15 weight percent of cerium contained rare earth elements, the rest is magnesium. The material mainly consists of nano-crystalline; in the nano-crystalline, the grain size of more than 70 percent of crystalline is lower than 10 nm. The invention further relates to a manufacture method of the material.
Description
Technical field
The present invention relates to magnesium-base nano hydrogen-storage material and preparation method thereof.More specifically, the present invention relates to a kind of heavy body magnesium-base nano hydrogen-storage material and preparation method thereof of even grain size.
Background technology
The energy dilemma of the twentieth century outburst second half has not only been brought developing rapidly of energy and material, and makes the Application and Development of hydrogen storage material also become an emerging problem day by day.Hydrogen Energy receives much concern as the secondary energy that clean, and becomes the ideal green new forms of energy that solve problem of environmental pollution that traditional fuel brings.The transportation of hydrogen manufacturing, Chu Qing and hydrogen is the subject matter of restriction Hydrogen Energy development, and hydrogen storage technology is that the research and development of the key that practicability and mass-producing are moved towards in the Hydrogen Energy utilization, particularly hydrogen storage material are the important steps of hydrogen storage technology development.Mg base hydrogen bearing alloy has hydrogen-storage amount big (being more than 3 times of rare earth hydrogen storage alloy), (the magnesium atom amount is 24.3, and rare earth is about 140, is 138.9 such as lanthanum, and neodymium is 144.2) in light weight, (pure magnesium can be with MgH than (H/M ratio) with metal for high hydrogen
2The hydrogen of form reversible storage 7.6 weight %), abundant the containing and low price distinct advantages such as (being the 1/2-1/3 of rare earth) in the physical environment.Therefore, Mg base hydrogen bearing alloy is considered to the most desirable and one of the most potential hydrogen storage material.
At present, the preparation magnesium-base hydrogen storage material is used mechanical ball milling method (referring to the open CN1528939 of Chinese patent application) mostly.Magnesium-base hydrogen storage material by the traditional technology preparation has higher hydrogen discharging temperature (even being higher than 350 ℃), thereby limited its practical application (referring to J-L.Bobet, B.Chevalier, M.Y.Song, B.Darriet and J.E tourneau, J.AlloysCompd.336 (2002) 292-296).The problems referred to above are mainly caused by following reason, one, reaction kinetics slowly; Its two, MgH
2High stability, MgH under the situation of 285 ℃ and lbar hydrogen-pressure
2The formation heat content be-74.7kJ/mole.Hydrogenation kinetics is relevant in intrametallic diffusion at the decomposition and the hydrogen atom of metallic surface with hydrogen molecule, and magnesium is low to the capacity of decomposition of hydrogen atom, and the diffusion of hydrogen atom in magnesium (hydride) is very slow.This shows will make magnesium-base hydrogen storage material efficient, stable and that have the market competitiveness, most realistic problem at first is how to improve the suction hydrogen desorption kinetics of material, reduce the activation condition and further raising of material and fill hydrogen desorption capacity; Next is a working temperature too high when how to reduce mg-based material and putting hydrogen.
Such as the alloying of adding nickel and rare earth element is to improve one of thermodynamics of reactions and dynamic (dynamical) main method.Other method is to improve hydrogenation kinetics by refinement alloy organizing (as grain size and intermetallic compound particle size).Many technology all are used to prepare hydrogen storage material, and for example mechanical alloying (mechanical alloying:MA), gross distortion such as equal channel angular push (equal channel angular pressing:ECAP), rapid solidification method (rapid solidification:RS) and add dissimilar oxide compounds as methods such as catalyzer.According at document F.C.Gennari, F.J.Castro and G.Urretavizcaya, report among J.Alloys Compd.321 (2001) 46-53, pure magnesium under hydrogen behind reaction ball milling, find only to have 50% magnesium to be converted into hydride, and the grain-size that obtains is bigger, the more important thing is that ball milling just can be finished hydrogenation for a long time.In order to improve the ball milling effect, by adding second hydrogenation efficiency that improves magnesium in the reaction ball milling mutually, as Mg+Nb
2O
5, Mg+FeTi
1.2, Mg+Mg
2Ni or the like, the raising that the efficient of reaction has obtained to a certain extent has decline though inhale hydrogen discharging temperature, and is all very limited.
The develop rapidly of nanotechnology has brought new opportunity to develop to hydrogen storage material.The preparation of nano material occupies very consequence in the present material scientific research.The new material preparation process and the research of process have material impact to the microtexture and the performance of control nano material.Use rapid solidification method and prepare the nano Mg base hydrogen storage material, not only can overcome the deficiency (as be not suitable for producing in batches, tissue odds is even etc.) of methods such as mechanical ball milling, and can guarantee stabilized nano crystal grain.A nearest result of study shows (referring to T.Spassov, U.Koster, J.Alloys Compd.279 (1998) 279-286 and T.Spassov, U.Koster, J.Alloys Compd.287 (1999) 243-250), compare with traditional polycrystalline magnesium alloy, comprise nano particle in nano Mg base alloy and the tissue and have mutually than higher suction hydrogen desorption kinetics and lower hydrogen discharging temperature, nanometer Mg with noncrystal
2Ni base alloy ratio polycrystalline Mg
2Ni base alloy has higher hydrogen-absorbing ability and inhales hydrogen desorption kinetics faster.
But in above-mentioned two pieces of documents, therefore nickel in the alloying constituent and content of rare earth height cause the material cost height, and this large-scale practical application for magnesium-base hydrogen storage material is disadvantageous.Therefore, the magnesium-base hydrogen storage material that still requires further improvement in the prior art makes that its cost is lower, speed for hydrogen absorbing and releasing is faster and hydrogen discharging temperature is lower.
Summary of the invention
In view of the problems of the prior art, one of purpose of the present invention provides a kind of even grain size and is the following magnesium-base hydrogen storage material of 10nm substantially.Another object of the present invention provides a kind of magnesium-base hydrogen storage material that Hydrogen Energy power is put in better suction that has.Another object of the present invention provides a kind of magnesium-base hydrogen storage material with better suction hydrogen desorption kinetics.A further object of the present invention provides a kind of magnesium-base hydrogen storage material cheaply.A further object of the present invention provides the method that the magnesium-base hydrogen storage material of above-mentioned one or more purposes is satisfied in a kind of preparation.
The present invention has realized one or more in the above-mentioned purpose by following embodiment.
In one embodiment, the invention provides a kind of magnesium-base hydrogen storage material, this material comprises the nickel of 15-25 weight %, the rare earth element that contains cerium (Mm) of 5-15 weight % and the magnesium of surplus, this material is made up of nanocrystalline basically, and above-mentioned nanocrystalline in, the grain-size of the crystal grain more than 70% is below the 10nm.
In another embodiment, the invention provides the preparation method of described magnesium-base hydrogen storage material, the method comprising the steps of:
1) by the feedstock production mother alloy, the composition of gained mother alloy comprises the nickel of 15-25 weight %, the rare earth element that contains cerium of 5-15 weight % and the magnesium of surplus;
2) resulting mother alloy is melted in the storehouse, and adopt fast solidification technology, the mother alloy of described fusing is formed described magnesium-base hydrogen storage material; Wherein, the storehouse internal pressure by before and after the fusing of inert gas atmosphere control mother alloy makes that the storehouse internal pressure before the mother alloy fusing is 350-500mbar, and the storehouse internal pressure after the mother alloy fusing is 150-350mbar.
The invention provides a kind of technical feasible magnesium-base nano hydrogen-storage material and preparation method thereof.The rapid solidification method that employing is adopted when the preparation amorphous/nanocrystalline usually carries out rapid solidification to Mg-Ni-Mm ternary alloy system and prepares this nano material.Adopt this method can obtain thermodynamically stable nanocrystal, even at 350 ℃, grain size still keeps nano level, particularly below 10nm.Nano hydrogen-storage material with above-mentioned grain-size has good suction hydrogen desorption kinetics, higher hydrogen-storage amount and lower hydrogen discharging temperature.And nano Mg base hydrogen storage material of the present invention has made full use of the rare earth resources of China's abundant, can significantly reduce the cost of hydrogen storage material.
Nano Mg base hydrogen storage alloy of the present invention can improve the suction hydrogen desorption kinetics of Magnuminium effectively and further reduce hydrogen discharging temperature, particularly has high hydrogen storage capability under 28bar hydrogen pressure and 300 ℃.And the nano Mg base ternary hydrogen storage alloy that adopts the rapid solidification method preparation has all characteristics such as even easy batch process of high thermodynamic stability, nanocrystalline grain size.
Description of drawings
Fig. 1 is the material of embodiment 1 X-ray diffraction (XRD) spectrum during unhydrogenation after preparation.
Fig. 2 is the material of embodiment 1 transmission electron microscope (TEM) photo during unhydrogenation after preparation.
Fig. 3 is the hydrogenation curve of material under 28bar hydrogen pressure and 300 ℃ of embodiment 1.
Fig. 4 is that the material of embodiment 1 is to put the hydrogen curve under the 5 ℃/min in heating rate.
Fig. 5 is the XRD diffraction spectra of the material of embodiment 1 through 5 circulation hydrogenation afterreaction products.
Fig. 6 is the TEM photo of the material of embodiment 1 through 5 circulation hydrogenation afterreaction products.
Fig. 7 is the material of the embodiment 2 TEM photo during unhydrogenation after preparation.
Fig. 8 is the material of the embodiment 3 TEM photo during unhydrogenation after preparation.
Fig. 9 is the material of the embodiment 4 TEM photo during unhydrogenation after preparation.
Figure 10 is the material of the embodiment 5 TEM photo during unhydrogenation after preparation.
Figure 11 is the material of the comparative example 1 TEM photo during unhydrogenation after preparation.
Figure 12 is the hydrogenation curve of material under 28bar hydrogen pressure and 300 ℃ of comparative example 1.
Figure 13 is that the material of comparative example 1 is to put the hydrogen curve under the 5 ℃/min in heating rate.
Figure 14 is the material of the comparative example 2 TEM photo during unhydrogenation after preparation.
Embodiment
In one embodiment, the invention provides a kind of magnesium-base hydrogen storage material, this material comprises the nickel of 15-25 weight %, the rare earth element that contains cerium (Mm) of 5-15 weight % and the magnesium of surplus, this material is made up of nanocrystalline basically, and above-mentioned nanocrystalline in, the grain-size of the crystal grain more than 70% is below the 10nm.
In this application, the La that consists of about 73-77 atom % of described " rare earth element that contains cerium ", the Pr of the Ce of about 8-12 atom % and about 13-17 atom %.In addition, in the present invention, described " grain-size " grain-size for measuring by transmission electron microscope (TEM).The method of utilizing TEM to measure grain-size is to well known to a person skilled in the art method.
One preferred embodiment in, this material is made up of nano-crystalline and amorphous.
One preferred embodiment in, this material is made up of nanocrystalline.
In another preferred implementation, in this material above-mentioned nanocrystalline, the grain-size of the crystal grain more than 80% is below the 10nm, the grain-size of preferred crystal grain more than 90% is below the 10nm, more preferably the grain-size of the crystal grain more than 95% is below the 10nm, and most preferably the grain-size of all crystal grains is below the 10nm.
One preferred embodiment in, this magnesium-base hydrogen storage material comprises the nickel of 15-23 weight %, preferably includes the nickel of 17-23 weight %, more preferably comprises the nickel of 19-23 weight %.
Another preferred embodiment in, this magnesium-base hydrogen storage material comprises the rare earth element that contains cerium of 5-13 weight %, preferably includes the rare earth element that contains cerium of 5-11 weight %, more preferably comprises the rare earth element that contains cerium of 5-9 weight %.
One preferred embodiment in, magnesium-base hydrogen storage material of the present invention is made up of the nickel of 20 weight %, the rare earth element that contains cerium of 8 weight % and the magnesium of surplus.
Another preferred embodiment in, magnesium-base hydrogen storage material of the present invention is made up of the nickel of 22 weight %, the rare earth element that contains cerium of 6 weight % and the magnesium of surplus.
The invention provides the preparation method of described magnesium-base hydrogen storage material, the method comprising the steps of:
1) by the feedstock production mother alloy, the composition of gained mother alloy comprises the nickel of 15-25 weight %, the rare earth element that contains cerium of 5-15 weight % and the magnesium of surplus;
2) resulting mother alloy is melted in the storehouse, and adopt fast solidification technology, the mother alloy of described fusing is formed described magnesium-base hydrogen storage material; Wherein, the storehouse internal pressure by before and after the fusing of inert gas atmosphere control mother alloy makes that the storehouse internal pressure before the mother alloy fusing is 350-500mbar, and the storehouse internal pressure after the mother alloy fusing is 150-350mbar.
The present invention is not bound to any specific theory.But, in the mother alloy melting process, can prevent oxidation by feeding rare gas element.Simultaneously, prevent from the evaporation of magnesium to make the composition of alloy and weave construction reach design requirements by the storehouse internal pressure of control before and after the alloy melting.
In a preferred embodiment of the invention, the storehouse internal pressure before the mother alloy fusing can be 380-500mbar; In another preferred embodiment of the present invention, the storehouse internal pressure after the mother alloy fusing can be 200-300mbar.
In another preferred implementation, described rare gas element is an argon gas.
Fast solidification technology is one of common process of preparation amorphous/nanocrystalline material, so those skilled in the art are familiar with for this technology.In brief, " fast solidification technology " instigates alloy melt to contact with the cooling wheel disc of rotation obtaining enough rate of cooling, thereby obtains the amorphous/nanocrystalline material.In rapid solidification method,, can adopt the rotating speed of any cooling wheel disk material and cooling wheel disc, for example copper, stainless steel and graphite wheel disc etc. as long as can obtain required rate of cooling.As long as can obtain required rate of cooling, have no particular limits for the diameter of cooling roller wheel disc, for example can be 200mm.The microtexture of rate of cooling control alloy, the nano-structure that obtain being evenly distributed needs the suitably setting rate of control alloy.By selecting suitable wheel disk material and speed of rotation thereof, can obtain required microtexture.Do not limit for the rate of cooling that is adopted among the present invention is special, can adopt the rate of cooling that adopts in order to obtain amorphous or nanocrystalline material well-known to those skilled in the art.Equally as known to those skilled in the art, speed of cooling is fast more, and alloy structure is that the probability of nanometer and amorphous is big more.
In the present invention, the rotating speed by the controlled chilling wheel disc obtains required rate of cooling.Equally as well known to the skilled person, because the cooling power difference of different cooling wheel disk materials, so the cooling wheel disc of differing materials may need to select different rotating speeds.By way of example, if wheel disc is the copper wheel dish, the wheel disc rotating speed can be 10-15 meter per second (linear velocity of finger wheel dish outer rim, down together); If wheel disc is the stainless steel wheel disc, the wheel disc rotating speed can be the 20-25 meter per second; In addition, if wheel disc is the graphite wheel disc, the wheel disc rotating speed can be the 35-45 meter per second.Certainly, thinkable as those skilled in the art institute, used wheel disc is not limited to the wheel disc of above-mentioned materials among the present invention, and the rotating speed that is adopted also is not limited to above-mentioned rotating speed.Those skilled in the art can select suitable rotating speed according to required rate of cooling and wheel disk material fully.
In addition, in a preferred embodiment, the atmosphere oxygen level during the mother alloy fusing preferably is controlled at below the 0.02 weight %.
In another preferred embodiment, the distance between described cooling wheel disc and the nozzle is 5-15mm.
The present invention adopts rapid solidification method in the preparation process of magnesium-base hydrogen storage material, has produced special advantage thus.By the prepared Mg base hydrogen bearing alloy of traditional mechanical ball milling, though also can obtain the part nanocrystal, grain size range distributes big, even can reach micron order.In addition, the ball milling time is long, and along with the prolongation of ball milling time, the ball milling body also can be incorporated in the powder as impurity, and then reduces the hydrogen storage property of powder.Preparation method provided by the present invention has solved this difficult problem well, has directly obtained the nano Mg base alloy, under the alloy hydrogen absorption and desorption temperature, has avoided the gathering of crystal grain to grow up, and can keep crystal grain about 10nm or lower.
The present invention is suitable for the scale preparation of hydrogen storage material.Only in the prepared in laboratory process, use because traditional mechanical ball milling method is general, be not suitable for batch process, and limited the practical application of material.And the present invention not only is applicable to the research and development of laboratory novel material, and can be used for accomplishing scale production, for the development and application of hydrogen storage material brings profound influence.
The invention will be further described below in conjunction with specific embodiment and with reference to accompanying drawing.Below listed embodiment only be description to the preferred embodiments of the invention, do not constitute any qualification of the present invention.
In the following embodiments, consisting of of the employed rare earth element that contains cerium: the La of about 75 atom %, the Pr of the Ce of about 10 atom % and about 15 atom %.
The preparation of material
The proportioning raw materials of the mother alloy of embodiment 1 (weight percent) is
Purity is 99.98% magnesium: 72%
Purity is 99.98% nickel: 20%
Purity is 99.7% the rare earth element that contains cerium: 8%
According to the above ratio magnesium, nickel and the rare earth element that contains cerium are carried out vacuum induction melting and prepare mother alloy.Adopt then under the condition of copper cooling wheel disc and 10.5 meter per seconds (m/s) wheel disc rotating speed, under argon shield atmosphere, carry out rapid solidification, thereby obtain the material of embodiment 1.Wherein, before the mother alloy fusing, atmosphere pressures is controlled at 400mbar, and fusing back atmosphere pressures is controlled at 200mbar.Resulting material is to be the nanocrystalline ribbon Mg base hydrogen bearing alloy of forming of about 10nm by grain-size substantially.
The sign of material
The material of embodiment 1 at X-ray diffractometer, is carried out on the transmission electron microscope that phase structure is measured and tissue topography's observation, can learn composition, pattern and the grain size of sample, as depicted in figs. 1 and 2.The X ray result of Fig. 1 shows, the alloy of embodiment 1 is by Mg, Mg
2Ni and Mm
2Mg
17Form.The grain-size of the whole crystal grain of this material is about 10nm.
Under 28bar hydrogen pressure and 300 ℃ alloy is carried out hydrogenation, as shown in Figure 3, alloy strip has passed through 5 and has inhaled/put the hydrogen circulation, and after second circulation, curve is basicly stable.Fig. 4 is for to put the hydrogen curve through 4 round-robin, and after each circulation, hydrogen discharging temperature slightly descends, and heating rate is 5 ℃/min.Fig. 5 is the X-ray diffraction analysis result of alloy strip through the 5th circulation hydrogenation afterreaction product: by MgH
2, HT-Mg
2NiH
4, Mg
2NiH
0.3And MmH
3Hydride is formed.Fig. 6 is the transmission electron microscope photo of these reaction product correspondences, and alloy still keeps nano level through inhaling/put hydrogen processing back all crystal grains repeatedly.And by the result of this embodiment as can be seen, nano Mg base hydrogen storage material of the present invention is after having passed through 4 complete suctions/put the hydrogen circulation, and its suction/hydrogen discharging performance is stable.
The preparation of material
The proportioning raw materials of the mother alloy of embodiment 2 (weight percent) is
Purity is 99.98% magnesium: 72%
Purity is 99.98% nickel: 22%
Purity is 99.7% the rare earth element that contains cerium: 6%
According to the above ratio magnesium, nickel and the rare earth element that contains cerium are carried out vacuum induction melting and prepare mother alloy.Adopt then under the condition of copper cooling wheel disc and 15 meter per seconds (m/s) wheel disc rotating speed, under argon shield atmosphere, carry out rapid solidification, thereby obtain the material of embodiment 2.Wherein, before the mother alloy fusing, atmosphere pressures is controlled at 400mbar, and fusing back atmosphere pressures is controlled at 200mbar.Resulting material is to be the nanocrystalline ribbon Mg base hydrogen bearing alloy of forming of about 10nm by grain-size substantially.
The sign of material
The material of embodiment 2 is carried out phase structure mensuration and tissue topography's observation on transmission electron microscope, can determine composition, pattern and the grain size of sample.Microtexture shown in Figure 7 shows that the grain-size in this material is about 10nm.
The preparation of material
The proportioning raw materials of the mother alloy of embodiment 3 (weight percent) is
Purity is 99.98% magnesium: 72%
Purity is 99.98% nickel: 20%
Purity is 99.7% the rare earth element that contains cerium: 8%
According to the above ratio magnesium, nickel and the rare earth element that contains cerium are carried out vacuum induction melting and prepare mother alloy.Adopt then under the condition of copper cooling wheel disc and 10.5 meter per seconds (m/s) wheel disc rotating speed, under argon shield atmosphere, carry out rapid solidification, thereby obtain the material of embodiment 3.Wherein, before the mother alloy fusing, atmosphere pressures is controlled at 480mbar, and fusing back atmosphere pressures is controlled at 300mbar.Resulting material is to be the nanocrystalline ribbon Mg base hydrogen bearing alloy of forming of about 10nm by grain-size substantially.
The sign of material
The material of embodiment 3 is carried out phase structure mensuration and tissue topography's observation on transmission electron microscope, can determine composition, pattern and the grain size of sample.Microtexture shown in Figure 8 shows that the grain-size in this material is about 10nm.
The preparation of material
The proportioning raw materials of the mother alloy of embodiment 4 (weight percent) is
Purity is 99.98% magnesium: 72%
Purity is 99.98% nickel: 20%
Purity is 99.7% the rare earth element that contains cerium: 8%
According to the above ratio magnesium, nickel and the rare earth element that contains cerium are carried out vacuum induction melting and prepare mother alloy.Adopt then under the condition of stainless steel cooling wheel disc and 21m/s wheel disc rotating speed, under argon shield atmosphere, carry out rapid solidification, thereby obtain the material of embodiment 4.Wherein, before the mother alloy fusing, atmosphere pressures is controlled at 400mbar, and fusing back atmosphere pressures is controlled at 200mbar.Resulting material is to be the nanocrystalline ribbon Mg base hydrogen bearing alloy of forming of about 10nm by grain-size substantially.
The sign of material
The material of embodiment 4 is carried out phase structure mensuration and tissue topography's observation on transmission electron microscope, can determine composition, pattern and the grain size of sample.Microtexture shown in Figure 9 shows that the grain-size in this material is about 10nm.
The preparation of material
The proportioning raw materials of the mother alloy of embodiment 5 (weight percent) is
Purity is 99.98% magnesium: 72%
Purity is 99.98% nickel: 20%
Purity is 99.7% the rare earth element that contains cerium: 8%
According to the above ratio magnesium, nickel and the rare earth element that contains cerium are carried out vacuum induction melting and prepare mother alloy.Adopt then under the condition of graphite cooling wheel disc and 40m/s wheel disc rotating speed, under argon shield atmosphere, carry out rapid solidification, thereby obtain the material of embodiment 5.Wherein, before the mother alloy fusing, atmosphere pressures is controlled at 400mbar, and fusing back atmosphere pressures is controlled at 200mbar.Resulting material is to be the nanocrystalline ribbon Mg base hydrogen bearing alloy of forming of about 10nm by grain-size substantially.
The sign of material
The material of embodiment 5 is carried out phase structure mensuration and tissue topography's observation on transmission electron microscope, can determine composition, pattern and the grain size of sample.Microtexture shown in Figure 10 shows that the grain-size in this material is about 10nm.
Comparative example 1:
The preparation of material
The proportioning raw materials of the mother alloy of comparative example 1 (weight percent) is
Purity is 99.98% magnesium: 72%
Purity is 99.98% nickel: 20%
Purity is 99.7% the rare earth element that contains cerium: 8%
According to the above ratio magnesium, nickel and the rare earth element that contains cerium are carried out vacuum induction melting and prepare mother alloy.Adopt then under the condition of copper cooling wheel disc and 10.5m/s wheel disc rotating speed, under argon shield atmosphere, carry out rapid solidification, thereby obtain the material of comparative example 1.Wherein, before the mother alloy fusing, atmosphere pressures is controlled at 550mbar, and fusing back atmosphere pressures is controlled at 100mbar.Resulting material is the Mg base hydrogen bearing alloy of micron order crystal grain, waits spool a shape Mg and a Mm
2Mg
17Grain-size is about 0.5 μ m, bar-shaped Mg
2The Ni grain-size is about 0.4 μ * 1.2 μ m.
The sign of material
The material of comparative example 1 is carried out phase structure mensuration and tissue topography's observation on transmission electron microscope, can determine composition, pattern and the grain size of sample, as shown in figure 11, the alloy of comparative example 1 is made up of micron order crystal grain.Because grain-size is bigger, the velocity of diffusion of hydrogen atom reduces, and causes the hydrogen storage property of material relatively poor.
Under 28bar hydrogen pressure and 300 ℃ alloy is carried out hydrogenation, as shown in figure 12, alloy strip has passed through 2 and has inhaled/put the hydrogen circulation, and it is still slow to inhale hydrogen, and hydrogen is few.Figure 13 is for to put the hydrogen curve through 2 round-robin, and its hydrogen discharging rate is low.By the result of this comparative example as can be seen, the suction/hydrogen discharging performance of the magnesium-base hydrogen storage material that crystal grain is thick is obviously relatively poor.
Comparative example 2:
The preparation of material
The proportioning raw materials of the mother alloy of comparative example 2 (weight percent) is
Purity is 99.98% magnesium: 72%
Purity is 99.98% nickel: 20%
Purity is 99.7% the rare earth element that contains cerium: 8%
According to the above ratio magnesium, nickel and the rare earth element that contains cerium are carried out vacuum induction melting and prepare mother alloy.Adopt then under the condition of stainless steel cooling wheel disc and 21m/s wheel disc rotating speed, under argon shield atmosphere, carry out rapid solidification, thereby obtain the material of comparative example 2.Wherein, before the mother alloy fusing, atmosphere pressures is controlled at 550mbar, and fusing back atmosphere pressures is controlled at 100mbar.Resulting material is the Mg base hydrogen bearing alloy of micron order crystal grain, waits spool a shape Mg and a Mm
2Mg
17Grain-size is about 0.3 μ m, bar-shaped Mg
2The Ni grain-size is about 0.2 μ * 0.4 μ m.
The sign of material
The material of comparative example 2 is carried out phase structure mensuration and tissue topography's observation on transmission electron microscope, can determine composition, pattern and the grain size of sample, as shown in figure 14, the alloy of comparative example 2 is made up of micron order crystal grain.Because grain-size is bigger, the velocity of diffusion of hydrogen atom reduces, and causes the hydrogen storage property of material relatively poor.
Claims (13)
1. magnesium-base hydrogen storage material, the composition of this material comprises the nickel of 15-25 weight %, the rare earth element that contains cerium of 5-15 weight % and the magnesium of surplus, this material is made up of nanocrystalline basically, and above-mentioned nanocrystalline in, the grain-size of the crystal grain more than 70% is below the 10nm.
2. the magnesium-base hydrogen storage material of claim 1, wherein this material is made up of nano-crystalline and amorphous.
3. the magnesium-base hydrogen storage material of claim 1, wherein this material is made up of nanocrystalline.
4. the magnesium-base hydrogen storage material of claim 1, wherein in this material nanocrystalline, the grain-size of the crystal grain more than 80% is below the 10nm, the grain-size of preferred crystal grain more than 90% is below the 10nm, more preferably the grain-size of the crystal grain more than 95% is below the 10nm, and most preferably all the grain-size of crystal grain is below the 10nm.
5. the magnesium-base hydrogen storage material of any one among the claim 1-4, wherein this magnesium-base hydrogen storage material comprises the nickel of 15-23 weight %, preferably includes the nickel of 17-23 weight %, more preferably comprises the nickel % of 19-23 weight %.
6. the magnesium-base hydrogen storage material of any one among the claim 1-4, wherein this magnesium-base hydrogen storage material comprises the rare earth element that contains cerium of 5-13 weight %, preferably includes the rare earth element that contains cerium of 5-11 weight %, more preferably comprises the rare earth element that contains cerium of 5-9 weight %.
7. the magnesium-base hydrogen storage material of any one among the claim 1-4, wherein this magnesium-base hydrogen storage material is made up of the nickel of 20 weight %, the rare earth element that contains cerium of 8 weight % and the magnesium of surplus.
8. the magnesium-base hydrogen storage material of any one among the claim 1-4, wherein this magnesium-base hydrogen storage material is made up of the nickel of 22 weight %, the rare earth element that contains cerium of 6 weight % and the magnesium of surplus.
9. the preparation method of the described magnesium-base hydrogen storage material of claim 1, the method comprising the steps of:
1) by the feedstock production mother alloy, the composition of gained mother alloy comprises the nickel of 15-25 weight %, the rare earth element that contains cerium of 5-15 weight % and the magnesium of surplus;
2) resulting mother alloy is melted in the storehouse, and adopt fast solidification technology, the mother alloy of described fusing is formed described magnesium-base hydrogen storage material; Wherein, the storehouse internal pressure by before and after the fusing of inert gas atmosphere control mother alloy makes that the storehouse internal pressure before the mother alloy fusing is 350-500mbar, and the storehouse internal pressure after the mother alloy fusing is 150-350mbar.
10. the described method of claim 9, wherein said rare gas element is an argon gas.
11. the described method of claim 9, wherein in fast solidification technology, employed wheel disc is copper, stainless steel or graphite wheel disc.
12. any one described method among the claim 9-11, wherein the storehouse internal pressure before the alloy melting is 380-500mbar.
13. any one described method among the claim 9-11, wherein the storehouse internal pressure after the mother alloy fusing is 200-300mbar.
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| CN101857947A (en) * | 2010-06-07 | 2010-10-13 | 安徽工业大学 | Amorphous magnesium-yttrium-transition metal hydrogen storage material and preparation method thereof |
| CN102392167A (en) * | 2011-11-17 | 2012-03-28 | 上海交通大学 | Magnesium-based hydrogen storage material with added rare earth element and preparation method thereof |
| CN103952647A (en) * | 2011-08-09 | 2014-07-30 | 安泰科技股份有限公司 | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method |
| CN105316501A (en) * | 2015-11-12 | 2016-02-10 | 国网智能电网研究院 | Rare earth-magnesium-based hydrogen storage alloy and preparation method thereof |
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| CN101857947A (en) * | 2010-06-07 | 2010-10-13 | 安徽工业大学 | Amorphous magnesium-yttrium-transition metal hydrogen storage material and preparation method thereof |
| CN103952647A (en) * | 2011-08-09 | 2014-07-30 | 安泰科技股份有限公司 | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method |
| CN102392167A (en) * | 2011-11-17 | 2012-03-28 | 上海交通大学 | Magnesium-based hydrogen storage material with added rare earth element and preparation method thereof |
| CN102392167B (en) * | 2011-11-17 | 2013-03-20 | 上海交通大学 | Magnesium-based hydrogen storage material with added rare earth element and preparation method thereof |
| CN105316501B (en) * | 2015-11-12 | 2018-05-29 | 国网智能电网研究院 | A kind of rare earth-magnesium base hydrogenous alloy and preparation method thereof |
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| CN107190193A (en) * | 2017-06-11 | 2017-09-22 | 烟台大学 | A kind of nano-amorphous Mg M Y hydrogen bearing alloys and its production and use |
| CN111745154A (en) * | 2020-07-10 | 2020-10-09 | 洛阳理工学院 | Mg-Ni alloy particle with surface embedded with rare earth element Ce and preparation method thereof |
| CN111745154B (en) * | 2020-07-10 | 2022-07-08 | 洛阳理工学院 | Mg-Ni alloy particle with surface embedded with rare earth element Ce and preparation method thereof |
| CN112225174A (en) * | 2020-10-16 | 2021-01-15 | 南京工程学院 | Oxidation-resistant magnesium-based composite hydrogen storage material and preparation method thereof |
| CN113512674A (en) * | 2021-04-20 | 2021-10-19 | 安泰科技股份有限公司 | Modified Mg-Ni-La nanocrystalline hydrogen storage alloy and preparation method thereof |
| CN114507798A (en) * | 2022-02-18 | 2022-05-17 | 广东省科学院新材料研究所 | Magnesium-based hydrogen storage alloy block and preparation method thereof |
| CN114507798B (en) * | 2022-02-18 | 2022-07-15 | 广东省科学院新材料研究所 | Magnesium-based hydrogen storage alloy block and preparation method thereof |
| CN116043080A (en) * | 2022-12-09 | 2023-05-02 | 重庆大学 | Magnesium-based rare earth hydrogen storage material based on reciprocating extrusion regulation and control and preparation method thereof |
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