CN101574742A - Method for preparing nano-structure of magnesium - Google Patents
Method for preparing nano-structure of magnesium Download PDFInfo
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- CN101574742A CN101574742A CNA2009100868193A CN200910086819A CN101574742A CN 101574742 A CN101574742 A CN 101574742A CN A2009100868193 A CNA2009100868193 A CN A2009100868193A CN 200910086819 A CN200910086819 A CN 200910086819A CN 101574742 A CN101574742 A CN 101574742A
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Abstract
The invention provides a method for preparing a nano-structure of magnesium, which includes the following steps of: fully mixing MgO powder with C powder to make a block; then adopting an electric-arc heating method for evaporation to generate the nano-structure of magnesium; and selecting a variety of carbons to adjust the appearances of the nano-structure of magnesium. The method is simple in the device, high in resultant velocity, low in cost, and easy for realizing industrialized batch production. Products of the nano-structure of magnesium, which is obtained via the method, are less than 30 nanometers in dimension, with high purity and controllable appearances and structures. Besides, products of the nano-structure of magnesium have superb kinetic property for absorbing/desorbing hydrogen, with promising application prospects.
Description
Technical field
The present invention relates to the preparation field of metal and the preparation method and the application thereof of hydrogen storage technology field, especially nano-structure of magnesium.
Background technology
At present, develop the topic that the new energy has become whole world close attention because traditional energy such as coal, oil, natural gas etc. are exhausted day by day and human that environmental issue is more and more paid attention to.Wherein hydrogen energy source is because the characteristic of its specific mass energy content height and cleanliness without any pollution is to be hopeful one of energy of being used widely in 21 century most.But the utilization of hydrogen energy source relates to and stores this committed step, and therefore how storing hydrogen safely and effectively becomes the problem that needs to be resolved hurrily.The research of hydrogen storage material at present mainly contains metal hydride, metallic organic frame complex (MOF), aluminium hydrogen compound, hydroboron and amino-compound etc.Magnesium satisfies the needs of commercial vehicle-mounted hydrogen energy source automobile because its hydrogen storage content is big and aboundresources low price and very likely become practical application hydrogen storage material of new generation.
But Mg simple substance also has certain distance as hydrogen storage material from practicability at present.Matter of utmost importance is that suction hydrogen desorption kinetics character is too poor, and common magnesium granules needs could put hydrogen in suction slowly more than 250 ℃ after hydrogen activation is repeatedly put in suction under 400 ℃ the condition.In addition, though put the hydrogen activation through suction repeatedly, it is complete that common magnesium simple substance still can not be inhaled hydrogen.Nearest research (J.Am.Chem.Soc.127,16675 (2005)) shows that the suction hydrogen desorption kinetics character of Mg and its granular size have the relation that approaches inverse ratio, and particle is more little, and its suction hydrogen desorption kinetics character is good more.But the activity of Mg is very strong, and the nano particle that obtains easily polymerization takes place and grows up, and easy hydrolysis of nano particle and oxidation.Therefore, the Mg of granular size below 30 nanometers rarely has report at present, and the Mg nano particle of being reported also contains a large amount of impurity, and the actual content of Mg (is seen Chem.Mater.19,6052 (2007) less than 20%; Chem.Mater.20,376 (2008) .).Therefore, the higher nanoscale Mg structure of preparation purity has very important theory and practical significance.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing nanoscale Mg structure, prepared Mg structure is suitable for as hydrogen storage material and reducing agent.
Technical scheme of the present invention is as follows:
A kind of preparation method of nano-structure of magnesium comprises the steps:
(1) be to make block after 1: 1～1: 6 MgO powder and carbon (C) powder fully mix with mol ratio;
(2) prepared block is being lower than 1bar but makes its evaporation with electric arc heated in more than or equal to the inert atmosphere of 0.5bar, MgO is at first generated Mg by the C reduction, and magnesium vapor breaks away from heating region then, and nucleation and condensation form the Mg nanostructured;
(3) nano-structure of magnesium is carried out Passivation Treatment.
After above-mentioned steps (1) normally weighed up micron-sized MgO powder and carbon dust according to a certain percentage, the method by mechanical ball milling mixed.The mol ratio of MgO and C preferably in 1: 1～1: 4 scope, more preferably 1: 3.Described carbon dust comprises the carbon of all different shapes and structure, and for example graphite, diamond, activated carbon, CNT, fullerene, carbon fiber etc. may be used to the present invention.
Above-mentioned steps (2) normally is placed on the block of MgO and C in the reaction chamber (as the reaction chamber of plasma arc furnace) of sealing, vacuumizes the back and feeds inert gas, the preferred 0.8～0.9bar of air pressure.Described inert gas comprises all inert gases in the periodic table of chemical element: helium, neon, argon gas, krypton gas, xenon, radon gas.In order to accelerate the evaporation rate of magnesium, after playing arc discharge, can extract a part of inert gas out, feed a certain amount of active gases such as hydrogen or nitrogen again, also can directly add active gases, condition is that total gas pressure maintains and is lower than 1bar but in the scope more than or equal to 0.5bar, the percent by volume that active gases accounts for whole system is for greater than 0 smaller or equal to 90%, and preferred version is the percent by volume of the shared whole system 40-50% of active gases.
The purpose of above-mentioned steps (3) Passivation Treatment is to avoid nano-structure of magnesium to take out the back vigorous oxidation takes place, common way be with reaction chamber vacuumize the back with speed more slowly to wherein filling air, more than maintenance a few hours.
By selecting different types of C (C of different shape and structure) can control structure and the pattern of the Mg that is obtained, for example when C is graphite powder, can prepare dendritic Mg nanostructured; When C was active carbon powder, what prepare was the Mg nano particle.
The present Mg complicated process of preparation of scale size below 30 nanometers, the condition harshness, and sample is impure.The magnesium physical dimension size of the present invention preparation is nanoscale (referring to its diameter for wire or structure such as dendritic), its Size Distribution scope is at 10～30nm, and majority is about 20nm, so specific area is big, defective is many, has more reaction site with H-H reaction.During in addition with H-H reaction, the diffusion length of hydrogen in the magnesium structure reduces greatly, inhales hydrogen desorption kinetics character thereby improved it greatly.The inventive method has that equipment is simple, and aggregate velocity is fast, and cost is low, and the product purity advantages of higher is than being easier to realize industrialized mass production.In addition, by selecting the structure that can control Mg and the pattern of different types of C, thereby obtain the suction hydrogen desorption kinetics character that novel structure further improves Mg.Mg nanostructured of the present invention has very good suction hydrogen desorption kinetics character when being used for hydrogen storage material, very likely become the hydrogen storage material of a new generation, therefore has extremely important using value and application prospects in the hydrogen storage technology field.
Description of drawings
Fig. 1 is the X-ray powder diffraction figure of the Mg nanostructured of the present invention's preparation, and wherein the C of (a) employing is an activated carbon, and (b) C of Cai Yonging is a graphite.
Fig. 2 a utilizes the transmission electron microscope photo of the Mg nano particle of MgO and Preparation of Activated Carbon for the present invention.
Fig. 2 b utilizes the transmission electron microscope photo of the Mg nanometer branch of MgO and graphite preparation for the present invention.
Fig. 3 is the absorption of hydrogen curve of preparation Mg nanostructured of the present invention at 473K, and wherein (a) is the Mg nano particle, (b) is Mg nanometer branch, (c) is common micron order Mg particle.
The specific embodiment
(1) be that 1: 2 MgO and activated carbon put into ball grinder with mol ratio, ball milling took out after 2 hours under the rotating speed of 200rpm, at the pressure lower sheeting of 700bar;
(2) sheet that will press is put in the hydrogen plasma arc heating furnace, after vacuumizing, is under the Ar atmosphere of 0.8bar in gross pressure, applies DC arc plasma and obtains the Mg nano particle;
(3) stop to heat and vacuumizing, slowly bubbling air passivation in stove after the system cools, passivation was taken out sample after 48 hours.
(1) be that 1: 3 MgO and activated carbon put into ball grinder with mol ratio, ball milling took out after 2 hours under the rotating speed of 200rpm, at the pressure lower sheeting of 700bar;
(2) sheet that will press is put in the hydrogen plasma arc heating furnace, after vacuumizing, is to play arc discharge under the Ar atmosphere of 0.9bar at pressure, extracts part Ar gas then out, feeds N
2Gas is the 40%N of 0.9bar in gross pressure
2Under/Ar the mixed atmosphere, apply DC arc plasma and obtain the Mg nano particle;
(3) stop to heat and vacuumizing, slowly bubbling air passivation in stove after the system cools, passivation was taken out sample after 48 hours.
Embodiment 3, synthetic granular size are the Mg particle of 20nm
(1) be that 1: 3 MgO and activated carbon put into ball grinder with mol ratio, ball milling took out after 2 hours under the rotating speed of 200rpm, added a spot of polyvinylidene fluoride (PVDF) as binding agent, made bead;
(2) bead being put in the hydrogen plasma arc heating furnace, after vacuumizing, is to play arc discharge under the Ar atmosphere of 0.5bar at pressure, extracts part Ar gas then out, feeds H
2Gas is the 40%H of 0.5bar in gross pressure
2Under/Ar the mixed atmosphere, apply DC arc plasma and obtain the Mg nano particle;
(3) stop to heat and vacuumizing, slowly bubbling air passivation in stove after the system cools, passivation was taken out sample after 48 hours.
(1) be that 1: 4 MgO and graphite is put into ball grinder with mol ratio, ball milling took out after 2 hours under the rotating speed of 200rpm, added a spot of polyvinylidene fluoride (PVDF) as binding agent, made bead;
(2) bead being put in the hydrogen plasma arc heating furnace, after vacuumizing, is under the Ar atmosphere of 0.8bar in gross pressure, applies DC arc plasma and obtains Mg nanometer branch;
(3) stop to heat and vacuumizing, slowly bubbling air passivation in stove after the system cools, passivation was taken out sample after 48 hours.
(1) be that 1: 3 MgO and graphite is put into ball grinder with mol ratio, ball milling took out after 2 hours under the rotating speed of 200rpm, added a spot of polyvinylidene fluoride (PVDF) as binding agent, made bead.
(2) bead being put in the hydrogen plasma arc heating furnace, after vacuumizing, is to play arc discharge under the Ar atmosphere of 0.5bar at pressure, extracts part Ar gas then out, feeds H
2Gas is the 40%H of 0.5bar in gross pressure
2Under/Ar the mixed atmosphere, apply DC arc plasma and obtain Mg nanometer branch;
(3) stop to heat and vacuumizing, slowly bubbling air passivation in stove after the system cools, passivation was taken out sample after 48 hours.
Embodiment 6, synthetic diameter are the Mg nanometer branch of 25nm
(1) be that 1: 3 MgO and graphite is put into ball grinder with mol ratio, ball milling took out after 2 hours under the rotating speed of 200rpm, at the pressure lower sheeting of 700bar;
(2) sheet that will press is put in the hydrogen plasma arc heating furnace, after vacuumizing, is to play arc discharge under the Ar atmosphere of 0.9bar at pressure, extracts part Ar gas then out, feeds N
2Gas is the 40%N of 0.9bar in gross pressure
2Under/Ar the mixed atmosphere, apply DC arc plasma and obtain Mg nanometer branch;
(3) stop to heat and vacuumizing, slowly bubbling air passivation in stove after the system cools, passivation was taken out sample after 48 hours.
Fig. 1 is the product Mg nano particle of above-mentioned experiment and XRD (X-ray powder diffraction) figure of nanometer branch, and wherein the C of (a) employing is an activated carbon, and (b) C of Cai Yonging is a graphite, can see clearly that prepared magnesium purity is higher.
Fig. 2 a and 2b are respectively TEM (transmission electron microscope) figure of above-mentioned experimental product Mg nano particle and nanometer branch, can see that Mg nano particle size is that Mg nanometer branch diameter is about 25nm about 20nm.
In addition, results of elemental analyses shows in the Mg nano particle (sample 1) of the inventive method preparation and the Mg nanometer branch (sample 2) and all contains Mg, O and three kinds of elements of C, and wherein the ratio of C is 28.0wt% in the sample 1, and the ratio of Mg is 58.4wt%; The ratio of C is 4.9wt% in the sample 2, and the ratio of Mg is 72wt%.The XRD result of Fig. 1 shows only contains Mg and MgO mutually in the sample 1, do not detect the form of any carbon, and possible cause is that the existence form of C is an amorphous state.When reducing agent is graphite, 26.5 ° of the diffraction maximums (2 θ) of graphite appear in the gained sample 2, and it is corresponding to graphite (JCPDS 75-2078).The result of powder diffraction shown the O element only be present in MgO mutually in, in conjunction with results of elemental analyses, can draw that the mol ratio of Mg and MgO is respectively 1.9 and 0.8 in sample 1 and 2, the content proportion by subtraction of pure Mg is 38.0wt% and 34.9wt%.
(1) prepared Mg nano particle and nanometer branch are put in respectively in the volumetric method hydrogen-storing device, vacuumize, feed 1barH
2, be warming up to 350 ℃, vacuumized then 2 hours, feed 10bar H
2Inhaled hydrogen 2 hours, three times so repeatedly.
(2) sample activation back decline temperature to 200 ℃ is to inhale the hydrogen test under the condition of 40bar at initial hydrogen pressure, inhales the hydrogen curve and sees Fig. 3.As seen from Figure 3, hydrogen is respectively 6.5wt% and 3.4wt% in magnesium nano particle (curve (a)) and the nanometer branch (curve (b)) 30 minutes, and common micron order Mg particle (curve (c)) hydrogen only reaches 2wt% under this temperature.Demonstrated the superior storage hydrogen character of nanometer Mg structure thus.In addition, if prepared nanometer Mg particle or the interpolation catalyst of further ball milling will show more superior hydrogen storage property.
Claims (10)
1. the preparation method of a nano-structure of magnesium comprises the steps:
1) be to make block after 1: 1～1: 6 MgO powder and C powder fully mix with mol ratio;
2) prepared block is being lower than 1bar but makes its evaporation with electric arc heated in more than or equal to the inert atmosphere of 0.5bar, MgO is at first generated Mg by the C reduction, and magnesium vapor breaks away from heating region then, and nucleation and condensation form the Mg nanostructured;
3) nano-structure of magnesium is carried out Passivation Treatment.
2. preparation method as claimed in claim 1 is characterized in that: step 1) mixes MgO powder and the carbon dust method by mechanical ball milling.
3. preparation method as claimed in claim 1 is characterized in that: the used C of step 1) is selected from a kind of in the following kind: graphite, diamond, activated carbon, CNT, fullerene and carbon fiber.
4. preparation method as claimed in claim 1 is characterized in that: the mol ratio of step 1) MgO and C is 1: 1～1: 4.
5. preparation method as claimed in claim 1 is characterized in that: step 2) in plasma arc furnace, carry out, air pressure is 0.8～0.9bar.
6. the preparation method of a nano-structure of magnesium comprises the steps:
1) be to make block after 1: 1～1: 6 MgO powder and C powder fully mix with mol ratio;
2) prepared block is being lower than 1bar but makes its evaporation with electric arc heated in more than or equal to the inert atmosphere of 0.5bar, for accelerating evaporation rate, after electric arc plays arc discharge, extract a part of inert gas out, feed hydrogen or nitrogen again, perhaps directly add hydrogen or nitrogen; Make percent by volume that hydrogen or nitrogen accounts for whole system for greater than 0 smaller or equal to 90%, and total gas pressure maintain and is lower than 1bar but in the scope more than or equal to 0.5bar; MgO is at first generated Mg by the C reduction, and magnesium vapor breaks away from heating region then, and nucleation and condensation form the Mg nanostructured;
3) nano-structure of magnesium is carried out Passivation Treatment.
7. preparation method as claimed in claim 6 is characterized in that: step 1) mixes MgO powder and the carbon dust method by mechanical ball milling.
8. preparation method as claimed in claim 6 is characterized in that: the used C of step 1) is selected from a kind of in the following kind: graphite, diamond, activated carbon, CNT, fullerene and carbon fiber.
9. preparation method as claimed in claim 6 is characterized in that: step 2) in plasma arc furnace, carry out, air pressure is 0.8～0.9bar.
10. preparation method as claimed in claim 6 is characterized in that: step 2) hydrogen or the nitrogen percent by volume that accounts for whole system is 40～50%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102233435A (en) * | 2010-04-30 | 2011-11-09 | 北京大学 | Method for preparing Mg nano particles under carbon source atmosphere |
| CN103028734A (en) * | 2013-01-14 | 2013-04-10 | 北京科技大学 | Method for preparing nanometer magnesium |
| CN106216705A (en) * | 2016-09-19 | 2016-12-14 | 北京工业大学 | A kind of preparation method of 3D printing fine grained simple substance globular metallic powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005125282A (en) * | 2003-10-27 | 2005-05-19 | Denso Corp | Catalyst particle and method for manufacturing the same |
| CN100554142C (en) * | 2006-08-04 | 2009-10-28 | 北京大学 | Magnesium hydride nano particle and its production and application |
| CN101397609A (en) * | 2008-09-18 | 2009-04-01 | 昆明理工大学 | Method for preparing magnesium metal by giobertite vacuum carbon thermal reduction |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102233435A (en) * | 2010-04-30 | 2011-11-09 | 北京大学 | Method for preparing Mg nano particles under carbon source atmosphere |
| CN102233435B (en) * | 2010-04-30 | 2014-09-10 | 北京大学 | Method for preparing Mg nano particles under carbon source atmosphere |
| CN103028734A (en) * | 2013-01-14 | 2013-04-10 | 北京科技大学 | Method for preparing nanometer magnesium |
| CN103028734B (en) * | 2013-01-14 | 2015-02-11 | 北京科技大学 | Method for preparing nanometer magnesium |
| CN106216705A (en) * | 2016-09-19 | 2016-12-14 | 北京工业大学 | A kind of preparation method of 3D printing fine grained simple substance globular metallic powder |
| CN106216705B (en) * | 2016-09-19 | 2018-04-27 | 北京工业大学 | A kind of preparation method of 3D printing fine grained simple substance globular metallic powder |
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