CN100513605C - Quaternary magnesium base hydrogen storage alloy, its producing method and use - Google Patents
Quaternary magnesium base hydrogen storage alloy, its producing method and use Download PDFInfo
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- CN100513605C CN100513605C CNB2006100511568A CN200610051156A CN100513605C CN 100513605 C CN100513605 C CN 100513605C CN B2006100511568 A CNB2006100511568 A CN B2006100511568A CN 200610051156 A CN200610051156 A CN 200610051156A CN 100513605 C CN100513605 C CN 100513605C
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Abstract
本发明公开了一种四元系镁基储氢合金、其生产方法及应用，四元系镁基储氢合金由Mg1.5-2Al0.02-0.08Ni0.5-1.0A0.05-0.1组成，其中A为V、Ti、Fe、Nd、Pd，显微组织中分布有弥散的纳米晶团簇和非晶团簇。合金元素粉末经充分混合后压制成片状，然后在真空烧结炉内进行烧结，得到的合金样品进行粉碎、球磨、筛选，得到粒度＜25μm以下的合金粉末；称取少量的微细Ni粉进行球磨，得到纳米晶Ni粉；把粒度＜25μm以下的Mg1.5-2Al0.02-0.08Ni0.5-1.0A0.05-0.1合金粉末和纳米晶Ni粉及第二相活性粒子充分混合后进行高能球磨，得到具有纳米晶和非晶组织的活性储氢合金材料，经过活化后得成品。成品具有吸/解氢温度低、性能稳定、具有实用性，价格便宜的特点。The invention discloses a quaternary magnesium-based hydrogen storage alloy, its production method and application. The quaternary magnesium-based hydrogen storage alloy is composed of Mg 1.5-2 Al 0.02-0.08 Ni 0.5-1.0 A 0.05-0.1 , wherein A V, Ti, Fe, Nd, Pd, dispersed nanocrystalline clusters and amorphous clusters are distributed in the microstructure. Alloy element powders are fully mixed and pressed into flakes, and then sintered in a vacuum sintering furnace. The obtained alloy samples are crushed, ball milled, and screened to obtain alloy powders with a particle size of less than 25 μm; weigh a small amount of fine Ni powder for ball milling , to obtain nanocrystalline Ni powder; Mg 1.5-2 Al 0.02-0.08 Ni 0.5-1.0 A 0.05-0.1 alloy powder with a particle size below 25 μm is fully mixed with nanocrystalline Ni powder and second-phase active particles and then subjected to high-energy ball milling to obtain The active hydrogen storage alloy material with nanocrystalline and amorphous structures is activated to obtain a finished product. The finished product has the characteristics of low hydrogen absorption/decomposition temperature, stable performance, practicality and low price.
Description
Technical field
The invention belongs to the material field, relate in particular to Mg base hydrogen bearing alloy, also relate to its preparation method and application simultaneously.
Background technology
Hydrogen storage alloy system is a lot, as La-Ni system, Ti-Fe system, Zr system, rare earth system or the like, but their ubiquity hydrogen-storage amounts low, inhale/separate hydrogen temperature height, shortcoming such as cost an arm and a leg, seriously limited its use.And Mg base hydrogen bearing alloy should cause people's extensive concern thus.By adding two component system that alloying element forms or three component system Mg base hydrogen bearing alloy (as Mg-Ni, Mg-Mn-Ni), these alloys are greatly improved on hydrogen storage property and chemical property, and its hydrogen-storage amount can be in 5% above level, but moving/thermomechanical property and corrosion resistance are relatively poor.In view of the above, people further add the second phase active ion and have nanostructure by different preparation technology's acquisitions again in Mg base hydrogen bearing alloy alloy material, this makes performance obtain remarkable improvement, but owing to inhales/separate hydrogen temperature higher (more than 250 ℃) and the technology stability problem fails well to be used.
At present, the polynary system Mg-base hydrogen-bearing alloy material has obtained deep exploitation, particularly quaternary magnesium base hydrogen storage alloy.Chinese patent Granted publication CN1142904C discloses a kind of denomination of invention and has been " Mg-base hydrogen-bearing alloy material and preparation method and application thereof ", and Chinese patent publication number CN1644737A discloses a kind of denomination of invention and has been: " magnesium based hydrogen storing alloy composite material and preparation method thereof ".These two kinds of Mg base hydrogen bearing alloys have all adopted the mechanical ball milling alloyage process to prepare the alloy material that contains nanometer crystal microstructure, and its suction/separate hydrogen performance is good, and electrochemistry capacitance can reach 300mAhg
-1, physicochemical property obviously improves than binary, three component system Mg base hydrogen bearing alloy, but its suction/separate hydrogen temperature higher (more than 250 ℃), thereby unstable properties, practicality is low.
Summary of the invention
The hydrogen temperature is low for a kind of suction that the objective of the invention is to overcome above-mentioned shortcoming and provide/separate, stable performance, have practicality, low-cost quaternary magnesium base hydrogen storage alloy.
Another object of the present invention also is to provide this quaternary magnesium base hydrogen storage alloy production method.
A further object of the present invention also is to provide the purposes of this quaternary magnesium base hydrogen storage alloy.
Quaternary magnesium base hydrogen storage alloy of the present invention is by Mg
1.5-2Al
0.02-0.08Ni
0.5-1.0A
0.05-0.1Form, wherein A is V, Ti, Fe, Nd or Pd etc., is distributed with the nanocrystalline cluster and the amorphous cluster of disperse in the microstructure.
The production method of quaternary magnesium base hydrogen storage alloy of the present invention comprises the steps:
(1) according to Mg
1.5-2Al
0.02-0.08Ni
0.5-1.0A
0.05-0.1Take by weighing alloying element powder,, be pressed into sheet then through thorough mixing; To put into vacuum tightness be 1 * 10 being pressed into flaky sample
-3Carry out sintering in the vacuum sintering furnace of Pa, sintering temperature is at 500-800 ℃, and sintering time was at 1.5-4 hour; Next the alloy sample that sintering is obtained pulverize, ball milling, screening, obtain the following Mg of granularity＜25 μ m
1.5-2Al
0.02-0.08Ni
0.5-1.0A
0.05-0.1Powdered alloy;
(2) press Mg
1.5-2Al
0.02-0.08Ni
0.5-1.0A
0.05-0.1The 3-5% of powdered alloy weight takes by weighing Ni powder and carries out ball milling, obtains nanometer crystalline Ni powder;
(3) the following Mg of granularity＜25 μ m
1.5-2Al
0.02-0.08Ni
0.5-1.0A
0.05-0.1Powdered alloy and nanometer crystalline Ni powder and Mg
1.5-2Al
0.02-0.08Ni
0.5-1.0A
0.05-0.1Carry out high-energy ball milling behind the 2-3% second phase active particle of powder weight and the 0.1-1% carbon nanotube thorough mixing, ball material mass ratio is 20:1, rotating speed is 400-450rpm, the ball milling time is 12-72 hour, obtain having the active alloy material storing hydrogen of nano-crystalline and amorphous tissue, behind overactivation, get finished product.
The production method of above-mentioned quaternary magnesium base hydrogen storage alloy, wherein the second phase active particle is TiO
2Or halogenide particle.
The present invention compared with prior art by above technical scheme as can be known, selects main alloying element kind and proportioning content.Select V, Ni, Al, Ti, Fe, Pd, Nd etc. as main alloy element, these alloying elements have two characteristics: the one, and they all can be easily and the hydrogen evolution alloy hydride; The 2nd and magnesium form alloy the time, have special electronic structure, corrosion resistance is also better.In addition, the amount of these alloying elements in alloy followed Mg
1.5-2Al
0.02-0.08Ni
0.5-1.0A
0.05-0.1The quantitative relation of (wherein A is V, Ti, Fe, Nd or Pd etc.); Next is that the preparation technology of alloy has mainly adopted vacuum sintering and mechanical alloying (high-energy ball milling) technology.Vacuum sintering is 10
-3Carry out under the vacuum tightness of Pa, in the ball milling mechanical alloy after the vacuum sintering, obtain different microstructures by controlling the ball milling time with rotating speed, ball milling time length can obtain more nanocrystalline cluster tissue, and the rotating speed height can obtain more amorphous cluster tissue.At last by adding the second phase active ion (as TiO
2Or halogenide etc.) and micro-multi-walled carbon nano-tubes (CNT), can further improve the hydrogen storage alloy performance.The quaternary magnesium base hydrogen storage alloy of the present invention that collocation and preparation technology by above-mentioned alloy species and proportioning obtains has following performance: have following performance: hydrogen-storage amount〉4.5% (weight percent); Inhale/separate the hydrogen temperature and be lower than 220 ℃; Electrical capacity is not less than 400mAhg
-1Good erosion resistance.This functional, low-cost Magnuminium functional materials, its temperature has reached the degree of practicability, will improve the practicability level of hydrogen storage alloy greatly.And be the high product innovation that foundational development has actual application value and commercial value with this functional materials, be prepared into electrode and be applied in secondary cell and the hydrogen power set; Or, be applied to fields such as fuel cell, hydrogen energy converting system and national defence as the main carrier that stores up hydrogen.
Embodiment
Embodiment 1:
(1) according to Mg
1.95Al
0.05Ni
0.92V
0.08Take by weighing alloying element powder,, be pressed into sheet then through thorough mixing; To put into vacuum tightness be 1 * 10 being pressed into flaky sample
-3Carry out sintering in the vacuum sintering furnace of Pa, sintering temperature is at 500-800 ℃, and sintering time was at 1.5-4 hour; Next the alloy sample that sintering is obtained pulverize, ball milling, screening, obtain the following Mg of granularity＜25 μ m
1.95Al
0.05Ni
0.92V
0.08Powdered alloy;
(2) press Mg
1.95Al
0.05Ni
0.92V
0.083.5% of powdered alloy weight takes by weighing Ni powder and carries out ball milling, observes microstructure with x x ray diffractometer x (XRD) in the mechanical milling process, sees whether become nanometer crystalline Ni powder, nanometer crystal microstructure occurs usually after 15 hours;
(3) the following Mg of granularity＜25 μ m
1.95Al
0.05Ni
0.92V
0.08Powdered alloy and nanometer crystalline Ni powder and Mg
1.95Al
0.05Ni
0.92V
0.082.5% TiO of powder weight
2(ball material mass ratio is 20:1 with carrying out high-energy ball milling behind the 0.6% carbon nanotube thorough mixing, rotating speed is 450rpm), in the high-energy ball milling process, in conjunction with XRD, transmission electron microscope (TEM) and selected area electron diffraction (SED) microstructure is observed and monitored, so that obtain nanometer crystal microstructure and further obtain amorphous structure, usually process will obtain having the active Mg-Al-Ni-V alloy material storing hydrogen of nano-crystalline and amorphous tissue after 20-30 hour, got finished product behind overactivation.
The finished product that obtains has following performance index after tested: hydrogen storage ability 3-5.5% (weight percent), inhale/separate hydrogen temperature＜220 ℃, and inhale/separate hydrogen pressure＜4MPa,＜0.02Mpa inhales/separates the hydrogen cycle index〉500, electrochemistry capacitance 450mAhg
-1
Embodiment 2:
(1) with embodiment 1;
(2) press Mg
1.95Al
0.05Ni
0.92V
0.083% of powdered alloy weight takes by weighing Ni powder and carries out ball milling, and all the other are with embodiment 1;
(3) the following Mg of granularity＜25 μ m
1.95Al
0.05Ni
0.92V
0.08Powdered alloy and nanometer crystalline Ni powder and Mg
1.95Al
0.05Ni
0.92V
0.08The 2-3% TiO of powder weight
2With carry out high-energy ball milling behind the 0.1% carbon nanotube thorough mixing, all the other are with embodiment 1.
The finished product that obtains has following performance index after tested: hydrogen storage ability 3-5.5% (weight percent), inhale/separate hydrogen temperature＜220 ℃, and inhale/separate hydrogen pressure＜4MPa,＜0.02Mpa inhales/separates the hydrogen cycle index〉500, electrochemistry capacitance 450mAhg
-1
Embodiment 3:
(1) with embodiment 1;
(2) press Mg
1.95Al
0.05Ni
0.92V
0.085% of powdered alloy weight takes by weighing Ni powder and carries out ball milling, and all the other are with embodiment 1;
(3) the following Mg of granularity＜25 μ m
1.95Al
0.05Ni
0.92V
0.08Powdered alloy and nanometer crystalline Ni powder and Mg
1.95Al
0.05Ni
0.92V
0.083% TiO of powder weight
2With carry out high-energy ball milling behind the 1% carbon nanotube thorough mixing, all the other are with embodiment 1.
The finished product that obtains has following performance index after tested: hydrogen storage ability 3-5.5% (weight percent), inhale/separate hydrogen temperature＜220 ℃, and inhale/separate hydrogen pressure＜4MPa,＜0.02Mpa inhales/separates the hydrogen cycle index〉500, electrochemistry capacitance 450mAhg
-1
Embodiment 4-7
| Embodiment | Chemical general formula | Production method | Performance index |
| 4 | Mg 1.95Al 0.05Ni 0.92Ti 0.08 | Rotating speed is 400rpm, during ball milling | With embodiment 1 |
| Between be 12 hours, all the other are with embodiment 1 | |||
| 5 | Mg 1.95Al 0.05Ni 0.92Fe 0.08 | Rotating speed is 430rpm, and the ball milling time is 20 hours, and all the other are with embodiment 2 | With embodiment 1 |
| 6 | Mg 1.95Al 0.05Ni 0.92Nd 0.08 | Rotating speed is 450rpm, and the ball milling time is 72 hours, and all the other are with embodiment 3 | With embodiment 1 |
| 7 | Mg 1.95Al 0.05Ni 0.92Pd 0.08 | Rotating speed is 450rpm, and the ball milling time is 60 hours, and all the other are with embodiment 1 | With embodiment 1 |
| 8 | Mg 1.5Al 0.02Ni 0.5V 0.05 | Rotating speed is 420rpm, and the ball milling time is 50 hours, and all the other are with embodiment 2 | With embodiment 1 |
| 9 | Mg 2Al 0.08Ni 1.0V 0.1 | Rotating speed is 400rpm, and the ball milling time is 40 hours, and all the other are with embodiment 3 | With embodiment 1 |
Test example 1
Take by weighing embodiment 1 prepared powdered alloy 0.5 and restrain, under 50MPa pressure, be pressed into 10 * 10 sheet sample then, and as test electrode and NiOH/Ni (OH)
2Supporting electrode is with Hg/HgO reference electrode component alloy electrochemistry capacitance test macro electrode, and electrolyte solution is the KOH aqueous solution of 5mol/L.Charging and discharging currents density is 80mA/g and 40mA/g, and the charge and discharge cycles number of times is more than 150 times, and as seen the electrochemistry capacitance of this alloy can remain on 450mAhg
-1More than.
Test example 2.
Utilize embodiment 1 prepared powdered alloy to be prepared into electrode, and according to Mg-Al-V-Ni (quaternary hydrogen storage alloy)/Mg (AlCl
2BuEt)
2+ THF/Mg
xMo
3S
4What form discharges and recharges battery system, i.e. secondary Mg battery system.It is discharged and recharged test, reached following index: battery output open circuit voltage 1.0-1.5V; The charge and discharge cycles number of times〉1000 (0.5-1.3mA/cm
2Under the discharging rate); Depth of discharge〉95%; Working temperature-20 ℃-50 ℃.Performance index have as above reached the practicability level.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, any technical solution of the present invention content that do not break away from,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (3)
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|---|---|---|---|
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| CN100513605C true CN100513605C (en) | 2009-07-15 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453212C (en) * | 2007-07-17 | 2009-01-21 | 南京航空航天大学 | Mechanical preparation method of nano-ceramic and micro-metal composite powder |
| TWI400340B (en) | 2008-08-25 | 2013-07-01 | Ind Tech Res Inst | Nanotization of magnesium-based hydrogen storage material |
| CN101671788B (en) * | 2008-09-12 | 2013-06-19 | 财团法人工业技术研究院 | Nanotechnology of Magnesium-Based Hydrogen Storage Materials |
| CN101716676B (en) * | 2009-12-21 | 2011-11-16 | 南京工业大学 | A2B-type titanium-based hydrogen storage alloy and preparation method thereof |
| CN104084592A (en) * | 2014-07-28 | 2014-10-08 | 中国科学院重庆绿色智能技术研究院 | Method for preparing spherical powder material used for three-dimensional printing |
| CN106086491A (en) * | 2016-07-07 | 2016-11-09 | 厦门理工学院 | A kind of Mg-based composite hydrogen storage material and preparation method thereof |
| CN108493436B (en) * | 2018-03-09 | 2021-01-08 | 燕山大学 | 2H-type A5B19 super-stacking structure lanthanum-M-magnesium-nickel-based quaternary hydrogen storage alloy electrode material and preparation method thereof |
| CN108754266B (en) * | 2018-06-29 | 2019-06-28 | 南通朝旭环保科技有限公司 | A kind of metallic composite |
| CN110039042B (en) * | 2019-05-06 | 2021-04-13 | 安徽工业大学 | Preparation method of carbon nano tube reinforced titanium-magnesium alloy composite material |
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