CN101130845A - Rare earth hydrogen storage alloy containing Mg and preparing method thereof - Google Patents
Rare earth hydrogen storage alloy containing Mg and preparing method thereof Download PDFInfo
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- CN101130845A CN101130845A CNA2007101574520A CN200710157452A CN101130845A CN 101130845 A CN101130845 A CN 101130845A CN A2007101574520 A CNA2007101574520 A CN A2007101574520A CN 200710157452 A CN200710157452 A CN 200710157452A CN 101130845 A CN101130845 A CN 101130845A
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a magnesium-bearing rare earth series hydrogen storage alloy and its preparation method. Its chemical structure formula is La1-X-Y-ZPrXNdYMgZ (NiCoAlM)3.5 plus or minus 0.5. Its preparation method includes the following steps: preparing raw materials according to said chemical structure formula, except for magnesium placing all the metals into a vacuum induction smelting furnace, evacuating to make vacuum degree be less than or equal to 0.5Pa, introducing inert gas, controlling pressure to make the pressure be 0.04-0.07MPa, heating, after all the metals are melted, stopping heating, after the molten alloy surface is film-formed, adding metal magnesium, heating, after all the metals are uniformly melted, stopping heating, reducing gas pressure in the vacuum induction smelting furnace to 0.005-0.04MPa, pouring the molten alloy into a water-cooling mould, cooling and solidifying.
Description
Technical field:
The present invention relates to a kind of heavy body power type MH-Ni battery material, belong to the battery material field, particularly a kind of Mg lanthanon hydrogen storage alloy and preparation method thereof that contains.
Background technology:
In recent years; because the increase of motor vehicle exhaust amount; urban air pollution is on the rise; and the crisis of global energy, the especially Greenhouse effect of Chan Shenging, human existence is had a strong impact on; being subjected to countries in the world man pays much attention to; greatly promoted the MH-Ni battery to the development of heavy body power type, to satisfy the needs of power truck, hybrid electric vehicle, electric bicycle, power tool and military tank, aircraft and submarine etc., its market potential is boundless.At present, can be used for having only AB on the heavy body power type MH-Ni battery in batches
5Lanthanon hydrogen storage alloy, other have the alloy of development, as AB
2Be the Laves' phases hydrogen storage alloy, though loading capacity is high and have extended cycle life, initial activation is slow and heavy-current discharge performance is poor, is not suitable for superpower MH-Ni battery, does not also have practicability.AB
3The rare-earth magnesium series hydrogen storage alloy has higher loading capacity, compares AB
5The high 10-30%[of lanthanon hydrogen storage alloy day disclosure special permission communique 2002-105563], and good heavy current, be the most promising heavy body power type MH-Ni battery alloy.But AB
3Alloy causes the less stable of alloy mass and performance in process of production because of easy oxidation of Mg and volatilization, alloying constituent is wayward.General preparation contains the magnesium lanthanon hydrogen storage alloy two kinds of methods, a kind of is to adopt the traditional preparation process method: with rare earth metal, raw materials such as metal M g and metal Ni add fusing simultaneously in the crucible together, another kind method is earlier Mg and Ni to be prepared into master alloy, adds fusing once more in the crucible with other raw materials again.Because the fusing point of Mg and Ni differs bigger, be respectively 649 ℃ and 1453 ℃, and the vapour pressure of Mg is lower, when if Mg and Ni melt with stove, then Mg fusing earlier and volatilization causes alloying constituent and design to produce deviation, even therefore adopt the MgNi master alloy can not stablize the control alloying constituent.
Summary of the invention:
In order to address the above problem, the object of the present invention is to provide a kind of heavy body power type MH-Ni battery with containing magnesium lanthanon hydrogen storage alloy and preparation method thereof, that can guarantee to prepare contains magnesium lanthanon hydrogen storage alloy chemical ingredients evenly and stable, and production process is easy to control.
The technical solution used in the present invention is: a kind of Mg lanthanon hydrogen storage alloy that contains is characterized in that chemical structural formula is: La
1-X-Y-ZPr
XNd
YMg
Z(NiCoAlM)
3.5 ± 05, 0＜X≤0.5,0＜Y≤0.5,0.1＜Z≤0.3 wherein, X+Y+Z＜1, M is that one or more elements among Fe, Ti, Zr, Zn, Y or the Cr mix.
The described preparation method who contains the Mg lanthanon hydrogen storage alloy is as follows:
1) by the chemical structural formula La that contains the Mg lanthanon hydrogen storage alloy
1-X-Y-ZPr
XNd
Y(NiCoAlM)
3.5 ± 0.5Prepare burden;
2) earlier other metals except Mg are put into vacuum induction melting furnace, vacuumize≤0.5Pa, charge into rare gas element, control pressure is 0.04-0.07MPa, begins heating, after other melting of metal are even, stops heating;
3) treat alloy melt surface conjunctiva after, add metal M g again, and begin heating, all after the fusing evenly, the gaseous tension in the vacuum induction melting furnace is reduced to 0.005-0.04MPa;
4) the alloy liquation is poured in the water cooling mould cooled and solidified.
Described rare gas element is an Ar gas.
When preparation contains the Mg lanthanon hydrogen storage alloy, after vacuumizing, charge into the Ar gas of certain pressure, fusing other metals except that metal M g, the pressure-controlling that sets is at 0.04-0.07MPa.If be lower than 0.04MPa, when exhaust, can not clearly see liquid level, greater than 0.07MPa, be unfavorable for the removal of impurity in the alloy.The adding method of metal M g is very crucial, add metal M g before, stop heating, treat alloy melt surface conjunctiva after, could add metal M g (if needless to say after the alloy cooling, directly add Mg, volatilize, influence the content of Mg in the alloy) owing to high temperature also easily makes Mg.Begin heating then, after the whole fusings of alloy are even once more, the gaseous tension in the stove is dropped to 0.005-0.04MPa, the alloy liquation accurately is poured in the special water cooling mould then, make the melt rapid solidification, thereby obtain chemical composition stability and uniform hydrogen storage alloy.If the gaseous tension in the stove is lower than 0.005MPa, metal M g velocity of evaporation is accelerated, and influence stablizing of alloying constituent, and splash easily takes place melt, greater than 0.04MPa, can not clearly see liquid level, can't be accurately with melt cast in special water cooling mould.
The invention has the beneficial effects as follows: the inventive method is simple, and production technique is easy to control.Owing to adopted magnesium in independent heat fused of later stage, made the fusing earlier of dystectic other metals, after the film forming to be cooled, add Mg again, melt magnesium more at a lower temperature, guaranteed the non-volatile of magnesium, alloy composition is even and stable, and alloying constituent is very little, almost nil with design generation deviation.
Description of drawings:
Fig. 1 is PCT (the pressure composition temperature) curve of embodiment 1 and comparative example 1.(
Be the figure of embodiment 1,
Figure for comparative example 1)
Embodiment
Containing magnesium lanthanon hydrogen storage alloy chemical structural formula is La
0.5Pr
0.1Nd
0.2Mg
0.2(NiCoAlZr)
3.6
Its preparation method is:
1) by the chemical structural formula La that contains the Mg lanthanon hydrogen storage alloy that designs
0.5Pr
0.1Nd
0.2Mg
0.2(NiCoAlZr)
3.6Prepare burden, material purity is greater than 99%.
2) rare earth metal, Mg, Ni, Co, Al and Zr are put into vacuum induction melting furnace together, wherein Mg is placed on auxiliary the adding in the feed bin in the stove, other metals directly add in the crucible, be evacuated to 0.5Pa, the stop pumping vacuum charges into rare gas element Ar, control pressure 0.05MPa, begin heating, after feed metal all melts evenly, stop heating, cooling;
3) treat alloy melt surface conjunctiva after, add metal M g again, and begin heating, treat that alloy all after the fusing evenly, reduces to 0.03MPa with the gaseous tension in the vacuum induction melting furnace;
4) alloy melt accurately is poured in the water cooling mould cooled and solidified.
The results are shown in Table 1 and Fig. 1.
Containing magnesium lanthanon hydrogen storage alloy chemical structural formula is La
0.4Pr
0.2Nd
0.2Mg
0.2(NiCoAlY)
3.6
Its preparation method is:
1) by the chemical structural formula La that contains the Mg lanthanon hydrogen storage alloy that designs
0.4Pr
0.2Nd
0.2Mg
0.2(NiCoAlY)
3.6Prepare burden, material purity is greater than 99%.
2) rare earth metal, Mg, Ni, Co, Al and Y are put into vacuum induction melting furnace together, wherein Mg is placed on auxiliary the adding in the feed bin in the stove earlier, other metals directly add in the crucible, be evacuated to 0.5Pa, the stop pumping vacuum charges into rare gas element Ar, control pressure 0.07MPa, begin heating, after feed metal all melts evenly, stop heating, cooling;
3) treat alloy melt surface conjunctiva after, add metal M g again, and begin heating, treat that alloy all after the fusing evenly, reduces to 0.04MPa with the gaseous tension in the vacuum induction melting furnace;
4) alloy melt accurately is poured in the water cooling mould cooled and solidified.
The results are shown in Table 1.
Containing magnesium lanthanon hydrogen storage alloy chemical structural formula is La
0.5Pr
0.2Nd
0.1Mg
0.2(NiCoAlZrFe)
3.4
Its preparation method is:
1) by the chemical structural formula La that contains the Mg lanthanon hydrogen storage alloy that designs
0.5Pr
0.1Nd
0.2Mg
0.2(NiCoAlZrFe)
3.4Prepare burden, material purity is greater than 99%.
2) rare earth metal, Mg, Ni, Co, Al and Y are put into vacuum induction melting furnace together, wherein Mg is placed on auxiliary the adding in the feed bin in the stove earlier, other metals directly add in the crucible, be evacuated to 0.5Pa, the stop pumping vacuum charges into rare gas element Ar, control pressure 0.04MPa, begin heating, after feed metal all melts evenly, stop heating, cooling;
3) treat alloy melt surface conjunctiva after, add metal M g again, and begin heating, treat that alloy all after the fusing evenly, reduces to 0.005MPa with the gaseous tension in the vacuum induction melting furnace;
4) alloy melt accurately is poured in the water cooling mould cooled and solidified.
The results are shown in Table 1.
Comparative example 1
Containing magnesium lanthanon hydrogen storage alloy chemical structural formula is La
0.5Pr
0.1Nd
0.2Mg
0.2(NiCoAlZr)
3.6
The preparation method:
The magnesium lanthanon hydrogen storage alloy chemical structural formula that contains by design is La
0.5Pr
0.1Nd
0.2Mg
0.2(NiCoAlZr)
3.6Prepare burden, material purity is greater than 99%.
The rare earth metal, Mg, Ni, Co, Al and the Zr that prepare are put into the vacuum induction melting furnace crucible together, be evacuated to below the 0.5Pa, the stop pumping vacuum, charge into Ar gas, pressure is 0.05MPa, begins heating, after raw material all melts evenly, alloy melt accurately is poured in the water cooling mould cooled and solidified.The results are shown in Table 1 and Fig. 1.
Comparative example 2
Containing magnesium lanthanon hydrogen storage alloy chemical structural formula is La
0.5Pr
0.1Nd
0.2Mg
0.2(NiCoAlZr)
3.6
The preparation method:
The magnesium lanthanon hydrogen storage alloy chemical structural formula that contains by design is La
0.5Pr
0.1Nd
0.2Mg
0.2(NiCoAlZr)
3.6Prepare burden, material purity is greater than 99%.
The rare earth metal, Mg, Ni, Co, Al and the Zr that prepare are put into vacuum induction melting furnace together, and wherein Mg is placed on auxiliary the adding in the feed bin in the stove, and other metals directly add in the crucible, be evacuated to below the 0.5Pa, the stop pumping vacuum charges into Ar gas, pressure is 0.07MPa, begin heating, after raw material all melts evenly, add metal M g at once, after alloy evenly melts once more, furnace pressure is reduced to 0.04MPa, then alloy melt accurately is poured in the water cooling mould cooled and solidified.The results are shown in Table 1.
Table 1
| Design Mg content/% | Mg content/% in the alloy of | |
| Embodiment | ||
| 1 | 1.50 | 1.51 |
| |
1.50 | 1.48 |
| |
1.53 | 1.50 |
| Comparative example 1 | 1.50 | 1.17 |
| Comparative example 2 | 1.50 | 1.36 |
By Fig. 1 and table 1 as seen, that adopts the inventive method preparation contains magnesium lanthanon hydrogen storage alloy chemical ingredients, and design is very little with actual deviation, and Mg and other metals are melted simultaneously, and design and actual deviation are very big; And with the fusing earlier of other metals, to be cooled and directly add Mg, design is not bigger with actual deviation yet.As seen, of the present invention contain the magnesium lanthanon hydrogen storage alloy not only chemical ingredients evenly, stable, and design and actual deviation are very little, have guaranteed the steady quality of alloy production process and the excellence of alloy electrochemical performance.
Claims (3)
1. one kind contains the Mg lanthanon hydrogen storage alloy, it is characterized in that chemical structural formula is: La
1-X-Y-ZPr
XNd
YMg
Z(NiCoAlM)
3.5 ± 0.5, 0＜X≤0.5,0＜Y≤0.5,0.1＜Z≤0.3 wherein, X+Y+Z＜1, M is that one or more elements among Fe, Ti, Zr, Zn, Y or the Cr mix.
2. described preparation method who contains the Mg lanthanon hydrogen storage alloy of claim 1 is characterized in that the preparation method is as follows:
1) by the chemical structural formula La that contains the Mg lanthanon hydrogen storage alloy
1-X-Y-ZPr
XNd
Y(NiCoAlM)
3.5 ± 05Prepare burden;
2) earlier other metals except Mg are put into vacuum induction melting furnace, vacuumize≤0.5Pa, charge into rare gas element, control pressure is 0.04-0.07MPa, begins heating, after other melting of metal are even, stops heating;
3) treat alloy melt surface conjunctiva after, add metal M g again, and begin heating, all after the fusing evenly, the gaseous tension in the vacuum induction melting furnace is reduced to 0.005-0.04MPa;
4) the alloy liquation is poured in the water cooling mould cooled and solidified.
3. the preparation method who contains the Mg lanthanon hydrogen storage alloy according to claim 2 is characterized in that described rare gas element is an Ar gas.
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|---|---|---|---|
| CNB2007101574520A CN100537810C (en) | 2007-10-15 | 2007-10-15 | A kind of Mg lanthanon hydrogen storage alloy and preparation method thereof that contains |
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|---|---|---|---|
| CNB2007101574520A CN100537810C (en) | 2007-10-15 | 2007-10-15 | A kind of Mg lanthanon hydrogen storage alloy and preparation method thereof that contains |
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| Publication Number | Publication Date |
|---|---|
| CN101130845A true CN101130845A (en) | 2008-02-27 |
| CN100537810C CN100537810C (en) | 2009-09-09 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277508A (en) * | 2011-08-09 | 2011-12-14 | 安泰科技股份有限公司 | Preparation method of magnesium-based hydrogen storage alloy |
| CN102286684A (en) * | 2011-08-09 | 2011-12-21 | 安泰科技股份有限公司 | Magnesium-based hydrogen storage alloy |
| CN102660700A (en) * | 2012-05-27 | 2012-09-12 | 桂林理工大学 | AB3-type hydrogen storage alloy and preparation method |
| CN103855370A (en) * | 2014-03-11 | 2014-06-11 | 微山钢研稀土材料有限公司 | Low-magnesium RE-Mg-Ti-Ni-Al-B series hydrogen-storage alloy for Ni-MH secondary battery and preparation method |
| CN106191547A (en) * | 2016-08-29 | 2016-12-07 | 江苏华企铝业科技股份有限公司 | A kind of alumal and powder metallurgy forming method thereof |
-
2007
- 2007-10-15 CN CNB2007101574520A patent/CN100537810C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277508A (en) * | 2011-08-09 | 2011-12-14 | 安泰科技股份有限公司 | Preparation method of magnesium-based hydrogen storage alloy |
| CN102286684A (en) * | 2011-08-09 | 2011-12-21 | 安泰科技股份有限公司 | Magnesium-based hydrogen storage alloy |
| CN102660700A (en) * | 2012-05-27 | 2012-09-12 | 桂林理工大学 | AB3-type hydrogen storage alloy and preparation method |
| CN103855370A (en) * | 2014-03-11 | 2014-06-11 | 微山钢研稀土材料有限公司 | Low-magnesium RE-Mg-Ti-Ni-Al-B series hydrogen-storage alloy for Ni-MH secondary battery and preparation method |
| CN106191547A (en) * | 2016-08-29 | 2016-12-07 | 江苏华企铝业科技股份有限公司 | A kind of alumal and powder metallurgy forming method thereof |
| CN106191547B (en) * | 2016-08-29 | 2017-08-25 | 江苏华企铝业科技股份有限公司 | A kind of alumal and its powder metallurgy forming method |
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| Publication number | Publication date |
|---|---|
| CN100537810C (en) | 2009-09-09 |
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