CN1208487C - Nano crystal multiphase mixed rare earth-magnesium system hydrogen-storing alloy and its preparation method - Google Patents
Nano crystal multiphase mixed rare earth-magnesium system hydrogen-storing alloy and its preparation method Download PDFInfo
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- CN1208487C CN1208487C CNB031142346A CN03114234A CN1208487C CN 1208487 C CN1208487 C CN 1208487C CN B031142346 A CNB031142346 A CN B031142346A CN 03114234 A CN03114234 A CN 03114234A CN 1208487 C CN1208487 C CN 1208487C
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Abstract
The present invention relates to nanometer crystal multiphase mixed rare earth-magnesium system hydrogen-storage alloy and a preparation method thereof, which is characterized in that the alloy has a molecular formula of M1<1-x>Mg<x>Ni<y>, wherein M1 is mixed lanthanum-rich rare earth, x is from at least 0.02 to at most 0.8, and y is from at least 2 to at most 4. The preparation method of the alloy comprises the steps of smelting, homogenizing annealing, etc., wherein the smelting step comprises: the mixed lanthanum-rich rare earth, metal magnesium and metal nickel are put into a crucible of an induction smelting furnace according to a certain proportion; vacuum is pumped; protective gas is filled in the crucible; power and temperature are regulated to melt metal; the temperature is preserved, and the melted metal is fully stirred; the molten metal filled into a water-cooling ingot mould to be taken out from the furnace after being cooled. The alloy of the present invention has special components, a multiphase nanometer crystal structure and the hydrogen-storage content which is higher than that of the traditional rare earth system, and the alloy has the advantages of high cyclical stability, proper pressure platform, easy activation and good dynamic performance. The preparation method of the present invention has the advantages of simplicity, low cost, no pollution and easy quality control, and the preparation method is suitable for mass production.
Description
(1) technical field
The present invention relates to the hydrogen storage material technical field, specifically be meant a kind of nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy and preparation method thereof.
(2) background technology
Owing to seek the enforcement of the Hydrogen Energy plan of clean energy, the research of metal-hydrogen system has obtained development fast in recent years, successively develop the hydrogen-storage alloy of number of different types, but still failed to prepare the storage alloy material for hydrogen that can satisfy the Hydrogen Energy plan up to now.(J.Alloys andCompounds 334 (2002) 219-223) such as Tony Spassov have produced Mg-Ni-RE9 (RE=Y or Mm) alloy with quick quenching technique, and this alloy has two phase structure, wherein Mg
75Ni
20Mm
5Nanocrystalline/non-crystaline amorphous metal has best storage hydrogenation property, and the storage hydrogen capacity is 4.0% (weight percent).But this method does not solve the subject matter of the existing cyclical stability difference of Mg base alloy.Kadir (J.Alloys andCompounds 257 (1997) 115-121) has also synthesized a series of rare-earth magnesium series alloy, but their capacity is not high.
No. 01131896.1 application for a patent for invention of China discloses a kind of Mm with vacuum magnetic suspension stove or arc melting preparation
1-yM
y(NiCoN)
xSeries alloy, in the formula, Mm is a cerium-rich mischmetal, 0.01≤y≤0.8,2≤y≤4; One or both or two or more composition among M=Mg, Ca, Be, Sr, the Ba, one or both or two or more composition among N=Mn, Fe, Mo, Co, Al, Si, Ga, S, Pt, Sc, Ti, V, Cr, Cu, Zn, Zr, Nb, Ru, Rh, Pd, Cd, W, Hf, Ta, B, P, Ge, As, Se, In, the Sn have comprised that metal and part nearly all in the periodic table of elements are nonmetal.No. 01131898.8 application for a patent for invention of China has also related to Mm
1-yM
y(NiCoN)
xSeries alloy, Mm is a mishmetal in the formula, the composition range of x, y, the element of M and N representative is with last identical.No. 01131899.6 application for a patent for invention of China " nickel-metal hydride secondary battery New-type hydrogen-storing RE electrode alloy " relates to AB
xAlloy, A=La in the formula
1-yM
y, B=(NiCoN), the composition range of x, y, the element of M and N representative also uses as electrode metal with last identical.China's No. 01145250.1 application for a patent for invention " New-type hydrogen-storing RE electrode alloy and heat treating method thereof " and Chinese 01131897.x application for a patent for invention " New-type hydrogen-storing RE electrode alloy and quenching process thereof " disclose a kind of preparation method and quenching process of novel rare-earth series hydrogen storage alloy electrode, and its molecular formula is A
1-yB
yC
xWherein A is one or more compositions among La, rich La mishmetal Ml, Ce, rich Ce mishmetal Mm, Pr, the Nd, B is one or more compositions among Mg, Ca, Be, Sr, the Ba, and C is one or more compositions in the elements such as Mn, Fe, Mo, Co, Al.The subject matter that the rare-earth magnesium series hydrogen-storage alloy of addressing in above-mentioned document and the patent exists is:
(1) the rare-earth magnesium series hydrogen-storage alloy is (as Mg
75Ni
20Mm
5) the dehydrogenation pressure platform is low excessively, not easily-activated, desorption temperature is difficult to be generalized to practical application more than 200 ℃;
(2) the rare-earth magnesium series hydrogen-storage alloy is (as Mm
1-yM
y(NiCoN)
x) contain expensive metallic elements such as Mo, Co, Pt, Hf, Ta, Ge, cost height;
(3) rare-earth magnesium series hydrogen-storage alloy Mm
1-yM
y(NiCoN)
xContain V, Zr, Pd, Cd, In etc. and can produce the metallic element of serious environmental pollution, environment is polluted;
(4) rare-earth magnesium series hydrogen-storage alloy A
1-yB
yC
xDo not contain the Ni element, thereby make its hydrogen storage performance very poor;
(5) existing production technique adopts vacuum magnetic suspension stove or arc melting preparation, and operational difficulty is difficult to produce in enormous quantities.
(3) summary of the invention
Purpose of the present invention is exactly in order to solve above-mentioned the deficiencies in the prior art part, and a kind of nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy and preparation method thereof is provided.This alloy hydrogen storage performance is good, easily-activated, pollution-free, and preparation technology is simple, can realize producing in enormous quantities.
A kind of nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy of the present invention is characterized in that its molecular formula is Ml
1-xMg
xNi
y, wherein, Ml is a lanthanum rich mischmetal, 0.02≤x≤0.8,2≤y≤4.
In order to realize the present invention better, described lanthanum rich mischmetal can be selected RELa-56 or La-REM for use; In described lanthanum rich mischmetal, the weight percent content of rare earth element is not less than 90%, and the weight percent content of lanthanoid metal (La) is not less than 30%, and the weight percent content of metallic cerium (Ce) is not higher than 10%.
The preparation method of a kind of nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy of the present invention, comprise melting, homogenizing annealing process, it is characterized in that, described fusion process, be that lanthanum rich mischmetal (Ml), MAGNESIUM METAL (Mg) and metallic nickel (Ni) are placed the induction melting furnace crucible by certain proportioning (will consider the loss that the element volatilization causes), be evacuated to vacuum tightness 10
-2More than the Pa, charge into shielding gas argon (Ar) gas or helium or nitrogen to air pressure again and reach 0.002～0.1Mpa, the adjusting power range is 5～35kw, temperature is controlled at 900～1200 ℃, make melting of metal, insulation is also fully stirred, and smelting time is 0.5～3 hour, the melt metal liquation is injected water cooling ingot mould, come out of the stove after cooling; Described homogenizing annealing process is that alloy cast ingot is placed sample carrier or silica tube, vacuumizes or feed argon gas or helium or nitrogen protection, is warming up to 700～1100 ℃ in heat treatment furnace, is incubated 2～10 hours, is chilled to room temperature with stove again; Nanocrystalline in order to obtain; after described homogenizing annealing process, carry out ma process again; described ma process is to pack in 10: 1 to 60: 1 by ball material volume ratio can ventilate in the ball grinder; after vacuumizing, ball grinder charges into argon shield; the good seal ball grinder; ball milling is 5～100 hours on planetary high-energy ball mill, and it is nanocrystalline that powdered alloy is formed.
In order to realize the present invention better, described MAGNESIUM METAL is that purity is 99.9% magnesium ingot metal, and described metallic nickel is that purity is 99.99% sheet nickel; Described induction melting furnace crucible is plumbago crucible or corundum crucible.
The fusing point of Mg and Ml, Ni (Mg is 648.8 ℃, and La is 921 ℃, and Ni is 1453 ℃) differs greatly, and it has been generally acknowledged that being difficult for carrying out melting synthesizes.The present invention has proposed to utilize heterogeneous structure to improve the thought of traditional rare earth series hydrogen storage alloy performance first, select appropriate parameters, prepared the Ml-Mg-Ni hydrogen-storage alloy with induction melting, utilize each out of phase hydrogen storage performance and alternate mutual katalysis, make it have high hydrogen storage amount, the moderate characteristics of plateau pressure.In preparation process, based on Metallkunde and crystallography theory, by the microtexture of control alloy, the composition of each phase and relative content reach the purpose of controlling alloy property.
Alloy of the present invention is a heterogeneous structure, and it is AB mutually that its heterogeneous structure constitutes
5, AB
3, AB
2, A
2B
7Phase, concrete AB
5Be (Ml Mg) Ni
4.8To (Ml Mg) Ni
5.2, AB
3Be (Ml Mg) Ni
3, AB
2Be (Ml Mg) Ni
2, A
2B
7Be (Ml Mg)
2Ni
7AB
5The phase platform area is broad, but pressure platform is too high, particularly as MlNi
4.8The about 13atm of phase plateau pressure; AB
3, AB
2, A
2B
7The phase hydrogen is big, but pressure platform is low, difficult activation.The mutual katalysis of alternate existence when alloy has heterogeneous structure.
The hydrogen storage amount of the heterogeneous structure of alloy of the present invention can reach 1.7% (weight percent), AB in the alloy
5Corresponding plateau pressure is reduced to about 5～7atm, and easily-activated; Other plateau pressure that contains the magnesium phase rises than Magnuminium, is about 1atm.
The present invention compared with prior art has following advantage and beneficial effect:
1. hydrogen-storage alloy of the present invention has unique composition and heterogeneous, nanocrystalline structure, has AB
5, AB
2, AB
3, A
2B
7Deng two or more the heterogeneous structure in mutually.
2. hydrogen-storage alloy hydrogen storage amount of the present invention is than traditional rare earth series hydrogen storage alloy height, and weight percent is greater than 1.7%.
3. hydrogen-storage alloy of the present invention has good cyclical stability, suitable pressure platform.
4. hydrogen-storage alloy of the present invention is easy to activation, and dynamic performance is good.
5. preparation method of the present invention is simple, and composition does not contain expensive metallic elements such as Mo, Co, Pt, Hf, Ta, Ge, In, and cost is low.
6. hydrogen-storage alloy of the present invention does not contain V, Zr, Pd, Cd etc. can produce the metallic element of serious environmental pollution, and material source is abundant, is green material, thereby is particularly suitable as the hydrogen storage material use, has wide actual application prospect.
7. China's rare earth resources is abundant, and magnesium resource is abundant, and manufacturing process of the present invention is simple, and quality is controlled easily, is fit to produce in enormous quantities.
(4) description of drawings
Fig. 1 is Ml in the embodiment of the invention two
0.7Mg
0.3Ni
3.2XRD figure spectrum at 25 ℃;
Fig. 2 is Ml in the embodiment of the invention two
0.7Mg
0.3Ni
3.2900 ℃ of annealed alloys are at 25 ℃ P-C-I curve, and its pressure platform is at MmNi
5Alloy and Mg
2Between the Ni alloy;
Fig. 3 is Ml in the embodiment of the invention two
0.7Mg
0.3Ni
3.2Suction hydrogen kinetic curve at 25 ℃.
(5) embodiment
Below in conjunction with drawings and Examples, the present invention is done detailed description further.
Embodiment one
Preparation Ml
0.98Mg
0.02Ni
4Hydrogen-storage alloy powder 10kg.The weight percent composition of choosing mishmetal Ml is La40%, Nd41%, Ce5%, Pr13%, and all the other are other rare earth element and impurity.Magnesium employing purity is 99% reguline metal, and nickel is the electrolytic nickel of purity 99.99%.Raw metal is brushed away surface oxide layer, clean, dry, weigh, take by weighing 3.7 kilograms of mishmetals by stoichiometric ratio, 0.2 kilogram of MAGNESIUM METAL, 6.2 kilograms of metallic nickels place in the plumbago crucible of vacuum induction furnace, build bell, are evacuated to vacuum tightness 10-3Pa, charge into argon gas to air pressure and reach 0.002Mpa, adjusting power encloses and is 35kw, and temperature is controlled at 1200 ℃, makes melting of metal, insulation is also fully stirred, and smelting time is 1 hour.Keep a close eye on the variation of stove internal gas pressure in the fusion process, in case hypertonia is washed bell open.The melt metal liquation is injected water cooling ingot mould, come out of the stove after cooling.
Alloy cast ingot places sample carrier, vacuumizes or feed argon shield, is warming up to 800 ℃ in heat treatment furnace, is incubated 2 hours, is chilled to room temperature with stove again.Alloy cast ingot behind alloy cast ingot and the homogenizing annealing is at first inlayed with mounting press with plastic pellet, and the observation of polishing, the laggard line scanning electron microscope of polishing is with observe its metallographic structure after the 3% nitric acid alcohol etch under metaloscope.
Prepared alloy is pulverized alloy with high energy ball mill, packed at 5: 1 by ball material volume ratio and can ventilate in the ball grinder, ball grinder vacuumizes or charges into argon shield, the good seal ball grinder.Ball milling is 10 minutes on planetary high-energy ball mill, makes the powdered alloy particle diameter at 100～20 mu m ranges.The powdered alloy particle diameter is measured with centrifugal particle size analyzer.
Prepared alloy cast ingot can be with crusher with the sample carrier direct activation of packing into of its broken frustillatum, activation method is: the high-purity hydrogen that feeds 1.0Mpa with gas reaction (GAS REACTION CONTROLLER) device carries out room temperature activation 8 hours, treat the sample carrier internal pressure reduce to stable after, alloy promptly is activated.After the activation sample carrier was vacuumized 0.5～1.5 hour or vacuumize and be heated to 100～200 ℃, the time is 20～40 minutes, with the alloy cast ingot dehydrogenation to carry out next step test.
Alloy after the activation is measured its P-C-I curve with gas reaction (GAS REACTION CONTROLLER) device, and prepared alloy hydrogen storage amount is 1.3% (weight percent), the about 10atm of pressure platform.Composition with chemical analysis and electron probe microanalysis alloy product is Ml
0.98Mg
0.02Ni
4Alloy is handled through 2 hours homogenizing of 800 ℃ of insulations, and hydrogen changes little, but pressure platform is more smooth.
Powdered alloy packed by ball material volume ratio at 60: 1 can ventilate in the ball grinder, charge into argon shield after ball grinder vacuumizes, the good seal ball grinder.Ball milling is 5 hours on planetary high-energy ball mill, and it is nanocrystalline that XRD analysis shows that powdered alloy partly forms.On the PCI curve, hydrogen can reach 1.25% (weight percent) under its room temperature, than slightly reduction before the ball milling change, but the speed for hydrogen absorbing and releasing quickening, hysteresis reduces.
Embodiment two
Preparation Ml
0.7Mg
0.3Ni
3.2Hydrogen-storage alloy powder 10kg.The weight percent composition of choosing mishmetal Ml is La55%, Na31%, Ce5%, Pr8%, and all the other are other rare earth element and impurity.Magnesium employing purity is 99% reguline metal, and nickel is the electrolytic nickel of purity 99.99%.With raw metal brush away surface oxide layer, clean, dry, weigh by stoichiometric ratio, take by weighing 3.36 kilograms of mishmetals, 2.8 kilograms of MAGNESIUM METAL, 6.2 kilograms of metallic nickels place in the corundum crucible of vacuum induction furnace, build bell, are evacuated to vacuum tightness 10
-2Pa charges into helium to air pressure and reaches 0.1Mpa, and regulate power and enclose and be 10kw, 30 minutes, 20kw, 5 minutes, temperature is controlled at 1000 ℃, makes melting of metal, insulation and fully stirs.Keep a close eye on the variation of stove internal gas pressure in the fusion process, in case hypertonia is washed bell open.The melt metal liquation is injected water cooling ingot mould, come out of the stove after cooling.
Alloy cast ingot places silica tube, vacuumizes protection, is warming up to 900 ℃ in heat treatment furnace, is incubated 4 hours, is chilled to room temperature with stove again.Alloy cast ingot behind alloy cast ingot and the homogenizing annealing is at first inlayed with mounting press with plastic pellet, and the observation of polishing, the laggard line scanning electron microscope of polishing is with observe its metallographic structure after the 3% nitric acid alcohol etch under metaloscope.
Prepared alloy is pulverized alloy with high energy ball mill, packed at 20: 1 by ratio of grinding media to material and can ventilate in the ball grinder, ball grinder vacuumizes or charges into helium protection, good seal ball grinder.On planetary high-energy ball mill,, make the powdered alloy particle diameter at 100～20 mu m ranges with 200 rev/mins of ball millings 20 minutes.The powdered alloy particle diameter is measured with centrifugal particle size analyzer.Get an amount of powdered alloy and carry out X-ray diffraction (XRD) analysis, as shown in Figure 1.
Prepared alloy cast ingot can be with crusher with the sample carrier direct activation of packing into of its broken frustillatum, and activation method is: the high-purity hydrogen that feeds 3.3Mpa with gas reaction (GAS REACTION CONTROLLER) device carries out room temperature activation 12 hours.Treat that the sample carrier internal pressure reduces to stable back alloy and promptly be activated.After the activation sample carrier was vacuumized 1.5 hours, with the alloy cast ingot dehydrogenation to carry out next step test.
Alloy after the activation is measured its P-C-I curve with gas reaction (GAS REACTION CONTROLLER) device, as shown in Figure 2, prepared alloy hydrogen storage amount is that hydrogen can reach 1.7% (weight percent) under the room temperature, and the corresponding hydrogen of pressure platform is 1.6% (weight percent); Good cycling stability; Be easy to activation, dynamic performance is good, as shown in Figure 3.Composition with chemical analysis and electron probe microanalysis alloy product is Ml
0.7Mg
0.3Ni
3.2
Powdered alloy packed by ratio of grinding media to material at 20: 1 can ventilate in the ball grinder, charge into argon shield after ball grinder vacuumizes, the good seal ball grinder.Ball milling is 50 hours on planetary high-energy ball mill, and XRD analysis shows that the most of formation of powdered alloy is nanocrystalline, grain-size 20～100nm.On the PCI curve, hydrogen can reach 1.6% (weight percent) under its room temperature, reduce before the ratio nanoization, but speed for hydrogen absorbing and releasing obviously accelerates, and hysteresis reduces.
Embodiment three
Preparation Ml
0.2Mg
0.8Ni
2Hydrogen-storage alloy powder 10kg.The weight percent composition of choosing mishmetal Ml is La81%, Nd8.5%, Ce4%, Pr5%, and all the other are other rare earth element and impurity.Magnesium employing purity is 99% reguline metal, and nickel is the electrolytic nickel of purity 99.99%.With raw metal brush away surface oxide layer, clean, dry, weigh by stoichiometric ratio, take by weighing 1.7 kilograms of mishmetals, 1.2 kilograms of MAGNESIUM METAL, 7.1 kilograms of metallic nickels place in the plumbago crucible of vacuum induction furnace, build bell, are evacuated to vacuum tightness greater than 10
-3Pa charges into nitrogen to air pressure and reaches 0.02Mpa, and adjusting power encloses and is 15kw, and temperature is controlled at 900 ℃, makes melting of metal, and insulation is also fully stirred, and smelting time is 1.5 hours.Keep a close eye on the variation of stove internal gas pressure in the fusion process, in case hypertonia is washed bell open.The melt metal liquation is injected water cooling ingot mould, come out of the stove after cooling.
Alloy cast ingot places sample carrier, vacuumizes or feed nitrogen protection, is warming up to 700 ℃ in heat treatment furnace, is incubated 10 hours, is chilled to room temperature with stove again.Alloy cast ingot behind alloy cast ingot and the homogenizing annealing is at first inlayed with mounting press with plastic pellet, and the observation of polishing, the laggard line scanning electron microscope of polishing is with observe its metallographic structure after the 3% nitric acid alcohol etch under metaloscope.
Prepared alloy is pulverized alloy with high energy ball mill, packed at 5: 1 by ratio of grinding media to material and can ventilate in the ball grinder, ball grinder vacuumizes or charges into nitrogen protection, the good seal ball grinder.Ball milling is 10 minutes on planetary high-energy ball mill, makes the powdered alloy particle diameter at 100～20 mu m ranges.The powdered alloy particle diameter is measured with centrifugal particle size analyzer.
Prepared alloy cast ingot can be with crusher with the sample carrier direct activation of packing into of its broken frustillatum, and activation method is: feed the high-purity hydrogen of 2.0Mpa with gas reaction (GAS REACTION CONTROLLER) device, be heated to 300 ℃ of activation 8 hours.Treat that the sample carrier internal pressure reduces to stable back alloy and promptly be activated.After the activation sample carrier is vacuumized and be heated to 200 ℃, the time is 40 minutes, with the alloy cast ingot dehydrogenation to carry out next step test.
Alloy after the activation is measured its P-C-I curve with gas reaction (GAS REACTION CONTROLLER) device, and hydrogen can reach 2.6% (weight percent) under the room temperature, but not dehydrogenation at ambient temperature, 200 ℃ of beginning dehydrogenations.Composition with chemical analysis and electron probe microanalysis alloy product is Ml
0.2Mg
0.8Ni
2
Powdered alloy packed by ratio of grinding media to material at 10: 1 can ventilate in the ball grinder, charge into argon shield after ball grinder vacuumizes, the good seal ball grinder.Ball milling is 100 hours on planetary high-energy ball mill, and it is nanocrystalline that XRD analysis shows that powdered alloy forms.On the PCI curve, hydrogen can reach 1.9% (weight percent) under its room temperature, obviously reduce before the ratio nanoization, but speed for hydrogen absorbing and releasing obviously accelerates, and hysteresis reduces.
As mentioned above, can realize the present invention preferably.
Claims (5)
1. nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy, the molecular formula that it is characterized in that it is Ml
1-xMg
xNi
y, wherein, Ml is a lanthanum rich mischmetal, 0.02≤x≤0.8,2≤y≤4.
2. a kind of nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy according to claim 1, it is characterized in that, in described lanthanum rich mischmetal, the weight percent content of rare earth element is not less than 90%, the weight percent content of lanthanoid metal is not less than 30%, and the weight percent content of metallic cerium is not higher than 10%.
3. the preparation method of the described nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy of claim 1, comprise melting, homogenizing annealing process, it is characterized in that, described fusion process, be that lanthanum rich mischmetal, MAGNESIUM METAL and metallic nickel are placed the induction melting furnace crucible by the proportioning of each element in the described nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy molecular formula, be evacuated to vacuum tightness 10
-2More than the Pa, charge into shielding gas argon gas or helium or nitrogen to air pressure again and reach 0.002～0.1Mpa, the adjusting power range is 5～35kw, temperature is controlled at 900～1200 ℃, make melting of metal, insulation is also fully stirred, and smelting time is 0.5～3 hour, the melt metal liquation is injected water cooling ingot mould, come out of the stove after cooling; Described homogenizing annealing process is that alloy cast ingot is placed sample carrier or silica tube, vacuumizes or feed argon gas or helium or nitrogen protection, is warming up to 700～1100 ℃ in heat treatment furnace, is incubated 2～10 hours, is chilled to room temperature with stove again; After described homogenizing annealing process, carry out ma process again; described ma process is to pack in 10: 1 to 60: 1 by ball material volume ratio can ventilate in the ball grinder; after vacuumizing, ball grinder charges into argon shield; the good seal ball grinder, ball milling is 5～100 hours on planetary high-energy ball mill.
4. the preparation method of a kind of nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy according to claim 3 is characterized in that, described MAGNESIUM METAL is that purity is 99.9% magnesium ingot metal, and described metallic nickel is that purity is 99.99% sheet nickel.
5. the preparation method of a kind of nanocrystalline heterogeneous mishmetal magnesium series hydrogen storage alloy according to claim 3 is characterized in that, described induction melting furnace crucible is plumbago crucible or corundum crucible.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100351413C (en) * | 2005-12-01 | 2007-11-28 | 广州有色金属研究院 | Preparation method of high capacity rare earth magnesium base hydrogen storage alloy |
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| JP4290023B2 (en) * | 2004-01-26 | 2009-07-01 | 三洋電機株式会社 | Hydrogen storage alloy for alkaline storage battery, method for producing the same, and alkaline storage battery |
| CN101985710B (en) * | 2010-09-03 | 2012-03-14 | 燕山大学 | Multiphase Mg-RE-Ni hydrogen storage alloy |
| CN103066251B (en) * | 2012-11-08 | 2014-07-02 | 华南理工大学 | A2B7 nickel hydrogen battery cathode material and preparation method thereof |
| CN103101880B (en) * | 2013-01-29 | 2014-11-12 | 广州有色金属研究院 | Lithium borohydride/rare earth magnesium base alloy composite hydrogen storage material and preparation method thereof |
| CN105349841B (en) * | 2014-08-19 | 2019-09-06 | 株式会社杰士汤浅国际 | Hydrogen-storage alloy and its manufacturing method |
| CN109202062B (en) * | 2018-10-30 | 2021-03-02 | 长沙新材料产业研究院有限公司 | Al-Mg-Li-Sc-Zr aluminum alloy powder for additive manufacturing and preparation method thereof |
| CN110629091B (en) * | 2019-11-12 | 2021-09-07 | 山东钢研中铝稀土科技有限公司 | High-capacity multi-phase hydrogen storage alloy for fuel cell and preparation method thereof |
| CN111682197B (en) * | 2020-06-02 | 2021-11-23 | 格林美股份有限公司 | Single crystal type anion and cation co-doped nickel-magnesium binary cobalt-free precursor, positive electrode material and preparation method |
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| CN100351413C (en) * | 2005-12-01 | 2007-11-28 | 广州有色金属研究院 | Preparation method of high capacity rare earth magnesium base hydrogen storage alloy |
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