CN102888545B - A kind of preparation method of Mg base hydrogen bearing alloy - Google Patents
A kind of preparation method of Mg base hydrogen bearing alloy Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 title claims abstract description 16
- 239000001996 bearing alloy Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 53
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 32
- 230000008018 melting Effects 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 229910052786 argon Inorganic materials 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 5
- 238000003701 mechanical milling Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000003723 Smelting Methods 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 3
- 229910018095 Ni-MH Inorganic materials 0.000 abstract description 6
- 229910018477 Ni—MH Inorganic materials 0.000 abstract description 6
- 239000000725 suspension Substances 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019083 Mg-Ni Inorganic materials 0.000 description 1
- 229910017961 MgNi Inorganic materials 0.000 description 1
- 229910019403 Mg—Ni Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses the preparation method of a kind of Mg base hydrogen bearing alloy, comprise the steps: to prepare (Sm0.3Mg0.7)(Ni0.8Co0.05Al0.1Cu0.05)3Structure cell and carbon nano-tube material；Sm, Co, Al and Cu are sequentially placed into vacuum magnetic suspension stove melting under argon shield, evacuation before melting, carry out melting for the first time, make alloy just ingot；First alloy just ingot is taken out crucible, nickel magnesium dust is placed on crucible bottom, on nickel magnesium alloy, then place alloy just ingot, carry out second time melting, make alloy cast ingot；Alloy cast ingot taken out crucible and is broken into bulk, carrying out third time melting, make hydrogen-storage alloy；Heat treatment；After hydrogen-storage alloy coarse crushing after annealing, applying argon gas protection is ground, and adds CNT in mechanical milling process.Magnesium base hydrogen-storing alloy prepared by the present invention, has good cyclical stability and high-quality specific capacity, and when Ni-MH battery, capacity is high, and good cycling stability, service life is long.
Description
Technical field
The present invention relates to the preparation method of a kind of hydrogen storage material, particularly relate to a kind of Mg base hydrogen bearing alloy and preparation side thereof
Method.
Background technology
Ni-MH battery because its specific energy is high, free from environmental pollution, memory-less effect, have extended cycle life and have good resistance to
Super-charge super-discharge electrical characteristics, are widely used.Ni-MH battery is higher than nickel-cadmium cell with its capacity, with its security performance, valency
Lattice advantage is better than lithium ion battery, is better than the advantages such as lead-acid battery with its clean environment firendly, so that its range of application is promoted.
If Ni-MH battery is established oneself in an unassailable position in the market competition, its performance indications such as capacity, life-span have to constantly carry
High.The key factor determining its performance is both positive and negative polarity active material, but its positive electrode Ni (OH)2Capacity have arrived at
280mAh/g, close to its theoretical capacity 289mAh/g, if so improving its capacity, or replaces Ni with novel positive electrode
(OH)2, or set about improving the performance of Ni-MH battery from negative material, from the point of view of current technology level, the former fails
Realize, the most only set about from the latter.
In recent years, in order to be developed for the high-performance hydrogen bearing alloy of MH/Ni battery cathode active material, to magnesium base alloy
Research gives the attention of height.The theoretical electrochemistry capacity of magnesium-base hydrogen storage material is high, low price, most promises to be MH/
Ni battery a new generation high performance-price ratio hydrogen storage negative material.Chemical activity due to magnesium so that electrode material is at alkaline electrolyte
Middle formation Mg (OH)2Passivation layer, hinders and inhales/put hydrogen process, therefore capacity attenuation；Additionally alloying element in the electrolytic solution molten
Solving, electrode efflorescence during inhaling/put hydrogen is also the reason causing capacity attenuation.Such alloy has high electrochemistry capacitance
Confirmed by domestic and international researcher, but the shortcoming of its charge and discharge circulation life difference is never obviously improved, and limits this
The business application of alloy.
Summary of the invention
The present invention, by methods such as optimized alloy composition and annealing heat treatments, develops a kind of high power capacity, long-life nickel
Hydrogen battery superlattices RE-Mg-Ni series hydrogen storage alloy.
It is an object of the invention to provide the preparation method of a kind of Mg base hydrogen bearing alloy, use Mg-base hydrogen-bearing prepared by the method
The Ni-MH battery of alloy has the features such as cyclicity is good, capacity is high, length in service life.
To achieve these goals, the preparation method of a kind of Mg base hydrogen bearing alloy that the present invention provides comprises the steps:
Step 1, prepares raw material
The raw material of Mg base hydrogen bearing alloy is prepared: the molecular formula of 99-99.5% is by following weight proportion and molecular formula
(Sm0.3Mg0.7)(Ni0.8Co0.05Al0.1Cu0.05)3Structure cell and the carbon nano-tube material of 0.5-1% that caliber is 10-20nm,
During preparing raw material, electrolysis gained rare-earth Sm metal dust is melted under lightweight fused salt chlorimation sodium and lithium fluoride cover
Refining, allows be mingled with entering fused salt with oxide etc., makes Sm metal be purified；
Step 2, melting once ingot
It is placed under argon shield true after Sm, Co, Al and Cu are prepared according to the molar ratio of above-mentioned molecular formula successively
Empty magnetic suspension stove melting, evacuation before melting, Sm is placed in the superiors, other raw materials under, carry out in the way of progressively heating up
Melting for the first time, makes alloy just ingot, and wherein smelting temperature is 1600 DEG C-1800 DEG C, and smelting time is 5-10 minute；
Step 3, secondary smelting ingot
First alloy just ingot is taken out crucible, after being configured by the molar ratio of above-mentioned molecular formula by nickel magnesium dust, be placed on crucible
Bottom, then places alloy just ingot on nickel magnesium alloy, then carries out second time melting in the way of progressively heating up, make alloy cast
Ingot；
Step 4, three melting ingots
Alloy cast ingot taken out crucible and is broken into bulk, placing into and crucible carries out in the way of progressively heating up third time
Melting, makes hydrogen-storage alloy；
Step 5, heat treatment
Hydrogen-storage alloy is put into flat-temperature zone in vacuum annealing furnace, after being evacuated to 10Pa-50Pa after then being sealed by burner hearth, is passed through
Argon, then it is evacuated to 10Pa-50Pa, the most repeatedly for three times, finally it is filled with the argon of 0.05MPa-0.1MPa, makes sample protect at argon
Protecting down and carry out heat treatment of annealing, the temperature of annealing heat treatment is 900 DEG C-950 DEG C, and the time is 10-20 hour；
Step 6, ball milling
After the hydrogen-storage alloy coarse crushing after above-mentioned fire, grind under argon shield, and add above-mentioned in mechanical milling process
CNT, obtain final magnesium base hydrogen-storing alloy.
Wherein, in step 1, the elemental powders material that Mg, Ni, Co, Al and Cu all can use purity to be more than 99.9%.
Wherein, in step 6, after ball milling, it is also possible to gained alloyed powder is crossed 300 mesh sieves, obtain final magnesium base hydrogen-storing and close
Gold.
The present invention also provides for Mg base hydrogen bearing alloy prepared by a kind of above-mentioned any means.
Magnesium base hydrogen-storing alloy prepared by the present invention, has good cyclical stability and high-quality specific capacity, for ni-mh
During battery, capacity is high, and good cycling stability, service life is long.
Detailed description of the invention
Embodiment one
Prepare raw material
The raw material of Mg base hydrogen bearing alloy is prepared: the molecular formula of 99% purity is by following weight proportion and molecular formula
(Sm0.3Mg0.7)(Ni0.8Co0.05Al0.1Cu0.05)3Structure cell and caliber is 10nm 1% carbon nano-tube material, preparing raw material
During electrolysis gained rare-earth Sm metal dust is carried out melting under lightweight fused salt chlorimation sodium and lithium fluoride cover, allow and be mingled with
Enter fused salt with oxide etc., make Sm metal be purified, the list that Mg, Ni, Co, Al and Cu all use purity to be more than 99.9%
Matter dusty material.
Melting ingot
It is placed under argon shield true after Sm, Co, Al and Cu are prepared according to the molar ratio of above-mentioned molecular formula successively
Empty magnetic suspension stove melting, evacuation before melting, Sm is placed in the superiors, other raw materials under, carry out in the way of progressively heating up
Melting for the first time, makes alloy just ingot, and wherein smelting temperature is 1600 DEG C, and smelting time is 5 minutes.
Alloy just ingot is taken out crucible, is placed at the bottom of crucible after nickel magnesium dust is configured by the molar ratio of above-mentioned molecular formula
Portion, then places alloy just ingot on nickel magnesium alloy, then carries out second time melting in the way of progressively heating up, make alloy cast
Ingot.
Alloy cast ingot taken out crucible and is broken into bulk, placing into and crucible carries out in the way of progressively heating up third time
Melting, makes hydrogen-storage alloy.
Heat treatment
Hydrogen-storage alloy is put into flat-temperature zone in vacuum annealing furnace, after being evacuated to 10Pa after then being sealed by burner hearth, is passed through argon,
It is evacuated to 10Pa again, the most repeatedly for three times, is finally filled with the argon of 0.05MPa, make sample carry out annealing at heat under argon shield
Reason, the temperature of annealing heat treatment is 900 DEG C, and the time is 10 hours.
Ball milling
After the hydrogen-storage alloy coarse crushing after above-mentioned fire, in vacuum sphere grinding machine, applying argon gas protection is ground, and in ball milling mistake
Add above-mentioned CNT during journey, and gained alloyed powder is crossed 300 mesh sieves, obtain final magnesium base hydrogen-storing alloy.
Embodiment two
Prepare raw material
The raw material of Mg base hydrogen bearing alloy is prepared: the molecular formula of 99.5% purity is by following weight proportion and molecular formula
(Sm0.3Mg0.7)(Ni0.8Co0.05Al0.1Cu0.05)3Structure cell and caliber is 20nm 0.5% carbon nano-tube material, prepare former
During material, electrolysis gained rare-earth Sm metal dust is carried out melting under lightweight fused salt chlorimation sodium and lithium fluoride cover, allow folder
Miscellaneous and oxide etc. enters fused salt, makes Sm metal be purified, and Mg, Ni, Co, Al and Cu all use purity to be more than 99.9%
Elemental powders material.
Melting ingot
It is placed under argon shield true after Sm, Co, Al and Cu are prepared according to the molar ratio of above-mentioned molecular formula successively
Empty magnetic suspension stove melting, evacuation before melting, Sm is placed in the superiors, other raw materials under, carry out in the way of progressively heating up
Melting for the first time, makes alloy just ingot, and wherein smelting temperature is 1800 DEG C, and smelting time is 10 minutes.
Alloy just ingot is taken out crucible, is placed at the bottom of crucible after nickel magnesium dust is configured by the molar ratio of above-mentioned molecular formula
Portion, then places alloy just ingot on nickel magnesium alloy, then carries out second time melting in the way of progressively heating up, make alloy cast
Ingot.
Alloy cast ingot taken out crucible and is broken into bulk, placing into and crucible carries out in the way of progressively heating up third time
Melting, makes hydrogen-storage alloy.
Heat treatment
Hydrogen-storage alloy is put into flat-temperature zone in vacuum annealing furnace, after being evacuated to 50Pa after then being sealed by burner hearth, is passed through argon,
It is evacuated to 50Pa again, the most repeatedly for three times, is finally filled with the argon of 0.1MPa, make sample carry out annealing at heat under argon shield
Reason, the temperature of annealing heat treatment is 950 DEG C, and the time is 20 hours.
Ball milling
After the hydrogen-storage alloy coarse crushing after above-mentioned fire, in vacuum sphere grinding machine, applying argon gas protection is ground, and in ball milling mistake
Add above-mentioned CNT during journey, and gained alloyed powder is crossed 300 mesh sieves, obtain final magnesium base hydrogen-storing alloy.
Comparative example
According to MgNi alloy 1: 1 stoichiometric proportion, by 1.28 grams of analytical pure Mg powder (purity 99.5%), analytical pure Ni
3.07 grams of powder (purity 99.5%), 0.08 gram of amorphous B powder, 0.13 gram of fluorographite (CFn) powder load stainless steel ball-milling
Tank, ratio of grinding media to material is 30: 1, is filled with protection gas Ar gas after evacuation.Ball milling operation is carried out in QM-1SP planetary ball mill, ball
Mill speed is 450 revs/min, continuous ball milling discharging in 40 hours, obtains Mg base hydrogen bearing alloy powder.
The embodiment one, two of synthesis and the sample of comparative example are cold-pressed under 3.5MPa pressure thin slice as research electricity
Pole, auxiliary electrode is sintered type hydroxide nickel electrode, and reference electrode is hydrargyrum/mercury oxide (Hg/HgO) electrode, and electrolyte is 7M/
L KOH solution, barrier film is polypropylene mat.Electrochemical property test equipment is domestic DC-5 type cell tester.This is real after tested
Execute example one with two material compared with the material of comparative example, first discharge specific capacity improves more than 40-50%, cycle life
Improve more than 1.5 times.
Being described in detail the specific embodiment of the present invention above, but it is intended only as example, the present invention does not limit
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and
Substitute the most all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Amendment, all should contain within the scope of the invention.
Claims (4)
1. the preparation method of a Mg base hydrogen bearing alloy, it is characterised in that comprise the steps:
Step 1, prepares raw material
The raw material of Mg base hydrogen bearing alloy is prepared: the molecular formula of 99-99.5% is by following weight proportion and molecular formula
(Sm0.3Mg0.7)(Ni0.8Co0.05Al0.1Cu0.05)3Structure cell and the carbon nano-tube material of 0.5-1% that caliber is 10-20nm,
During preparing raw material, electrolysis gained rare-earth Sm metal dust is melted under lightweight fused salt chlorimation sodium and lithium fluoride cover
Refining, allows be mingled with entering fused salt with oxide, makes Sm metal be purified；
Step 2, melting once ingot
Vacuum Magnetic under argon shield it is placed according to the molar ratio of above-mentioned molecular formula after Sm, Co, Al and Cu being prepared successively
Shower furnace melting, evacuation before melting, Sm is placed in the superiors, other raw materials under, in the way of progressively heating up, carry out first
Secondary melting, makes alloy just ingot, and wherein smelting temperature is 1600 DEG C-1800 DEG C, and smelting time is 5-10 minute；
Step 3, secondary smelting ingot
First alloy just ingot is taken out crucible, be placed at the bottom of crucible after nickel magnesium dust is configured by the molar ratio of above-mentioned molecular formula
Portion, then places alloy just ingot on nickel magnesium alloy, then carries out second time melting in the way of progressively heating up, make alloy cast
Ingot；
Step 4, three melting ingots
Alloy cast ingot taken out crucible and is broken into bulk, placing into and crucible is carried out in the way of progressively heating up melt for the third time
Refining, makes hydrogen-storage alloy；
Step 5, heat treatment
Hydrogen-storage alloy is put into flat-temperature zone in vacuum annealing furnace, after being evacuated to 10Pa-50Pa after then being sealed by burner hearth, is passed through argon
Gas, then it is evacuated to 10Pa-50Pa, the most repeatedly for three times, finally it is filled with the argon of 0.05MPa-0.1MPa, makes sample in argon shield
Under carry out anneal heat treatment, annealing heat treatment temperature be 900 DEG C-950 DEG C, the time is 10-20 hour；
Step 6, ball milling
After the hydrogen-storage alloy coarse crushing after above-mentioned annealing, grind under argon shield, and add above-mentioned in mechanical milling process
CNT, obtains final magnesium base hydrogen-storing alloy.
Method the most according to claim 1, it is characterised in that in step 1, Mg, Ni, Co, Al and Cu all use the purity to be
The elemental powders material of more than 99.9%.
Method the most according to claim 1, it is characterised in that in step 6, after ball milling, crosses 300 mesh by gained alloyed powder
Sieve, obtains final magnesium base hydrogen-storing alloy.
4. the Mg base hydrogen bearing alloy that prepared by a method as claimed in claim 1.
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| CN105039815B (en) * | 2015-08-20 | 2017-03-22 | 广西大学 | Preparation method of Mg-Li solid solution hydrogen storage material |
| CN105514399A (en) * | 2015-12-21 | 2016-04-20 | 宁波高新区锦众信息科技有限公司 | Magnesium-based hydrogen storage alloy for Ni-MH secondary batteries and preparation method of magnesium-based hydrogen storage alloy |
| CN108796323B (en) * | 2018-06-29 | 2020-12-01 | 延海港 | MgLaNi-based environment-friendly material |
| CN108715962B (en) * | 2018-07-04 | 2020-06-23 | 南通志乐新材料有限公司 | Rare earth doped Mg-based hydrogen storage alloy |
| CN118073551B (en) * | 2024-04-17 | 2024-06-21 | 内蒙古科技大学 | Preparation method of anti-corrosion nanoscale Ce-Mg-Ni negative electrode composite material for battery |
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|---|---|---|---|---|
| CN101353733A (en) * | 2008-08-07 | 2009-01-28 | 上海交通大学 | Preparation method of La-Mg-Ni series hydrogen storage alloy |
| CN101599545A (en) * | 2009-07-29 | 2009-12-09 | 钢铁研究总院 | Hydrogen storage alloy for Re-Mg-Ni type metal hydride secondary battery and preparation method thereof |
| CN102191416A (en) * | 2011-04-26 | 2011-09-21 | 燕山大学 | Magnesium-based hydrogen storage alloy composite material and preparation method thereof |
| CN102337438A (en) * | 2011-09-26 | 2012-02-01 | 华南理工大学 | Magnesium-based hydrogen storage alloy with long period structure and preparation method thereof |
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| US6491866B1 (en) * | 1999-11-06 | 2002-12-10 | Energy Conversion Devices, Inc. | High storage capacity, fast kinetics, long cycle-life, hydrogen storage alloys |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353733A (en) * | 2008-08-07 | 2009-01-28 | 上海交通大学 | Preparation method of La-Mg-Ni series hydrogen storage alloy |
| CN101599545A (en) * | 2009-07-29 | 2009-12-09 | 钢铁研究总院 | Hydrogen storage alloy for Re-Mg-Ni type metal hydride secondary battery and preparation method thereof |
| CN102191416A (en) * | 2011-04-26 | 2011-09-21 | 燕山大学 | Magnesium-based hydrogen storage alloy composite material and preparation method thereof |
| CN102337438A (en) * | 2011-09-26 | 2012-02-01 | 华南理工大学 | Magnesium-based hydrogen storage alloy with long period structure and preparation method thereof |
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