CN101552337A - Superlattice hydrogen storage alloy and preparation method thereof - Google Patents

Superlattice hydrogen storage alloy and preparation method thereof Download PDF

Info

Publication number
CN101552337A
CN101552337A CNA2009100507335A CN200910050733A CN101552337A CN 101552337 A CN101552337 A CN 101552337A CN A2009100507335 A CNA2009100507335 A CN A2009100507335A CN 200910050733 A CN200910050733 A CN 200910050733A CN 101552337 A CN101552337 A CN 101552337A
Authority
CN
China
Prior art keywords
alloy
storage alloy
hydrogen storage
superlattice
annealing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2009100507335A
Other languages
Chinese (zh)
Inventor
汪保国
张灏
韩伟娜
金彩虹
何丹农
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Original Assignee
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai National Engineering Research Center for Nanotechnology Co Ltd filed Critical Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority to CNA2009100507335A priority Critical patent/CN101552337A/en
Publication of CN101552337A publication Critical patent/CN101552337A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

A superlattice hydrogen storage alloy and the preparation method thereof belong to the battery technology field. The ingredients and mass percentages in the alloy are: 99.9-99.95% of unit cell with molecular formula of RExMgyNikCoaAlbMncn and 0.05-0.1% of nano carbon material; in the RExMgy, x+y=1, 0.6<=x<=0.9; in the NikCoaAlbMncn, k+a+b+c=1, 0.1<=a<=0.2, 0.01<=b<=0.1, 0<=c<=0.1, 3.0<= n<=4.0. Compared with the prior arts, The invention can prepare superlattice hydrogen storage alloy having the following advantages: it has higher electrochemical capacity and longer circulation life; C200/Cmax% can reach more than 80% after adding carbon nano-tube, and can basically reach the actual application standard; and the hydrogen storage alloy has better reactivity and electrochemical catalysis property.

Description

Superlattice hydrogen storage alloy and preparation method thereof
Technical field
What the present invention relates to is the Alloy And Preparation Method in a kind of battery technology field, specifically is a kind of superlattice hydrogen storage alloy that is used for Ni-MH battery and preparation method thereof.
Background technology
Ni-MH battery is higher than nickel-cadmium cell with its capacity, is better than lithium ion battery with its security performance, price advantage, is better than advantages such as lead-acid battery with its clean environment firendly, thereby its range of application is promoted.Ni-MH battery is if stand on the invincible position in market competition, its performance index such as capacity, life-span must improve constantly.The key factor that determines its performance is the both positive and negative polarity active material, however its positive electrode Ni (OH) 2Capacity arrived 280mAh/g, near its theoretical capacity 289mAh/g, so if improve its capacity, or with novel positive electrode replacement Ni (OH) 2, or set about improving the performance of Ni-MH battery from negative material, from present technical merit, the former fails to realize therefore have only from the latter and set about.
The research of nickel-hydrogen battery negative pole material hydrogen-storage alloy is of long duration, from last century the eighties developed polytype hydrogen-storage alloy gradually, wherein be able to extensive use and the commercial AB of being 5The type hydrogen-storage alloy, the advantage of this alloy is a stable cycle performance, but its capacity is only between 300mAh/g～330mAh/g.When the lithium ion battery advantage is come on stage, the requirement that its lower capacity can not have been met competition.AB among the patent JP11264041 (A) of Toshiba Corp's application in 1999 3Type and AB 3.5Type RE-Ni series hydrogen storage alloy has higher capacity.Propositions such as T.Kohno in 2000 have the ternary series alloy that RE-Mg-Ni forms, and find La 0.7Mg 0.3Ni 2.8Co 0.5The discharge capacity of alloy can reach 410mAh/g, and this numerical value is far above commodity rare earth based AB 5The electrochemistry capacitance of hydrogen-storage alloy, cycle-index can reach 30 times.
The superlattice RE-Mg-Ni series hydrogen storage alloy that uses for nickel-hydrogen battery has just got more and more people's extensive concerning with its high power capacity, easily-activated advantage since coming out.The capacity of such alloy exceeds AB up to 410mAh/g 5Type hydrogen-storage alloy capacity nearly 20%.Why such alloy has high power capacity, and reason is to comprise the high AB of hydrogen storage amount in such alloy phase structural lattice unit 2Substructure unit can be regarded the principal phase lattice element of RE-Mg-Ni series hydrogen storage alloy as AB 5Substructure unit and AB 2The alternately laminated arrangement of substructure unit forms, so the RE-Mg-Ni series hydrogen storage alloy b referred to as superlattice hydrogen storage alloy.Such alloy has high electrochemistry capacitance by researcher's confirmation both at home and abroad, but the never obviously improvement of the shortcoming of its charge and discharge circulation life difference has limited the commerce of this alloy and used.The present invention develops a kind of high power capacity, long-life superlattice RE-Mg-Ni series hydrogen storage alloy that uses for nickel-hydrogen battery by optimizing methods such as alloying component and annealing heat treatment.
Find through retrieval prior art; number of patent application 200610088905.4; Granted publication CN100478466C; put down in writing a kind of " preparation method of RE-Mg-Ni-M series hydrogen storage alloy "; under the protection of inert gas; adopt the melting of cold crucible magnetic suspension stove to obtain RE-Mg-Ni-M series hydrogen storage alloy as cast condition product, get the heat treatment of as cast condition product and obtain the heat treatment state product.Comprise: get the raw materials ready (1); (2) once with Ni and M metal melting together; (3) once with the RE Metal Melting; (4) once with step (2) and (3) gained ingot casting melting together; (5) be the alloy liquation with step (4) gained ingot casting upset melting, add the magnesium intermediate alloy, cooling obtains RE-Mg-Ni-M series hydrogen storage alloy as cast condition product, and (6) as cast condition product obtains the heat treatment state product through heat treatment.Above-mentioned technology is with B side element and the melting respectively of A side element, close refining afterwards again, help element evenly to distribute like this, but the melting number of times is more, will certainly have influence on efficient, is unfavorable for industrialization, after adding the magnesium intermediate alloy in addition, do not have repeated capacity again, the even distributivity of element can not get guaranteeing, can have influence on the final performance of alloy like this.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of superlattice hydrogen storage alloy and preparation method thereof be provided, make the capacity of RE-Mg-Ni series hydrogen storage alloy and cyclical stability be improved significantly, thereby improved the chemical property of Ni-MH battery.
The present invention is achieved by the following technical solutions, and the component and the mass percent thereof that the present invention relates to superlattice hydrogen storage alloy are: 99.9～99.95% molecular formula is (RE xMg y) (Ni kCo aAl bMn c) nStructure cell and 0.05～0.10% nano-carbon material, described RE xMg yIn: x+y=1,0.6≤x≤0.9; Described (Ni kCo aAl bMn c) nMiddle k+a+b+c=1,0.1≤a≤0.2,0.01≤b≤0.1,0≤c≤0.1,3.0≤n≤4.0.
Described structure cell is the basic constituent element of the superlattice crystal that forms after melting;
Described nano-carbon material is meant: Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, the external diameter of described carbon nano-tube are 1nm-200nm;
Described RE is meant a kind of or its combination in pure lanthanum, praseodymium neodymium alloy or the pure praseodymium;
Described Co, Al and Mn are respectively cobalt, aluminium and the manganese of impurity content less than the simple substance of mass percent 1%.
The present invention relates to the preparation method of superlattice hydrogen storage alloy, may further comprise the steps:
The first step, with RE, Co, Al and Mn successively according to x: be placed in the crucible of high frequency suspension smelting furnace under the inert atmosphere protection after the molar ratio of a: b: c prepares, RE is placed the superiors, other raw materials are following, carry out the melting first time in the mode that progressively heats up, make alloy ingot just, wherein: 0.6≤x≤0.9,0.1≤a≤0.2,0.01≤b≤0.1,0≤c≤0.1;
Described RE is meant a kind of or its combination in pure lanthanum, praseodymium neodymium alloy or the pure praseodymium;
Described Co, Al and Mn are respectively cobalt, aluminium and the manganese of impurity content less than the simple substance of mass percent 1%.
The described mode that progressively heats up is meant: smelting temperature is 1500 ℃～2000 ℃, and smelting time is 1～3 minute, and the melting electric current is 20A～50A;
Described crucible is the copper crucible.
Second step, elder generation are placed on crucible bottom with alloy ingot taking-up just crucible with nickel magnesium alloy, place alloy ingot just then on nickel magnesium alloy, carry out the melting second time in the mode of progressively intensification again, make alloy cast ingot;
The mass ratio of nickel and magnesium is 4: 1 in the described nickel magnesium alloy;
The 3rd goes on foot, alloy cast ingot is taken out crucible and smashes bulk, puts into crucible again and carries out melting for the third time in the mode that progressively heats up, and makes hydrogen-storage alloy, and three meltings are to have guaranteed alloy cast ingot composition and structural homogenity and suppressed segregation.
The 4th the step, under inert gas shielding, place the tubular type vacuum annealing furnace to carry out annealing in process hydrogen-storage alloy;
Described annealing in process is meant: hydrogen-storage alloy is put into the quartz boat of vacuum annealing furnace and deliver to annealing burner hearth the flat-temperature zone; then with after being evacuated to 2Pa～500Pa after the burner hearth sealing; feed argon gas; be evacuated to 2Pa～500Pa again; three times so repeatedly, charge into the argon gas of 0.01MPa～1MPa at last, make the sample heat treatment of under argon shield, annealing; the heat treated temperature of annealing is 800 ℃～1000 ℃, and the time is 4～24 hours.
The 5th step, the hydrogen-storage alloy after will annealing carry out mechanical ball milling under inert gas shielding; and when mechanical milling process, add the carbon nano-tube of 0.05～0.10wt% of the weight of hydrogen-storage alloy; and the gained alloyed powder crossed 200 mesh sieves and 400 mesh sieves, obtain final superlattice hydrogen storage alloy.
Described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, and the external diameter of described carbon nano-tube is 1nm-200nm.
Described inert gas is an argon gas.
The superlattice hydrogen storage alloy that the present invention compared with prior art prepares has the following advantages: have higher electrochemistry capacitance and long cycle life, C200/Cmax (%) reaches more than 80% after adding carbon nano-tube, can reach the standard of practical application substantially; The reactivity of this hydrogen-storage alloy, electrochemical catalysis are better simultaneously.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1;
Fig. 2 is the volume test curve of embodiment 1;
Fig. 3 is the cycle performance curve comparison diagram of embodiment 1;
Fig. 4 is the XRD figure spectrum of embodiment 2;
Fig. 5 is the volume test curve of embodiment 2;
Fig. 6 is the cycle life curve comparison diagram of embodiment 2;
Fig. 7 is the XRD figure spectrum of embodiment 3;
Fig. 8 is the activation curve figure of embodiment 3;
Fig. 9 is the cycle life curve comparison diagram of embodiment 3.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The La of preparation 99.95% 0.5Pr 0.2Nd 0.1Mg 0.2(Ni 0.83Co 0.15Al 0.02) 3.5The superlattice hydrogen storage alloy of+0.05wt% carbon nano-tube
The first step, be placed in the copper crucible of high frequency suspension smelting furnace under the inert atmosphere protection after RE, Co and Al prepared according to 0.7: 0.525: 0.07 molar ratio successively, RE is placed the superiors, other raw materials are following, with smelting temperature is 1500 ℃, smelting time is 3 minutes, the melting electric current is that 20A carries out the melting first time, makes alloy ingot just;
Described RE is meant La, Pr and Nd, and its molar ratio was followed successively by 0.5: 0.2: 0.1;
Described Co, Al and Mn are respectively cobalt, aluminium and the manganese of impurity content less than the simple substance of mass percent 1%.
Second step, elder generation are placed on the copper crucible bottom with alloy ingot taking-up just copper crucible with nickel magnesium alloy, place the first ingot of alloy then on nickel magnesium alloy, it is 1500 ℃ with smelting temperature again, smelting time is 3 minutes, and the melting electric current is that 20A carries out the melting second time, makes alloy cast ingot;
The mass ratio of nickel and magnesium is 4: 1 in the described nickel magnesium alloy;
The 3rd goes on foot, alloy cast ingot is taken out crucible and smash block, putting into crucible again is 1500 ℃ with smelting temperature, and smelting time is 3 minutes, and the melting electric current is that 20A carries out melting for the third time, make hydrogen-storage alloy, three meltings are to have guaranteed alloy cast ingot composition and structural homogenity and suppressed segregation.
The 4th step, hydrogen-storage alloy put into the quartz boat of vacuum annealing furnace and deliver to the flat-temperature zone of annealing burner hearth, will be evacuated to 1 * 10 after the burner hearth sealing then 2Behind the Pa, feed argon gas, be evacuated to 1 * 10 again 2Pa, three times so repeatedly, charge into the argon gas of 0.5MPa at last, make the sample heat treatment of under argon shield, annealing, the heat treated temperature of annealing is 850 ℃, the time is 10 hours.
The 5th step, the hydrogen-storage alloy after will annealing carry out mechanical ball milling under argon shield; and when mechanical milling process, add the carbon nano-tube carbon nano-tube of 0.05wt% of the weight of hydrogen-storage alloy; and the gained alloyed powder crossed 200 mesh sieves and 400 mesh sieves, obtain final superlattice hydrogen storage alloy.
Described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, and the external diameter of described carbon nano-tube is 1nm-200nm.
Superlattice hydrogen storage alloy below 400 orders that prepare is done the phase structure test of alloy on X-ray diffractometer, test result as shown in Figure 1, the principal phase of alloy is La 2Ni 7, 200 orders are made simulated battery with the method for compressing tablet again carry out electrochemistry capacitance and life test on DC-5 to alloyed powder between 400 orders, and test result is as shown in Figure 2.Directly annealed alloy is done the life-span test as a comparative example in addition, the result shows the life-span conservation rate of embodiment, as shown in Figure 3, is 200 capability value C after the circulation 200Divided by maximum capacity C Max, C 200/ C MaxBring up to 83% by 75%.
Embodiment 2: preparation La 0.5Pr 0.2Nd 0.1Mg 0.2(Ni 0.81Co 0.15Al 0.04) 3.5The superlattice hydrogen storage alloy of+0.1wt% carbon nano-tube carbon nano-tube
The first step, be placed in the copper crucible of high frequency suspension smelting furnace under the inert atmosphere protection after RE, Co and Al prepared according to 0.7: 0.525: 0.14 molar ratio successively, RE is placed the superiors, other raw materials are following, with smelting temperature is 1750 ℃, smelting time is 2 minutes, the melting electric current is that 35A carries out the melting first time, makes alloy ingot just;
Described RE is meant La, Pr and Nd, and its molar ratio was followed successively by 0.5: 0.2: 0.1;
Described Co, Al and Mn are respectively cobalt, aluminium and the manganese of impurity content less than the simple substance of mass percent 1%.
Second step, elder generation are placed on the copper crucible bottom with alloy ingot taking-up just copper crucible with nickel magnesium alloy, place the first ingot of alloy then on nickel magnesium alloy, it is 1750 ℃ with smelting temperature again, smelting time is 2 minutes, and the melting electric current is that 35A carries out the melting second time, makes alloy cast ingot;
The mass ratio of nickel and magnesium is 4: 1 in the described nickel magnesium alloy;
The 3rd goes on foot, alloy cast ingot is taken out crucible and smash block, putting into crucible again is 1750 ℃ with smelting temperature, and smelting time is 2 minutes, and the melting electric current is that 35A carries out melting for the third time, make hydrogen-storage alloy, three meltings are to have guaranteed alloy cast ingot composition and structural homogenity and suppressed segregation.
The 4th step, hydrogen-storage alloy put into the quartz boat of vacuum annealing furnace and deliver to the flat-temperature zone of annealing burner hearth, will be evacuated to 1 * 10 after the burner hearth sealing then 2Behind the Pa, feed argon gas, be evacuated to 1 * 10 again 2Pa, three times so repeatedly, charge into the argon gas of 0.5MPa at last, make the sample heat treatment of under argon shield, annealing, the heat treated temperature of annealing is 900 ℃, the time is 6 hours.
The 5th step, the hydrogen-storage alloy after will annealing carry out mechanical ball milling under argon shield; and when mechanical milling process, add the carbon nano-tube carbon nano-tube of 0.1wt% of the weight of hydrogen-storage alloy; and the gained alloyed powder crossed 200 mesh sieves and 400 mesh sieves, obtain final superlattice hydrogen storage alloy.
Described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, and the external diameter of described carbon nano-tube is 1nm-200nm.
Superlattice hydrogen storage alloy below 400 orders that prepare is done the phase structure test of alloy on X-ray diffractometer, test result as shown in Figure 4, the principal phase of alloy is La 2Ni 7, 200 orders are made simulated battery with the method for compressing tablet again carry out electrochemistry capacitance (test result as shown in Figure 5) and life test on DC-5 to alloyed powder between 400 orders.Directly annealed alloy is done the life-span test as a comparative example in addition, the result shows life-span conservation rate (the capability value C after 200 circulations of embodiment 200Divided by maximum capacity C Max, C 200/ C MaxBring up to 84% by 76%, as shown in Figure 6).
Embodiment 3: preparation La 0.5Pr 0.2Nd 0.1Mg 0.2(Ni 0.81Co 0.15Al 0.02Mn 0.02) 3.5The superlattice hydrogen storage alloy of+0.05wt% carbon nano-tube
The first step, with RE, Co, Al and Mn successively according to 0.7: 0.525: 0.07: be placed in the copper crucible of high frequency suspension smelting furnace under the inert atmosphere protection after 0.07 molar ratio prepares, RE is placed the superiors, other raw materials are following, with smelting temperature is 2000 ℃, smelting time is 1 minute, the melting electric current is that 50A carries out the melting first time, makes alloy ingot just;
Described RE is meant La, Pr and Nd, and its molar ratio was followed successively by 0.5: 0.2: 0.1;
Described Co, Al and Mn are respectively cobalt, aluminium and the manganese of impurity content less than the simple substance of mass percent 1%.
Second step, elder generation are placed on the copper crucible bottom with alloy ingot taking-up just copper crucible with nickel magnesium alloy, place the first ingot of alloy then on nickel magnesium alloy, it is 2000 ℃ with smelting temperature again, smelting time is 1 minute, and the melting electric current is that 50A carries out the melting second time, makes alloy cast ingot;
The mass ratio of nickel and magnesium is 4: 1 in the described nickel magnesium alloy;
The 3rd goes on foot, alloy cast ingot is taken out crucible and smash block, putting into crucible again is 2000 ℃ with smelting temperature, and smelting time is 1 minute, and the melting electric current is that 50A carries out melting for the third time, make hydrogen-storage alloy, three meltings are to have guaranteed alloy cast ingot composition and structural homogenity and suppressed segregation.
The 4th step, hydrogen-storage alloy put into the quartz boat of vacuum annealing furnace and deliver to the flat-temperature zone of annealing burner hearth, will be evacuated to 1 * 10 after the burner hearth sealing then 2Behind the Pa, feed argon gas, be evacuated to 1 * 10 again 2Pa, three times so repeatedly, charge into the argon gas of 0.5MPa at last, make the sample heat treatment of under argon shield, annealing, the heat treated temperature of annealing is 950 ℃, the time is 6 hours.
The 5th step, the hydrogen-storage alloy after will annealing carry out mechanical ball milling under argon shield; and when mechanical milling process, add the carbon nano-tube carbon nano-tube of 0.05wt% of the weight of hydrogen-storage alloy; and the gained alloyed powder crossed 200 mesh sieves and 400 mesh sieves, obtain final superlattice hydrogen storage alloy.
Described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes, and the external diameter of described carbon nano-tube is 1nm-200nm.
Superlattice hydrogen storage alloy below 400 orders that prepare is done the phase structure test of alloy on X-ray diffractometer, test result as shown in Figure 7, the principal phase of alloy is La 2Ni 7, 200 orders are made simulated battery with the method for compressing tablet again carry out electrochemistry capacitance (test result as shown in Figure 8) and life test on DC-5 to alloyed powder between 400 orders.Directly annealed alloy is done the life-span test as a comparative example in addition, the result shows life-span conservation rate (the capability value C after 200 circulations of embodiment 200Divided by maximum capacity C Max, C 200/ C MaxBring up to 83% by 74%, as shown in Figure 9).

Claims (10)

1, a kind of superlattice hydrogen storage alloy is characterized in that, the component of this alloy and mass percent thereof are: 99.9～99.95% molecular formula is (RE xMg y) (Ni kCo dAl bMn c) nStructure cell and 0.05～0.10% nano-carbon material,
Described RE xMg vIn: x+y=1,0.6≤x≤0.9;
Described (Ni kCo aAl bMn c) nMiddle k+a+b+c=1,0.1≤a≤0.2,0.01≤b≤0.1,0≤c≤0.1,3.0≤n≤4.0.
2, superlattice hydrogen storage alloy according to claim 1 is characterized in that, described structure cell is the basic constituent element of the superlattice crystal that forms after melting.
3, superlattice hydrogen storage alloy according to claim 1 is characterized in that, described RE is meant a kind of or its combination in pure lanthanum, praseodymium neodymium alloy or the pure praseodymium.
4, superlattice hydrogen storage alloy according to claim 1 is characterized in that, described nano-carbon material is meant that external diameter is Single Walled Carbon Nanotube or the multi-walled carbon nano-tubes of 1nm-200nm.
5, the preparation method of superlattice hydrogen storage alloy according to claim 1 is characterized in that, may further comprise the steps:
The first step, with RE, Co, Al and Mn successively according to x: be placed in the crucible of high frequency suspension smelting furnace under the inert atmosphere protection after the molar ratio of a: b: c prepares, RE is placed the superiors, other raw materials are following, carry out the melting first time in the mode that progressively heats up, make alloy ingot just, wherein: 0.6≤x≤0.9,0.1≤a≤0.2,0.01≤b≤0.1,0≤c≤0.1;
Second step, elder generation take out crucible with alloy ren ingot, and nickel magnesium alloy is placed on crucible bottom, place alloy ren ingot then on nickel magnesium alloy, carry out the melting second time in the mode that progressively heats up again, make alloy cast ingot;
The 3rd goes on foot, alloy cast ingot is taken out crucible and smashes bulk, puts into crucible again and carries out melting for the third time in the mode that progressively heats up, and makes hydrogen-storage alloy, and three meltings are to have guaranteed alloy cast ingot composition and structural homogenity and suppressed segregation;
The 4th the step, under inert gas shielding, place the tubular type vacuum annealing furnace to carry out annealing in process hydrogen-storage alloy;
The 5th step, the hydrogen-storage alloy after will annealing carry out mechanical ball milling under inert gas shielding; and when mechanical milling process, add 0.05～0.10% carbon nano-tube of the weight of hydrogen-storage alloy; and the gained alloyed powder crossed 200 mesh sieves and 400 mesh sieves, obtain final superlattice hydrogen storage alloy.
6, the preparation method of superlattice hydrogen storage alloy according to claim 5 is characterized in that, described RE is meant a kind of or its combination in pure lanthanum, praseodymium neodymium alloy or the pure praseodymium.
7, the preparation method of superlattice hydrogen storage alloy according to claim 5 is characterized in that, described Co, Al and Mn are respectively cobalt, aluminium and the manganese of impurity content less than the simple substance of mass percent 1%.
8, the preparation method of superlattice hydrogen storage alloy according to claim 5 is characterized in that, the described mode that progressively heats up is meant: smelting temperature is 1500 ℃～2000 ℃, and smelting time is 1～3 minute, and the melting electric current is 20A～50A.
9, the preparation method of superlattice hydrogen storage alloy according to claim 5 is characterized in that, the mass ratio of nickel and magnesium is 4: 1 in the described nickel magnesium alloy.
10, the preparation method of superlattice hydrogen storage alloy according to claim 5; it is characterized in that; described annealing in process is meant: hydrogen-storage alloy is put into the quartz boat of vacuum annealing furnace and deliver to annealing burner hearth the flat-temperature zone; then with after being evacuated to 2Pa～500Pa after the burner hearth sealing; feed argon gas; be evacuated to 2Pa～500Pa again; three times so repeatedly; charge into the argon gas of 0.01MPa～1MPa at last; make the sample heat treatment of under argon shield, annealing; the heat treated temperature of annealing is 800 ℃～1000 ℃, and the time is 4～24 hours.
CNA2009100507335A 2009-05-07 2009-05-07 Superlattice hydrogen storage alloy and preparation method thereof Pending CN101552337A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2009100507335A CN101552337A (en) 2009-05-07 2009-05-07 Superlattice hydrogen storage alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2009100507335A CN101552337A (en) 2009-05-07 2009-05-07 Superlattice hydrogen storage alloy and preparation method thereof

Publications (1)

Publication Number Publication Date
CN101552337A true CN101552337A (en) 2009-10-07

Family

ID=41156410

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2009100507335A Pending CN101552337A (en) 2009-05-07 2009-05-07 Superlattice hydrogen storage alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101552337A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899591A (en) * 2010-07-06 2010-12-01 上海纳米技术及应用国家工程研究中心有限公司 Superlattice hydrogen storage alloy material for nickel hydrogen battery and preparation method thereof
CN102820457A (en) * 2012-08-30 2012-12-12 上海锦众信息科技有限公司 Preparation method of negative pole of power battery
CN102832380A (en) * 2012-08-29 2012-12-19 上海锦众信息科技有限公司 Preparation method of cathode hydrogen storage material of power battery
CN102891298A (en) * 2012-08-14 2013-01-23 青岛大学 Surface modification method for Mg-Ni-Nd system hydrogen storage electrode alloy
CN104404280A (en) * 2014-12-01 2015-03-11 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for superlattice RE-Mg-Ni hydrogen storage alloy
CN105489907A (en) * 2015-11-30 2016-04-13 北京化工大学 Carbon-nanotube-loaded platinum-iron superlattice alloy nanoparticles and preparation method therefor
CN106711423A (en) * 2017-01-11 2017-05-24 江苏科技大学 High-capacity nickel-metal hydroxide battery negative electrode material and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899591A (en) * 2010-07-06 2010-12-01 上海纳米技术及应用国家工程研究中心有限公司 Superlattice hydrogen storage alloy material for nickel hydrogen battery and preparation method thereof
CN102891298A (en) * 2012-08-14 2013-01-23 青岛大学 Surface modification method for Mg-Ni-Nd system hydrogen storage electrode alloy
CN102891298B (en) * 2012-08-14 2015-06-03 青岛大学 Surface modification method for Mg-Ni-Nd system hydrogen storage electrode alloy
CN102832380A (en) * 2012-08-29 2012-12-19 上海锦众信息科技有限公司 Preparation method of cathode hydrogen storage material of power battery
CN102820457A (en) * 2012-08-30 2012-12-12 上海锦众信息科技有限公司 Preparation method of negative pole of power battery
CN104404280A (en) * 2014-12-01 2015-03-11 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for superlattice RE-Mg-Ni hydrogen storage alloy
CN105489907A (en) * 2015-11-30 2016-04-13 北京化工大学 Carbon-nanotube-loaded platinum-iron superlattice alloy nanoparticles and preparation method therefor
CN105489907B (en) * 2015-11-30 2018-02-13 北京化工大学 A kind of carbon nanotube loaded platinum iron superlattices alloy nano particle and preparation method thereof
CN106711423A (en) * 2017-01-11 2017-05-24 江苏科技大学 High-capacity nickel-metal hydroxide battery negative electrode material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN101353733B (en) Preparation of La-Mg-Ni system hydrogen occluding alloy
CN101552337A (en) Superlattice hydrogen storage alloy and preparation method thereof
CN102104146B (en) Cobalt-free AB3.5-type hydrogen storage alloy anode material used for nickel-hydrogen battery and preparation method thereof
CN101626076A (en) High-capacity long-life low-cost rare earth and magnesium-based hydrogen storage alloy
CN106654240A (en) Ce2Ni7-type single-phase superlattice hydrogen storage alloy electrode material and preparation method thereof
CN104513925A (en) Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy
CN101613818B (en) Low cost hydrogen storage alloy, preparation method and application thereof
CN101899591B (en) Superlattice hydrogen storage alloy material for nickel hydrogen battery and preparation method thereof
CN110257649A (en) A kind of High-performance Single-Phase La0.6R0.15Mg0.25Ni3.5Electrode metal and preparation method thereof
CN104404280A (en) Preparation method for superlattice RE-Mg-Ni hydrogen storage alloy
CN102205412A (en) Fluoridation modifying method for MLNi3.5Co0.0Mn0.4Al0.5 hydrogen storage alloy
CN102888545B (en) A kind of preparation method of Mg base hydrogen bearing alloy
CN102383011B (en) Rare earth magnesium-based hydrogen storage alloy with low cost and long life and applications thereof
CN100467640C (en) AB3.5 type hydrogen-storing negative pole material and its prepn process and use
CN107075617A (en) A kind of lanthanon hydrogen storage alloy and application thereof
CN110492086B (en) Preparation method of hydrogen storage alloy composite material
CN108172817A (en) A kind of single-phase Gd2Co7Type rare earth magnesium nickel system hydrogen storage alloy, preparation method and applications
CN102286678A (en) Non-stoichiometric-ratio LaNi5 base cobalt-free hydrogen storage alloy and preparation method thereof
CN104294087B (en) The preparation method of superlattice hydrogen storage alloy
EP2554694A1 (en) Hydrogen storage alloy, hydrogen storage alloy electrode, and secondary battery
CN114107740B (en) Low-cost high-performance rare earth hydrogen storage alloy and preparation method thereof
CN101295784A (en) Non-cobalt AB5 hydrogen storage alloy
CN105463256A (en) Hydrogen storage alloy for nickel-metal hydride battery and manufacturing method of hydrogen storage alloy
CN1234891C (en) New-type of hydrogen-storing alloy and its fast solidifying prepn process
Ying et al. Effect of heat-treatment process on properties of rare earth Mg-based system hydrogen storage alloys with AB3-type

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20091007