CN104404280A - Preparation method for superlattice RE-Mg-Ni hydrogen storage alloy - Google Patents
Preparation method for superlattice RE-Mg-Ni hydrogen storage alloy Download PDFInfo
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Abstract
The invention relates to a preparation method for a superlattice RE-Mg-Ni hydrogen storage alloy. The molecular formula of the hydrogen storage alloy is (RExMgy)(NikCoaAlbMnc)n+zwt% graphene, wherein x+y=1; x is more than or equal to 0.6 and less than or equal to 0.7; n is more than or equal to 3.0 and less than or equal to 4.0; k+a+b+c=1; a is more than or equal to 0.1 and less than or equal to 0.2; b is more than or equal to 0.01 and less than or equal to 0.1; c is more than or equal to 0 and less than or equal to 0.1; z is less than or equal to 8; RE is at least one rare earth element or a mixture of multiple rare earth elements. The preparation method comprises the following steps of melting raw materials under the protection of inert gas in a high-frequency suspension melting furnace, then annealing an obtained alloy ingot to obtain a required alloy ingot under the protection of inert gas in a vacuum annealing furnace, crushing the alloy ingot, adding graphene, and performing mechanical ball milling. The prepared alloy is high in activation property, higher in electrochemical capacity and longer in cycle life.
Description
Technical field
The present invention relates to a kind of preparation method of superlattice hydrogen storage alloy, belong to battery electrode material field.
Background technology
Long-standing to the research of nickel-hydrogen battery negative pole material hydrogen-storage alloy, from last century the eighties, development plays polytype hydrogen-storage alloy gradually, be wherein able to widespread use and commercial be AB
5type hydrogen-storage alloy, the advantage of this alloy is stable cycle performance, but its capacity is only between 300 mAh/g ~ 330 mAh/g.When lithium ion battery advantage is come on stage, the requirement that its lower capacity can not have been met competition.AB in 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.T.Kohno in 2000 etc. propose the ternary series alloy with RE-Mg-Ni composition, find La
0.7mg
0.3ni
2.8co
0.5the loading 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 just has got more and more people's extensive concerning with its heavy body, easily-activated advantage since appearance.The capacity of such alloy, up to 410mAh/g, exceeds AB
5type hydrogen-storage alloy capacity nearly 20%.Why such alloy has heavy body, and reason comprises the high AB of hydrogen storage amount in such phase structure of alloy lattice element
2substructure unit, can regard the principal phase lattice element of RE-Mg-Ni series hydrogen storage alloy as AB as
5substructure unit and AB
2the alternately laminated arrangement of substructure unit forms, and therefore RE-Mg-Ni series hydrogen storage alloy is referred to as superlattice hydrogen storage alloy.Such alloy has high electrochemistry capacitance and is confirmed by domestic and international investigator, but the shortcoming of its charge and discharge circulation life difference is never obviously improved, and limits the commercial applications of this alloy.The present invention by methods such as optimized alloy composition and annealing thermal treatments, and carries out modification by adding Graphene to material, develops a kind of heavy body, long-life superlattice RE-Mg-Ni series hydrogen storage alloy that uses for nickel-hydrogen battery.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of superlattice RE-Mg-Ni series hydrogen storage alloy.
A preparation method for superlattice RE-Mg-Ni series hydrogen storage alloy, is characterized in that, comprise the following steps:
The first step, each composition of design superlattice RE-Mg-Ni series hydrogen storage alloy meets the following conditions: (RE
xmg
y) (Ni
kco
aal
bmn
c)
n+ zwt% Graphene, wherein: x+y=1; 0.6≤x≤0.7; 3.0≤n≤4.0; K+a+b+c=1; 0.1≤a≤0.2; 0.01≤b≤0.1; 0≤c≤0.1; Z≤8; RE is the mixing of at least one or several rare earth element;
Second step, puts into the copper crucible melting of high frequency suspension smelting furnace under protection of inert gas, melt back three times by the alloy that the above-mentioned the first step designs;
3rd step, heat-treats the alloy of second step gained, and condition is vacuum tightness 1 × 10
2pa, is then filled with argon gas, is warming up to 800 DEG C-1000 DEG C, is incubated and obtains with A for 4 hours-24 hours
2b
7for the alloy of principal phase;
4th step, by the alloy of the 3rd step gained mechanical ball milling under protection of inert gas, adds Graphene during ball milling, obtains final superlattice type hydrogen-storage alloy.
Melting described in second step is carried out under inert atmosphere protection, and process divides three steps to complete:
First all raw materials except nickel magnesium alloy are put into crucible in the lump, nickel, cobalt under, rare earth, manganese, aluminium, upper, carry out first time melting in the mode progressively heated up;
Following taking-up ingot casting, is placed on crucible bottom by nickel magnesium alloy, it is placed first time melting gained ingot casting, carries out melting equally in the mode progressively heated up;
Second time melting gained alloy cast ingot takes out by final step, and smash into bulk, out of order crucible of putting into carries out third time melting, and so far, alloy melting is complete.
Described melting electric current is 20 A-50A, smelting time 1 to 3 minutes.
The equipment that described thermal treatment adopts is the tube vacuum annealing furnace of sealing.Cast alloy is put into quartz boat, delivers to the flat-temperature zone of tubulose burner hearth.Vacuumize after burner hearth sealing, after being evacuated to 2Pa ~ 500Pa, logical rare gas element; and then vacuumize, three times so repeatedly, be finally filled with the argon gas of 0.01MPa ~ 1MPa; make sample carry out annealing thermal treatment under argon shield, thermal treatment temp is 800 DEG C ~ 1000 DEG C, 4 to 24 hours time.
In material choice, RE selects pure lanthanum, praseodymium neodymium alloy, pure praseodymium, and Mg selects nickel magnesium alloy, and alloy mass is than nickel: magnesium is 4:1, and other are elemental nickel, cobalt, aluminium, manganese, and its foreign matter content is less than 1%.RE selects main commercially available rare earth kind and price factor thereof to consider.Mg selection nickel magnesium alloy reason is that the fusing point of magnesium is low, vapour pressure is high, if directly pure magnesium and other raw materials are mixed carry out melting, then be difficult to the content controlling magnesium in alloy, therefore pure magnesium must be substituted with nickel magnesium alloy, then by this nickel magnesium alloy and the melting in argon gas atmosphere in the lump of other raw materials.
In the present invention, by the raw material of purity more than 99% according to molar percentage proportioning, then alloy melting adopts high frequency suspension induction furnace.Melting is carried out under inert atmosphere protection; process divides three steps to complete; first all raw materials except nickel magnesium alloy are put into crucible in the lump; rare earths material is upper; other raw materials under; first time melting is carried out in the mode progressively heated up; following taking-up ingot casting; nickel magnesium alloy is placed on crucible bottom, it is placed first time melting gained alloy, carry out melting in the mode progressively heated up equally; so far; alloy melting is complete, and three meltings are for ensureing alloy cast ingot composition and homogeneity of structure, suppress segregation.
Described mechanical ball milling carries out under ar gas environment, adds Graphene during mechanical ball milling, gained alloy powder is crossed 200 mesh sieves and 400 mesh sieves, gets the alloy powder in the middle of it.Add the capacity of alloy powder after Graphene and cycle life be improved significantly, C200/Cmax (%) reaches 80 more than %, substantially can reach the standard of practical application.
The method make the capacity of RE-Mg-Ni series hydrogen storage alloy and cyclical stability be improved significantly, thus improve the chemical property of nickel metal hydride battery.
Accompanying drawing explanation
Fig. 1 La
0.3pr
0.2nd
0.1mg
0.4(Ni
0.8co
0.14al
0.06)
3.4the XRD figure spectrum of+1wt% Graphene alloy.
Fig. 2 La
0.4pr
0.1nd
0.2mg
0.3(Ni
0.81co
0.15al
0.04)
3.5the volume test curve of+5wt% Graphene alloy.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The present embodiment is based on a large amount of orthogonal experiment, and comprehensive proportioning is as follows,
embodiment 1:
Design alloying constituent is: La
0.3pr
0.2nd
0.1mg
0.4(Ni
0.8co
0.14al
0.06)
3.4+ 1wt% Graphene; prepare melting on the high frequency suspension induction melting furnace of argon gas atmosphere protection after raw material in proportion; ingot casting is heat-treated; condition is vacuum tightness 200Pa; then 0.05 atmospheric argon gas is filled with; under argon shield; at being warming up to 800 DEG C; be incubated 12 hours, mechanical ball milling in argon gas atmosphere, add the 3wt% Graphene of annealed alloy weight; alloy powder is broken into 200 mesh sieves and 400 mesh sieves; alloy powder below 400 orders does the phase structure test of alloy on X-ray diffractometer, and as shown in Figure 1, the principal phase of alloy is La to test result
2ni
7.
embodiment 2:
Design alloying constituent is: La
0.4pr
0.1nd
0.2mg
0.3(Ni
0.81co
0.15al
0.04)
3.5+ 5wt% Graphene, prepare melting on the high frequency suspension induction melting furnace of argon gas atmosphere protection after raw material in proportion, ingot casting is heat-treated, condition is vacuum tightness 100Pa, then 0.5 atmospheric argon gas is filled with, under argon shield, at being warming up to 850 DEG C, be incubated 6 hours, mechanical ball milling in argon gas atmosphere, add the 5wt% Graphene of annealed alloy weight, alloy powder is broken into 200 mesh sieves and 400 mesh sieves, the making simulated battery by the method for compressing tablet again carry out electrochemistry capacitance and life test on DC-5 of the alloy powder obtained, test result as shown in Figure 2.
embodiment 3:
Design alloying constituent is: La
0.4pr
0.2nd
0.1mg
0.3(Ni
0.81co
0.15al
0.02mn
0.02)
3.5+ 8wt% Graphene; prepare melting on the high frequency suspension induction melting furnace of argon gas atmosphere protection after raw material in proportion, heat-treat ingot casting, condition is vacuum tightness 300Pa; then 1 atmospheric argon gas is filled with; under argon shield, at being warming up to 950 DEG C, be incubated 18 hours; mechanical ball milling in argon gas atmosphere; add the 1wt% Graphene of annealed alloy weight, alloy powder is broken into 200 mesh sieves and 400 mesh sieves, obtains final product.
Claims (4)
1. a preparation method for superlattice RE-Mg-Ni series hydrogen storage alloy, is characterized in that, comprises the following steps:
The first step, each composition of design superlattice RE-Mg-Ni series hydrogen storage alloy meets the following conditions: (RE
xmg
y) (Ni
kco
aal
bmn
c)
n+ zwt% Graphene, wherein: x+y=1; 0.6≤x≤0.7; 3.0≤n≤4.0; K+a+b+c=1; 0.1≤a≤0.2; 0.01≤b≤0.1; 0≤c≤0.1; Z≤8; RE is the mixing of at least one or several rare earth element;
Second step, puts into the copper crucible melting of high frequency suspension smelting furnace under protection of inert gas, melt back three times by the alloy that the above-mentioned the first step designs;
3rd step, heat-treats the alloy of second step gained, and condition is vacuum tightness 1 × 10
2pa, is then filled with argon gas, is warming up to 800 DEG C-1000 DEG C, is incubated and obtains with A for 4 hours-24 hours
2b
7for the alloy of principal phase;
4th step, by the alloy of the 3rd step gained mechanical ball milling under protection of inert gas, adds Graphene during ball milling, obtains final superlattice type hydrogen-storage alloy.
2. the preparation method of a kind of superlattice RE-Mg-Ni series hydrogen storage alloy according to claim 1, it is characterized in that, melting described in second step is carried out under inert atmosphere protection, and process divides three steps to complete:
First all raw materials except nickel magnesium alloy are put into crucible in the lump, nickel, cobalt under, rare earth, manganese, aluminium, upper, carry out first time melting in the mode progressively heated up;
Following taking-up ingot casting, is placed on crucible bottom by nickel magnesium alloy, it is placed first time melting gained ingot casting, carries out melting equally in the mode progressively heated up;
Second time melting gained alloy cast ingot takes out by final step, and smash into bulk, out of order crucible of putting into carries out third time melting, and so far, alloy melting is complete.
3. the preparation method of a kind of superlattice RE-Mg-Ni series hydrogen storage alloy according to claim 1, it is characterized in that, described melting electric current is 20 A-50A, smelting time 1 to 3 minutes.
4. the preparation method of a kind of superlattice RE-Mg-Ni series hydrogen storage alloy according to claim 1, is characterized in that, the equipment that described thermal treatment adopts is the tube vacuum annealing furnace of sealing; Cast alloy is put into quartz boat, delivers to the flat-temperature zone of tubulose burner hearth; Vacuumize after burner hearth sealing, after being evacuated to 2Pa ~ 500Pa, logical rare gas element, and then vacuumize, three times so repeatedly, be finally filled with the argon gas of 0.01MPa ~ 1MPa, make sample carry out annealing thermal treatment under argon shield.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349843A (en) * | 2015-11-19 | 2016-02-24 | 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 series hydrogen storage alloy |
| CN106623965A (en) * | 2016-09-23 | 2017-05-10 | 青岛大学 | Improved magnesium-nickel-lanthanide series hydrogen storage electrode alloy graphene modification method |
| CN106784705A (en) * | 2016-12-27 | 2017-05-31 | 中科泰能高铭科技发展有限公司 | A kind of hydrogen storing alloy powder and its surface treatment method |
| CN108220728A (en) * | 2017-12-26 | 2018-06-29 | 钢铁研究总院 | A kind of high power capacity light graphite alkene catalytic rare earth magnesium-aluminum-based hydrogen storage material and preparation method |
| CN108687355A (en) * | 2018-06-28 | 2018-10-23 | 西京学院 | A kind of Mg-based hydrogen storage alloy preparation method based on mechanical ball mill technology |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349843A (en) * | 2015-11-19 | 2016-02-24 | 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 series hydrogen storage alloy |
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| CN106784705A (en) * | 2016-12-27 | 2017-05-31 | 中科泰能高铭科技发展有限公司 | A kind of hydrogen storing alloy powder and its surface treatment method |
| CN106784705B (en) * | 2016-12-27 | 2017-10-31 | 中科泰能高铭科技发展有限公司 | A kind of hydrogen storing alloy powder and its surface treatment method |
| CN108220728A (en) * | 2017-12-26 | 2018-06-29 | 钢铁研究总院 | A kind of high power capacity light graphite alkene catalytic rare earth magnesium-aluminum-based hydrogen storage material and preparation method |
| CN108687355A (en) * | 2018-06-28 | 2018-10-23 | 西京学院 | A kind of Mg-based hydrogen storage alloy preparation method based on mechanical ball mill technology |
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