CN103633301A - RE-Mg-Ni-Zr-B electrode alloy used for Ni-MH secondary battery and preparation method thereof - Google Patents

RE-Mg-Ni-Zr-B electrode alloy used for Ni-MH secondary battery and preparation method thereof Download PDF

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CN103633301A
CN103633301A CN201310498912.1A CN201310498912A CN103633301A CN 103633301 A CN103633301 A CN 103633301A CN 201310498912 A CN201310498912 A CN 201310498912A CN 103633301 A CN103633301 A CN 103633301A
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张羊换
张建福
郭世海
林玉芳
祁焱
赵栋梁
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Central Iron and Steel Research Institute
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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Abstract

The invention relates to a hydrogen storage electrode alloy for a Ni-MH secondary battery and a preparation method thereof. The hydrogen storage electrode alloy contains amorphous forming elements of zirconium and boron and multi-component rear earth elements. A chemical formula of the alloy is RE(1-x)MgxZryNizAlmBn, wherein x, y, z, m and n are atomic ratios; x is not less than 0.2 and not greater than 0.3, y is not less than 0.01 and not greater than 0.05, z is not less than 3.0 and not greater than 3.5, m is not less than 0.05 and not greater than 0.15, and n is not less than 0.0005 and not greater than 0.002; in addition to lanthanum with the atomic ratio of 0.5-0.65, the rear earth elements further must contain at least one of cerium, samarium, yttrium, neodymium and gadolinium. The preparation method comprises the following steps of: smelting under protection of inert gases by adopting induction heating; pouring molten alloy into a tundish, continuously spraying and dropping on the surface of a water-cooling copper roller rotating at a certain speed by a spray nozzle on the bottom of the tundish to obtain quick-quenching alloy; then, carrying out vacuum annealing in a vacuum thermal treatment furnace. According to the invention, zirconium, boron and the multi-component rear earth elements are added, a small amount of amorphous phase is formed by quick quenching, and electrochemical cyclic service life of the alloy is greatly prolonged; meanwhile, comprehensive effects of the rear-earth elements are sufficiently utilized, so that chemical capacity of the alloy is kept. Besides, the preparation process of the alloy has characteristics of being easy to grasp and suitable for large-scale production.

Description

A kind of RE-Mg-Ni-Zr-B for Ni-MH secondary cell is electrode metal and preparation method thereof
Technical field
The invention belongs to storage alloy material for hydrogen technical field, it is A that a kind of high-capacity and long-life Re-Mg-Ni-Zr-B is particularly provided 2b 7type hydrogen-storing alloy as electrode and preparation method thereof.
Background technology
Ni-MH secondary cell is widely used in owing to having good large current density performance and safety non-pollution the auxiliary power that various small portable electronic device ，Bing Yibei Ministry of Industry and Information is defined as hybrid-electric car (HEV).The hybrid electric vehicle that the Ni-MH battery of take is auxiliary power is classified as matured product, allows to sell use in China.Along with the progress of technology, the performance of battery has been proposed to more and more higher requirement, particularly capacity and cycle life.Rare earth based AB 5type hydrogen-storage alloy has been realized extensive industrialization in China and Japan.Yet, due to its capacity (about 330mAh/g) on the low side, be difficult to meet the requirement of electrokinetic cell to capacity.In recent years, a kind of novel La-Mg-Ni is A 2b 7type alloy receives publicity owing to having high electrochemistry capacitance (>380mAh/g).Kadir.K etc. have reported that a class has PuNi the earliest 3the novel hydrogen-storage alloy of type superlattice structure, as (Y 0.5ca 0.5) (MgCa) Ni 9alloy, its reversible hydrogen adsorption and desorption amount reaches 1.98wt%.Kohno etc. find La 0.7mg 0.3ni 2.8co 0.5the maximum discharge capacity of alloy can reach 410mAh/g, compares AB 5type alloy is high by 20%, and being recognized is the new electrode materials that tool is wished.But the electrochemistry cyclical stability of alloy is poor, guaranteeing that under the prerequisite of high power capacity, carrying heavy alloyed electrochemistry cyclical stability becomes the challenge that researcher faces.Domestic Zhejiang University, Iron and Steel Research Geueral Inst, non-ferrous metal research Zong Yuandeng unit are the domestic units that early carries out this series alloy research, and after finding to anneal, principal phase is Ce 2ni 7the A of type superlattice structure 2b 7type alloy ratio AB 3type alloy has better cycle life.After this, both at home and abroad the research of rare earth magnesium base hydrogen storage alloy is started by AB 3type turns to A gradually 2b 7type.For example, ' RE-Mg-Ni materials-aluminium base hydrogen storage alloy and made Ni-MH battery use for nickel-hydrogen battery ' of Beijing Non-Ferrous Metal Research General Academy's application, application number 201010597158.3, December 10 2010 applying date.
Summary of the invention
The object of the present invention is to provide a kind of high-capacity and long-life Ni-MH battery is A with Re-Mg-Ni-Zr-B 2b 7type hydrogen-storage alloy and preparation method thereof, by the present invention, makes the electrochemistry cyclical stability of hydrogen-storing alloy as electrode wait until large increase.
For achieving the above object, the invention provides technical scheme below:
A Ni-MH secondary cell hydrogen-storing alloy as electrode, contains micro-amorphous formation element zirconium, boron and multicomponent rare earth, and its chemical formula consists of: RE 1-xmg xzr yni zal mb n, x in formula, y, z, m, n is atomic ratio, and 0.2≤x≤0.3,0.01≤y≤0.05,3.0≤z≤3.5,0.05≤m≤0.15,0.0005≤n≤0.002, rare earth element, except containing the lanthanum that atomic ratio is 0.5-0.65, also must contain at least one in cerium, samarium, yttrium, neodymium, gadolinium.
The preferred atomic ratio x:y:z:m:n=0.24:0.02:3.4:0.1:0.0015 that described hydrogen-storing alloy as electrode chemical formula forms.
This alloy adopts the preparation of vacuum quick quenching method, and the quenched alloy thin slice obtaining has crystallite-nanocrystalline-a small amount of non crystalline structure, and metallographic structure is mainly along the column crystal perpendicular to roll surface direction.
This alloy is prepared by the following method: under inert gas shielding, adopt inducing melting; pour molten alloy into tundish; nozzle continuous spraying by tundish bottom drops on the surface with the water-cooled copper roller of given pace rotation; obtain quenched alloy, then in vacuum heat treatment furnace, carry out vacuum annealing.
A preparation method for Ni-MH electrode for secondary battery alloy, comprises the steps:
A presses chemical formula and forms RE 1-xmg xzr yni zal mb nprepare burden, 0.2≤x≤0.3 in formula, 0.01≤y≤0.05,3.0≤z≤3.5,0.05≤m≤0.15,0.0005≤n≤0.002, rare earth element, except containing the lanthanum that atomic ratio is 0.5-0.65, also must contain at least one in cerium, samarium, yttrium, neodymium, gadolinium;
B carries out induction heating by the raw material that prepare, and is evacuated to 1 * 10 -2-5 * 10 -5pa, applies the inert gas of 0.01-0.1MPa as protective gas, melt temperature 1300-1600 ℃, the RE of acquisition melting 1-xmg xzr yni zal mb nliquid foundry alloy;
C keeps after 5 minutes under molten condition, under protective gas atmosphere, liquid foundry alloy is directly injected to tundish, and the nozzle continuous spraying by tundish bottom drops on the surface of water-cooled copper roller that linear velocity is 3-20m/s rotation, obtains thickness quenched alloy thin slice between 500-1500 μ m;
D puts into vacuum heat treatment furnace by quenched alloy thin slice, is evacuated to 10 -2-10 -4pa, is heated to 400-700 ℃, and insulation 2-5 hour, cools to room temperature with the furnace after insulation;
E by mechanical crushing, crosses 200 mesh sieves by the above-mentioned alloy obtaining, and obtains the alloy powder of diameter≤74 μ m, by alloyed powder and carbonyl nickel powder (particle diameter 2.5 μ m) in mass ratio 1:4 mix, under the pressure of 35MPa, be cold-pressed into electrode slice.
Side in described step B, induction heating mode comprises electric arc melting, inducing melting maybe can make that raw material melt completely other add hot smelting mode.
Protective gas is pure helium or helium+argon gas mist, and the volume ratio of described mist is about 1:1.
Quenched alloy thin slice has crystallite-nanocrystalline-a small amount of non crystalline structure, and its metallographic structure is mainly along the column crystal perpendicular to roll surface direction.
The scaling loss amount that magnesium during chemical formula forms and rare earth increase 5%-10% ratio when proportioning.
Dominant mechanism of the present invention is: research discovery, and poor reason comprises two aspects to cause alloy cyclical stability: first alloy rare earth elements and magnesium are by potassium hydroxide electrolyte corrosion oxidation; The 2nd, expansion and contraction due to lattice in alloy hydrogen absorption and desorption process cause alloying pellet efflorescence, thereby further accelerate the corrosion of alloy electrode.The institutional framework of adjusting the composition of alloy and improving alloy is the effective ways of the raising alloy property of generally acknowledging.Optimizing components is mainly by regulating the lanthanum/magnesium ratio in stoichiometric proportion and A side, and with suction protiums such as rare earth element (lanthanum, cerium, samarium, yttrium, neodymium, gadolinium), titanium, zirconiums, A side lanthanum, magnesium are carried out to part and substitute, or with transition metal manganese, cobalt, aluminium, tungsten, chromium, iron, copper, partly substitute the nickel element of B side, such alternative energy significantly improves the comprehensive electrochemical of alloy, but the cyclical stability of alloy still has distance apart from practical requirement.Obviously, only by Composition Design, can not make the chemical property of alloy meet the requirement of Ni/MH battery anticathode material.Research is thought, can significantly improve the comprehensive electrochemical of alloy by improving the microstructure of alloy, particularly makes the electrochemistry cyclical stability of alloy increase substantially.Vacuum quick quenching technology is particularly effective to carrying heavy alloyed electrochemistry cyclical stability.Research discovery, rapid quenching is the institutional framework of refinement alloy significantly, carries heavy alloyed productive technique; Meanwhile, fast quenching may form a small amount of amorphous phase, can significantly improve alloy electrode electrolyte resistance corrosive nature.
The present invention adopts with zirconium Substitute For Partial magnesium on Composition Design, and adds trace B element.Because zirconium and boron are all amorphous formation elements, and boron is crystal boundary absorption element, by rapid quenching, easily at crystal boundary, forms micro-amorphous, improves the decay resistance of alloy crystal boundary.The effect of different rare earth element alloys is different, adds multicomponent rare earth in alloy, can bring into play the comprehensive advantage of rare earth element.On the basis of science design mix, by vacuum quick quenching technology, prepare alloy, obtain the uniform column microstructure of composition, not only kept the high power capacity of alloy, and the electrochemistry cyclical stability of alloy significantly promotes, meet the performance requirement of Ni-MH secondary cell anticathode material completely.
Compare with traditional RE-Mg-Ni series hydrogen storage alloy and preparation method, the present invention has following advantage:
(1) on Composition Design, add micro-amorphous formation element zirconium and boron, be conducive to promote the formation of amorphous phase, carry heavy alloyed electrochemistry cyclical stability; Adopt multicomponent rare earth element to combine alternative, the comprehensive function of performance rare earth element.
(2) adopt helium protection, the volatilization loss of magnesium metal while substantially having avoided induction melting, guarantees that its composition of alloy of preparation meets design component mole proportioning.
(3) with traditional founding+annealing process comparison, the present invention can suppress the component segregation of alloy completely, obtains crystallite-nanocrystalline and amorphous structure of uniformity.The hydrogen-storage alloy productive technique with this structure is strong, and electrochemistry cyclical stability is good.
(4) owing to substantially there is not component segregation in melt spun alloy, can significantly reduce annealing temperature and shorten annealing time, enhance productivity, reduce production costs.Meanwhile, there is technique and be easy to grasp, be applicable to the feature of large-scale production.
Accompanying drawing explanation
Fig. 1 is the present invention by after fast quenching and annealing, the XRD diffraction spectra schematic diagram of each embodiment alloy.
Embodiment
Below in conjunction with accompanying drawing and exemplary embodiment, design philosophy of the present invention is described in further detail and forms mechanism, so that technical solution of the present invention is clearer.
The present invention finds by research, and micro-amorphous phase can increase substantially alloy and put productive technique and the anticorrosive oxidability in hydrogen process in suction, and the electrochemistry cyclical stability of alloy is increased substantially.By experiment, on Composition Design, adopt and add micro-amorphous formation element zirconium and boron.In alloy, add multicomponent rare earth, so that the comprehensive advantage of performance rare earth element is further carried heavy alloyed electrochemistry cyclical stability simultaneously.
The quenched alloy that adopts vacuum quick quenching technology to prepare has uniform crystallite-nanocrystalline and amorphous structure and edge becomes column crystal to arrange perpendicular to roll surface direction; By quenched alloy is carried out to suitable annealing in process, discharge fast quenching stress, improved the comprehensive electrochemical of hydrogen-storage alloy, overcome the poor bottleneck problem of hydrogen-storage alloy cyclical stability, meet the instructions for use of Ni-MH battery completely.
The present invention's application induction furnace melting adds helium protection; substantially avoided the volatilization loss of magnesium metal; the component segregation that can suppress alloy completely; guarantee that prepared hydrogen-storage alloy composition meets design component mole proportioning, the crystallite-nanocrystalline and amorphous structure and the edge that obtain uniformity become column crystal to arrange perpendicular to roll surface.And the hydrogen-storage alloy productive technique of this structure is strong, electrochemistry cyclical stability is good.Owing to not there is not component segregation, can significantly reduce annealing temperature and shorten annealing time, enhance productivity, reduce production costs.
The present invention is further described Ni-MH battery hydrogen-storage alloy composition and preparation method involved in the present invention by the following examples.
Ni-MH battery of the present invention contains multicomponent rare earth and micro-amorphous formation element zirconium, boron with hydrogen-storing alloy as electrode, and its composition chemical formula is: RE 1-xmg xzr yni zal mb n, x in formula, y, z, m, n is atomic ratio, and 0.2≤x≤0.3,0.01≤y≤0.05,3.0≤z≤3.5,0.05≤m≤0.15,0.0005≤n≤0.002; Preferred atomic ratio x:y:z:m:n=0.24:0.02:3.4:0.1:0.0015(is embodiment 2,4,5,6,8,9 for example).Rare earth element, except containing the lanthanum that atomic ratio is 0.5-0.65, also must contain at least one in cerium, samarium, yttrium, neodymium, gadolinium.
The preparation method of Ni-MH of the present invention high power capacity, long-life hydrogen-storing alloy as electrode for battery comprises the following steps:
A, by designed chemical formula atomic ratio, carry out weighing and proportioning.Due to magnesium and rare earth element fusing point lower be easy to volatilization, therefore, when proportioning, increase the scaling loss amount of 5%-10% ratio, take 5% left and right as good;
B, the raw material preparing is placed in to magnesia crucible, demagging is placed in outside crucible top layer, and other materials adds crucible in no particular order.Adopt induction heating to carry out melting, be evacuated to 1 * 10 -2-5 * 10 -5pa, is then filled with 0.01-0.1MPa inert protective gas, i.e. argon gas+helium mix gas, and its mist volume ratio is about 1:1, or is filled with high-purity helium; Smelting temperature 1300-1600 ℃, carries out temperature adjustment depending on the composition of alloy, to guarantee that raw metal melts completely; Under inert gas atmosphere protection, obtain the RE of melting 1-xmg xzr yni zal mb nliquid foundry alloy keeps 1-5 minute under molten condition;
C, under inert gas atmosphere protection, after alloy melting, after approximately 5 minutes, directly liquid foundry alloy is injected to tundish, carry out rapid quenching; Boron nitride nozzle continuous spraying by tundish bottom drops on the smooth surface of the water-cooled copper roller rotating with given pace, the linear resonance surface velocity 3-20m/s that keeps copper roller, preferred 8m/s, obtain thickness quenched alloy thin slice between 500-1500 μ m, this quenched alloy has columanar structure's structure, the crystallite that this structure is uniformity-nanocrystalline-micro-non crystalline structure;
D, quenched alloy is put into vacuum heat treatment furnace, be evacuated to 10 -2-10 -4pa, is heated to 400-700 ℃, can be preferably 600 ℃, and be incubated 2-5 hour, can be preferably 3 hours; Hydrogen-storage alloy after insulation cools to room temperature with the furnace, obtains annealed state alloy.
Then the alloy of above-mentioned preparation is carried out to structural characterization and performance test, adopt the structure of x x ray diffractometer x (XRD) test fast quenching and annealed state alloy, with the electrochemical hydrogenation and dehydrogenation capacity of simulated battery tester beta alloy, and the chemical property parameter such as cyclical stability.
The chemical composition of the specific embodiment of the invention and ratio are selected as follows:
Embodiment 1:La 0.6nd 0.1ce 0.1mg 0.20zr 0.05ni 3.4al 0.1b 0.002
Embodiment 2:La 0.55nd 0.21mg 0.24zr 0.02ni 3.4al 0.1b 0.0015
Embodiment 3:La 0.5y 0.2mg 0.3zr 0.02ni 3.0al 0.15b 0.0015
Embodiment 4:La 0.65pr 0.11mg 0.24zr 0.02ni 3.4al 0.1b 0.0015
Embodiment 5:La 0.55sm 0.21mg 0.24zr 0.02ni 3.4al 0.1b 0.0015
Embodiment 6:La 0.55sm 0.1y 0.11mg 0.24zr 0.02ni 3.4al 0.1b 0.0015
Embodiment 7:La 0.55y 0.2ce 0.05mg 0.2zr 0.05ni 3.4al 0.1b 0.0015
Embodiment 8:La 0.5pr 0.2ce 0.06mg .0.24zr 0.02ni 3.4al 0.1b 0.0015
Embodiment 9:La 0.6gd 0.1ce 0.06mg .0.24zr 0.02ni 3.4al 0.1b 0.0015
Comparative example: La 0.55nd 0.21mg 0.24ni 3.4al 0.1(contrast sample is annealed state)
By the chemical formula of each embodiment, form and choose block rare earth metal, magnesium metal, metallic nickel, metallic aluminium, metal zirconium and nickel boron intermediate alloy.These metal purity >=99.5%, weigh by chemical dosage ratio.Wherein, magnesium metal and rare earth metal increase the scaling loss amount of 5%-10% ratio when proportioning, especially take 5% left and right as good; In preparation process, each stage technique parameter is as vacuum to 1 during induction heating * 10 -2-5 * 10 -5pa, applies pure helium or the helium+argon gas mist of 0.01-0.1MPa, and the volume ratio of mist is about 1:1; Melt temperature is 1300-1600 ℃; During fast quenching heating, be evacuated to 10 -2-10 -4pa, adopting water-cooled copper roller linear resonance surface velocity is that 3-20m/s carries out rapid quenching.Fast quenching thin slice is heated to 400-700 ℃, and insulation 2-5 hour, cools to room temperature with the furnace after insulation, and all technological parameters all can suitably be selected in above-mentioned scope, prepare qualified hydrogen-storing alloy as electrode.Therefore, although the present invention only for a typical embodiment, this embodiment is applicable to the preparation method of different parameters.
The technical data of embodiment 1: by form the magnesia crucible that the raw metal weighing up is placed in intermediate frequency furnace according to chemical formula, then build bell, being evacuated to vacuum degree is 2.5 * 10 -2more than Pa, be filled with again argon gas+helium mix gas and reach 0.04MPa negative pressure, regulating power all melts metal, become fused solution foundry alloy, temperature is controlled at 1550 ℃ of left and right, keeps 5 minutes under melting condition, then liquid alloy is injected to tundish, boron nitride nozzle continuous spraying by tundish bottom drops on the smooth surface of the water-cooled copper roller rotating with 8m/s linear velocity, obtains quenched alloy thin slice; Quenched alloy is put into vacuum heat treatment furnace, be evacuated to 5 * 10 -3pa, was heated to 600 ℃ of insulations after 3 hours, cooled to room temperature with the furnace, obtained annealed state alloy, can be used as the negative material of Ni-MH battery.
Fig. 1 is embodiment 1-9 and the alloy XRD diffraction spectra schematic diagram of fast quenching+annealed state.Can find out, the alloy of all embodiment all has heterogeneous structure, comprises principal phase (La, Mg) 2ni 7and LaNi 5and a small amount of LaNi 2phase.Element substitution and rapid quenching do not change the phase composition of alloy, but in alloy, obvious change (can determine the content that respectively forms phase according to Jade6 software) has occurred the content of each phase.
The alloy of the above-mentioned variant composition embodiment obtaining, by mechanical crushing, is crossed to 200 mesh sieves, obtain the alloy powder of diameter≤74 μ m.After by alloyed powder, 1:4 mixes in mass ratio with carbonyl nickel powder (particle diameter≤2.5 μ m), under the pressure of 35MPa, being cold-pressed into diameter is the round electrode slice of 15mm, then it is carried out to electrochemical property test.Electro-chemical test adopts three electrode test methods of standard.
The discharge system that the activity function of beta alloy and maximum discharge capacity adopt is: charging and discharging currents density is 60mA/g, charging interval 480min, and discharge cut-off voltage is-0.5V; The discharge system that the electrochemistry cyclical stability of beta alloy adopts is: charging and discharging currents density is 300mA/g, charging interval 80min, and discharge cut-off voltage is-0.6V.When charging or discharging current density is 300mA/g, the cycle-index that the discharge capacity of alloy drops to 60% correspondence of maximum discharge capacity is defined as the cycle life of alloy.Use S 500the conservation rate that represents 500 rear alloy capacity of circulation, i.e. S 500=C 500,300/ C max, 300* 100%.C max, 300maximum discharge capacity when-charging or discharging current density is 300mA/g; C 500,300discharge capacity through charging and discharging after circulation for 500 times when-charging or discharging current density is 300mA/g.
The results are shown in Table 1 after tested for the prepared alloy of above-described embodiment.
The chemical property of table 1 embodiment alloy
Technic metal Maximum discharge capacity (mAh/g) Cycle life (inferior) S 500（%）
Embodiment 1 379.4 710 72.1
Embodiment 2 388.6 645 69.2
Embodiment 3 400.5 502 60.2
Embodiment 4 392.7 533 62.5
[0058]?
Embodiment 5 387.3 667 70.2
Embodiment 6 393.1 694 71.2
Embodiment 7 391.7 716 72.1
Embodiment 8 385.6 707 71.7
Embodiment 9 386.9 712 71.9
Comparative example 389.2 388 48.5
Test result shows, the chemical property of the alloy rare earth based AB that particularly discharge capacity is sold higher than existing market far away 5type alloy (330mAh/g).With domestic and international similar alloy comparison, the performance of alloy of the present invention particularly electrochemistry cyclical stability has shown obvious advantage.
Although the present invention is described its preferred embodiment; those skilled in the art can take other execution mode obviously; for example change component content; the technical parameters such as heating-up temperature; within not departing from the scope of design philosophy of the present invention; can carry out various changes and modifications, these variations all belong to protection scope of the present invention.

Claims (9)

1. a Ni-MH secondary cell hydrogen-storing alloy as electrode, is characterized in that containing micro-amorphous formation element zirconium, boron and multicomponent rare earth, and its chemical formula consists of: RE 1-xmg xzr yni zal mb n, x in formula, y, z, m, n is atomic ratio, and 0.2≤x≤0.3,0.01≤y≤0.05,3.0≤z≤3.5,0.05≤m≤0.15,0.0005≤n≤0.002, rare earth element, except containing the lanthanum that atomic ratio is 0.5-0.65, also must contain at least one in cerium, samarium, yttrium, neodymium, gadolinium.
2. hydrogen-storing alloy as electrode according to claim 1, is characterized in that, the preferred atomic ratio x:y:z:m:n=0.24:0.02:3.4:0.1:0.0015 that described chemical formula forms.
3. hydrogen-storing alloy as electrode according to claim 1, is characterized in that, this alloy adopts the preparation of vacuum quick quenching method, and the quenched alloy thin slice obtaining has crystallite-nanocrystalline-a small amount of non crystalline structure, and metallographic structure is mainly along the column crystal perpendicular to roll surface direction.
4. hydrogen-storing alloy as electrode according to claim 1; it is characterized in that; this alloy is prepared by the following method: under inert gas shielding, adopt inducing melting; pour molten alloy into tundish; nozzle continuous spraying by tundish bottom drops on the surface with the water-cooled copper roller of given pace rotation; obtain quenched alloy, then in vacuum heat treatment furnace, carry out vacuum annealing.
5. the preparation method of Ni-MH electrode for secondary battery alloy as claimed in claim 1, is characterized in that, comprises the steps:
A presses chemical formula and forms RE 1-xmg xzr yni zal mb nprepare burden, 0.2≤x≤0.3 in formula, 0.01≤y≤0.05,3.0≤z≤3.5,0.05≤m≤0.15,0.0005≤n≤0.002, rare earth element, except containing the lanthanum that atomic ratio is 0.5-0.65, also must contain at least one in cerium, samarium, yttrium, neodymium, gadolinium;
B carries out induction heating by the raw material that prepare, and is evacuated to 1 * 10 -2-5 * 10 -5pa, applies the inert gas of 0.01-0.1MPa as protective gas, melt temperature 1300-1600 ℃, the RE of acquisition melting 1-xmg xzr yni zal mb nliquid foundry alloy;
C keeps after 5 minutes under molten condition, under protective gas atmosphere, liquid foundry alloy is directly injected to tundish, and the nozzle continuous spraying by tundish bottom drops on the surface of water-cooled copper roller that linear velocity is 3-20m/s rotation, obtains thickness quenched alloy thin slice between 500-1500 μ m;
D puts into vacuum heat treatment furnace by quenched alloy thin slice, is evacuated to 10 -2-10 -4pa, is heated to 400-700 ℃, and insulation 2-5 hour, cools to room temperature with the furnace after insulation;
E by mechanical crushing, crosses 200 mesh sieves by the above-mentioned alloy obtaining, and obtains the alloy powder of diameter≤74 μ m, by alloyed powder and carbonyl nickel powder (particle diameter 2.5 μ m) in mass ratio 1:4 mix, under the pressure of 35MPa, be cold-pressed into electrode slice.
6. preparation method according to claim 5, is characterized in that, side in described step B, induction heating mode comprises electric arc melting, inducing melting maybe can make that raw material melt completely other add hot smelting mode.
7. preparation method according to claim 5, is characterized in that, described protective gas is pure helium or helium+argon gas mist, and the volume ratio of described mist is about 1:1.
8. preparation method according to claim 5, is characterized in that, described quenched alloy thin slice has crystallite-nanocrystalline-a small amount of non crystalline structure, and its metallographic structure is mainly along the column crystal perpendicular to roll surface direction.
9. preparation method according to claim 5, is characterized in that, the scaling loss amount that the magnesium during described chemical formula forms and rare earth increase 5%-10% ratio when proportioning.
CN201310498912.1A 2013-10-22 2013-10-22 RE-Mg-Ni-Zr-B electrode alloy used for Ni-MH secondary battery and preparation method thereof Pending CN103633301A (en)

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