CN102286678A - Non-stoichiometric-ratio LaNi5 base cobalt-free hydrogen storage alloy and preparation method thereof - Google Patents
Non-stoichiometric-ratio LaNi5 base cobalt-free hydrogen storage alloy and preparation method thereof Download PDFInfo
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- CN102286678A CN102286678A CN 201110248840 CN201110248840A CN102286678A CN 102286678 A CN102286678 A CN 102286678A CN 201110248840 CN201110248840 CN 201110248840 CN 201110248840 A CN201110248840 A CN 201110248840A CN 102286678 A CN102286678 A CN 102286678A
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Abstract
The invention discloses a non-stoichiometric-ratio LaNi5 base cobalt-free hydrogen storage alloy, which is characterized in that the alloy material has a composition formula of A(NiM)5+x, wherein A is a combination of two or more than two elements in La, Ce, Pr and Nd, M is any one element or a combination of more than one element in Mn, Al, Cu, Fe, Si, Sn and Zr, and x is greater than or equal to -0.2 but is smaller than or equal to +0.8. The invention also discloses a preparation method of the cobalt-free hydrogen storage alloy. The cobalt-free hydrogen storage alloy and the method provided by the invention have the advantages that the cyclic stability is good, the service life is long, and the electrochemical performance is good.
Description
Technical field
The present invention relates to be used for the technical field of function materials of Chu Qing, be specifically related to a kind of non-stoichiometric LaNi
5No cobalt hydrogen storage alloy of base and preparation method thereof.
Background technology
Domestic in recent years nickel-hydrogen battery negative pole AB
5The demand of type alloy powder is very big, reaches 8000～10000 tons/year.In this class alloy, cobalt is considered to have irreplaceable effect aspect the electrode metal electrochemistry cyclical stability improving, but cobalt also is a kind of noble metal element of comparison costliness simultaneously, the content of cobalt is usually up to about 10wt% in the alloy, and only the cost of this a kind of element just occupies 40～50% of alloy raw material total cost.Therefore, the cost that how to reduce alloy becomes the problem of current people's extensive concern.And market accounts for about 60% of aggregate demand for low cobalt, no cobalt-base alloy powder product demand; Therefore, the low cobalt of development, no cobalt-base alloy powder product are the main trend of the sector future development.
At present aspect low cobalt, the research of no cobalt hydrogen storage alloy, utilize one or more built-up sections among cheap metal such as Mn, Al, Cu, Fe, Si, Sn, the Zr mostly or all replace cobalt, the alloy powder gram volume that makes can satisfy the market requirement that nickel metal hydride battery replaces nickel-cadmium cell substantially generally at 270 ~ 310mAh/g.But this kind battery is undesirable aspect cyclical stability and work-ing life, and its 1C cycle life generally only maintains about 200 times under the room temperature.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, the good non-stoichiometric LaNi of chemical property of a kind of good cycling stability, long service life is provided
5The no cobalt hydrogen storage alloy of base.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: a kind of non-stoichiometric LaNi
5The no cobalt hydrogen storage alloy of base, the ingredient formula of this alloy material is A(NiM)
5+x, wherein A is rich La mishmetal: two kinds of combinations or two or more combinations among La, Ce, Pr, the Nd; M wherein is the combination (i.e. two kinds or two or more combinations) of any one or more elements among Mn, Al, Cu, Fe, Si, Sn, the Zr; Wherein-0.2≤x≤+ 0.8.
Another technical problem that the present invention solves provides a kind of above-mentioned non-stoichiometric LaNi
5The preparation method of the no cobalt hydrogen storage alloy of base, its step comprises:
(1) each element with formula rate is placed in the vacuum induction furnace, 1 ~ 7Pa will be evacuated down in the vacuum induction furnace, applying argon gas is 0.05 ~ 0.08Mpa to furnace pressure then, repeats 2 ~ 4 prepurgings, carries out melting at last under furnace pressure 0.05 ~ 0.08Mpa and argon shield; Carry out concise 25 ~ 45min after the complete fusion of alloy again;
(2) alloy liquid after concise pours into water cooling ingot mould and carries out cooled and solidified with step (1), speed of cooling obtains alloy block within an hour the alloy block temperature being reduced to below 50 ℃, then alloy block is placed vacuum annealing furnace under argon shield, to heat-treat: pressure to the 0.1 ~ 1Pa that is evacuated to vacuum annealing furnace, charging into the pressure that makes behind the argon gas in the stove then reaches 0.05 ~ 0.08Mpa and carries out anneal, promptly with temperature to 850 in the speed kindling of 3 ~ 5 ℃/min ~ 1100 ℃, be incubated 6 ~ 24 hours, be cooled to room temperature then;
(3) the good alloy block of step (2) thermal treatment is carried out Mechanical Crushing ball milling powdered (mechanical impact is made the metal powder of demand from the bulk to the fritter).
After above-mentioned steps (3) obtains the alloy of ball milling powdered, also comprise it is loaded on stand-by step in the vacuum packaging.
Refining in the above-mentioned steps of the present invention (1) is: after all raw material is melted fully, the power of melting suitably reduced the charge amount of the concrete parameter visual fusion of 10 ~ 30%(furnace and rated output size and fixed) be standard alloy liquid can be rolled to stir volatilization strongly, so that the alloy homogenizing, concise 25 ~ 45 minutes.
The room temperature that is cooled in the above-mentioned steps of the present invention (2) is: allow alloy cool to the furnace below 600 ℃ earlier, the flue that alloy will be housed is then put into air-cooled cooling tower and is carried out the air-cooled alloy block temperature that promptly makes and reduced to below 50 ℃ at 10 hours.
Mechanical Crushing ball milling powdered in the above-mentioned steps of the present invention (3) is: under the Ar gas shiled, alloy block is carried out the Mechanical Crushing ball milling become size to satisfy the powder of 150 ~ 250 orders (being 150 ~ 250 mesh sieve hole dimensions that powder can pass through screen cloth).
The existence of cobalt element mainly is in order to improve the electrochemistry cyclical stability of electrode metal, but use cost is higher, cheap among the present invention in order to elements such as the Mn, the Al that replace cobalt element, Cu, Fe, Si, Sn, Zr, can reduce cost on the one hand, on the other hand, the nonstoichiometry proportioning of rational design of these elements and certain limit can be improved the electrochemistry cyclical stability of no cobalt hydrogen storage alloy to a great extent.Adding as Fe and Cu element can effectively reduce the alloy equilibrium hydrogen pressure, improve the electrochemistry cyclical stability of alloy, the Cu element has also reduced the activating velocity of alloy simultaneously, suitably add part Fe on this basis and just can improve the activating velocity of alloy, the adding of Mn element can improve the electrochemistry capacitance of no cobalt-base alloy.The suitable adding of same Al, Si, elements such as Sn, Zr can improve the high magnification and the performance such as anticorrosive of no cobalt hydrogen storage alloy.
Advantage of the present invention exists: LaNi of the present invention
5The no cobalt hydrogen storage alloy of base, because the nonstoichiometry alloy is to weave construction, phase composite, equilibrium hydrogen pressure, loading capacity, activation performance and high-multiplying power discharge, cycle life etc. have produced influence, thereby when having reduced the hydrogen storing alloy powder cost, improved the chemical property of no cobalt-base alloy, improved cyclical stability and work-ing life.Meanwhile, the alloy preparation method of this invention is applicable to the big production technique of present commercialization, with Ni-HM battery performance and preparation technology's coupling.
Description of drawings
No cobalt hydrogen storage alloy 0.2C discharges and recharges maximum discharge capacity under Fig. 1 room temperature.
No cobalt hydrogen storage alloy 1C charge and discharge circulation life under Fig. 2 room temperature.
The hydrogen storage alloy apparatus structure synoptic diagram that Fig. 3 the present invention uses.
As shown in the figure: 1. ruhmkorff coil, 2. crucible, 3. alloy, 4. water cooling ingot mould, 5. heat exchange water pipe, 6. nitrogen gas-filled valve, 7. intermediate frequency power supply.
Embodiment
Below by embodiment the present invention is described in further detail, embodiment is all by non-stoichiometric A(NiM)
5+x, wherein-0.2≤x≤+ 0.8 general formula batching, the batching selection principle is used starting material always for business-like Ni-HM battery cathode hydrogen storage alloy at present, but the present invention not only is confined to following examples.
The equipment that uses in the embodiment of the invention is the industry conventional equipment, does not repeat them here.
As shown in Figure 3, the hydrogen storage alloy device that the present invention uses is the industry conventional equipment, general configuration: mainly constitute by ruhmkorff coil 1, crucible 2, rotation water cooling ingot mould 4, by nitrogen gas-filled valve 6 after vacuum chamber charges into Ar, intermediate frequency power supply 7 advanced ruhmkorff coil alloy 3 was heated melting, refining, liquid alloy is slowly poured into the water cooling ingot mould 4 of rotation, and 5 water is cooled to alloy block fast with hydrogen storage alloy in the heat exchange water pipe.This device is common to following four embodiment.
Embodiment 1
Alloy composition of the present invention (mass percent) is: Rare Earth Lanthanum 23.44%, and rare earth cerium 8.9%, nickel 51.26%, manganese are 8.32%, and aluminium is 1.2%, and copper is 5.38%, iron 1.5%.Nonstoichiometry molecular formula AB
5.07(x=0.07).
Above-mentioned raw materials is placed crucible in the vacuum induction furnace, vacuum is evacuated to 1Pa, charging into Ar gas makes furnace pressure to 0.08Mpa, 3 prepurgings repeatedly, under 0.08Mpa pressure, carry out induction melting, refining then, smelting furnace melting power is controlled at 90 ~ 110KW, refining power was controlled at 80 ~ 90KW(refining 25 ~ 40 minutes), alloy after the refining slowly is poured on the rotation water cooling ingot mould, speed of cooling obtains alloy block within an hour the alloy block temperature is reduced to below 50 ℃ until being cooled to room temperature.With alloy thermal treatment: be evacuated to heat treatment furnace (vacuum annealing furnace) internal pressure 1Pa, charging into Ar gas makes furnace pressure carry out anneal to 0.08Mpa, promptly the speed with 3 ~ 5 ℃/min is warming up to 850 ~ 1100 ℃ of insulations 18 ~ 20 hours, allow alloy cool to the furnace below 600 ℃ then earlier, the flue that alloy will be housed is then put into air-cooled cooling tower and is carried out the air-cooled alloy block temperature that promptly makes and reduced to below 50 ℃ at 10 hours, until being cooled to room temperature; Under the Ar gas shiled, alloy block is carried out Mechanical Crushing ball milling (routine techniques) become size to satisfy the metal-powder that to cross 150 ~ 250 mesh sieves then.The AB that makes
5.07Type does not have cobalt-base alloy at room temperature, and 0.2C discharges and recharges maximum discharge capacity and reaches 320mAh/g, shown in a curve among Fig. 1; Under the room temperature, can keep 80% of initial capacity after the 1C charge and discharge cycles 320 times, shown in a curve among Fig. 2.
Alloy composition (mass percent) is: Rare Earth Lanthanum 27.7%, and rare earth cerium 1.5%, praseodymium 1.2%, rare earth neodymium 2.4%, nickel 54.96%, aluminium are 1.79%, copper is 10.45%.Nonstoichiometry molecular formula AB
4.96(x=-0.04).Its preparation method and condition and embodiment one are identical, the alloy of making at room temperature, 0.2C discharges and recharges maximum discharge capacity and reaches 320mAh/g, shown in b curve among Fig. 1; Under the room temperature, can keep 78% of initial capacity after the 1C charge and discharge cycles 320 times, shown in b curve among Fig. 2.
Embodiment 3
Alloy composition (mass percent) is: Rare Earth Lanthanum 23.5%, and rare earth cerium 8.4%, nickel 51.2%, manganese are 8.4%, and aluminium is 1.5%, and copper is 7.0%.Nonstoichiometry molecular formula AB
5.20(x=0.2).Its preparation method and condition and embodiment one are identical, the alloy of making at room temperature, 0.2C discharges and recharges maximum discharge capacity and reaches 312mAh/g, shown in c curve among Fig. 1; Under the room temperature, can keep 75% of initial capacity after the 1C charge and discharge cycles 320 times, shown in c curve among Fig. 2.
Embodiment 4
Alloy composition (mass percent) is: Rare Earth Lanthanum 21.50%, and rare earth cerium 8.50%, nickel 52.0%, manganese are 11.0%, and iron is 2.0%, and copper is 5.0%.Nonstoichiometry molecular formula AB
5.80(x=0.8).Its preparation method and condition and embodiment one are identical, the alloy of making at room temperature, 0.2C discharges and recharges maximum discharge capacity and reaches 308mAh/g, shown in d curve among Fig. 1; Under the room temperature, can keep 85% of initial capacity after the 1C charge and discharge cycles 480 times, shown in d curve among Fig. 2.
From the foregoing description as can be known, non-stoichiometric LaNi of the present invention
5It is big that the no cobalt hydrogen storage alloy of base has a charge/discharge capacity, 1C charge and discharge cycles number of times height, the advantage of long service life.
Claims (5)
1. non-stoichiometric LaNi
5The no cobalt hydrogen storage alloy of base, it is characterized in that: the ingredient formula of this alloy material is A(NiM)
5+x, wherein A is two or more the combination among La, Ce, Pr, the Nd; M wherein is any or the wherein combination of more than one elements among Mn, Al, Cu, Fe, Si, Sn, the Zr; Wherein-0.2≤x≤+ 0.8.
2. described non-stoichiometric LaNi of claim 1
5The preparation method of the no cobalt hydrogen storage alloy of base, it is characterized in that: preparation process comprises:
(1) each element with formula rate is placed in the vacuum induction furnace, 1 ~ 7Pa will be evacuated down in the vacuum induction furnace, applying argon gas is 0.05 ~ 0.08Mpa to furnace pressure then, repeats 2 ~ 4 prepurgings, carries out melting at last under furnace pressure 0.05 ~ 0.08Mpa and argon shield; Carry out concise 25 ~ 45min after the complete fusion of alloy again;
(2) alloy liquid after concise pours into water cooling ingot mould and carries out cooled and solidified with step (1), speed of cooling obtains alloy block within an hour the alloy block temperature being reduced to below 50 ℃, then alloy block is placed vacuum annealing furnace under argon shield, to heat-treat: pressure to the 0.1 ~ 1Pa that is evacuated to vacuum annealing furnace, charging into the pressure that makes behind the argon gas in the stove then reaches 0.05 ~ 0.08Mpa and carries out anneal, promptly with temperature to 850 in the speed kindling of 3 ~ 5 ℃/min ~ 1100 ℃, be incubated 6 ~ 24 hours, be cooled to room temperature then;
(3) the good alloy block of step (2) thermal treatment is carried out Mechanical Crushing ball milling powdered.
3. non-stoichiometric LaNi according to claim 2
5The preparation method of the no cobalt hydrogen storage alloy of base, it is characterized in that: the refining in the described step (1) is: after all raw material is melted fully, with the power of melting suitably reduce by 10 ~ 30% alloy liquid can be rolled stir not volatilize strongly again be standard.
4. non-stoichiometric LaNi according to claim 2
5The preparation method of the no cobalt hydrogen storage alloy of base, it is characterized in that: the room temperature that is cooled in the described step (2) is: allow alloy cool to the furnace below 600 ℃ earlier, the flue that alloy will be housed is then put into air-cooled cooling tower, and to carry out air-cooled be that the alloy block temperature was reduced to below 50 ℃ at 10 hours.
5. non-stoichiometric LaNi according to claim 2
5The preparation method of the no cobalt hydrogen storage alloy of base, it is characterized in that: the Mechanical Crushing ball milling powdered in the described step (3) is: under the argon gas gas shiled, alloy block is carried out the Mechanical Crushing ball milling become size to satisfy 150 ~ 250 purpose powder.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104451264A (en) * | 2014-12-09 | 2015-03-25 | 桂林电子科技大学 | Laceni magnetic wave absorbing material and preparation method thereof |
| CN104451265A (en) * | 2014-12-09 | 2015-03-25 | 桂林电子科技大学 | Ni-based alloy magnetic microwave absorbing material and preparation method thereof |
| CN106001584A (en) * | 2016-07-26 | 2016-10-12 | 大连理工大学 | Technology for producing silicon-zirconium uniformly-mixed alloy powder through casting method |
| CN111979449A (en) * | 2020-08-13 | 2020-11-24 | 兰州金川科力远电池有限公司 | Low-cost power type hydrogen storage alloy and preparation method thereof |
| CN115466879A (en) * | 2022-08-11 | 2022-12-13 | 甘肃稀土新材料股份有限公司 | Cobalt-free yttrium-containing long-life hydrogen storage alloy powder and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451264A (en) * | 2014-12-09 | 2015-03-25 | 桂林电子科技大学 | Laceni magnetic wave absorbing material and preparation method thereof |
| CN104451265A (en) * | 2014-12-09 | 2015-03-25 | 桂林电子科技大学 | Ni-based alloy magnetic microwave absorbing material and preparation method thereof |
| CN106001584A (en) * | 2016-07-26 | 2016-10-12 | 大连理工大学 | Technology for producing silicon-zirconium uniformly-mixed alloy powder through casting method |
| CN111979449A (en) * | 2020-08-13 | 2020-11-24 | 兰州金川科力远电池有限公司 | Low-cost power type hydrogen storage alloy and preparation method thereof |
| CN115466879A (en) * | 2022-08-11 | 2022-12-13 | 甘肃稀土新材料股份有限公司 | Cobalt-free yttrium-containing long-life hydrogen storage alloy powder and preparation method thereof |
| CN115466879B (en) * | 2022-08-11 | 2023-12-26 | 甘肃稀土新材料股份有限公司 | Cobalt-free yttrium-containing long-life hydrogen storage alloy powder and preparation method thereof |
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Application publication date: 20111221 |