CN1124412A - Hydrogen storage alloy for secondary cell - Google Patents
Hydrogen storage alloy for secondary cell Download PDFInfo
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- CN1124412A CN1124412A CN94118776A CN94118776A CN1124412A CN 1124412 A CN1124412 A CN 1124412A CN 94118776 A CN94118776 A CN 94118776A CN 94118776 A CN94118776 A CN 94118776A CN 1124412 A CN1124412 A CN 1124412A
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- secondary cell
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- 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
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Abstract
The Composition of the invented hydrogen storing alloy is Mm1-xXxNi5-a-b-c-yMnaCobAlcYy, where Mm being mixed rare earth metal, in which the content of lanthanum greater than 25%, sigma RE>99%, X being Zr, Ti, x=0.01-0.2, a=0.2-0.5, b=0.1-0.5, c=0.1-0.4, y=0.01-0.2, 0.5 less then a+b+c+y less then 1.6. The making method consists of putting the raw material in smelting furnace, evacuating, passing over argon, heating under 1450-1550 deg.C until the raw material completely smelting, thermal preseving for 5-30 min and ingot casting. Said hydrogen storing alloy features good heavy current property, large capacity and low cost.
Description
The present invention relates to the active material of electrode, a kind of more precisely as the AB5 type mishmetal nickel base hydrogen storage alloy material of inhaling the hydrogen electrode active material.
Inhaling hydrogen electrode is the critical material of Ni-H cell, and the quality of alloy material storing hydrogen is directly determining to inhale the quality of hydrogen electrode performance.In the last few years, people were devoted to improve the composition of alloy material storing hydrogen always, improved life-span, the specific capacity of alloy material storing hydrogen, and reduced its cost.
Alloy material storing hydrogen that it is generally acknowledged AB5 type mixed rare-earth hydrogen-bearing alloy material such as MmNi5 system is that cost is low, and the cell negative electrode material of function admirable, Mm are the mixture of rare earth metal, mainly consist of La, Ce, Pr, Nd.On the basis of MmNi5, substitute part Ni, its cycle life is significantly increased with Co, Al, Mn, and little to the size influence of its capacity.
People [power Sources, 12, (1988) 393] such as Dgawa Ikoma have studied a kind of well behaved alloy material storing hydrogen, and it consists of MmNi3,55CoO.75Mn 0.4Al0.3.Though in this system, adopted norium, but added expensive metal Co, the content of cobalt has accounted for about 40% of this alloy material storing hydrogen cost, therefore the cost that reduces this alloy material storing hydrogen improves the heavy-current discharge performance of this alloy material storing hydrogen, does not reduce the problem of other performances with regard to having become numerous researchers to pay close attention to of this hydrogen bearing alloy again.
The Japanese documentation spy opens the alloy material storing hydrogen that flat 3-294444 has proposed a kind of Mml-xZrxNiACoBMncAlD of consisting of, Mm is a cerium lanthanum didymium alloy in the formula, 0.01≤x≤0.08,4.9≤A+B+C+D≤5.1,3.2≤A≤3.6,0.50≤B≤1.0,0.3≤C≤0.5,0.3 after≤D≤0.5. had used a spot of zirconium to replace sub-fraction among the Mm in this patent documentation, the zirconium compounds surface formed oxide-film, has suppressed the oxidation of alloy, not only improved cycle life, also suppressed the stripping of manganese, returned for a long time when discharging and recharging operation again thereby make, electrode characteristic is unlikely to degenerate.But the content of cobalt is still high in this alloy material storing hydrogen, and the scope of B is 0.5≤B≤1.0, so the cost height.
The objective of the invention is to develop a kind of hydrogen bearing alloy of new low cobalt as negative active core-shell material, made it have good heavy-current discharge performance, and the capacity height, the cost of material is low.
Another object of the present invention just is to work out produces the above-mentioned preparation method as the negative active core-shell material hydrogen bearing alloy, makes its technology simple, and the new hydrogen bearing alloy of making as negative active core-shell material has good heavy-current discharge performance, the capacity height.
The alloy material storing hydrogen that a kind of secondary cell of the present invention is used, its chemical composition are Mm1-xXxNi5-a-b-c-yMnaCobAlcYy, and wherein Mm is a norium, wherein contain lanthanum 〉=25% (percetage by weight, down together) ∑ RE 〉=99% (RE is the summation of various thuliums), X is Zr, Ti or their alloy, Y is Zn or Zn alloy, x=0.01-0.2, a=0.2-0.5, b=0.1-0.5, c=0.1-0.4, y=0.01-0.2,0.5≤a+b+c+y≤1.6.
The present invention reduces the content of metallic cobalt, and improves the cost that heavy-current discharge performance has reduced hydrogen bearing alloy by adding metallic zinc, adds zirconium or titanium and improves its life characteristic, adds Co and can reduce the hydrogen bearing alloy plateau pressure, and increase the life-span of hydrogen bearing alloy.But Co content can reduce specific capacity during greater than 0.8 atomic ratio, increases the cost of hydrogen bearing alloy simultaneously again, so the content b=0.1-0.5 of Co is good with b=0.1-0.45 again.
But,, can improve by adding metallic Z r or Ti owing to the reduction of Co consumption has brought the problem of alloy material storing hydrogen life-span decline.Zr or Ti consumption are x=0.01-0.2 in the present invention, are good with x=0.09-0.2 again, and total amount is lower than at 0.01 o'clock, do not have the effect that prolongs the hydrogen bearing alloy life-span, and its total amount is higher than the reversible hydrogen that reduced hydrogen bearing alloy at 0.2 o'clock again.The Zr, the Ti that add also can adopt alloys such as ZrAl, TiMn except that simple metal.
The consumption of Zn or Zn alloy is y=0.01-0.2, is lower than at 0.01 o'clock and does not have the purpose that reduces hydrogen bearing alloy cost of the present invention and improve heavy-current discharge.Total amount was greater than 0.2 o'clock, and alloy life and capacity can be affected.Add Zn except that simple metal, also can adopt ZnMn, ZnAl alloy.
The present invention is the preparation method of the alloy material storing hydrogen used of a kind of secondary cell, press the composition of chemical general formula Mm1-xXxNi5-a-b-c-yMnaCobAlcYy, [wherein Mm is a norium, wherein contain lanthanum 〉=25% (percetage by weight, ∑ RE 〉=99% down together), (RE is the summation of various thuliums), X is Zr, and Ti or their alloy, Y are the alloy of Zn or Zn, x=0.01-0.2, a=0.2-0.5, b=0.1-0.5, c=0.1-0.4, y=0.01-0.2,0.5≤a+b+c+y≤1.6.Various metallic elements or alloy with requirement in the intermediate frequency furnace of packing into, vacuumize, feed inert gas, under 1450-1550 ℃ temperature, heat melting, after melting fully to all metallic elements or alloy, be incubated 5-30 minute again, pour cooling rapidly in the water jacketed copper crucible into, ingot casting.
Also can carry out melting with arc furnace, use water jacketed copper crucible, melt back is more than three times.Be smelted into button ingot or ingot casting with arc furnace or intermediate frequency furnace.The ingot coarse crushing to 1-20mm, is fed 3-6Mpa hydrogen again in autoclave, hydrogenation is 1-5 time repeatedly, and the formation granularity is the alloy powder of 40-70 μ m or is milled to same granularity through machinery.
During with arc furnace or intermediate frequency furnace melting, be evacuated to 0.1pa-20pa for well; The inert gas that feeds is advisable with argon gas, and the pressure of argon gas remains on 0.08Mpa-0.1Mpa, used Mm contain the lanthanum amount with 40-80% (percetage by weight) for well.
Copper powder or nickel powder with alloy material storing hydrogen powder of the present invention and 40 μ m, mix by 1: 1 (weight ratio), pressure with 1-5 ton/square centimeter is pressed into the negative pole of the thin slice of suitable size as battery, as positive pole, carries out solid measure with sintered type nickel electrode.The hydrogen storing alloy powder of the present invention and the PTFE (polytetrafluoroethylene) of constant weight are pressed 90: 10 (weight ratio) furnishing pasty states, through repeatedly being rolled into the thin slice of 0.3-0.4mm thickness, be pressed on conduction nickel screen two sides, pressure with 1-5 ton/square centimeter is pressed into the thick negative electrode of 0.4mm, do anodal with sintered type nickel electrode, the 6NKOH aqueous solution is electrolyte, form simulated battery and carry out life test, experimental condition is that 1C discharges and recharges, discharging and recharging the degree of depth is 100%, measuring capacity rate of descent after 200 circulations, with same condition respectively with 50mA/g, 100mA/g, 500mA/g, the electric current of 1000mA/g carries out the efficiency for charge-discharge test of alloy material storing hydrogen, and concrete data are seen embodiment.
A kind of alloy material storing hydrogen of the present invention has good high-rate performance, the capacity height, and it is low to contain cobalt, and the cost of material is low.
The method for preparing alloy material storing hydrogen of the present invention, technology is simple, the alloy material storing hydrogen function admirable of making, low cost product.The cost of hydrogen bearing alloy of the present invention is lower than contrast hydrogen bearing alloy E, and its amplitude that has can reduce and reaches 20%, illustrates that hydrogen bearing alloy of the present invention has good potential industrial production and is worth.
Fig. 1 is the contrast of the discharging efficiency of A, B among each embodiment, C, D hydrogen bearing alloy and contrast hydrogen bearing alloy E.
Abscissa is discharging current I (mA/g) in the formula, and ordinate is discharging efficiency %.
More specifically describe the present invention in more detail with following non-limiting example, will help the understanding to the present invention and advantage thereof, protection scope of the present invention is not subjected to the qualification of these embodiment, and protection scope of the present invention is decided by claims.
Embodiment 1
The chemical composition of the alloy material storing hydrogen that the secondary cell of present embodiment is used is Mm0.9Zr0.1Ni3.8Mn0.4Co0.4Al0.3Zn0.1, is hydrogen bearing alloy A.Containing lanthanum 41% (percetage by weight, down together) ∑ RE among the norium Mm is 99.1%,
Its manufacture method is for pressing the various metallic elements (or alloy) of above-mentioned chemical formula with requirement, pack in the medium frequency induction melting furnace, be evacuated to 10pa, feed argon gas, the pressure of argon gas is 0.09Mpa, under 1500 ± 20 ℃ temperature, after heating melting to all metals (or alloy) melt fully, be incubated 15 minutes again, pour in the water-cooled copper crucible, cooling rapidly, cast the hydrogen bearing alloy ingot, coarse crushing is to the 15mm, in the autoclave of packing into, feed the high-purity hydrogen of 6Mpa, to not inhaling till the hydrogen, be heated to 90 ± 10 ℃ of dehydrogenations, make the hydrogen storing alloy powder A of 40-70 μ m repeatedly for 3 times, test capacity and life-span as stated above, contrast hydrogen bearing alloy E is MmNi3.55Mn0.4Co0.75Al0.3, and its result is as follows, and sees Fig. 1, curve A, curve E is the contrast hydrogen bearing alloy.After the hydrogen bearing alloy specific capacity 200 times behind the capacity 200 times kind (mAh/g) (mAh/g) capacity descend % hydrogen bearing alloy A 302 288.1 4.6 contrast hydrogen bearing alloy E 285 267.9 6.0
Hydrogen bearing alloy A is 50mA/g at discharging current, 100mA/g, and 200mA/g, 500mA/g, 1000mA/g, its corresponding discharging efficiency is respectively 97%, 96%, and 95%, 88%, 80%.
And contrast hydrogen bearing alloy E is 50mA/g in discharge stream, 100mA/g, and 200mA/g, 500mA/g, 1000mA/g, its corresponding discharging efficiency are respectively 96%, 95%, 92%, 81%, 66%.
From above-mentioned data, as can be seen, adopt method of the present invention, add the purpose that a small amount of Zr and Zn can reach increase capacity and life-span, improved heavy-current discharge efficient simultaneously again.If the cost with contrast hydrogen bearing alloy E is 1, the cost of the hydrogen bearing alloy A of present embodiment is 0.943.
Embodiment 2
The chemical composition of the alloy material storing hydrogen of the secondary cell of present embodiment is Mm0.85-Zr0.15Ni3.9Co0.25Mn0.4Al0.3Zn0.15, is hydrogen bearing alloy B.
Its manufacture method is with embodiment 1, and E compares with the contrast hydrogen bearing alloy, and its result is as follows, and sees Fig. 1, curve B.After the hydrogen bearing alloy specific capacity 200 times behind the capacity 200 times kind (mAh/g) (mAh/g) capacity descend % hydrogen bearing alloy B 291 275.6 5.3 contrast hydrogen bearing alloy E 285 267.9 6.0
Hydrogen bearing alloy B is 50mA/g at discharging current, 100mA/g, and 200mA/g, 500mA/g, 1000mA/g, its corresponding discharging efficiency is respectively 98%, 97%, and 96%, 90%, 83%.
The correction data of contrast hydrogen bearing alloy E is seen embodiment 1.If the cost with contrast hydrogen bearing alloy E is 1, the cost of the hydrogen bearing alloy B of present embodiment is 0.789.
Embodiment 3
The chemical composition of the alloy material storing hydrogen of the secondary cell of present embodiment is Mm0.95Ti0.05Ni3.95Co0.3Mn0.4Al0.3Zn0.05, is hydrogen bearing alloy C.
Its manufacture method is with embodiment 1, and E compares with the contrast hydrogen bearing alloy, and its result is as follows, and sees Fig. 1, curve C.After the hydrogen bearing alloy specific capacity 200 times behind the capacity 200 times kind (mAh/g) (mAh/g) capacity descend % hydrogen bearing alloy C 280 258.2 7.8 contrast hydrogen bearing alloy E 285 267.9 6.0
Hydrogen bearing alloy C is 50mA/g at discharging current, 100mA/g, and 200mA/g, 500mA/g, 1000mA/g, its corresponding discharging efficiency is respectively 96%, 94%, and 92%, 83%, 68%.
The correction data of contrast hydrogen bearing alloy E is seen embodiment 1.If the cost with contrast hydrogen bearing alloy E is 1, the cost of the hydrogen bearing alloy C of present embodiment is 0.776.
Embodiment 4
The chemical composition of the alloy material storing hydrogen of the secondary cell of present embodiment is Mm0.9Ti0.1Ni3.6Co0.5Mn0.4Al0.3Zn0.2, is hydrogen bearing alloy D.
Its manufacture method is with embodiment 1, and E compares with the contrast hydrogen bearing alloy, and its result is as follows, and sees Fig. 1, curve D.After the hydrogen bearing alloy specific capacity 200 times behind the capacity 200 times kind (mAh/g) (mAh/g) capacity descend % hydrogen bearing alloy D 273 249.8 8.5 contrast hydrogen bearing alloy E 285 267.9 6.0
Hydrogen bearing alloy D is 50mA/g at discharging current, 100mA/g, and 200mA/g, 500mA/g, 1000mA/g, its corresponding discharging efficiency is respectively 96%, 95%, and 93%, 86%, 70%.
The correction data of contrast hydrogen bearing alloy E is seen embodiment 1.If the cost with contrast hydrogen bearing alloy E is 1, the cost of the hydrogen bearing alloy D of present embodiment is 0.857.
Claims (8)
1. alloy material storing hydrogen that secondary cell is used, it is characterized in that: its chemical composition is Mm1-xXxNi5-a-b-c-yMnaCobAlcYy, wherein Mm is a norium, wherein contain lanthanum 〉=25% (percetage by weight, down together), ∑ RE 〉=99%, (RE is the summation of various thuliums), X is Zr, Ti or their alloy, Y is the alloy of Zn or Zn, x=0.01-0.2, a=0.2-0.5, b=0.1-0.5, c=0.1-0.4, y=0.01-0.2,0.5≤a+b+c+y≤1.6.
2. the alloy material storing hydrogen of using according to a kind of secondary cell of claim 1 is characterized in that b=0.1-0.45.
3. the alloy material storing hydrogen of using according to a kind of secondary cell of claim 1 is characterized in that x=0.09-0.2.
4. the preparation method of the alloy material storing hydrogen used of a secondary cell is characterized in that,
(1) [wherein Mm is a norium by the composition of chemical general formula Mm1-xXxNi5-a-b-c-yMnaCobAlcYy, wherein contain lanthanum 〉=25% (percetage by weight, down together), ∑ RE 〉=99%, (RE is the summation of various thuliums), X is Zr, and Ti or their alloy, Y are the alloy of Zn or Zn, x=0.01-0.2, a=0.2-0.5, b=0.1-0.5, c=0.1-0.4, y=0.01-0.2,0.5≤a+b+c+y≤1.6], with the various metallic elements or the alloy of requirement, in the intermediate frequency furnace of packing into;
(2) vacuumize, feed inert gas, under 1450-1550 ℃ temperature, heat melting, after melting fully to all metallic elements or alloy, be incubated 5-30 minute again, pour cooling rapidly in the water jacketed copper crucible into, ingot casting.
5. the preparation method of the alloy material storing hydrogen of using according to a kind of secondary cell of claim 4 is characterized in that, is evacuated to 0.1-20pa.
6. the preparation method of the alloy material storing hydrogen of using according to a kind of secondary cell of claim 4 is characterized in that the inert gas that is fed is an argon gas, and the pressure of argon gas is 0.08-0.1Mpa.
7. the preparation method of the alloy material storing hydrogen of using according to a kind of secondary cell of claim 4 is characterized in that the alloy pig coarse crushing is to 1-20mm, and hydrogenation or mechanical crushing are to 40-70 μ m again.
8. the preparation method of the alloy material storing hydrogen of using according to a kind of secondary cell of claim 4 is characterized in that it is 40-80% (percetage by weight) that Mm contains the lanthanum amount.
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| Application Number | Priority Date | Filing Date | Title |
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| CN94118776A CN1045690C (en) | 1994-12-05 | 1994-12-05 | Hydrogen storage alloy for secondary cell |
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| CN94118776A CN1045690C (en) | 1994-12-05 | 1994-12-05 | Hydrogen storage alloy for secondary cell |
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| CN1124412A true CN1124412A (en) | 1996-06-12 |
| CN1045690C CN1045690C (en) | 1999-10-13 |
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| CN94118776A Expired - Lifetime CN1045690C (en) | 1994-12-05 | 1994-12-05 | Hydrogen storage alloy for secondary cell |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0756343A1 (en) * | 1995-07-27 | 1997-01-29 | VARTA Batterie Aktiengesellschaft | Alloys for use as active material for the negative electrode of an alkaline,rechargeable, nickel metal-hybride battery and its method of preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03294444A (en) * | 1990-04-11 | 1991-12-25 | Agency Of Ind Science & Technol | Hydrogen occluding electrode |
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1994
- 1994-12-05 CN CN94118776A patent/CN1045690C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0756343A1 (en) * | 1995-07-27 | 1997-01-29 | VARTA Batterie Aktiengesellschaft | Alloys for use as active material for the negative electrode of an alkaline,rechargeable, nickel metal-hybride battery and its method of preparation |
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| CN1045690C (en) | 1999-10-13 |
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Expiration termination date: 20141205 Granted publication date: 19991013 |