CN100568591C - A kind of hydrogen storage alloy for low temperature Ni-MH power cell - Google Patents
A kind of hydrogen storage alloy for low temperature Ni-MH power cell Download PDFInfo
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- CN100568591C CN100568591C CNB2008100279692A CN200810027969A CN100568591C CN 100568591 C CN100568591 C CN 100568591C CN B2008100279692 A CNB2008100279692 A CN B2008100279692A CN 200810027969 A CN200810027969 A CN 200810027969A CN 100568591 C CN100568591 C CN 100568591C
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Abstract
A kind of hydrogen storage alloy for low temperature Ni-MH power cell.Its composed atom ratio is: La
1-x-y-zCe
xPr
yNd
zNi
aCo
bMn
cAl
dB
e, x=0.45～0.60 wherein, y=0.05～0.07, z=0.15～0.21, a=3.50～3.80, b=0.40～0.65, c=0.25～0.45, d=0.10～0.35, e=0.05～0.15.This hydrogen-storage alloy can generate the CeCo with high catalytic activity
4Type B second phase, thus the heavy-current discharge performance and the low temperature performance of raising hydrogen-storage alloy not only are used in the low temperature nickel hydrogen battery that uses under-40 ℃ of conditions, still have good heavy-current discharge performance simultaneously under-20 ℃ of conditions.
Description
Technical field
The present invention relates to a kind of battery hydrogen-storage alloy, particularly a kind of low temperature battery hydrogen-storage alloy.
Background technology
But Ni-MH battery has obtained extensive use with its higher specific energy fast charging and discharging, pollution-free and advantage such as have extended cycle life.Take all factors into consideration from reliability, fail safe, the resource and environment problem of battery material and the development trend of secondary cell performance of secondary cell, Ni-MH battery is the automobile-used first-selected electrokinetic cell of near and mid-terms hybrid electrically.In addition, Ni-MH battery also is considered to the optional power supply of the military electronic equipment of many novel portables.Yet these new applications are had higher requirement to the heavy-current discharge performance and the serviceability temperature scope of battery.In cold district and Military Application, require Ni-MH battery under-40 ℃ of conditions, to discharge.At present, Ni-MH battery mainly uses under 0～40 ℃ of condition, when temperature is lower than 0 ℃, the Ni-MH battery heavy-current discharge performance sharply descends, and when temperature was lower than-20 ℃, Ni-MH battery low discharging current capacity descended obviously, when temperature reaches-40 ℃, Ni-MH battery can not put substantially.The low temperature performance of Ni-MH battery and positive and negative pole material, barrier film and electrolyte all have certain relation, but depend primarily on the low temperature performance of hydrogen-storage alloy.Chinese patent 200410040649.2 and 200510123747.7 all discloses a kind of free neodymium rare-earth hydrogen-storage alloy La that is used for low temperature (being low to moderate-40 ℃) Ni-MH battery
1-x-yCe
xPr
y(NiCoMnAl)
5, but the heavy-current discharge performance of not mentioned hydrogen-storage alloy.
Summary of the invention
The present invention proposes a kind of hydrogen-storage alloy that is used for the low temperature power nickel-hydrogen cell.This hydrogen-storage alloy not only is used in the low temperature nickel hydrogen battery that uses under-40 ℃ of conditions, still has good heavy-current discharge performance simultaneously under-20 ℃ of conditions.
The composed atom ratio of hydrogen-storage alloy of the present invention is: La
1-x-y-zCe
xPr
yNd
zNi
aCo
bMn
cAl
dB
e, x=0.45～0.60 wherein, y=0.05～0.07, z=0.15～0.21, a=3.50～3.80, b=0.40～0.65, c=0.25～0.45, d=0.10～0.35, e=0.05～0.15.
It is AB that described hydrogen-storage alloy belongs to rare earth
5The type hydrogen-storage alloy, the A side is made up of the cerium-rich rare earth hydrogen-storage alloy, wherein contains element La, Ce, Pr and Nd, and the B side contains element Ni, Co, Mn, Al and B.By adding element B, in hydrogen-storage alloy, can generate CeCo with high catalytic activity
4Type B second phase, thereby the heavy-current discharge performance and the low temperature performance of raising hydrogen-storage alloy.
Description of drawings
Fig. 1 embodiment 4 hydrogen-storage alloy XRD figure;
Fig. 2 embodiment 4 hydrogen-storage alloy PCT curves (45 ℃);
Fig. 3 comparative example hydrogen-storage alloy PCT curve (45 ℃);
Fig. 4 Ni-MH battery 5C discharge curve.
Embodiment
According to the alloying component ratio, wherein rare earth element is with the form of cerium-rich rare earth alloy, and element B is added with the form of ni-b alloy; other metal purities are more than 99.5%; with the confected materials vacuum quick quenching furnace, be evacuated to 0.05Pa, logical then argon shield pressure 0.05MPa; melting is also got rid of into the hydrogen-storage alloy sheet of 0.05～0.1mm; alloy sheet heat treatment 4 hours under 900 ℃ of conditions is after the cooling, through mechanical ball milling powder process; sieve, obtain the hydrogen-storage alloy powder of granularity less than 0.075mm.
According to above-mentioned hydrogen-storage alloy powder preparation technique, obtain hydrogen-storage alloy powder embodiment 1～6 as table 1 composition, comparative example adopts the commercially available hydrogen-storage alloy powder that uses for nickel-hydrogen battery.
The composition of table 1 hydrogen-storage alloy
The about 0.2g of hydrogen-storage alloy powder is evenly mixed with 1: 3 weight ratio with carbonyl nickel powder, under the pressure of 250MPa, make diameter and be the electrode wafer of 15mm and make negative pole, with the capacity is the sintered type nickel hydroxide electrode work positive pole of 1200mAh, electrolyte is the KOH solution of 6mol/L, be assembled into simulated battery, under 25 ℃ of room temperature conditions, with the specific discharge capacity of 0.2C charge-discharge test hydrogen-storage alloy powder, with 2C charging, the heavy-current discharge performance and the cycle life of 10C discharge test hydrogen-storage alloy powder.
The normal temperature discharge performance that records above-mentioned hydrogen-storage alloy with simulated battery is as shown in table 2.Can find out that from table 2 hydrogen-storage alloy powder of the present invention is compared with the comparative example hydrogen-storage alloy powder, the 10C specific discharge capacity obviously improves, and has heavy-current discharge performance preferably.Can find out that from the PCT curve of Fig. 2, Fig. 3 the PCT platform of embodiment 4 alloyed powders can find out that from the battery 5C discharge curve of Fig. 4 the heavy-current discharge platform of hydrogen-storage alloy of the present invention significantly improves apparently higher than the comparative example hydrogen-storage alloy.Can find out that from the XRD figure of Fig. 1 embodiment 4 hydrogen-storage alloys hydrogen-storage alloy of the present invention is except by CaCu
5Outside the phase composition, also contain the CeCo of high catalytic activity
4Type B second phase.Owing to the existence of high catalytic activity second phase, improve the heavy-current discharge performance and the low temperature performance of hydrogen-storage alloy greatly.
25 ℃ of following hydrogen-storage alloy discharge performances of table 2
Hydrogen-storage alloy powder is mixed with binding agent, make slurry, be coated on then on the perforated steel ribbon, drying, compacting, severing make the nickel-hydrogen battery negative pole sheet; Add CoO, binding agent in spherical hickelous nydroxide (containing 3%Zn and 1%Co), make slurry, this slurry is filled in the foaming nickel, drying, compacting, severing obtain anode of nickel-metal hydride battery.Around, encapsulation, the KOH solution with 30% is electrolyte, is assembled into battery, obtains battery after changing into above-mentioned positive and negative electrode and membrane coil, and the theoretical capacity of Ni-MH battery is 1500mAh.
Under 25 ℃ of room temperature conditions, with 1C charging, the heavy-current discharge performance of 5C discharge test battery.
Ni-MH battery was filled 2.5 hours with 0.5C, under 0 ℃ ,-20 ℃ conditions, placed 5 hours respectively, be discharged to 1V with 0.5C, the discharge performance of 0 ℃ in beta alloy powder and-20 ℃, after placing 5 hours under-40 ℃ of conditions, be discharged to 1V with 0.2C, the discharge performance of test hydrogen-storage alloy powder-40 ℃.
Table 3 is the low temperature performance of the Ni-MH battery of embodiment and the assembling of comparative example hydrogen-storage alloy powder, can find out from table 3, the low temperature performance of hydrogen-storage alloy powder of the present invention obviously improves, the Ni-MH battery of embodiment 4 hydrogen-storage alloy powders assembling is under-40 ℃ of conditions, 0.2C can reach 202min discharge time, reaches 67.3% of its specified discharge capacity.
The low temperature performance of table 3 Ni-MH battery
Claims (1)
1. a hydrogen storage alloy for low temperature Ni-MH power cell is characterized in that the composed atom ratio is: La
1-x-y-zCe
xPr
yNd
zNi
aCo
bMn
cAl
dB
e, x=0.45～0.60 wherein, y=0.05～0.07, z=0.15～0.21, a=3.50～3.80, b=0.40～0.65, c=0.25～0.45, d=0.10～0.35, e=0.05～0.15.
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| CNB2008100279692A CN100568591C (en) | 2008-05-08 | 2008-05-08 | A kind of hydrogen storage alloy for low temperature Ni-MH power cell |
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|---|---|---|---|
| CNB2008100279692A CN100568591C (en) | 2008-05-08 | 2008-05-08 | A kind of hydrogen storage alloy for low temperature Ni-MH power cell |
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| CN100568591C true CN100568591C (en) | 2009-12-09 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102808107A (en) * | 2012-07-25 | 2012-12-05 | 鞍山鑫普新材料有限公司 | Low-cost AB5 hydrogen storage alloy without cobalt, praseodymium and neodymium |
| CN103101880B (en) * | 2013-01-29 | 2014-11-12 | 广州有色金属研究院 | Lithium borohydride/rare earth magnesium base alloy composite hydrogen storage material and preparation method thereof |
| CN103103380A (en) * | 2013-01-30 | 2013-05-15 | 广州有色金属研究院 | Samarium-containing praseodymium and neodymium-free hydrogen storage alloy for nickel-hydrogen power battery |
| CN105463256B (en) * | 2015-12-03 | 2017-08-25 | 内蒙古稀奥科贮氢合金有限公司 | A kind of Hydrogen storage alloy for nickel-metal hydride battery and preparation method thereof |
| CN111180697A (en) * | 2019-12-31 | 2020-05-19 | 深圳拓量技术有限公司 | Nickel-hydrogen battery for ultralow temperature environment |
| CN111180718A (en) * | 2019-12-31 | 2020-05-19 | 深圳拓量技术有限公司 | Hydrogen storage alloy powder of nickel-hydrogen battery for ultralow temperature environment and preparation method thereof |
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Effective date of registration: 20171227 Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee after: GUANGDONG INSTITUTE OF RARE METALS Address before: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee before: Guangzhou Research Institute of Non-ferrous Metals |
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