CN103103380A - Samarium-containing praseodymium and neodymium-free hydrogen storage alloy for nickel-hydrogen power battery - Google Patents
Samarium-containing praseodymium and neodymium-free hydrogen storage alloy for nickel-hydrogen power battery Download PDFInfo
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- CN103103380A CN103103380A CN201310035757XA CN201310035757A CN103103380A CN 103103380 A CN103103380 A CN 103103380A CN 201310035757X A CN201310035757X A CN 201310035757XA CN 201310035757 A CN201310035757 A CN 201310035757A CN 103103380 A CN103103380 A CN 103103380A
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Abstract
The invention discloses a samarium-containing praseodymium and neodymium-free hydrogen storage alloy for a nickel-hydrogen power battery. The hydrogen storage alloy is characterized in that the atomic ratio of the composition is La(1-x-y)CexSmyNiaCobMncAldMe, wherein M is one or two of Fe, Cu and B; and x is 0.20-0.70, y is 0.01-0.30, a is 3.30-4.20, b is 0.10-0.70, c is 0.40-0.65, d is 0.10-0.35 and e is 0.05-0.30. The samarium-containing praseodymium and neodymium-free hydrogen storage alloy for a nickel-hydrogen power battery disclosed by the invention does not contain relatively expensive rare earth elements such as praseodymium, neodymium and the like and thus reduces the production cost, and also has the performance such as easy activation, high discharge voltage and capacity, good high-current discharge and the like.
Description
Technical field
The present invention relates to a kind of hydrogen storage alloy that uses for nickel-hydrogen battery, particularly a kind of Ni-MH power cell is with containing samarium without praseodymium neodymium hydrogen storage alloy.
Background technology
But adopting lanthanon hydrogen storage alloy to have the characteristics of high-energy-density fast charging and discharging, pollution-free and long service life as the nickel metal hydride battery of negative electrode active material, is the first-selected battery of hybrid vehicle both at home and abroad at present.But along with rising steadily of rare earth element price, the ratio that accounts for its integral battery door cost for the preparation of the rare earth element of hydrogen storage alloy approximately progressively rises to 55% by 14%.As present main nickel-hydrogen battery negative pole material, Rare Earth AB
5Type hydrogen storage alloy has comparatively successfully carried out industrialization production, typical AB on current market
5The capacity of type hydrogen storage alloy is 310 ~ 330mAh/g, and its cost, heavy-current discharge characteristic (5C and more than, lower with), the neither ideal of low self-discharge performance.Therefore exploitation is without praseodymium, neodymium and AB that have good heavy-current discharge performance
5The type hydrogen storage material helps the cost that reduces the hybrid vehicle nickel-hydrogen battery negative pole material, and improves the market competitiveness of nickel metal hydride battery.
At present, the general commercially available rare earth AB that is used for electrical source of power
5Type hydrogen storage alloy, composition is generally La
0.6Ce
0.2Pr
0.05Nd
0.15Ni
4Co
0.45Mn
0.4Al
0.25Or approximate, contain Pr and Nd amount in its proportioning larger, though have certain heavy-current discharge performance, production cost is higher, causes using the nickel metal hydride battery holistic cost of this type of alloy production to rise, competitive power descends.And general commercially available rare earth AB
5Type is without Pr, Nd hydrogen storage alloy, and composition is generally La
0.6Ce
0.4Ni
3.8Co
0.5Mn
0.4Al
0.3Or approximate, its large current discharging capability is undesirable again.Chinese patent 102492873A and 102758104A all disclose a kind of without praseodymium neodymium AB
5Type hydrogen storage alloy, though the former has higher loading capacity (during 0.2C) and is easy to activation, the heavy-current discharge performance of alloy is mentioned at the end; Though the latter has carried out the test of heavy-current discharge aspect, its maximum discharge capacity and storage hydrogen platform are all lower, and the activation characteristic of not mentioned alloy.
Summary of the invention
The present invention proposes a kind of Ni-MH power cell with containing samarium without praseodymium neodymium hydrogen storage alloy.This alloy is not only
Contain the higher rare earth elements of price such as praseodymium, neodymium, reduced production cost, have simultaneously easily-activated, high sparking voltage and capacity, good performances such as heavy-current discharge.
Hydrogen storage alloy composed atom ratio of the present invention is: La
1-x-yCe
xSm
yNi
aCo
bMn
cAl
dM
e, M is one or both in Fe, Cu or B, x=0.20 ~ 0.70 wherein, y=0.01 ~ 0.30, a=3.30 ~ 4.20, b=0.10 ~ 0.70, c=0.40 ~ 0.65, d=0.10 ~ 0.35, e=0.05 ~ 0.30.
Described hydrogen storage alloy belongs to Rare Earth AB
5Type hydrogen storage alloy, the A side is comprised of the lanthanum rich rare earth hydrogen storage alloy, wherein contains element La, Ce, Sm, it is one or both in Fe, Cu or B that B side content has element Ni, Co, Mn, Al and M(M).Improve the heavy-current discharge performance of hydrogen storage alloy by adding element S m, can improve loading capacity, low temperature performance and the cyclical stability of hydrogen storage alloy by adding element M.
Description of drawings
Fig. 1 embodiment 2 hydrogen storage alloy XRD figure.
Embodiment
Table
The composition of hydrogen storage alloy
According to the alloying constituent ratio, rare earth element is with the form of lanthanum rich rare earth alloy, and element S m adds with the form of simple substance; other metal purity is more than 99.5%, and the raw material vacuum quick quenching furnace with preparing is evacuated to 0.05Pa; then logical argon shield; pressure is 0.05MPa approximately, and melting is also got rid of into the hydrogen storage alloy sheet of 0.05 ~ 0.1mm, alloy slice thermal treatment 4 ~ 8 hours under 800 ~ 1050 ° of C conditions; after cooling; through mechanical ball milling powder process, sieve, obtain granularity less than the hydrogen storing alloy powder of 0.08mm.
According to above-mentioned hydrogen storage alloy powder preparation technique, obtain the hydrogen storing alloy powder embodiment 1 ~ 6 as table 1 composition, comparative example adopts commercially available power-type Ni-H battery hydrogen storing alloy powder.
With hydrogen storing alloy powder approximately 0.2g evenly mix with the mass ratio of carbonyl nickel powder with 1:3, make diameter and be the electrode wafer of 15mm under the pressure of 25MPa and make negative pole, sintered type nickel hydroxide electrode take capacity as 1200mAh is done anodal, electrolytic solution is the KOH solution of 6mol/L, after being assembled into simulated battery, under 25 ° of C conditions, with the specific discharge capacity of 0.2C charge-discharge test hydrogen storing alloy powder, with the 2C charging, heavy-current discharge performance and the cycle life of hydrogen storing alloy powder is surveyed in the 10C discharge.
The chemical property of test implementation example is as shown in table 2.From the results shown in Table 2, comparative example 2(is general commercially available without Pr, Nd rare earth AB
5Type hydrogen storage alloy) in, in hydrogen storage alloy, owing to not containing Pr, Nd in A side rare earth, the heavy-current discharge performance of hydrogen storage alloy obviously reduces.In an embodiment of the present invention, after adding samarium metal, the heavy-current discharge performance of hydrogen storage alloy be improved significantly.When the addition of samarium surpasses the 0.10(atomic ratio) time, the 10C loading capacity of hydrogen storage alloy surpasses general commercially available Pr, the Nd rare earth AB of containing of comparative example 1(
5Type hydrogen storage alloy), its heavy-current discharge performance is improved significantly, but when samarium content was higher, the 0.2C loading capacity of hydrogen storage alloy descended obviously.Test result can be found out from table, and the hydrogen storage alloy of embodiment 3 has over-all properties preferably, and its 0.2C loading capacity is 326 mAh/g, and the 10C loading capacity is 256 mAh/g.
[0012] discharge performance of hydrogen storage alloy during 25 ° of C of table 2
Fig. 1 is the XRD figure of embodiment 2 hydrogen storage alloys, and this figure shows, hydrogen storage alloy of the present invention is mainly CaCu
5The phase structure of type in addition, also contains the CeCo of high catalytic activity
4The Type B second-phase.This hydrogen storage alloy is by adding rare earth element Sm, make the average grain size of alloy reduce, thereby strengthened the anti-polarization performance of alloy, and then the heavy-current discharge performance and the charge and discharge cycles that have strengthened alloy are stable, and the second-phase of high catalytic activity exists and further improved the heavy-current discharge performance of alloy.
Claims (1)
1. a Ni-MH power cell with containing samarium without praseodymium neodymium hydrogen storage alloy, is characterized in that hydrogen storage alloy composed atom ratio is: La
1-x-yCe
xSm
yNi
aCo
bMn
cAl
dM
e, M is one or both in Fe, Cu or B, x=0.20 ~ 0.70 wherein, y=0.01 ~ 0.30, a=3.30 ~ 4.20, b=0.10 ~ 0.70, c=0.40 ~ 0.65, d=0.10 ~ 0.35, e=0.05 ~ 0.30.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110157951A (en) * | 2019-06-06 | 2019-08-23 | 宜宾天原集团股份有限公司 | The preparation method of alloy material storing hydrogen |
| CN111118345A (en) * | 2019-11-28 | 2020-05-08 | 包头稀土研究院 | Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method |
| CN111118342A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111118341A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111224092A (en) * | 2019-12-05 | 2020-06-02 | 包头稀土研究院 | Zirconium or titanium doped samarium-containing hydrogen storage alloy, negative electrode, battery and preparation method |
| CN113881872A (en) * | 2021-10-27 | 2022-01-04 | 厦门钨业股份有限公司 | Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof |
| CN115261677A (en) * | 2022-08-08 | 2022-11-01 | 内蒙古稀奥科贮氢合金有限公司 | Low-cobalt praseodymium-free neodymium AB 5 Hydrogen storage alloy and low self-discharge nickel-metal hydride battery thereof |
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| CN101320801A (en) * | 2008-05-08 | 2008-12-10 | 广州有色金属研究院 | Hydrogen storage alloy for low temperature Ni-MH power cell |
| CN102492873A (en) * | 2011-12-13 | 2012-06-13 | 广州有色金属研究院 | Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy |
| CN102758104A (en) * | 2012-06-27 | 2012-10-31 | 鞍山鑫普新材料有限公司 | Low-cobalt and praseodymium-neodymium-free AB5 type hydrogen storage alloy with low cost and preparation method thereof |
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| CN102492873A (en) * | 2011-12-13 | 2012-06-13 | 广州有色金属研究院 | Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy |
| CN102758104A (en) * | 2012-06-27 | 2012-10-31 | 鞍山鑫普新材料有限公司 | Low-cobalt and praseodymium-neodymium-free AB5 type hydrogen storage alloy with low cost and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110157951A (en) * | 2019-06-06 | 2019-08-23 | 宜宾天原集团股份有限公司 | The preparation method of alloy material storing hydrogen |
| CN110157951B (en) * | 2019-06-06 | 2020-08-18 | 宜宾天原集团股份有限公司 | Preparation method of hydrogen storage alloy material |
| CN111118342A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111118341A (en) * | 2019-09-16 | 2020-05-08 | 包头稀土研究院 | Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111118341B (en) * | 2019-09-16 | 2021-08-06 | 包头稀土研究院 | Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111118342B (en) * | 2019-09-16 | 2021-08-06 | 包头稀土研究院 | A2B7 type RE-Sm-Ni series hydrogen storage alloy, negative electrode, battery and preparation method |
| CN111118345A (en) * | 2019-11-28 | 2020-05-08 | 包头稀土研究院 | Multi-element samarium-nickel hydrogen storage material, negative electrode, battery and preparation method |
| CN111224092A (en) * | 2019-12-05 | 2020-06-02 | 包头稀土研究院 | Zirconium or titanium doped samarium-containing hydrogen storage alloy, negative electrode, battery and preparation method |
| CN113881872A (en) * | 2021-10-27 | 2022-01-04 | 厦门钨业股份有限公司 | Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof |
| CN115261677A (en) * | 2022-08-08 | 2022-11-01 | 内蒙古稀奥科贮氢合金有限公司 | Low-cobalt praseodymium-free neodymium AB 5 Hydrogen storage alloy and low self-discharge nickel-metal hydride battery thereof |
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Application publication date: 20130515 |