CN102492873A - Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy - Google Patents
Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy Download PDFInfo
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- CN102492873A CN102492873A CN2011104179638A CN201110417963A CN102492873A CN 102492873 A CN102492873 A CN 102492873A CN 2011104179638 A CN2011104179638 A CN 2011104179638A CN 201110417963 A CN201110417963 A CN 201110417963A CN 102492873 A CN102492873 A CN 102492873A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy. The praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy is characterized in that the formula of the AB5 type hydrogen storage alloy is La1-xCexNiaCobMncAldCUeMf, wherein M is one, two or more than two of Fe, Sn and B; x, a, b, c, d, e and f represent a molar ratio; x is more than or equal to 0.05 and less than or equal to 0.35; a is more than or equal to 3.70 and less than or equal to 4.2; b is more than 0 and less than or equal to 0.75; c is more than or equal to 0.15 and less than or equal to 0.42; d is more than or equal to 0.20 and less than or equal to 0.40; e is more than or equal to 0.02 and less than or equal to 0.30; f is more than or equal to 0 and less than or equal to 0.10; and the sum of a, b, c, d, e is more than or equal to 4.70 and less than or equal to 5.30. The hydrogen storage alloy does not contain praseodymium or neodymium, so production cost can be reduced, the corrosion resistance of the alloy can be improved, the service life of the alloy can be prolonged, and the alloy is easy to activate.
Description
Technical field
The present invention relates to a kind of rare earth storage alloy material for hydrogen, particularly a kind of no praseodymium neodymium-nickel is AB
5The type hydrogen-storage alloy.
Background technology
Nickel metal hydride battery with it than height ratio capacity, but fast charging and discharging, overcharging resisting, pollution-free, advantage such as have extended cycle life are used widely in fields such as aerospace, mobile telephone, notebook computer, electromobiles.AB
5The type rare earth based hydrogen storage alloy inhale at normal temperatures and pressures reversiblely put hydrogen, easily-activated, inhale advantages such as hydrogen discharge reaction speed is fast, obtain a large amount of research as the Ni/MH cell negative electrode material.
Present commercial rare earth based AB
5Type hydrogen-storage alloy specific storage is about 300～340mAh/g, and what wherein the A side adopted is battery grade mischmetal, mainly contains lanthanum rich mischmetal, cerium-rich mischmetal or (LaCePrNd)
1In recent years; Rare earth material obtains fast development at aspects such as magneticsubstance, luminescent material, nuclear energy materials; The consumption market of elements such as neodymium, praseodymium, samarium, yttrium is constantly enlarged; And didymum that to be light rare earths concentrate middle-weight rare earths distribute is high, be worth one of good element in height and market, this causes rare earth lanthanum, cerium excessive, the by product of bulk deposition has a strong impact on the balanced growth of rare earth industry; Simultaneously, rare earth metal on the world market, particularly cell-grade mixed rare earth, metal praseodymium, the rising all the way of neodymium metal price cause the hydrogen-storage alloy cost high, and the market competitiveness descends.Therefore, comprehensive utilization rare earth metal, the high AB of research and development cost performance
5The type rare earth based hydrogen storage alloy becomes the problem that each researcher is paid close attention to.Praseodymium in the norium, neodymium partly replace LaNi
5In La the time, the loading capacity of alloy is increased, so activation performance improvement, cycle life prolongation etc. are to AB
5The research of type A side lanthanum, cerium, praseodymium and neodymium composed atom ratio becomes AB
5One of direction of type rare earth based hydrogen storage alloy research.
USP 6106768 has been announced multiple AB
5The type hydrogen-storage alloy, its A side adopts lanthanum rich mischmetal, its weight consists of 63.0%La, 17.4%Ce, 10.68%Pr, 2.24%Nd, 6.68% other; The B side is mainly elementary composition by Ni, Mn and three kinds of Al, and has added at least a in Co, Si, Cu, Cr, Zn, V and the Fe element.The maximum discharge capacity that this alloy 0.2C discharges and recharges is 290～311mAh/g, and the loading capacity after the 0.2C charge and discharge cycles 300 times and the ratio of maximum discharge capacity are 80～86%.
Chinese patent 200710124454.X has announced a kind of MmNi
3.55Co
0.75Mn
0.4Al
0.3The type commodity are with the heat-treat condition of hydrogen-storage alloy; Wherein Mm is a cerium-rich mischmetal; Its weight consists of 27.28%La, 50.41%Ce, 5.03%Pr, 17.04%Nd; The maximum discharge capacity that this alloy 1C discharges and recharges is 320mAh/g, and the loading capacity after the 1C charge and discharge cycles 200 times and the ratio of maximum discharge capacity are 90～96%.
Summary of the invention
The object of the present invention is to provide a kind of no praseodymium neodymium-nickel is AB
5The type hydrogen-storage alloy.This hydrogen-storage alloy does not contain the praseodymium neodymium, and production cost is reduced, and can improve the corrosion resistance of alloy, prolongs alloy life, is easy to activation.
For realizing above-mentioned purpose, technical scheme of the present invention is: be AB
5The type hydrogen-storage alloy consists of La
1-xCe
xNi
aCo
bMn
cAl
dCu
eM
f, M be among Fe, Sn or the B one or both or two or more, x, a, b, c, d, e and f represent mol ratio; 0.05≤x≤0.35,3.70≤a≤4.2,0＜b≤0.75 wherein; 0.15≤c≤0.42,0.20≤d≤0.40,0.02≤e≤0.30; 0≤f≤0.10,4.70≤a+b+c+d+e≤5.30.
The preferred version that no praseodymium neodymium-nickel of the present invention is AB5 type hydrogen-storage alloy is: 0.10≤x≤0.20,3.75≤a≤3.90,0.40≤b≤0.60; 0.24≤c≤0.40,0.20≤d≤0.27,0.02≤e≤0.10; 0≤f≤0.07,4.95≤a+b+c+d+e≤5.10.
No praseodymium neodymium-nickel of the present invention is AB
5The preferred plan of type hydrogen-storage alloy is: La
0.8Ce
0.2Ni
3.85Co
0.55Mn
0.40Al
0.2Cu
0.05
AB
5Type hydrogen-storage alloy A side composition accounts for about 33% of hydrogen-storage alloy weight, and no praseodymium neodymium-nickel of the present invention is AB
5Type hydrogen-storage alloy powder and A side element adopt the AB of mishmetal
5The elementary composition production cost of type hydrogen-storage alloy powder A side is compared, and practices thrift about 30%/Kg.
Hydrogen-storage alloy of the present invention and existing AB
5The type hydrogen-storage alloy is compared, and lanthanum content increases in the hydrogen-storage alloy, and the loading capacity of hydrogen-storage alloy is increased, and a spot of cerium can improve the corrosion resistance of alloy, prolongs alloy life, and does not contain the praseodymium neodymium, and production cost is reduced; Metallic elements such as a small amount of Cu, Fe, Sn and B add can prolong alloy life, makes alloy be easy to activation.Hydrogen-storage alloy of the present invention is compared with the hydrogen-storage alloy that above-mentioned USP and Chinese patent are announced, its loading capacity increases, and charge and discharge circulation life is higher than the former, and is suitable with the latter.
Description of drawings
Fig. 1 is the room temperature PCT curve of embodiment 2 hydrogen-storage alloys.
Embodiment
According to alloying constituent ratio batching, wherein lanthanoid metal, cerium purity are more than 99%, and other metal purities are more than 99.5%.Confected materials is placed vacuum quick quenching furnace, be evacuated to 0.05Pa, applying argon gas begins to protect melting then, and pressure 0.05MPa gets rid of into the alloy slice of 0.05～0.1mm after the melting; Alloy slice is at 900～1000 ℃ of following insulation 3～4h, and cooling can make the alloy powder of granularity less than 0.075mm after mechanical ball milling powder process, sieve.
According to above-mentioned alloy powder preparation technology, obtain the 8 kind hydrogen-storage alloy powders listed like table 1; Comparative example 1 is a USP 6106768; Comparative example 2 is Chinese patent 200710124454.X.
Table 1 hydrogen-storage alloy chemical constitution
With the hydrogen-storage alloy powder about 0.2g and hydroxyl nickel powder with 1: 3 weight ratio uniform mixing; The electrode wafer of under the pressure of 24～25MPa, processing diameter and be 15mm is as the electrode negative pole, as electrode anode, is electrolytic solution with the KOH solution of 6mol/L with the netted nickel hydroxide electrode (capacity is 1200mAh) of sintered type; Be assembled into simulated battery; Under 25 ℃, with the specific discharge capacity of 0.2C charge-discharge test hydrogen-storage alloy, in heavy-current discharge performance and cycle life with 2C charge-discharge test hydrogen-storage alloy powder; Decay to 80% terminal point of maximum capacity as cycling life test with loading capacity; And calculate discharge capacitance S200 after the hydrogen-storage alloy charge and discharge cycles 200 times, i.e. the ratio of loading capacity and maximum discharge capacity after the charge and discharge cycles 200 times, result such as table 2 are listed.
Table 2 hydrogen-storage alloy discharge performance
* comparative example 2 hydrogen-storage alloys are maximum specific discharge capacity, discharge performance and the cycle life with 1C charge-discharge test hydrogen-storage alloy powder.
Visible from the PCT curve of Fig. 1 embodiment 2 hydrogen-storage alloys, hydrogen-storage alloy of the present invention has hydrogen storage property preferably, and the hydrogen platform of putting under its room temperature condition is 0.07MPa.
Visible from table 2, the loading capacity of hydrogen-storage alloy powder of the present invention all improves than the hydrogen-storage alloy powder of prior art, and production cost is lower.Compare with comparative example, add the capacity that a spot of Ce can not influence alloy, and can effectively increase the cycle life of hydrogen-storage alloy of the present invention, and add stability and capacity that a spot of metallic element Cu, Fe, Sn and B etc. help increasing alloy.The highest specific discharge capacity of 0.2C like embodiment 2 reaches 334mAh/g, and cycle life is 405 times.
Claims (3)
1. a no praseodymium neodymium-nickel is AB
5The type hydrogen-storage alloy is characterized in that being AB
5The type hydrogen-storage alloy consists of La
1-xCe
xNi
aCo
bMn
cAl
dCu
eM
f, M be among Fe, Sn or the B one or both or two or more, x, a, b, c, d, e and f represent mol ratio; 0.05≤x≤0.35,3.70≤a≤4.2,0＜b≤0.75 wherein; 0.15≤c≤0.42,0.20≤d≤0.40,0.02≤e≤0.30; 0≤f≤0.10,4.70≤a+b+c+d+e≤5.30.
2. no praseodymium neodymium-nickel according to claim 1 is AB5 type hydrogen-storage alloy, it is characterized in that x, a, b, c, d, e and f represent that mol ratio is 0.10≤x≤0.20,3.75≤a≤3.90; 0.40≤b≤0.60; 0.24≤c≤0.40,0.20≤d≤0.27,0.02≤e≤0.10; 0≤f≤0.07,4.95≤a+b+c+d+e≤5.10.
3. no praseodymium neodymium-nickel according to claim 1 is AB5 type hydrogen-storage alloy, it is characterized in that La
0.8Ce
0.2Ni
3.85Co
0.55Mn
0.40Al
0.2Cu
0.05
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN102888539A (en) * | 2012-10-25 | 2013-01-23 | 厦门钨业股份有限公司 | Low-cost AB5 type hydrogen storage alloy having ultrahigh capacity characteristic, and preparation method and application 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119791A (en) * | 1994-09-30 | 1996-04-03 | 北京科技大学 | Cheap rare-earth hydrogen storage electrode alloy containing copper and low cobalt |
| CN1285621A (en) * | 2000-09-22 | 2001-02-28 | 中国科学院上海冶金研究所 | Hydroyen stored alloy for megative electrode of high power nickel metal hydride cell |
| CN101295784A (en) * | 2008-06-12 | 2008-10-29 | 广州有色金属研究院 | Non-cobalt AB5 hydrogen storage alloy |
| CN101613818A (en) * | 2009-07-21 | 2009-12-30 | 厦门钨业股份有限公司 | A kind of low-cost hydrogen storage alloy and its production and application |
-
2011
- 2011-12-13 CN CN2011104179638A patent/CN102492873A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119791A (en) * | 1994-09-30 | 1996-04-03 | 北京科技大学 | Cheap rare-earth hydrogen storage electrode alloy containing copper and low cobalt |
| CN1285621A (en) * | 2000-09-22 | 2001-02-28 | 中国科学院上海冶金研究所 | Hydroyen stored alloy for megative electrode of high power nickel metal hydride cell |
| CN101295784A (en) * | 2008-06-12 | 2008-10-29 | 广州有色金属研究院 | Non-cobalt AB5 hydrogen storage alloy |
| CN101613818A (en) * | 2009-07-21 | 2009-12-30 | 厦门钨业股份有限公司 | A kind of low-cost hydrogen storage alloy and its production and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN102888539A (en) * | 2012-10-25 | 2013-01-23 | 厦门钨业股份有限公司 | Low-cost AB5 type hydrogen storage alloy having ultrahigh capacity characteristic, and preparation method and application thereof |
| CN102888539B (en) * | 2012-10-25 | 2015-07-29 | 厦门钨业股份有限公司 | A kind of there is ultra-high capacity characteristic low cost AB5 type hydrogen-storage alloy and method for making and application |
| 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 |
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Application publication date: 20120613 |