CN102492873A - Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy - Google Patents

Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
storage alloy
equal
hydrogen
alloy
neodymium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2011104179638A
Other languages
Chinese (zh)
Inventor
彭能
黄玲
黄奇书
雷一锋
张四奇
郑爱勤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Research Institute of Non Ferrous Metals
Original Assignee
Guangzhou Research Institute of Non Ferrous Metals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Research Institute of Non Ferrous Metals filed Critical Guangzhou Research Institute of Non Ferrous Metals
Priority to CN2011104179638A priority Critical patent/CN102492873A/en
Publication of CN102492873A publication Critical patent/CN102492873A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

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

A kind of no praseodymium neodymium-nickel is AB 5The type hydrogen-storage alloy
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
Figure BSA00000636067900031
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
Figure BSA00000636067900041
* 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
CN2011104179638A 2011-12-13 2011-12-13 Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy Pending CN102492873A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011104179638A CN102492873A (en) 2011-12-13 2011-12-13 Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011104179638A CN102492873A (en) 2011-12-13 2011-12-13 Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy

Publications (1)

Publication Number Publication Date
CN102492873A true CN102492873A (en) 2012-06-13

Family

ID=46184734

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011104179638A Pending CN102492873A (en) 2011-12-13 2011-12-13 Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy

Country Status (1)

Country Link
CN (1) CN102492873A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
CN104532095B (en) Yttrium-nickel rare earth-based hydrogen storage alloy
CN104195372A (en) Rare earth-magnesium-nickel system heterogeneous hydrogen storage alloys used for nickel-hydrogen batteries and preparing method thereof
CN102828069B (en) Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof
CN104518204A (en) Rare earth-yttrium-nickel family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy
CN104513925B (en) Yttrium-nickel rare earth family hydrogen storage alloy, and secondary battery containing hydrogen storage alloy
CN107275626B (en) A kind of single-phase AB4Type superlattice hydrogen storage alloy electrode material and preparation method thereof
CN104532062A (en) Yttrium-nickel rare earth-based hydrogen storage alloy
CN104152749A (en) A5B19 type rare earth-yttrium-nickel system hydrogen storage alloy added with zirconium and titanium elements
CN107799735A (en) One kind uses for nickel-hydrogen battery AB5Type hydrogen storage alloy and preparation method thereof
CN106654240A (en) Ce2Ni7-type single-phase superlattice hydrogen storage alloy electrode material and preparation method thereof
CN102104146B (en) Cobalt-free AB3.5-type hydrogen storage alloy anode material used for nickel-hydrogen battery and preparation method thereof
CN104513915A (en) Zirconium and titanium-doped AB3 type rare earth-yttrium-nickel family hydrogen storage alloy
CN102492873A (en) Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy
CN104513916A (en) Zirconium and titanium-doped A2B7 type rare earth-yttrium-nickel family hydrogen storage alloy
CN102758104A (en) Low-cobalt and praseodymium-neodymium-free AB5 type hydrogen storage alloy with low cost and preparation method thereof
CN100568591C (en) A kind of hydrogen storage alloy for low temperature Ni-MH power cell
CN101633985A (en) Preparation method of RE-Fe-B part hydrogen storage alloy
CN102634692B (en) Hydrogen storage alloy material for nickel-hydrogen battery and preparation method thereof
CN102383011B (en) Rare earth magnesium-based hydrogen storage alloy with low cost and long life and applications thereof
CN106544535B (en) Preparation method of hydrogen storage alloy containing yttrium and nickel elements
CN105779822A (en) Hydrogen storage alloy for nickel-hydrogen power battery
CN101740768B (en) Hydrogen storage alloy and preparation method thereof and cathode and battery using same
CN101295784A (en) Non-cobalt AB5 hydrogen storage alloy
CN102286678A (en) Non-stoichiometric-ratio LaNi5 base cobalt-free hydrogen storage alloy and preparation method thereof
CN102888539B (en) A kind of there is ultra-high capacity characteristic low cost AB5 type hydrogen-storage alloy and method for making and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120613