CN102703764A - Cu-contained rare earth system AB5-type hydrogen storage alloy and preparation method thereof - Google Patents

Cu-contained rare earth system AB5-type hydrogen storage alloy and preparation method thereof Download PDF

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CN102703764A
CN102703764A CN2012101782223A CN201210178222A CN102703764A CN 102703764 A CN102703764 A CN 102703764A CN 2012101782223 A CN2012101782223 A CN 2012101782223A CN 201210178222 A CN201210178222 A CN 201210178222A CN 102703764 A CN102703764 A CN 102703764A
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hydrogen storage
storage alloy
rare earth
type hydrogen
alloy
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林建雄
杨金洪
钱文连
张永健
蒋义淳
张鹏
陈跃辉
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Xiamen Tungsten Co Ltd
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Abstract

The invention discloses a Cu-contained rare earth system AB5-type hydrogen storage alloy and a preparation method thereof and relates to a hydrogen storage alloy. The invention provides the Cu-contained rare earth system AB5-type hydrogen storage alloy with low cost, higher capacity and a long service life and a preparation method and application of the AB5-type hydrogen storage alloy. The general formula of the Cu-contained rare earth system AB5-type hydrogen storage alloy is MlNiaCobMncAldCue. Under protective gas, a pretreated raw material is formed into an alloy through induction melting, and the alloy is solidified into a sheet through a rapid cooling mode; then, the Cu-contained rare earth system AB5-type hydrogen storage alloy is obtained through thermal treatment. The obtained Cu-contained rare earth system AB5-type hydrogen storage alloy is a thermally-treated Cu-contained rare earth system AB5-type hydrogen storage alloy sheet, and the sheet can be 0.1-0.3mm in thickness. The Cu-contained rare earth system AB5-type hydrogen storage alloy can be applied to preparing anode materials of nickel-metal hydride batteries.

Description

A kind of Cu of containing rare earth is AB 5Type hydrogen storage alloy and preparation method thereof
Technical field
The present invention relates to a kind of hydrogen storage alloy, especially relating to a kind of Cu rare earth that contains that is mainly used in nickel-hydrogen battery negative pole is AB 5Type hydrogen storage alloy and preparation method thereof.
Background technology
In recent years, because the development of mobile electronic device and the revolution of traffic power source, the research and development of high tension battery have become the emphasis of various countries' development.Wherein, receive much concern as the nickel metal hydride battery of civilian or Hybrid Vehicle and realized commercialization.Nickel metal hydride battery has following characteristics: the ⑴ capacity is higher; ⑵ anti-overcharges and discharges; ⑶ but high power charging-discharging; ⑷ memory-less effect; ⑸ non-environmental-pollution; ⑹ substitute the nickel-cadmium cell there is problem of environmental pollution etc. fully.
At present, AB 5Type hydrogen storage alloy becomes the main negative material of domestic and international Ni/MH battery production with its abundant raw materials, low price, easy to make, advantage such as comprehensive electrochemical is good.It represents composition is MmNi 3.55Al 0.4Mn 0.3Co 0.75, this alloy has advantages such as activation is fast, high-rate discharge ability good, the life-span is long.Research shows: the Co element plays crucial effects to improving hydrogen-storage alloy cycle life, and its mechanism of action mainly contains following 3 aspects:
⑴ reduce the unit cell volume rate of expansion in the alloy hydrogen absorption and desorption process;
⑵ suppress Mn and the stripping of Al element in alkali lye in the alloy compositions;
⑶ improve the plasticity and the toughness of alloy.But Co costs an arm and a leg as strategic element, is generally 10% (quality) or 15% (atom); Account for more than 35% of material cost, this has caused holding at high price of nickel metal hydride battery, concerning small-sized civilian and electromobile; A unfavorable factor certainly will hinder popularizing of its application beyond doubt.Therefore, under the prerequisite that keeps the alloy superperformance, development is hanged down Co or do not had the Co hydrogen storage alloy is the effective means that reduces cost.
U.S. Pat 6,773,667B1 has announced a kind of low-cost hydrogen storage alloy and method of manufacture thereof, chemical general formula is MmNi aMn bAl cCo dX e, wherein Mm is a cerium-rich mischmetal, X is Cu or Fe, and 4.0＜a≤4.3,0.25≤b≤0.4,0.25≤c≤0.4,0.3≤d≤0.5,0＜e≤0.1,5.05≤a+b+c+d+e≤5.25, c axial length is more than or equal to 404.9～409.8pm.This patent has moderate capacity and reaches the life-span preferably, and the more conventional hydrogen-storage alloy of Co content decreases, but cost is still higher, and wherein Co is higher than 0.3.
In addition, U.S. Pat 6,773,667B2 has announced another kind of low-cost hydrogen storage alloy and method of manufacture thereof, chemical general formula is MmNi aMn bAl cCo dX e, wherein Mm is a cerium-rich mischmetal, X is Cu or Fe, and 4.1＜a≤4.3,0.4＜b≤0.6,0.2≤c≤0.4,0.1≤d≤0.4,0＜e≤0.1,5.2≤b+c+d+e+f≤5.45, wherein c axial length is more than or equal to 406.2pm.The efflorescence speed of the disclosed hydrogen-storage alloy of this patent is little, and cycle life is high, and Co content has further reduction than B1, but cost is still higher, and wherein Ni is higher than 4.1.
Chinese patent CN101376941A has announced a low high Cu alloy of Co, and its chemical general formula is La aM (1-a)Ni xCu yFe zCo uMn vAl w0.4＜a≤0.9,2.5＜x≤3.6,0.4≤y≤1.0,0≤z≤0.2,0≤u≤0.2,0.4＜v≤0.7,0.2≤w≤0.4,4.8≤x+y+z+u+v+w≤5.3 wherein.This alloy has higher copper content, lower Ni content and extremely low Co content, obtains very big reduction on the cost.But the reduction of Co, Ni content has also caused the decline of alloy over-all properties.
On the basis that does not influence the hydrogen-storage alloy over-all properties, need further to reduce the cost of hydrogen-storage alloy.Therefore substitute the gordian technique that Part of Co and Ni just become the hydrogen-storage alloy preparation with other cheap metals as much as possible, and seeing that Co, Ni are bigger to the alloy performance impact, the trim point of searching Cost And Performance is particularly important.
Summary of the invention
First purpose of the present invention is to provide a kind of alloy that makes to realize that low cost, higher capacity and the long-life Cu of containing rare earth are AB 5Type hydrogen storage alloy.
It is AB that second purpose of the present invention is to provide a kind of Cu of containing rare earth 5The preparation method of type hydrogen storage alloy.
The 3rd purpose of the present invention is to provide that to contain the Cu rare earth be AB 5The application of type hydrogen storage alloy in the preparation nickel-hydrogen battery negative pole material.
The said Cu of containing rare earth is AB 5The general formula of type hydrogen storage alloy is:
MlNi aCo bMn cAl dCu e
In the formula, a, b, c, d, e represent mol ratio, and its numerical range is: 3.6＜a≤4.1,0.15＜b≤0.45,0.3＜c≤0.5,0.05≤d＜0.3,0.2＜e≤0.7,5.1≤a+b+c+d+e≤5.3; Ml is by La and be selected from least a composition the in Ce, Pr, Nd, Sm, Gd, Dy, Y, the Zr element, and wherein the mass percentage content of La accounts for 40%～80% in Ml, and the corresponding La content in alloy by mass percentage accounts for 10%～26%.
Said a, b, c, d, e represent mol ratio, and its numerical range can be 3.6＜a≤4.0,0.2＜b≤0.45,0.35＜c≤0.5,0.1≤d＜0.3,0.3≤e≤0.6.
The said Cu of containing rare earth is AB 5Type hydrogen storage alloy has over-stoichiometric ratio.
The said Cu of containing rare earth is AB 5The preparation method of type hydrogen storage alloy is following:
Under shielding gas, through pretreated raw material, form alloy, and be frozen into sheet through Cooling Mode through induction melting, heat-treat again, obtaining containing the Cu rare earth is AB 5Type hydrogen storage alloy.The resulting Cu of containing rare earth is AB 5Type hydrogen storage alloy is that to contain the Cu rare earth be AB to heat treatment state 5The type hydrogen storage alloy thin slice, the thickness of said thin slice can be 0.1～0.3mm.
Said shielding gas can adopt rare gas element.Said Cooling Mode can be single roller rapid quenching or two roller fast quenching, is about to melt temperature and remains on 1673～1873K, and cast is also cooled off through the water-cooled copper roller fast, and LV is 1～20ms -1Said heat treated temperature can be 1173～1273K, and heat treatment period can be 4～12h.
The said Cu of containing rare earth is AB 5Type hydrogen storage alloy can be used in the preparation nickel-hydrogen battery negative pole material.
This method is included under the protection of rare gas element, and the starting material that will meet above-mentioned hydrogen-storage alloy general formula carry out melting and adopt quick setting method to cool off, and quick setting method is single roller rapid quenching or two roller fast quenching, and smelting temperature is 1673～1873K; The thermal treatment temp that the as cast condition hydrogen-storage alloy is adopted is more than 1173K, and insulation is cooled off after finishing fast, obtains by single CaCu 5The alloy of phase composite.
The said Cu of containing rare earth is AB 5Type hydrogen storage alloy has CaCu 5The type structure is in the over-stoichiometric ratio structure between 5.1 and 5.3 for the B side simultaneously.
The said Cu of containing rare earth is AB 5In the general formula of type hydrogen storage alloy, the scope of Ni is 3.6＜a≤4.1, if the content of Ni, can reduce the electrochemical activation performance of alloy smaller or equal to 3.6, and the reduction capacity.If Ni content is higher than 4.1, can promote the cost of alloy, reduce the alloy cost performance.More be superior to 3.6＜a≤4.0 for this alloy Ni content.
In the general formula, the scope of Co is 0.15＜b≤0.45, if Co content is lower than 0.15, the cycle performance of alloy can worsen.If the content of Co greater than 0.45, can increase cost of alloy, reduce cost performance; More be superior to Co content 0.2～0.35 for this alloy.More be superior to 0.2＜b≤0.45 for this alloy Co content.
In the general formula, the scope of Mn is 0.3≤c≤0.5, if the content of Mn less than 0.3, the equilibrium hydrogen pressure of alloy can be too high, thereby cause inner pressure of battery high, leakage easily.If the content of Mn is greater than 0.5, the equilibrium hydrogen pressure of alloy can be too low, can reduce alloy loading capacity at normal temperatures.More be superior to 0.35＜c≤0.5 for this alloy Mn content.
In the general formula, the scope of Al is 0.05≤d＜0.3, if the content of Al is lower than 0.05, the capacity of alloy increases, but the obvious variation of cycle life.If the content of Al is higher than 0.35, the capacity of alloy can obviously reduce.More be superior to 0.1≤d＜0.3 for this alloy A l content.
In the general formula, the scope of Cu is 0.2＜e≤0.7, if the content of Cu is lower than 0.2, the cost of alloy is high; If the content of Cu is higher than 0.7, the capacity of alloy is too low.More be superior to 0.3≤e≤0.6 for this alloy Cu content.
In the general formula, the scope of alloy metering ratio is 5.1≤a+b+c+d+e≤5.3, if stoichiometric ratio is lower than 5.1, the cycle life of alloy can reduce.If stoichiometric ratio is higher than 5.3, the over-all properties of alloy is poor.
The invention has the advantages that:
In order to reduce the cost of hydrogen-storage alloy; The present invention is through Cu element substitution Ni and Co with cheapness; And combine with preparation technology; Other components are suitably adjusted, made to be reduced to 2% at Co content from 10% in the alloy and in 6%, to have kept higher capacity and the life-span, thereby obtained having the hydrogen-storage alloy of low-cost and high-performance; In addition, do not contain other element except that Ml, Ni, Co, Mn, Al, Cu in the alloy, the recycling performance is good.
Embodiment
Specify embodiments of the invention below, but the present invention is not limited thereto, in the scope that does not change claim of the present invention, suitably adjust, equally can embodiment of the present invention.
" % " in following examples all represents " wt% ".
Embodiment 1
According to design composition La 0.72Ce 0.2Pr 0.02Nd 0.06Ni 3.8Co 0.26Mn 0.39Al 0.2Cu 0.5, B/A=5.15.Preparation La (purity＞99.5%), Mm (La:30%, Ce:50%, Pr:5%, Nd:15%; La+Ce+Pr+Nd＞99%), Ni (purity＞99.5%), Co (purity＞99.5%), Mn (purity＞99.5%), Al (purity＞99.5%) amount to 5kg.Feed metal is put into Al by the order of Al, Mn, Ni, Co, La, Mm from the bottom to top 2O 3In the crucible.Be evacuated to 3Pa earlier, baker, prepurging then, applying argon gas is progressively regulated power 4kW, 6kW, 8kW, each melting 5min of 10kW to 0.05MPa, and controlled temperature is 1773 ± 30K, again refining 3min; Applying argon gas is to 0.05MPa, melt cast and through the water-cooled copper roller (LV is 5ms -1) cooling fast, obtain the alloy sheet that thickness is 0.1～0.3mm.The quenched state alloy carries out 1233K insulation 6.5h thermal treatment in argon shield gas, obtain the heat treatment state alloy.Process granularity subsequently less than 140 purpose powdered alloys.
Comparative example 1
Design mix La 0.62Ce 0.27Pr 0.03Nd 0.08Ni 4.1Co 0.26Mn 0.38Al 0.32Cu 0.14, B/A=5.2; Except that design mix was different from embodiment 1, other was with embodiment 1.
Comparative example 2
Design mix La 0.62Ce 0.27Pr 0.03Nd 0.08Ni 4.07Co 0.45Mn 0.38Al 0.3, B/A=5.2 is except that design mix is different from embodiment 1, and other is with embodiment 1.
It is as shown in table 1 to utilize inductively coupled plasma atomic emission spectrometry (ICP-AES) to measure in embodiment and the comparative example alloy each component content.
Table 1 alloy principal element is analyzed
La Ce Pr Nd Ni Co Mn Al Cu B/A
Embodiment 1 22.91 6.42 0.68 1.95 50.10 3.51 4.91 1.242 7.28 5.15
Comparative example 1 19.88 8.72 0.97 2.66 55.4 3.61 4.79 1.94 0.2 5.20
Comparative example 2 19.91 8.70 0.94 2.62 54.95 6.17 4.80 1.91 / 5.21
Electrochemical property test carries out in the clip type open cell.
At first accurately take by weighing 0.2g hydrogen storing alloy powder and 0.8g carbonyl nickel powder, uniform mixing is cold-pressed into electrode slice and spot-welded together with nickel strap, as alloy electrode to be measured.Supporting electrode is a sintered type hydroxide nickel electrode, and electrolytic solution is 6molL -1The KOH aqueous solution, the test environment temperature remains on 298K ± 0.5K.Testing tool is that a day secondary cell tester is held up in Guangzhou.Adopt 60mAg -1Constant current charge 450min leaves standstill 5min, then 60mAg -1Constant-current discharge, stopping potential is 1.0V, leaves standstill 5min, successively circulation; Obtain the maximum discharge capacity (C of alloy Max, mAhg -1) and activation number of times (N a, inferior).Adopt 300mAg -1Constant current charge 80min leaves standstill 5min, uses 300mAg then -1Constant-current discharge, stopping potential is 1.0V, leaves standstill 5min, successively circulation; Obtain the 1C loading capacity (C of alloy 1C, mAhg -1), and to use capability retention be the cycle life (N, inferior) that 80% o'clock pairing cycle index characterizes alloy.Respective electrical chemical property data are seen table 2.
Table 2 alloy electrochemical performance
Figure BDA00001713363800051
Visible by table 1, the Co content of embodiment 1 is 3.5%, and is identical with comparative example 1, is lower than 6% of comparative example 2.Simultaneously, the Ni content of embodiment 1 is 50.1%, also be lower than comparative example 1 55.4% with 54.95% of comparative example 2, so the cost of embodiment 1 is starkly lower than comparative example 1 and comparative example 2.
Can find out from table 2: the Co content of embodiment 1 is suitable with comparative example 1, and Ni content (50.1%) will be lower than comparative example 1 (55.4%); But embodiment 1 electrochemistry capacitance is suitable with comparative example 1, and cycle life is far above comparative example 1.And be that 6% standardized product comparative example 2 is compared with Co in the market, life-span gap slightly only.This explanation can improve the cycle life of alloy through the interpolation of Cu, improves the cost performance of alloy.
Embodiment 2
Design mix is La 0.65Ce 0.25Pr 0.02Nd 0.08Ni 3.75Co 0.26Mn 0.44Al 0.25Cu 0.55, B/A=5.25; Except that design mix was different from embodiment 1, other was with embodiment 1.
Comparative example 3
Design mix La 0.65Ce 0.25Pr 0.02Nd 0.08Ni 3.4Co 0.25Mn 0.7Al 0.1Cu 0.8, B/A=5.25; Except that design mix was different from embodiment 1, other was with embodiment 1.
Comparative example 4
Design mix La 0.65Ce 0.25Pr 0.02Nd 0.08Ni 4.25Co 0.26Mn 0.44Al 0.3, B/A=5.25; Except that design mix was different from embodiment 1, other was with embodiment 1.
The alloy main element analysis is referring to table 3.Alloy electrochemical performance is referring to table 4.
Table 3 alloy main element analysis
La Ce Pr Nd Ni Co Mn Al Cu
Embodiment 2 20.62 8.00 0.64 2.64 50.28 3.50 5.52 1.54 7.26
Comparative example 3 20.25 7.85 0.63 2.59 44.75 3.30 8.62 0.61 11.40
Comparative example 4 20.68 8.02 0.65 2.64 57.12 3.50 5.54 1.85 /
Table 4 alloy electrochemical performance
Figure BDA00001713363800061
Can find out that from table 3 the Cu content of embodiment is lower than comparative example 3 and is higher than comparative example 4, Ni content is higher than comparative example 3 thereupon, is lower than comparative example 4.Alloy is higher at Cu content, and promptly comparative example 3, and the alloy electrochemistry capacitance is low excessively; And Cu content is when being zero, and promptly comparative example 4, and the telephony capacity of alloy is higher, but the life-span is too poor.The over-all properties of embodiment 2 obviously is better than comparative example 3 and comparative example 4.

Claims (8)

  1. One kind to contain the Cu rare earth be AB 5Type hydrogen storage alloy is characterized in that its general formula is: MlNi aCo bMn cAl dCu eIn the formula, a, b, c, d, e represent mol ratio, and its numerical range is: 3.6＜a≤4.1,0.15＜b≤0.45,0.3＜c≤0.5,0.05≤d＜0.3,0.2＜e≤0.7,5.1≤a+b+c+d+e≤5.3; Ml is by La and be selected from least a composition the in Ce, Pr, Nd, Sm, Gd, Dy, Y, the Zr element, and wherein the mass percentage content of La accounts for 40%～80% in Ml, and the corresponding La content in alloy by mass percentage accounts for 10%～26%.
  2. 2. a kind of Cu of containing rare earth as claimed in claim 1 is AB 5Type hydrogen storage alloy is characterized in that said a, b, c, d, e represent mol ratio, and its numerical range is 3.6＜a≤4.0,0.2＜b≤0.45,0.35＜c≤0.5,0.1≤d＜0.3,0.3≤e≤0.6.
  3. 3. a kind of Cu of containing rare earth as claimed in claim 1 is AB 5Type hydrogen storage alloy is characterized in that the said Cu of containing rare earth is AB 5Type hydrogen storage alloy has over-stoichiometric ratio.
  4. 4. a kind of Cu of containing rare earth as claimed in claim 1 is AB 5The preparation method of type hydrogen storage alloy is characterized in that its concrete steps are following:
    Under shielding gas, through pretreated raw material, form alloy, and be frozen into sheet through Cooling Mode through induction melting, heat-treat again, obtaining containing the Cu rare earth is AB 5Type hydrogen storage alloy.The resulting Cu of containing rare earth is AB 5Type hydrogen storage alloy is that to contain the Cu rare earth be AB to heat treatment state 5The type hydrogen storage alloy thin slice, the thickness of said thin slice can be 0.1～0.3mm.
  5. 5. a kind of Cu of containing rare earth as claimed in claim 4 is AB 5The preparation method of type hydrogen storage alloy is characterized in that said shielding gas adopts rare gas element.
  6. 6. a kind of Cu of containing rare earth as claimed in claim 4 is AB 5The preparation method of type hydrogen storage alloy is characterized in that said Cooling Mode is single roller rapid quenching or two roller fast quenching, is about to melt temperature and remains on 1673～1873K, and cast is also cooled off through the water-cooled copper roller fast, and LV is 1～20ms -1
  7. 7. a kind of Cu of containing rare earth as claimed in claim 4 is AB 5The preparation method of type hydrogen storage alloy is characterized in that said heat treated temperature is 1173～1273K, and heat treatment period is 4～12h.
  8. 8. a kind of Cu of containing rare earth as claimed in claim 1 is AB 5The application of type hydrogen storage alloy in the preparation nickel-hydrogen battery negative pole material.
CN2012101782223A 2012-05-31 2012-05-31 Cu-contained rare earth system AB5-type hydrogen storage alloy and preparation method thereof Pending CN102703764A (en)

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Cited By (9)

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CN104313376A (en) * 2014-09-28 2015-01-28 江苏中容铜业有限公司 Preparation method of copper-containing hydrogen storage alloy and hydrogen storage alloy
CN108364740A (en) * 2018-04-10 2018-08-03 中国科学院物理研究所 A kind of nanocrystalline mischmetal permanent magnet and its preparation method and application
CN110241350A (en) * 2019-06-03 2019-09-17 中盈志合吉林科技股份有限公司 Cupric cobalt boron hydrogen storage material and its preparation method and application
CN110265655A (en) * 2019-06-27 2019-09-20 兰州金川科力远电池有限公司 Ni-MH power cell high-performance and low-cost hydrogen storing alloy powder and preparation method thereof
CN110714139A (en) * 2018-07-13 2020-01-21 有研工程技术研究院有限公司 Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof
CN111118344A (en) * 2019-11-15 2020-05-08 包头稀土研究院 Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method
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
CN114107740A (en) * 2021-11-16 2022-03-01 厦门钨业股份有限公司 Low-cost high-performance rare earth hydrogen storage alloy and preparation method thereof
CN114686728A (en) * 2022-04-02 2022-07-01 厦门钨业股份有限公司 Low-cobalt high-capacity AB5 type hydrogen storage alloy and preparation method thereof

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JP2001294958A (en) * 2000-04-11 2001-10-26 Sumitomo Metal Ind Ltd Hydrogen storage alloy for nickel-hydrogen secondary battery and its producing method
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

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JP2001294958A (en) * 2000-04-11 2001-10-26 Sumitomo Metal Ind Ltd Hydrogen storage alloy for nickel-hydrogen secondary battery and its producing method
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 (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104313376A (en) * 2014-09-28 2015-01-28 江苏中容铜业有限公司 Preparation method of copper-containing hydrogen storage alloy and hydrogen storage alloy
CN108364740A (en) * 2018-04-10 2018-08-03 中国科学院物理研究所 A kind of nanocrystalline mischmetal permanent magnet and its preparation method and application
CN110714139A (en) * 2018-07-13 2020-01-21 有研工程技术研究院有限公司 Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof
CN110241350A (en) * 2019-06-03 2019-09-17 中盈志合吉林科技股份有限公司 Cupric cobalt boron hydrogen storage material and its preparation method and application
CN110265655A (en) * 2019-06-27 2019-09-20 兰州金川科力远电池有限公司 Ni-MH power cell high-performance and low-cost hydrogen storing alloy powder and preparation method thereof
CN110265655B (en) * 2019-06-27 2022-08-02 兰州金川科力远电池有限公司 High-performance low-cost hydrogen storage alloy powder for nickel-hydrogen power battery and preparation method thereof
CN111118344A (en) * 2019-11-15 2020-05-08 包头稀土研究院 Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method
CN111118344B (en) * 2019-11-15 2021-07-27 包头稀土研究院 Multi-element gadolinium-containing rare earth hydrogen storage material, cathode, battery and preparation method
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
CN114107740A (en) * 2021-11-16 2022-03-01 厦门钨业股份有限公司 Low-cost high-performance rare earth hydrogen storage alloy and preparation method thereof
CN114686728A (en) * 2022-04-02 2022-07-01 厦门钨业股份有限公司 Low-cobalt high-capacity AB5 type hydrogen storage alloy and preparation method thereof

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Application publication date: 20121003