CN1129196C - Rare-earth alloys for hydrogen-bearing electrode and its preparing process - Google Patents

Rare-earth alloys for hydrogen-bearing electrode and its preparing process Download PDF

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CN1129196C
CN1129196C CN01131884A CN01131884A CN1129196C CN 1129196 C CN1129196 C CN 1129196C CN 01131884 A CN01131884 A CN 01131884A CN 01131884 A CN01131884 A CN 01131884A CN 1129196 C CN1129196 C CN 1129196C
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alloy
hydrogen
electrode
rare
composition
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CN1363962A (en
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潘洪革
刘永锋
高明霞
雷永泉
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Zhejiang University ZJU
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention discloses novel rare-earth series hydrogen-storage electrode alloy and a preparing method thereof. A molecular formula of the novel rare-earth series hydrogen-storage electrode alloy is A<1-y>B<y>C<x>, wherein A is composed of one or two or more than two kinds of components of La, mixed rare earth Ml rich in the La, Ce, mixed rare earth Mm rich in the Ce, Pr and Nd, B is composed of one or two or more than two kinds of components of Mg, Ca, Be, Sr and Ba C is composed of one or two or more than two kinds of Mn, Fe, Mo, Co, Al, Si, Ga, S, Pt, Sc, Ti, V, Cr, Cu, Zn, Zr, Nb, Ru, Rh, Pd, Cd, W, Hf, Ta, B and P, y is greater than or equal to 0.01 and is smaller than or equal to 0.8 and x is greater than or equal to 2.0 and is smaller than or equal to 4.0. The preparing method comprises a conventional melting method is used for obtaining hydrogen-storage electrode alloy firstly; then, after resmelted, the hydrogen-storage electrode alloy is quickly solidified under a higher cooling rate. The electrode alloy which is obtained by using the method of the present invention has the characteristics of fine grain, uniform composition distribution, high defect concentration, etc. Thus, the discharge capacity of an alloy electrode is raised, and the electrochemical performance of cycle life, etc. of the alloy electrode can be obviously improved.

Description

The preparation method of hydrogen-bearing rare-earth alloy as electrode
Technical field
The present invention relates to secondary cell, especially relate to a kind of preparation method of hydrogen-bearing rare-earth alloy as electrode.
Background technology
Compare with traditional Ni-Cd secondary cell, nickel-metal hydrides (Ni-MH) secondary cell becomes the focus of lot of domestic and foreign scholar's research owing to advantages such as having the specific energy height 1.5-2 of Ni-Cd battery (be doubly), have extended cycle life, memory-less effect, anti-over-charging are crossed the strong and non-environmental-pollution of exoergic power.
The anodal general nickel electrode that adopts of nickle-metal hydride secondary battery, negative material then adopts hydrogen-storage alloy.From at present, the more hydrogen-storing alloy as electrode of people's research comprises rare earth based AB 5Type alloy, AB 2Type alloy, magnesium base alloy and vanadium radical sosoloid alloy.Wherein, people are to rare earth based AB 5The research of type alloy is the most ripe, and it has high-energy-density density, high charge-discharge speed, and overcharging resisting, cross and put, memory-less effect, good comprehensive performances such as low pollution have now realized industrialization production.But, rare earth based AB 5Type hydrogen-occlussion alloy electrode finite capacity is about about 280～320mAh/g, and the shortcoming of their ubiquity battery lack of homogeneitys.Here except that cell integrated design, negative pole technology and the influence of other associated materials, unstable properties also was one of reason during storage alloy material for hydrogen was produced in enormous quantities.Therefore impelled people to remove the higher hydrogen-storing alloy as electrode of research and development capacity.
At present in the world the research of high-performance hydrogen-storage electrode metal is mainly concentrated on AB 2Type Laves hydrogen storage alloy phase, magnesium base hydrogen-storing alloy and vanadium radical sosoloid alloy.AB 2Type Laves hydrogen storage alloy phase exists alloy P-C-T curve platform gradient bigger, and the electrode surface reaction resistance is higher, causes the high-rate discharge ability of electrode relatively poor relatively bigger with the inclination of battery discharge voltage platform.In addition, AB 2Also there are problems such as the initial stage activation is difficult, the prices of raw and semifnished materials are higher relatively in type Laves hydrogen storage alloy phase.
The V radical sosoloid alloy is not owing to itself possess electrode activity, thereby its electrochemical applications seldom studied, though studies show that recently by after separating out the good TiNi grade in an imperial examination two-phase of electro catalytic activity on the crystal boundary of V based solid solution, can obtain high electrochemistry capacitance, but its cyclical stability is very poor, remain further to be studied to improve, and the price of V is higher.
Magnesium base hydrogen-storing alloy is a much-talked-about topic in the research of Ni/MH battery, but the chemical motive force of Mg-H reaction is very low, and the hydride of formation is too stable, is difficult to carry out more much practical applications.Alloy discharge capacity decline simultaneously is very fast, and the corrosion in alkaline electrolyte is still a great problem, and also need effort for a long time make a breakthrough.
The hydrogen-bearing rare-earth alloy as electrode of development has higher electrochemical discharge capacity recently.Kohno has studied La 5Mg 2Ni 23The electrochemical discharge capacity of type hydrogen-occlussion alloy electrode can reach 400mAh/g, has surmounted rare earth based commercialization AB greatly 5The discharge capacity of type hydrogen-occlussion alloy electrode.And its alloy electrode has good cyclical stability, good high magnification characteristic and advantage such as activation capacity and low price and has demonstrated powerful application prospect in electrolyte.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of hydrogen-bearing rare-earth alloy as electrode.
It comprises the following steps:
1) presses composition A 1-yB yC xProportion raw material places vacuum magnetic suspension smelting furnace or arc melting to obtain cast alloy, said composition A 1-yB yC xIn A be one or both or two or more composition among La, rich La mishmetal Ml, Ce, rich Ce mishmetal Mm, Pr, the Nd, B is one or both or the two or more composition among Mg, Ca, Be, Sr, the Ba, C is one or both or the two or more composition among Mn, Fe, Mo, Co, Al, Si, Ga, S, Pt, Sc, Ti, V, Cr, Cu, Zn, Zr, Nb, Ru, Rh, Pd, Cd, W, Hf, Ta, B, P, Ge, As, Se, In, the Sn, 0.01≤y≤0.8,2.0≤x≤4.0;
2) melted cast alloy is placed on remelting in single roller rapid quenching stove or two roller quick quenching furnace or the atomizing stove;
3) alloy of remelting is 10 3-10 7Rapid solidification prepares hydrogen-bearing rare-earth alloy as electrode under the cooldown rate of K/s.
The A that adopts preparation method of the present invention to prepare 1-yB yC xHydrogen-storing alloy as electrode is 1.5 * 10 in cooldown rate especially 6The hydrogen-bearing rare-earth alloy as electrode that obtains under the condition of K/s, the discharge capacity of alloy electrode is improved, and simultaneously, the cyclical stability of alloy electrode has obtained tangible improvement, thereby has improved A 1-yB yC xThe comprehensive electrochemical of hydrogen-storing alloy as electrode.A of the present invention 1-yB yC xThe preparation method of hydrogen-storing alloy as electrode will provide foundation for preparing other hydrogen-storing alloy as electrode.
Description of drawings
Fig. 1 is the discharge capacity of the cast alloy electrode that obtains of the alloy electrode that obtains according to the embodiment rapid solidification and conventional melting and the relation curve between the cycle-index;
Fig. 2 is according to the AB of commercialization rare earth based described in the comparative example 2 5It is A that rapid solidification described in hydrogen-storing alloy as electrode electrode and the embodiment prepares rare earth 1-yB yC xRelation curve between hydrogen-occlussion alloy electrode discharge capacity and the cycle-index.
Embodiment
Rare earth is A 1-yB yC xQuick quenching furnace among the preparation method of hydrogen-storing alloy as electrode is single roller rapid quenching stove or two roller quick quenching furnace or atomizing stove, and cooldown rate is 1.5 * 10 6K/s.
Embodiment
According to rare earth is A 1-yB yC xThe design mix of hydrogen-storing alloy as electrode at first adopts vacuum magnetic suspension stove or arc melting alloy, is designated as alloy X.Wherein, the purity of alloy constituent element is all more than 90%.Get the copper crucible that alloy part ingot casting X puts into the single roller rapid quenching stove respectively, the arc heating remelting is poured over the alloy melt of remelting on the water-cooled molybdenum roller of high speed rotating, rapid solidification, and the rotary speed of molybdenum roller is 20m/s.The test of chemical property is to carry out in an open type three-electrode system, and it comprises a work electrode (being hydrogen-occlussion alloy electrode), a sintering Ni (OH) 2/ NiOOH auxiliary electrode and a Hg/HgO reference electrode.Electrolyte adopts the 6N KOH aqueous solution, and probe temperature remains on 303K.All test electrodes all are to form by the even electrode slice that mixes 100mg hydrogen-storage alloy powder (300 order) and 300mg carbonyl nickel powder and be pressed into diameter 10mm, thickness 1mm under the pressure of 20Mpa.Electrode adopts the electric current of 400mA/g to charge and discharge, and wherein the charging interval is 5 hours, and the discharge stopping potential is-0.5V (with respect to the Hg/HgO reference electrode).
Comparing embodiment 1
The alloy X of melting does not do any processing among the selected part embodiment, makes electrode and carries out the test of electrochemistry cycle life according to the described method of embodiment.
Comparative example 2
The business-like rare earth based AB that selected part three general companies produce 5Hydrogen-storing alloy as electrode carries out the test of electrochemistry cycle life to it.The system and the condition of test are all identical with embodiment.
As can be seen from Figure 1, the cast alloy X that conventional melting obtains high electrochemistry capacitance 357mAh/g is only arranged, and the alloy that adopts rapid solidification method to obtain, its high electrochemistry capacitance becomes 376mAh/g, improved 19mAh/g, and through after 300 circulations, the discharge conservation rate is 88%.
As can be seen from Figure 2, under the same condition that discharges and recharges, adopt the mishmetal alloys for hydrogen-bearing electrode A of rapid solidification method preparation 1-yB yC xComprehensive electrochemical obviously be better than business-like rare earth based AB 5Hydrogen-storing alloy as electrode, its high discharge capacity is than business-like rare earth based AB 5The peak capacity of hydrogen-storing alloy as electrode exceeds 50mAh/g, and cyclical stability is also not second to business-like rare earth based AB 5Hydrogen-storing alloy as electrode.

Claims (2)

1. the preparation method of a hydrogen-bearing rare-earth alloy as electrode is characterized in that, it comprises the following steps:
1) presses composition A 1-yB yC xProportion raw material places vacuum magnetic suspension smelting furnace or arc melting to obtain cast alloy, said composition A 1-yB yC xIn A be one or both or two or more composition among La, rich La mishmetal Ml, Ce, rich Ce mishmetal Mm, Pr, the Nd, B is one or both or the two or more composition among Mg, Ca, Be, Sr, the Ba, C is one or both or the two or more composition among Mn, Fe, Mo, Co, Al, Si, Ga, S, Pt, Sc, Ti, V, Cr, Cu, Zn, Zr, Nb, Ru, Rh, Pd, Cd, W, Hf, Ta, B, P, Ge, As, Se, In, the Sn, 0.01≤y≤0.8,2.0≤x≤4.0;
2) melted cast alloy is placed on remelting in single roller rapid quenching stove or two roller quick quenching furnace or the atomizing stove;
3) alloy of remelting is 10 3-10 7Rapid solidification prepares hydrogen-bearing rare-earth alloy as electrode under the cooldown rate of K/s.
2. the preparation method of a kind of hydrogen-bearing rare-earth alloy as electrode according to claim 2 is characterized in that, said quick quenching furnace is the single roller rapid quenching stove.
CN01131884A 2001-12-26 2001-12-26 Rare-earth alloys for hydrogen-bearing electrode and its preparing process Expired - Fee Related CN1129196C (en)

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CN100352957C (en) * 2004-11-02 2007-12-05 内蒙古稀奥科镍氢动力电池有限公司 Preparation method of high content rare earth -magnesium base composite hydrogen storage alloy for MH-Ni battery
CN103633301A (en) * 2013-10-22 2014-03-12 钢铁研究总院 RE-Mg-Ni-Zr-B electrode alloy used for Ni-MH secondary battery and preparation method thereof
CN105316556A (en) * 2015-12-11 2016-02-10 王立鑫 Die-casting high-brightness zinc alloy as well as preparation method and application thereof

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