CN1453383A - New-type of hydrogen-storing alloy and its fast solidifying prepn process - Google Patents
New-type of hydrogen-storing alloy and its fast solidifying prepn process Download PDFInfo
- Publication number
- CN1453383A CN1453383A CN03115994A CN03115994A CN1453383A CN 1453383 A CN1453383 A CN 1453383A CN 03115994 A CN03115994 A CN 03115994A CN 03115994 A CN03115994 A CN 03115994A CN 1453383 A CN1453383 A CN 1453383A
- Authority
- CN
- China
- Prior art keywords
- alloy
- hydrogen
- electrode
- rapid solidification
- storage alloy
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The new type of hydrogen-storing alloy is A1-yBy(C+Ni)x, where y is 0.01-0.8; x is 2.0-4.5; A is one or more of La, La-rich mixed RE and Ce-rich mixed RE; B is one or more of Mg, Ca, Be, Sr and Ba; C is one or more of Mn, Fe, Mo, Co, Al, Si, Ti, V, Cr, Cu, Zn, Zr, Nb, W, Hf, Ta, B, P and Sn. The preparation process includes material smelting and fast solidification; or conventional smelting to obtain alloy ingot, re-melting and fast solidification. The said process can obtain electrode alloy with fine crystal grains, homogeneously distributed components, and thus raised alloy electrode discharge capacity and obviously improved alloy electrode electrochemical performance.
Description
Technical field
The present invention relates to metal hydride secondary battery, relate in particular to a kind of novel hydrogen-storage alloy and rapid solidification preparation method thereof.
Background technology
The Dutch Philips breadboard Willems of company was improving AB in 1984
5The important breakthrough that obtains on the problem of type hydrogen storage alloy charge and discharge cycles stability makes with AB
5Type hydrogen storage alloy is that nickel metal hydride (Ni/MH) secondary cell of negative material progressively replaces nickel/cadmium cell and enters the industrialization stage.Hydrogen-storing alloy as electrode is as the crucial trunk material of Ni/MH battery, and the various countries research worker has done a large amount of work and improved its comprehensive electrochemical.At present, in the hydrogen-storing alloy as electrode series of being studied, rare earth based AB
5The type alloy has now been realized industrialization in China, Japan and the U.S. owing to have better comprehensive performance, but it is subjected to single CaCu
5The restriction electrochemistry capacitance of type structure limited (280-320mAh/g).Aspect the research of high capacity hydrogen storage electrode metal, Ti base or Zr base AB
2Type Laves phase alloy because have the capacity height, advantage such as have extended cycle life once once causing people's extensive attention, but the initial stage of this alloy activation quite difficulty, high-rate discharge ability is poor, also exists problems such as the prices of raw and semifnished materials of alloy are higher relatively simultaneously and is difficult to practicability.The initial electrochemical discharge capacity of Magnuminium and vanadium radical sosoloid alloy is quite high, but owing to their too fast capacity that causes of circulation decline in electrolytic solution descend rapidly, also there is not good terms of settlement at present, also can't realize practicability within the short-term, this just impels people to go to research and develop to have the better and more hydrogen storage alloy of new generation of low price of high-energy-density, activation capacity.
Summary of the invention
The purpose of this invention is to provide a kind of novel hydrogen-storage alloy and rapid solidification preparation method thereof.
Its composition is: A
1-yB
y(C+Ni)
x, 0.01≤y≤0.8 wherein; 2.0≤x≤4.5; A is one or both or the 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, and C is one or both or the two or more composition among Mn, Fe, Mo, Co, Al, Si, Ti, V, Cr, Cu, Zn, Zr, Nb, W, Hf, Ta, B, P, the Sn.
The rapid solidification preparation method of novel hydrogen-storing alloy as electrode comprises the following steps:
1) novel hydrogen-storage alloy places vacuum magnetic suspension smelting furnace or arc melting;
2) melted alloy is directly 10
3-10
7Rapid solidification under the rate of cooling of K/s; Perhaps the as cast condition hydrogen-storing alloy as electrode is placed on remelting in single roller rapid quenching stove or two roller quick quenching furnace or the atomizing stove, the novel hydrogen-storage alloy of remelting is 10 then
3-10
7Rapid solidification under the rate of cooling of K/s.
The novel hydrogen-storage alloy that adopts rapid solidification preparation method of the present invention to obtain, the loading capacity of alloy electrode is improved, and simultaneously, the cyclical stability of alloy electrode has obtained tangible improvement, thereby has improved AB
xThe comprehensive electrochemical of hydrogen-storage alloy.A of the present invention
1-yB
y(C+Ni)
xThe quick setting method of hydrogen-storage alloy will provide important evidence for preparing other hydrogen-storing alloy as electrode.
Description of drawings
Fig. 1 is the loading 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 commercialization AB described in the comparative example 2
5It is A that rapid solidification described in hydrogen-occlussion alloy electrode and the embodiment prepares novel rare-earth
1-yB
y(C+Ni)
xRelation curve between hydrogen-occlussion alloy electrode loading capacity and the cycle index.
Embodiment
New A
1-yB
y(C+Ni)
xThe quick quenching furnace that the hydrogen-storage alloy rapid solidification is adopted is single roller rapid quenching stove or two roller quick quenching furnace or atomizing stove, and rate of cooling is 1.5 * 10
6K/s.
Embodiment 1
According to novel hydrogen-storing alloy as electrode La
1-yMg
y(NiCoMnAl)
x(0.1≤y≤0.5; 3.0 design mix≤x≤4.5) 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 X puts into the single roller rapid quenching stove respectively, the electric-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 speed of rotation 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 working electrode (being hydrogen-occlussion alloy electrode), a sintering Ni (OH)
2/ NiOOH supporting electrode and a Hg/HgO reference electrode.Electrolytic solution adopts the 6N KOH aqueous solution.All test electrodes all are to form by uniform mixing 100mg hydrogen-storage alloy powder (300 order) and 300mg carbonyl nickel powder and the electrode slice that is 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 duration of charging is 5 hours, and the discharge stopping potential is-0.5V (with respect to the Hg/HgO reference electrode) that probe temperature is 30 ℃.
Embodiment 2
Rapid solidification preparation method is identical with embodiment 1, and its alloying constituent is respectively: La
1-yMg
y(NiCoMn)
x, La
1-yMg
y(NiCoTi)
x, La
1-yMg
y(NiCoV)
x, La
1-yMg
y(NiCoCr)
x, La
1-yMg
y(NiCoCu)
x, La
1-yMg
y(NiCoSi)
x, La
1-yMg
y(NiCoZn)
x, La
1-yMg
y(NiCoZr)
x, La
1-yMg
y(NiCoNb)
x, La
1-yMg
y(NiCoW)
x, La
1-yMg
y(NiMo)
x, La
1-yMg
y(NiHf)
x, La
1-yMg
y(NiTa)
x, La
1-yMg
y(NiCoB)
x, La
1-yMg
y(NiCoP)
x, La
1-yMg
y(NiCoSn)
x, La
1-yMg
y(NiCoMnFe)
x, La
1-yMg
y(NiCoMnAlB)
x, Ml
1-yMg
y(NiCoMnAl)
x, Mm
1-yMg
y(NiCoMnAl)
x(La, Ce)
1-yMg
y(NiCoMnAl)
x, La
1-yCa
y(NiCoMnAl)
x, La
1-yBa
y(NiCoMnAl)
x, La
1-yMg
y(NiCoAlSn)
x, La
1-yMg
y(NiCoMnAlCu)
x, La
1-yCa
y(NiCoMnAlCu)
x, La
1-y(Mg, Ca)
y(NiCoMnAl)
x, La
1-y(Mg, Ca)
y(NiCoMnAlSi)
x, La
1-y(Mg, Ca)
y(NiCoMnSn)
x, La
1-y(Mg, Ca, Be)
y(NiCoMnAl)
x, La
1-y(Mg, Ca, Sr)
y(NiCoMnAl)
x, (La, Ce, Pr)
1-yMg
y(NiCoMnAl)
x, (La, Ce, Nd)
1-yMg
y(NiCoMnAl)
x, (La, Ce, Pr, Nd)
1-yMg
y(NiCoMnAl)
x, (La, Ce, Pr, Nd)
1-y(Mg, Ca)
y(NiCoMnAl)
x, 0.01≤y≤0.8 wherein; 2.0≤x≤4.5.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.Comparing embodiment 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 365mAh/g is only arranged, and the alloy that adopts rapid solidification method to obtain, its high electrochemistry capacitance becomes 383mAh/g, improved 18mAh/g, and through after 200 circulations, the discharge conservation rate is 92%.
As can be seen from Figure 2, under the same condition that discharges and recharges, adopt the novel mixing hydrogen-storage alloy La of rapid solidification method preparation
1-yMg
y(NiCoMnAl)
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 60mAh/g, and cyclical stability also is better than business-like rare earth based AB
5Hydrogen-storing alloy as electrode.
Claims (3)
1. novel hydrogen-storage alloy and rapid solidification preparation method thereof is characterized in that it comprises the following steps:
1) novel hydrogen-storage alloy places vacuum magnetic suspension smelting furnace or arc melting;
2) melted alloy is directly 10
3-10
8Rapid solidification under the rate of cooling of K/s; Perhaps the as cast condition hydrogen-storing alloy as electrode is placed on remelting in single roller rapid quenching stove or two roller quick quenching furnace or the atomizing stove, the novel hydrogen-storage alloy of remelting is 10 then
3-10
8Rapid solidification under the rate of cooling of K/s.
2. a kind of novel hydrogen-storage alloy according to claim 1 and rapid solidification preparation method thereof is characterized in that the molecular formula of said alloy is A
1-yB
y(C+Ni)
x, 0.01≤y≤0.8 wherein; 2.0≤x≤4.5; A is one or both or the 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, and C is one or both or the two or more composition among Mn, Fe, Mo, Co, Al, Si, Ti, V, Cr, Cu, Zn, Zr, Nb, W, Hf, Ta, B, P, the Sn.
3. a kind of novel hydrogen-storage alloy according to claim 1 and rapid solidification preparation method thereof is characterized in that said quick quenching furnace is the single roller rapid quenching stove, and rate of cooling is 1.5 * 10
6K/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03115994XA CN1234891C (en) | 2003-03-24 | 2003-03-24 | New-type of hydrogen-storing alloy and its fast solidifying prepn process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03115994XA CN1234891C (en) | 2003-03-24 | 2003-03-24 | New-type of hydrogen-storing alloy and its fast solidifying prepn process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1453383A true CN1453383A (en) | 2003-11-05 |
| CN1234891C CN1234891C (en) | 2006-01-04 |
Family
ID=29260045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03115994XA Expired - Fee Related CN1234891C (en) | 2003-03-24 | 2003-03-24 | New-type of hydrogen-storing alloy and its fast solidifying prepn process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1234891C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400690C (en) * | 2006-03-23 | 2008-07-09 | 中国工程物理研究院核物理与化学研究所 | Hydrogen storage alloy Zr3V3O preparing method |
| CN102517487A (en) * | 2011-12-13 | 2012-06-27 | 浙江大学 | Hydrogen-storage alloy producing high-pressure hydrogen |
| CN102832380A (en) * | 2012-08-29 | 2012-12-19 | 上海锦众信息科技有限公司 | Preparation method of cathode hydrogen storage material of power battery |
| CN111455218A (en) * | 2020-04-02 | 2020-07-28 | 江苏远航精密合金科技股份有限公司 | Nickel-based conductor material for new energy automobile power battery and preparation method thereof |
-
2003
- 2003-03-24 CN CNB03115994XA patent/CN1234891C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400690C (en) * | 2006-03-23 | 2008-07-09 | 中国工程物理研究院核物理与化学研究所 | Hydrogen storage alloy Zr3V3O preparing method |
| CN102517487A (en) * | 2011-12-13 | 2012-06-27 | 浙江大学 | Hydrogen-storage alloy producing high-pressure hydrogen |
| CN102517487B (en) * | 2011-12-13 | 2013-11-06 | 浙江大学 | Hydrogen-storage alloy producing high-pressure hydrogen |
| CN102832380A (en) * | 2012-08-29 | 2012-12-19 | 上海锦众信息科技有限公司 | Preparation method of cathode hydrogen storage material of power battery |
| CN111455218A (en) * | 2020-04-02 | 2020-07-28 | 江苏远航精密合金科技股份有限公司 | Nickel-based conductor material for new energy automobile power battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1234891C (en) | 2006-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102104146B (en) | Cobalt-free AB3.5-type hydrogen storage alloy anode material used for nickel-hydrogen battery and preparation method thereof | |
| CN101552337A (en) | Superlattice hydrogen storage alloy and preparation method thereof | |
| CN108149073A (en) | Low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys and preparation method thereof | |
| EP1652947A1 (en) | LOW Co HYDROGEN OCCLUSION ALLOY | |
| CN102758104A (en) | Low-cobalt and praseodymium-neodymium-free AB5 type hydrogen storage alloy with low cost and preparation method thereof | |
| CN101212047B (en) | Hydrogen storage alloy and its preparation method | |
| CN1754972A (en) | High-capacity rare earth-magnesium based multi-phase hydrogen strage alloy for MH-Ni battery and its preparation method | |
| CN102286678A (en) | Non-stoichiometric-ratio LaNi5 base cobalt-free hydrogen storage alloy and preparation method thereof | |
| CN1235302C (en) | New type hydrogen storage alloy for nickel-metal hydride secondary battery as well as method of preparation and annealing treatment | |
| CN1234891C (en) | New-type of hydrogen-storing alloy and its fast solidifying prepn process | |
| CN1235301C (en) | New type hydrogen storage alloy as well as method of its preparation and quench treatment method | |
| CN111224092B (en) | Zirconium or titanium doped samarium-containing hydrogen storage alloy, negative electrode, battery and preparation method | |
| CN1272461C (en) | Non crystal state hydrogen storge composite material and its producing method | |
| CN1129196C (en) | Rare-earth alloys for hydrogen-bearing electrode and its preparing process | |
| CN1175120C (en) | New-type hydrogen-storing RE electrode alloy and its heat treatment process | |
| CN1044175C (en) | Magnesium base hydrogen-storing alloy electrode | |
| CN105463256A (en) | Hydrogen storage alloy for nickel-metal hydride battery and manufacturing method of hydrogen storage alloy | |
| CN1175121C (en) | Hydrogen-bearing rare-earth alloy as electrode and its quenching process | |
| CN1110865C (en) | High-capacity hydrogen-bearing alloy powder with long service life for high-performance secondary MH-Ni battery | |
| CN1173057C (en) | Hydrogen-bearing mixed rare-earth alloy as electrodes of secondary nickel-metal oxide battery | |
| CN116200627B (en) | Long-cycle life pure-phase 2H-A2B7 hydrogen storage alloy electrode material and preparation method thereof | |
| CN1141745C (en) | Non-stoichiometric low-co hydrogen-bearing electrode material | |
| CN102628125B (en) | AB5 hydrogen storage alloy with high hydrogen diffusion coefficient and preparation method thereof of AB5 hydrogen storage alloy | |
| CN105895888B (en) | Ni MH batteries RE Mg Ni Ti Cu Al B system AB types electrode metals and preparation method | |
| CN1251472A (en) | Hydrogen-storage alloy electrode material of low-Co lanthanum-praseodymium-cerium-nickel series |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060104 Termination date: 20140324 |