CN1234891C - 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
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- CN1234891C CN1234891C CNB03115994XA CN03115994A CN1234891C CN 1234891 C CN1234891 C CN 1234891C CN B03115994X A CNB03115994X A CN B03115994XA CN 03115994 A CN03115994 A CN 03115994A CN 1234891 C CN1234891 C CN 1234891C
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 57
- 239000000956 alloy Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000003860 storage Methods 0.000 claims description 19
- 238000007712 rapid solidification Methods 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000005518 electrochemistry Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910004247 CaCu Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910006030 NiCoCu Inorganic materials 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- 229910006085 NiCoSn Inorganic materials 0.000 description 1
- 229910006083 NiCoZn Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 241000849798 Nita Species 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses novel hydrogen-storing alloy and a fast solidifying preparation method thereof. The composition of the novel hydrogen-storing alloy is A<1-y>By (C+Ni) x, wherein 0.01<=y<=0.8, and 2.0<=x<=4.5. In the A <1-y>By (C+Ni) x, 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, and C is composed of one or two or more than two kinds of components of Mn, Fe, Mo, Co, Al, Si, Ti, C, Cr, Cu, Zn, Zr, Nb, W, Hf, Ta, B, P and Sn. The fast solidifying preparation method of the present invention comprises the steps that after being smelted, raw materials are directly and quickly solidified under a higher cooling rate, or a conventional melting method is firstly used for obtaining a casting ingot of the hydrogen-storing alloy, and then, after being resmelted, the casting ingot of the hydrogen-storing alloy is quickly solidified under a higher cooling rate. Electrode alloy which is obtained in the method of the present invention has the advantages of fine crystal grain and uniform composition distribution. Thus, the discharge capacity of an alloy electrode is raised, and the electrochemical performance of cycle life, etc. of the alloy electrode is obviously improved.
Description
Technical field
The present invention relates to metal hydride secondary battery, relate in particular to a kind of hydrogen-storage alloy preparation method.
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 (280-320 mAh/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 hydrogen-storage alloy preparation method.
Its composition is: A
L-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.
Hydrogen-storage alloy is the preparation method comprise the following steps:
1) 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 hydrogen-storage alloy of remelting is 10 then
3-10
7Rapid solidification under the rate of cooling of K/s.
The 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 rare earth
1-yB
y(C+Ni)
xRelation curve between hydrogen-occlussion alloy electrode loading capacity and the cycle index.
Embodiment
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 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
Business-like rare basic AB of going up 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 (1)
1. hydrogen-storage alloy preparation method, the molecular formula of described 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.
Described method comprises the following steps:
1) hydrogen-storage alloy places vacuum magnetic suspension smelting furnace or arc melting; It is characterized in that,
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.
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CNB03115994XA CN1234891C (en) | 2003-03-24 | 2003-03-24 | New-type of hydrogen-storing alloy and its fast solidifying prepn process |
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---|---|---|---|
CNB03115994XA CN1234891C (en) | 2003-03-24 | 2003-03-24 | New-type of hydrogen-storing alloy and its fast solidifying prepn process |
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CN1453383A CN1453383A (en) | 2003-11-05 |
CN1234891C true CN1234891C (en) | 2006-01-04 |
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Families Citing this family (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 Zr3V3Process for producing O |
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 |
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