CN1445376A - New type hydrogen storage alloy for nickel-metal hydride secondary battery as well as method of preparation and annealing treatment - Google Patents
New type hydrogen storage alloy for nickel-metal hydride secondary battery as well as method of preparation and annealing treatment Download PDFInfo
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- CN1445376A CN1445376A CN03115993A CN03115993A CN1445376A CN 1445376 A CN1445376 A CN 1445376A CN 03115993 A CN03115993 A CN 03115993A CN 03115993 A CN03115993 A CN 03115993A CN 1445376 A CN1445376 A CN 1445376A
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- 238000000137 annealing Methods 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 9
- 239000001257 hydrogen Substances 0.000 title claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 title claims description 41
- 239000000956 alloy Substances 0.000 title claims description 41
- 238000003860 storage Methods 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052987 metal hydride Inorganic materials 0.000 title claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000003723 Smelting Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 4
- 239000001996 bearing alloy Substances 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 150000004678 hydrides Chemical class 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 238000007669 thermal treatment Methods 0.000 description 1
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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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Abstract
A novel hydrogen bearing alloy for secondary Ni-metallic hydride bettery has a formula: A1-yBy(Ni+C)x, where y=0.01-0.8, x=2.0-4.5, A is chosen from La, Ce, Pr and Nd, B is chosen from Mg, Ca, Be, Sr and Ba, and C is chosen from Mn, Fe, Mo, Co, Al, Si, Ti, V, Cr, Cu, Zn, Zr, Nb, W, Hf, Ta, B, P and Sn. It is prepared through smelting and annealing which includes heating in vacuum, holding the temp for several hr, and annealing. Its advantages are uniform structure, high discharge capacity and long cyclic life.
Description
Technical field
The present invention relates to metal hydride secondary battery, relate in particular to nickle-metal hydride secondary battery with novel hydrogen-storage alloy and preparation and annealing method.
Background technology
In recent years, because nickel-metal hydrides (Ni-MH) secondary cell, with respect to the Ni-Cd secondary cell, have the capacity height, have extended cycle life, memory-less effect, anti-over-charging, cross advantage such as the strong and non-environmental-pollution of exoergic power and become the focus of lot of domestic and foreign scholar's research.
The appearance of Ni/MH secondary cell, adapted to the more and more strict environmental requirement of human society, complied with the trend of microminiaturization, portability and energetic, therefore obtained development at full speed, calendar year 2001, the small-sized Ni/MH battery production of Japan was about 1,000,000,000, China is about 300,000,000, but since people to AB
5The research of type hydrogen storage electrode alloy reaches its maturity, its actual capacity (330mAh/g) is very near theoretical electrochemistry capacity (348mAh/g), further the space of lifting capacity is less, more and more be difficult to satisfy the demand of people to high energy density cells, this just impels the research worker to go to research and develop to have the more hydrogen storage electrode alloy of new generation of high-energy-density.China is a rare earth storage big country, and rare earth resources accounts for 80% of whole world reserves, for making full use of resource, promotes the development of China Ni/MH secondary cell, also is necessary to develop a kind of novel rare-earth hydrogen storage alloy and replaces traditional commercialization AB
5Type hydrogen storage alloy.
Summary of the invention
The purpose of this invention is to provide a kind of nickle-metal hydride secondary battery with novel hydrogen-storage alloy and preparation and annealing method.
Its composition is: A
1-yB
y(Ni+C)
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 preparation and the annealing method of novel hydrogen-storing alloy as electrode comprise the following steps:
1) the novel rare-earth series hydrogen storage alloy places vacuum magnetic suspension smelting furnace or arc melting;
2) melted as cast condition hydrogen-storage alloy is placed on is evacuated to 10 in the vacuum annealing furnace
-2-10
-6Pascal;
3) hydrogen-storage alloy is heated to 650-1300 ℃ and be incubated 1-72 hour;
4) the hydrogen-storage alloy furnace cooling after the insulation is handled or is cooled off in atmospheric environment.
The AB that the heat treating method that adopts the present invention to propose was handled
xHydrogen-storage alloy, the comprehensive electrochemical of its electrode comprises that loading capacity, cyclical stability and high magnification characteristic have all obtained tangible improvement.Charge and discharge under the condition at little electric current, its performance has surpassed business-like traditional AB
5Hydrogen-storing alloy as electrode.Preparation method of the present invention will for the preparation and annealing method will provide foundation to other hydrogen-storage alloy.
Description of drawings
Fig. 1 is according to the loading capacity of the cast alloy electrode of embodiment 1 preparation and alloy electrode of handling and unprocessed mistake and the relation curve between the cycle index;
Fig. 2 is according to the loading capacity of embodiment 1～3 preparation and the alloy electrode handled and the relation curve between the cycle index.
Embodiment
New A
1-yB
y(Ni+C)
xVacuum magnetic suspension stove or arc melting are adopted in the preparation of hydrogen-storage alloy, and the Heating temperature of the annealing furnace in the annealing method is respectively 850,950 and 1000 ℃, and soaking time is 8h, and the type of cooling is a furnace cooling.
Embodiment 1
According to novel hydrogen-storage alloy 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 alloy part X and enclose respectively in the vitreosil Glass tubing, the vacuum tightness in the quartz glass tube is 10
-3Pascal.Respectively pipe is put into annealing furnace then and carry out heat tracing.Heating condition is 850 ℃ * 8h, treat that soaking time arrives after, turn off annealing furnace, the alloy furnace cooling.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 6NKOH aqueous solution, and probe temperature remains on 303K.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 100mA/g to charge and discharge, and wherein the duration of charging is 5 hours, and the discharge stopping potential is-0.6V (with respect to the Hg/HgO reference electrode);
Embodiment 2
Heating condition is 950 ℃ * 8h, and all the other conditions are identical with embodiment 1;
Embodiment 3
Heating condition is 1050 ℃ * 8h, and all the other conditions are identical with embodiment 1;
Embodiment 4
Preparation and anneal condition are 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
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.
As can be seen from Figure 1, the high electrochemistry capacitance of alloy X under as-cast condition only has 364.6mAh/g, and after carrying out 850 ℃ * 8h anneal, its high electrochemistry capacitance becomes 400.0mAh/g, improved 35.4mAh/g, and after 200 circulations, its capacity is higher than the loading capacity of cast alloy far away, and the circulation conservation rate improves greatly.As can be seen from Figure 2, alloy has certain difference through the chemical property that thermal treatment showed of differing temps, and after the anneal of 850 ℃ * 8h, the electrochemistry capacitance of alloy is the highest, and after the anneal of 1000 ℃ * 8h, the cyclical stability of alloy is best.
Claims (4)
1. the novel negative material of nickle-metal hydride secondary battery is characterized in that its composition is: A
1-yB
y(Ni+C)
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.
2. the preparation of a novel hydrogen-storage alloy and annealing method is characterized in that, it comprises the following steps:
1) the novel rare-earth series hydrogen storage alloy places vacuum magnetic suspension smelting furnace or arc melting;
2) melted as cast condition hydrogen-storage alloy is placed on is evacuated to 10 in the vacuum annealing furnace
-2-10
-6Pascal;
3) hydrogen-storage alloy is heated to 650-1300 ℃ and be incubated 1-72 hour;
4) the hydrogen-storage alloy furnace cooling after the insulation is handled or is cooled off in atmospheric environment.
3. the annealing method of a kind of novel rare-earth series hydrogen storage alloy according to claim 2 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.
4. the annealing method of a kind of novel hydrogen-storage alloy according to claim 2 is characterized in that, the Heating temperature of said annealing furnace is 750-1150 ℃, and soaking time is 8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031159931A CN1235302C (en) | 2003-03-24 | 2003-03-24 | New type hydrogen storage alloy for nickel-metal hydride secondary battery as well as method of preparation and annealing treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031159931A CN1235302C (en) | 2003-03-24 | 2003-03-24 | New type hydrogen storage alloy for nickel-metal hydride secondary battery as well as method of preparation and annealing treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1445376A true CN1445376A (en) | 2003-10-01 |
| CN1235302C CN1235302C (en) | 2006-01-04 |
Family
ID=27814838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031159931A Expired - Fee Related CN1235302C (en) | 2003-03-24 | 2003-03-24 | New type hydrogen storage alloy for nickel-metal hydride secondary battery as well as method of preparation and annealing treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1235302C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329542C (en) * | 2005-05-31 | 2007-08-01 | 广州有色金属研究院 | Rare earth magnesium base hydrogen storage alloy |
| CN100453669C (en) * | 2007-02-08 | 2009-01-21 | 宜兴市远航合金厂 | High stabilization low resistivity nickel-base material and preparation method thereof |
| CN101906545A (en) * | 2010-07-13 | 2010-12-08 | 北京科技大学 | Preparation method of Mg-contained hydrogen storage alloy |
| CN101638740B (en) * | 2009-08-17 | 2011-05-18 | 济南大学 | Copper-bearing hydrogen storage alloy and preparation method thereof |
| CN102628114A (en) * | 2012-03-28 | 2012-08-08 | 东北大学 | Vacuum copper-based electrical contact composite material containing ceramic phase and preparation method of vacuum copper-based electrical contact composite material |
| CN103682281A (en) * | 2012-09-11 | 2014-03-26 | 湖南格瑞普新能源有限公司 | AB3-type hydrogen-storing alloy of nickel-metal hydride battery and preparation method thereof |
| CN104498774A (en) * | 2015-01-20 | 2015-04-08 | 中国人民解放军装甲兵工程学院 | Alloy powder for gray pig iron laser cladding repair and preparation method thereof |
| CN112899548A (en) * | 2021-01-20 | 2021-06-04 | 华南理工大学 | Yttrium-zirconium-iron-aluminum alloy material, preparation method and application |
| CN115807180A (en) * | 2022-12-19 | 2023-03-17 | 包头稀土研究院 | Hydrogen storage alloy containing yttrium and its preparation process |
-
2003
- 2003-03-24 CN CNB031159931A patent/CN1235302C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329542C (en) * | 2005-05-31 | 2007-08-01 | 广州有色金属研究院 | Rare earth magnesium base hydrogen storage alloy |
| CN100453669C (en) * | 2007-02-08 | 2009-01-21 | 宜兴市远航合金厂 | High stabilization low resistivity nickel-base material and preparation method thereof |
| CN101638740B (en) * | 2009-08-17 | 2011-05-18 | 济南大学 | Copper-bearing hydrogen storage alloy and preparation method thereof |
| CN101906545A (en) * | 2010-07-13 | 2010-12-08 | 北京科技大学 | Preparation method of Mg-contained hydrogen storage alloy |
| CN101906545B (en) * | 2010-07-13 | 2012-05-09 | 北京科技大学 | Preparation method of Mg-contained hydrogen storage alloy |
| CN102628114A (en) * | 2012-03-28 | 2012-08-08 | 东北大学 | Vacuum copper-based electrical contact composite material containing ceramic phase and preparation method of vacuum copper-based electrical contact composite material |
| CN103682281A (en) * | 2012-09-11 | 2014-03-26 | 湖南格瑞普新能源有限公司 | AB3-type hydrogen-storing alloy of nickel-metal hydride battery and preparation method thereof |
| CN103682281B (en) * | 2012-09-11 | 2017-05-17 | 湖南格瑞普新能源有限公司 | AB3-type hydrogen-storing alloy of nickel-metal hydride battery and preparation method thereof |
| CN104498774A (en) * | 2015-01-20 | 2015-04-08 | 中国人民解放军装甲兵工程学院 | Alloy powder for gray pig iron laser cladding repair and preparation method thereof |
| CN112899548A (en) * | 2021-01-20 | 2021-06-04 | 华南理工大学 | Yttrium-zirconium-iron-aluminum alloy material, preparation method and application |
| CN115807180A (en) * | 2022-12-19 | 2023-03-17 | 包头稀土研究院 | Hydrogen storage alloy containing yttrium and its preparation process |
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Granted publication date: 20060104 Termination date: 20140324 |