CN1738082A - AB5 type negative pole hydrogen-storage material - Google Patents
AB5 type negative pole hydrogen-storage material Download PDFInfo
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- CN1738082A CN1738082A CNA2005100998998A CN200510099899A CN1738082A CN 1738082 A CN1738082 A CN 1738082A CN A2005100998998 A CNA2005100998998 A CN A2005100998998A CN 200510099899 A CN200510099899 A CN 200510099899A CN 1738082 A CN1738082 A CN 1738082A
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- mmni
- storage material
- hydrogen storage
- type cathode
- cathode hydrogen
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- 239000011232 storage material Substances 0.000 title claims abstract description 63
- 239000001257 hydrogen Substances 0.000 claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910018007 MmNi Inorganic materials 0.000 claims description 87
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000956 alloy Substances 0.000 abstract description 18
- 229910045601 alloy Inorganic materials 0.000 abstract description 18
- 229910052802 copper Inorganic materials 0.000 abstract description 15
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 9
- -1 rare-earth compound Chemical class 0.000 abstract 2
- 238000010325 electrochemical charging Methods 0.000 abstract 1
- 238000010326 electrochemical discharging Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 109
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 103
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 72
- 239000010941 cobalt Substances 0.000 description 23
- 229910017052 cobalt Inorganic materials 0.000 description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 19
- 230000005518 electrochemistry Effects 0.000 description 17
- 229910052692 Dysprosium Inorganic materials 0.000 description 13
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910018095 Ni-MH Inorganic materials 0.000 description 9
- 229910018477 Ni—MH Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000001996 bearing alloy Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910004247 CaCu Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
Abstract
The invention provides a AB5 type negative hydrogen storage material prepared by the rapid hardening band method, wherein, the atom proportions comprise: Mm1-zDyZnI3.55Co0.75-x-yFexCuyMn0.4Al0.3, in which the x + y ranges from 0-0.7, the z ranges from 0-0.039, the Mm is rare-earth compound formed by La, Ce, Pr and Nd elements etc., the weight of rare-earth compound Mm is selected as standard, the weight of La is 64.5-67.5 %, the weight of Ce is 22.0-24.0 %, the weight of Pr is 2.5-3.5 % and the weight of Nd is 7.0-9.0 %. The cooling rate of used rapid hardening band method is decided by the controlled linear speed 1-3 m/s of rotating surface of cooling roll and the thickness of product 0.2-0.5. Since the invention utilizes the rapid hardening band method, selects the correct cooling rate, uses a little rare-earth element Dy, and replaces the element Co with the more cheaper element Fe and Cu, the alloy can keep excellent active property, electrochemical charging and discharging capacity and cycle life, while the cost is reduced markedly.
Description
Technical field
The present invention relates to the battery cathode hydrogen storage material.Especially, the present invention relates to be used for the AB of Ni-MH battery
5Type cathode hydrogen storage material and preparation method thereof, the characteristics of this cathode hydrogen storage material are lower more than 30% than used usually in the market hydrogen storage material cost.
Background technology
Ni-MH battery is since last century, put goods on the market the nineties, because it is long that it has capacity height, life-span, characteristics such as memory-less effect, non-environmental-pollution, extensively receive an acclaim, occupation rate of market is more and more higher, cell types is also developed to other polytypes by AA, AAA common batteries, and product is widely used in electric tool, household electrical appliance, computer, building, space flight, communication and vehicle using motor etc., develops very rapid.
For Ni-MH battery, used negative material mainly is mishmetal MmNi at present
5Generally about 300～330mAh/g, typical composition is MmNi for-type hydrogen storage alloy, alloy capacity
3.55Co
0.75Mn
0.4Al
0.3Wherein Mm is a mishmetal, main component is La, Ce, Pr, Nd, in this component prescription, the percentage by weight of cobalt is about 10wt%, because the cycle life of cobalt anticathode plays important effect, and reach optimum efficiency when about 10wt% at content, thereby become indispensable element, but the price of cobalt is relatively more expensive again simultaneously, is the most expensive element of price in this component prescription, except that cobalt, also contain about 50% the nickel that cost is only second to cobalt in the prescription, and nickel is hydrogen capacity to be put in its suction influence one of most important element, the existence of these two elements has caused the raising of hydrogen storage material and Ni-MH battery cost.Ni-MH battery is faced with the competition of two kinds of products at present in use in market, and the one, nickel-cadmium cell, the one, lithium ion battery will improve the competitive advantage of Ni-MH battery, just must improve from performance and cost two aspects, so the low-cost AB of low cobalt content
5The type cathode hydrogen storage material that uses for nickel-hydrogen battery is a hot research in recent years always.
Summary of the invention
The objective of the invention is to obtain a kind of AB of low cobalt content by composition adjustment and preparation technology's improvement
5The type hydrogen storage material keeps simultaneously its chemical property, particularly cycle life with commercial suitable with high cobalt hydrogen bearing alloy at present again, to satisfy on the market demand to the negative pole low cost hydrogen storage material product that uses for nickel-hydrogen battery.
On the one hand, the invention provides a kind of AB by the preparation of rapid hardening thin strip process
5The type cathode hydrogen storage material, this AB
5The atomic ratio composition of type cathode hydrogen storage material consists of Mm
1-zDy
zNi
3.55Co
0.75-x-yFe
xCu
yMn
0.4Al
0.3, 0＜x+y≤0.7 wherein; 0≤z≤0.039; Mm is the lucium of being made up of La, Ce, Pr, Nd element, and is benchmark with the weight of lucium Mm, and the content of La is 64.5-67.5%, and the content of Ce is 22.0-24.0%, and the content of Pr is 2.5-3.5%, and the content of Nd is 7.0-9.0%.The cooling rate of the rapid hardening thin strip process that wherein, is adopted is that 1-3m/s and product thickness are that 0.2～0.5mm determines by control chill roll surface of revolution linear velocity.
AB
5Type hydrogen storage alloy be by the elements A of easy generation stable hydride (as Mm, Ca, Zr) intermetallic compound of forming with other element B (as Ni, Al, Mn, Si, Zn, Cr, Fe, Cu, Co etc.) belongs to CaCu
5The type hexagonal structure, for Ni-MH battery, used negative material mainly is mishmetal MmNi at present
5Generally about 300mAh/g, typical composition is MmNi for-type hydrogen storage alloy, alloy capacity
3.55Co
0.75Mn
0.4Al
0.3Wherein Mm is a mishmetal, and main component is La, Ce, Pr, Nd.In order to reduce the cost of material, the inventor substitutes cobalt with cheap metallic iron and copper, and adds a spot of heavy rare earth element dysprosium (Dy) in rare earth, adopts strip rapid hardening method simultaneously on technology, has finally obtained the AB that can satisfy actual use
5The low-cost hydrogen storage material of type, this material can be reduced to the content of cobalt below the 5wt%, this material and cobalt content are that the commerce of 10wt% has very similarly electrochemistry capacitance with high cobalt hydrogen bearing alloy simultaneously, activity function and cycle life, low-cost cathode material in use for nickel-hydrogen battery therefore proposed by the invention become to be grouped into (atomic ratio): Mm
1-zDy
zNi
3.55Co
0.75-x-yFe
xCu
yMn
0.4Al
0.3, 0＜x+y≤0.7,0≤z≤0.039 wherein, wherein the composition of mishmetal Mm is formed as shown in table 1.
Each constituent content in table 1 mishmetal
| Element | Percentage by weight (wt%) |
| La | 64.5-67.5 |
| Ce | 22.0-24.0 |
| Pr | 2.5-3.5 |
| Nd | 7.0-9.0 |
Technical scheme of the present invention is to adopt cheap metallic iron and/or copper to substitute cobalt, and in rare earth, add a spot of heavy rare earth element dysprosium (Dy), on technology, adopt strip rapid hardening method simultaneously, finally both obtained and reduced cost, satisfy electrochemistry capacitance again, the AB that serviceabilities such as activity function and cycle life require
5The type hydrogen storage material.
From improving the product electrochemistry capacitance, the combination property aspect of activity function and cycle life considers that chill roll surface of revolution linear velocity is 2m/s in the preferred strip rapid hardening method that adopts.
For the electrochemistry capacitance of having relatively high expectations, serviceabilities such as activity function and cycle life, in the application that needs again suitably to reduce cost, preferred AB of the present invention
5X and y satisfy 0＜x+y＜0.4 in the type cathode hydrogen storage material.For further improving its serviceability, contain dysprosium in the cathode hydrogen storage material more preferably of the present invention, promptly satisfy 0＜z≤0.039.
Satisfy the AB of the present invention of above-mentioned application requirements
5The example of type cathode hydrogen storage material has:
MmNi
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Fe
0.1Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.1Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Fe
0.2Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.2Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Fe
0.3Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.3Mn
0.4Al
0.3。
Above-mentioned AB
5Especially preferredly in the type cathode hydrogen storage material be:
MmNi
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.1Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.2Cu
0.1Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.3Mn
0.4Al
0.3。
Significantly reduce cost for requiring, and electrochemistry capacitance, in the application that the satisfied use of serviceabilities such as activity function and cycle life needs get final product, preferred AB of the present invention
5X and y satisfy 0.4≤x+y≤0.7 in the type cathode hydrogen storage material.Under the prerequisite that significantly reduces cost, for further improving its serviceability, contain dysprosium in the cathode hydrogen storage material more preferably of the present invention, promptly satisfy 0＜z≤0.039.And reduce cost and keep in the another kind of mode of better serviceability taking into account, x and y satisfy 0.4≤x+y≤0.5 in the preferred cathode hydrogen storage material of the present invention.
Satisfy the AB of the present invention of above-mentioned application requirements
5The example of type cathode hydrogen storage material has:
MmNi
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.3Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.3Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.15Fe
0.3Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.15Fe
0.3Cu
0.3Mn
0.4Al
0.3；
MmNi
3.5Co
0.35Fe
0.4Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.4Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.4Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.4Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.15Fe
0.4Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.15Fe
0.4Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.05Fe
0.4Cu
0.3Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.05Fe
0.4Cu
0.3Mn
0.4Al
0.3。
Above-mentioned AB
5Especially preferredly in the type cathode hydrogen storage material be:
MmNi
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.3Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.15Fe
0.3Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.4Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.4Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.4Cu
0.1Mn
0.4Al
0.3。
Prepare AB of the present invention
5The rapid hardening thin strip process of type cathode hydrogen storage material is as follows:
To mol ratio is Mm: Dy: Ni: Co: Fe: Cu: Mn: Al=(1-z): z: 3.55: (0.75-x-y): x: y: 0.4: 0.3 raw material carries out melting, 0＜x+y≤0.7 wherein, 0≤z≤0.039, Mm is the lucium of being made up of La, Ce, Pr, Nd element, and the weight with lucium Mm is benchmark, and the content of La is 64.5-67.5%, and the content of Ce is 22.0-24.0%, the content of Pr is 2.5-3.5%, and the content of Nd is 7.0-9.0%;
The liquation that melting is obtained is directed to the chill roll surface with the linear resonance surface velocity rotation of 1-3m/s, and this chill roll is with the rapid cool to room temperature of melting liquation and be thrown in the sample divider, obtains the AB that thickness is 0.2～0.5mm
5The type cathode hydrogen storage material.Wherein, the surface of revolution linear velocity of chill roll and product thickness have determined the cooling rate of rapid hardening thin strip process of the present invention jointly.
In above-mentioned melting step, adopt the vaccum sensitive stove that vacuumizes the back and feed argon shield to carry out melting.
In above-mentioned rapid cooling step, can adopt bottom opening and place the crucible of chill roll top to compile the melting liquation, the hole of melting liquation below crucible is directed into the surface of chill roll.
In the step of above-mentioned rapid cooling, preferably adopt the copper roller as chill roll.
The linear resonance surface velocity of chill roll rotation is preferably 2m/s.
AB of the present invention
5The type cathode hydrogen storage material can be used for preparing nickel-hydrogen battery negative pole.Adopt AB of the present invention
5The type cathode hydrogen storage material has the advantages that as the Ni-MH battery of negative pole cost reduces, and it has kept good or has been the electrochemistry capacitance that satisfies instructions for use at least simultaneously, performances such as activity function and cycle life.
Adopt iron and copper to substitute expensive cobalt in the cathode hydrogen storage material of the present invention to reach the purpose that reduces cost, increase along with iron and copper content, the serviceability of cathode hydrogen storage material, especially cycle life sharply descends, for this reason, by in hydrogen storage material, being added into the dysprosium of trace, adopt the rapid hardening thin strip process to be prepared simultaneously, the cathode hydrogen storage material that has obtained to keep good serviceability or satisfied instructions for use.
Embodiment
Below in conjunction with embodiment the present invention is launched further description.But should be appreciated that following execution mode only is used for the present invention is illustrated and is not in order to limit scope of the present invention.
Percentage by weight according to each element of alloy in the table 2 is prepared burden, and adopts conventional smelting process and rapid hardening thin strip process that raw material is made AB respectively
5Type cathode hydrogen storage material, and the performance of the aspects such as activation number of times, heap(ed) capacity and cycle life of each product of comparison.
The composition that table 2 embodiment of the invention is compared with the prior art example compares (wt%)
| Composition | La | Ce | Pr | Nd | Dy | Ni | Co | Fe | Cu | Mn | Al | |
| The present invention | MmNi 3.55Co 0.65Cu 0.1Mn 0.4Al 0.3 | 21.81 | 7.60 | 0.99 | 2.64 | 0.00 | 49.28 | 9.06 | 0.00 | 1.50 | 5.20 | 1.91 |
| Mm 0.961Dy 0.039Ni 3.55Co 0.65Cu 0.1Mn 0.4Al 0.3 | 20.91 | 7.29 | 0.95 | 2.53 | 1.50 | 49.18 | 9.04 | 0.00 | 1.50 | 5.19 | 1.91 | |
| MmNi 3.55Co 0.55Cu 0.2Mn 0.4Al 0.3 | 21.78 | 7.59 | 0.99 | 2.64 | 0.00 | 49.23 | 7.66 | 0.00 | 3.00 | 5.19 | 1.91 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.55Cu 0.2Mn 0.4Al 0.3 | 20.89 | 7.28 | 0.95 | 2.53 | 1.49 | 49.13 | 7.64 | 0.00 | 3.00 | 5.18 | 1.91 | |
| MmNi 3.55Co 0.45Cu 0.3Mn 0.4Al 0.3 | 21.76 | 7.58 | 0.99 | 2.64 | 0.00 | 49.18 | 6.26 | 0.00 | 4.50 | 5.19 | 1.91 | |
| Mm 0.964Dy 0.039Ni 3.55Co 0.45Cu 0.3Mn 0.4Al 0.3 | 20.87 | 7.27 | 0.95 | 2.53 | 1.49 | 49.07 | 6.25 | 0.00 | 4.49 | 5.18 | 1.91 | |
| MmNi 3.55Co 0.65Fe 0.1Mn 0.4Al 0.3 | 21.85 | 7.61 | 0.99 | 2.65 | 0.00 | 49.38 | 9.08 | 1.32 | 0.00 | 5.21 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.65Fe 0.1Mn 0.4Al 0.3 | 20.95 | 7.30 | 0.95 | 2.54 | 1.50 | 49.27 | 9.06 | 1.32 | 0.00 | 5.20 | 1.91 | |
| MmNi 3.55Co 0.55Fe 0.1Cu 0.1Mn 0.4Al 0.3 | 21.82 | 7.60 | 0.99 | 2.65 | 0.00 | 49.32 | 7.67 | 1.32 | 1.50 | 5.20 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.55Fe 0.1Cu 0.1Mn 0.4Al 0.3 | 20.93 | 7.29 | 0.95 | 2.54 | 1.50 | 49.22 | 7.66 | 1.31 | 1.50 | 5.19 | 1.91 | |
| MmNi 3.55Co 0.45Fe 0.1Cu 0.2Mn 0.4Al 0.3 | 21.80 | 7.60 | 0.99 | 2.64 | 0.00 | 49.27 | 6.27 | 1.32 | 3.01 | 5.20 | 1.91 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.45Fe 0.1Cu 0.2Mn 0.4Al 0.3 | 20.90 | 7.28 | 0.95 | 2.53 | 1.50 | 49.17 | 6.26 | 1.31 | 3.00 | 5.19 | 1.91 | |
| MmNi 3.55Co 0.35Fe 0.1Cu 0.3Mn 0.4Al 0.3 | 21.77 | 7.59 | 0.99 | 2.64 | 0.00 | 49.21 | 4.87 | 1.31 | 4.50 | 5.19 | 1.91 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.35Fe 0.1Cu 0.3Mn 0.4Al 0.3 | 20.88 | 7.28 | 0.95 | 2.53 | 1.49 | 49.11 | 4.86 | 1.31 | 4.49 | 5.18 | 1.91 | |
| MmNi 3.55Co 0.55Fe 0.2Mn 0.4Al 0.3 | 21.86 | 7.62 | 0.99 | 2.65 | 0.00 | 49.41 | 7.69 | 2.64 | 0.00 | 5.21 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.55Fe 0.2Mn 0.4Al 0.3 | 20.97 | 7.31 | 0.95 | 2.54 | 1.50 | 49.31 | 7.67 | 2.63 | 0.00 | 5.20 | 1.92 | |
| MmNi 3.55Co 0.45Fe 0.2Cu 0.1Mn 0.4Al 0.3 | 21.84 | 7.61 | 0.99 | 2.65 | 0.00 | 49.36 | 6.28 | 2.64 | 1.51 | 5.21 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.45Fe 0.2Cu 0.1Mn 0.4Al 0.3 | 20.94 | 7.30 | 0.95 | 2.54 | 1.50 | 49.26 | 6.27 | 2.63 | 1.50 | 5.20 | 1.91 | |
| MmNi 3.55Co 0.35Fe 0.2Cu 0.2Mn 0.4Al 0.3 | 21.82 | 7.60 | 0.99 | 2.64 | 0.00 | 49.31 | 4.88 | 2.63 | 3.01 | 5.20 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.35Fe 0.2Cu 0.2Mn 0.4Al 0.3 | 20.92 | 7.29 | 0.95 | 2.54 | 1.50 | 49.20 | 4.87 | 2.63 | 3.00 | 5.19 | 1.91 | |
| MmNi 3.55Co 0.25Fe 0.2Cu 0.3Mn 0.4Al 0.3 | 21.79 | 7.59 | 0.99 | 2.64 | 0.00 | 49.25 | 3.48 | 2.63 | 4.51 | 5.19 | 1.91 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.25Fe 0.2Cu 0.3Mn 0.4Al 0.3 | 20.90 | 7.28 | 0.95 | 2.53 | 1.50 | 49.15 | 3.48 | 2.63 | 4.50 | 5.18 | 1.91 | |
| MmNi 3.55Co 0.45Fe 0.3Mn 0.4Al 0.3 | 21.88 | 7.62 | 0.99 | 2.65 | 0.00 | 49.45 | 6.29 | 3.96 | 0.00 | 5.22 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.45Fe 0.3Mn 0.4Al 0.3 | 20.98 | 7.31 | 0.95 | 2.54 | 1.50 | 49.35 | 6.28 | 3.95 | 0.00 | 5.20 | 1.92 | |
| MmNi 3.55Co 0.35Fe 0.3Cu 0.1Mn 0.4Al 0.3 | 21.86 | 7.62 | 0.99 | 2.65 | 0.00 | 49.40 | 4.89 | 3.96 | 1.51 | 5.21 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.35Fe 0.3Cu 0.1Mn 0.4Al 0.3 | 20.96 | 7.30 | 0.95 | 2.54 | 1.50 | 49.30 | 4.88 | 3.95 | 1.50 | 5.20 | 1.92 | |
| MmNi 3.55Co 0.25Fe 0.3Cu 0.2Mn 0.4Al 0.3 | 21.83 | 7.61 | 0.99 | 2.65 | 0.00 | 49.35 | 3.49 | 3.95 | 3.01 | 5.20 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.25Fe 0.3Cu 0.2Mn 0.4Al 0.3 | 20.94 | 7.30 | 0.95 | 2.54 | 1.50 | 49.24 | 3.48 | 3.95 | 3.00 | 5.19 | 1.91 | |
| MmNi 3.55Co 0.15Fe 0.3Cu 0.3Mn 0.4Al 0.3 | 21.81 | 7.60 | 0.99 | 2.64 | 0.00 | 49.29 | 2.09 | 3.95 | 4.51 | 5.20 | 1.91 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.15Fe 0.3Cu 0.3Mn 0.4Al 0.3 | 20.91 | 7.29 | 0.95 | 2.54 | 1.50 | 49.19 | 2.09 | 3.94 | 4.50 | 5.19 | 1.91 | |
| MmNi 3.55Co 0.35Fe 0.4Mn 0.4Al 0.3 | 21.90 | 7.63 | 1.00 | 2.65 | 0.00 | 49.49 | 4.90 | 5.29 | 0.00 | 5.22 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.35Fe 0.4Mn 0.4Al 0.3 | 21.00 | 7.32 | 0.95 | 2.55 | 1.50 | 49.39 | 4.89 | 5.28 | 0.00 | 5.21 | 1.92 | |
| MmNi 3.55Co 0.25Fe 0.4Cu 0.1Mn 0.4Al 0.3 | 21.87 | 7.62 | 0.99 | 2.65 | 0.00 | 49.44 | 3.50 | 5.28 | 1.51 | 5.21 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.25Fe 0.4Cu 0.1Mn 0.4Al 0.3 | 20.98 | 7.31 | 0.95 | 2.54 | 1.50 | 49.33 | 3.49 | 5.27 | 1.50 | 5.20 | 1.92 | |
| MmNi 3.55Co 0.15Fe 0.4Cu 0.2Mn 0.4Al 0.3 | 21.85 | 7.61 | 0.99 | 2.65 | 0.00 | 49.38 | 2.10 | 5.28 | 3.01 | 5.21 | 1.92 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.15Fe 0.4Cu 0.2Mn 0.4Al 0.3 | 20.95 | 7.30 | 0.95 | 2.54 | 1.50 | 49.28 | 2.09 | 5.26 | 3.01 | 5.20 | 1.91 | |
| MmNi 3.55Co 0.05Fe 0.4Cu 0.3Mn 0.4Al 0.3 | 21.79 | 7.59 | 0.99 | 2.64 | 0.00 | 49.24 | 0.70 | 3.95 | 6.01 | 5.19 | 1.91 | |
| Mm 0.961Dy 0.039Ni 3.55Co 0.05Fe 0.4Cu 0.3Mn 0.4Al 0.3 | 20.93 | 7.29 | 0.95 | 2.54 | 1.50 | 49.23 | 0.70 | 5.26 | 4.50 | 5.19 | 1.91 | |
| Comparative Examples | MmNi 3.55Co 0.75Mn 0.4Al 0.3 | 21.83 | 7.61 | 0.99 | 2.65 | 0.00 | 49.34 | 10.47 | 0.00 | 0.00 | 5.20 | 1.92 |
Sample for conventional melting; the alloy raw material for preparing is carried out melting and ingot casting in the induction furnace that vacuumizes afterwards and feed argon shield; then ingot casting being carried out homogenizing in the vacuum heat treatment furnace that vacuumizes afterwards and feed argon shield handles; treatment temperature is 980 ℃; temperature retention time is 15 hours, then takes out with the stove cool to room temperature.
For the rapid hardening sample; the alloy raw material for preparing is carried out melting in the induction furnace that vacuumizes afterwards and feed argon shield; then liquation is poured in the crucible of a bottom opening; this crucible is placed on water flowing cooling and copper roller rotating top; liquation passes through the surface of the orifice flow of crucible bottom to the copper roller; experimental requirement is respectively 1m/s, 2m/s and 3m/s with the rotational speed regulation of copper roller to its linear resonance surface velocity respectively; the water-cooled copper roller cools off the melting liquation rapidly and is thrown in the sample divider; obtain laboratory sample, sample thickness is between 0.2～0.5mm.
The test of electrochemistry capacitance at first becomes resulting hydrogen bearing alloy less than 200 purpose alloyed powders in grinding at room temperature, then will be less than 200 purpose negative alloy powders and nickel powder mixed by 1: 4, and add an amount of poly-vinyl alcohol solution as binding agent, be cold-pressed into diameter then and use [the Ni (OH) that used positive electricity is very identical with Ni-MH battery as negative electrode for the cake of (d=15mm)
2-NiOOH] electrode, the Capacity design of positive electrode is the capacity far above negative electrode, so that negative electrode material reaches fully saturated when charging, [Hg/HgO/6M KOH] is reference electrode.In the electrode performance test process, test for activity function and charge discharge capacity, 30 ℃ of current densities that adopt 60mA/g to the storage hydrogen negative material 400min that charges, paused 15 minutes in the charging back, then with the current density of 60mA/g discharge into the negative electrode current potential with respect to the electrode potential of reference electrode for till-0.5 volt, carry out the next round charge and discharge cycle again.Capacity of negative plates is along with the increase capacity that discharges and recharges number of times will reach a maximum gradually, and relatively stablely get off, our amount of trying to please reached the required number of times that discharges and recharges of maximum and was the activation number of times this moment, and this maximum capacity is the hydrogen storage capability of material under 30 ℃.
Test for cycle life, in order to shorten the testing time, charging and discharging currents density is chosen as 300mA/g, method of testing is as follows: at first adopt the current density of 60mA/g to activate by the method for top test capacity with the activation number of times at 30 ℃ specimen, after activation is good, 30 ℃ of current densities that adopt 300mA/g to the storage hydrogen negative material 75min that charges, paused 15 minutes in the charging back, then with the current density of 300mA/g discharge into the negative electrode current potential with respect to the electrode potential of reference electrode for till-0.5 volt, carrying out next round again fills, discharge cycles, in order to contrast conveniently, definite cycle-index of all getting when its capacity under this experiment condition drops to 160mAh/g of the cycle life of sample, its test result all is given in table 3 and the table 4.
Table 3
Compare with the hydrogen storage material of conventional smelting process acquisition and activity function, electrochemistry capacitance and the cycle life of prior art Comparative Examples
| x(Fe) | y(Cu) | z(Dy) | The activation number of times | Heap(ed) capacity (mAh/g) | Cycle life | |
| Hydrogen storage material with conventional smelting process acquisition | 0 | 0.1 | 0 | 3 | 329 | 675 |
| 0.039 | 3 | 331 | 683 | |||
| 0.2 | 0 | 3 | 331 | 598 | ||
| 0.039 | 3 | 331 | 604 | |||
| 0.3 | 0 | 3 | 325 | 498 | ||
| 0.039 | 3 | 328 | 507 | |||
| 0.1 | 0 | 0 | 3 | 321 | 663 | |
| 0.039 | 3 | 324 | 668 | |||
| 0.1 | 0 | 3 | 325 | 587 | ||
| 0.039 | 3 | 327 | 594 | |||
| 0.2 | 0 | 3 | 330 | 481 | ||
| 0.039 | 3 | 331 | 487 | |||
| 0.3 | 0 | 3 | 321 | 361 | ||
| 0.039 | 3 | 324 | 367 | |||
| 0.2 | 0 | 0 | 3 | 312 | 580 | |
| 0.039 | 3 | 314 | 588 | |||
| 0.1 | 0 | 3 | 315 | 484 | ||
| 0.039 | 3 | 318 | 489 | |||
| 0.2 | 0 | 3 | 320 | 368 | ||
| 0.039 | 3 | 323 | 377 | |||
| 0.3 | 0 | 3 | 310 | 221 | ||
| 0.039 | 3 | 313 | 231 | |||
| 0.3 | 0 | 0 | 3 | 301 | 478 | |
| 0.039 | 3 | 303 | 487 | |||
| 0.1 | 0 | 3 | 303 | 358 | ||
| 0.039 | 3 | 306 | 362 | |||
| 0.2 | 0 | 3 | 310 | 232 | ||
| 0.039 | 3 | 312 | 238 | |||
| 0.3 | 0 | 3 | 303 | 158 | ||
| 0.039 | 3 | 305 | 168 | |||
| 0.4 | 0 | 0 | 3 | 287 | 337 | |
| 0.039 | 3 | 291 | 342 | |||
| 0.1 | 0 | 3 | 291 | 221 | ||
| 0.039 | 3 | 293 | 227 | |||
| 0.2 | 0 | 3 | 295 | 148 | ||
| 0.039 | 3 | 297 | 154 | |||
| 0.3 | 0 | 3 | 288 | 112 | ||
| 0.039 | 3 | 291 | 123 | |||
| Comparative Examples | 0 | 0 | 0 | 3 | 328 | 725 |
Table 4
Compare with the hydrogen storage material of the present invention of rapid hardening thin strip process acquisition and activity function, electrochemistry capacitance and the cycle life of prior art Comparative Examples
| x(Fe) | y(Cu) | z(Dy) | Copper roller linear resonance surface velocity | |||||||||
| 1m/s | 2m/s | 3m/s | 1m/s | 2m/s | 3m/s | 1m/s | 2m/s | 3m/s | ||||
| The activation number of times | Heap(ed) capacity (mAh/g) | Cycle life | ||||||||||
| The present invention | 0 | 0.1 | 0 | 3 | 7 | 15 | 324 | 317 | 298 | 975 | 1083 | 1187 |
| 0.039 | 4 | 8 | 16 | 325 | 320 | 301 | 1027 | 1105 | 1214 | |||
| 0.2 | 0 | 3 | 8 | 15 | 326 | 320 | 301 | 888 | 998 | 1089 | ||
| 0.039 | 4 | 8 | 17 | 327 | 321 | 301 | 986 | 1094 | 1177 | |||
| 0.3 | 0 | 3 | 7 | 16 | 320 | 316 | 305 | 727 | 838 | 948 | ||
| 0.039 | 4 | 8 | 17 | 322 | 318 | 308 | 847 | 958 | 1108 | |||
| 0.1 | 0 | 0 | 3 | 8 | 15 | 320 | 316 | 295 | 963 | 1053 | 1143 | |
| 0.039 | 4 | 8 | 16 | 323 | 318 | 298 | 1008 | 1094 | 1186 | |||
| 0.1 | 0 | 3 | 7 | 16 | 323 | 318 | 299 | 867 | 968 | 1057 | ||
| 0.039 | 4 | 8 | 17 | 325 | 320 | 302 | 984 | 1078 | 1158 | |||
| 0.2 | 0 | 4 | 8 | 17 | 324 | 320 | 302 | 711 | 833 | 941 | ||
| 0.039 | 4 | 8 | 17 | 326 | 322 | 303 | 837 | 947 | 1081 | |||
| 0.3 | 0 | 4 | 8 | 17 | 318 | 316 | 294 | 601 | 711 | 837 | ||
| 0.039 | 4 | 8 | 17 | 320 | 318 | 296 | 733 | 847 | 965 | |||
| 0.2 | 0 | 0 | 3 | 8 | 17 | 310 | 305 | 290 | 832 | 920 | 1008 | |
| 0.039 | 3 | 8 | 17 | 312 | 308 | 294 | 984 | 1032 | 1083 | |||
| 0.1 | 0 | 4 | 8 | 17 | 313 | 306 | 292 | 701 | 804 | 914 | ||
| 0.039 | 4 | 8 | 17 | 314 | 308 | 295 | 827 | 941 | 1059 | |||
| 0.2 | 0 | 4 | 8 | 17 | 314 | 310 | 294 | 591 | 701 | 814 | ||
| 0.039 | 4 | 8 | 17 | 316 | 313 | 296 | 707 | 824 | 945 | |||
| 0.3 | 0 | 4 | 8 | 17 | 307 | 300 | 290 | 507 | 611 | 721 | ||
| 0.039 | 4 | 8 | 17 | 310 | 302 | 293 | 631 | 733 | 843 | |||
| 0.3 | 0 | 0 | 4 | 8 | 18 | 295 | 290 | 284 | 681 | 788 | 901 | |
| 0.039 | 4 | 8 | 18 | 298 | 294 | 288 | 803 | 907 | 1014 | |||
| 0.1 | 0 | 4 | 8 | 18 | 298 | 294 | 288 | 578 | 681 | 798 | ||
| 0.039 | 4 | 8 | 18 | 301 | 296 | 290 | 691 | 802 | 912 | |||
| 0.2 | 0 | 4 | 8 | 18 | 304 | 300 | 293 | 484 | 582 | 700 | ||
| 0.039 | 4 | 8 | 18 | 305 | 302 | 295 | 607 | 708 | 813 | |||
| 0.3 | 0 | 4 | 8 | 18 | 296 | 291 | 285 | 397 | 499 | 602 | ||
| 0.039 | 4 | 8 | 18 | 297 | 293 | 287 | 518 | 598 | 708 | |||
| 0.4 | 0 | 0 | 4 | 9 | 18 | 280 | 276 | 270 | 557 | 659 | 774 | |
| 0.039 | 4 | 9 | 18 | 283 | 281 | 274 | 672 | 777 | 887 | |||
| 0.1 | 0 | 4 | 9 | 18 | 283 | 280 | 275 | 451 | 557 | 671 | ||
| 0.039 | 4 | 9 | 18 | 285 | 283 | 277 | 577 | 677 | 781 | |||
| 0.2 | 0 | 4 | 9 | 18 | 287 | 295 | 295 | 365 | 458 | 564 | ||
| 0.039 | 4 | 9 | 18 | 290 | 297 | 297 | 476 | 564 | 674 | |||
| 0.3 | 0 | 4 | 9 | 18 | 280 | 288 | 288 | 272 | 365 | 468 | ||
| 0.039 | 4 | 9 | 18 | 282 | 291 | 291 | 373 | 463 | 565 | |||
| x(Fe) | y(Cu) | z(Dy) | The activation number of times | Heap(ed) capacity (mAh/g) | Cycle life | |||||||
| Comparative Examples | 0 | 0 | 0 | 3 | 328 | 725 | ||||||
Table 3 and table 4 have provided the Mm that handled 15 hours and prepared with the rapid hardening method with behind the conventional vacuum induction melting and 980 ℃ of homogenizing respectively
1-zDy
zNi
3.55Co
0.75-x-yFe
xCu
yMn
0.4Al
0.3(0＜x≤0.4; 0＜y≤0.3; 0＜z≤O.039) electrochemistry capacitance, activity function and the The cyclic lifetime test results of under 300mA/g charging and discharging currents density, measuring under 30 ℃ and 60mA/g charging and discharging currents density, measured of compound.
By data in the table as seen, adopt prescription of the present invention by conventional vacuum induction melting after and 980 ℃ of homogenizing handle the performance of alloy aspect cycle life that obtained in 15 hours be not so good as with prior art in do not mix the hydrogen storage material MmNi of iron, copper, dysprosium
3.55Co
0.75Mn
0.4Al
0.3, and along with the reduction of cobalt content, the cycle life of alloy also decreases, and drops to 5wt% when following at cobalt content, the cycle life of alloy also is reduced to below 400 times, as Mm by initial more than 700 time
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3The cycle life of alloy has only 377 times, and along with the increase of Fe and Cu content, the life-span can further reduce, and for the material of such cycle life, can not satisfy the needs of battery producer.
Different therewith is, the present invention can improve the cycle life of alloy significantly by the method for rapid hardening, and increase along with cooling rate (under the situation that product thickness is fixed, characterizing) by the chill roll rotating speed, the cycle life of alloy increases, reduce but can cause activating number of times and charge discharge capacity, therefore, from taking into account activation number of times, electrochemistry capacitance and cycle life three's angle, selected chill roll surface of revolution linear velocity is 1-3m/s, more preferably 2m/s among the present invention.In addition, the interpolation of heavy rare earth element dysprosium (Dy) can further improve the cycle life of alloy, simultaneously also capacity there is certain improvement, if select suitable rapid hardening speed (when product thickness is 0.2-0.5mm, chill roll surface of revolution linear velocity is 1-3m/s) and add a spot of heavy rare earth element dysprosium (Dy) (0＜z≤0.039) simultaneously, not only can keep good activity function and charge discharge capacity, the cycle life of low cobalt alloy is reached or a little less than commercial cycle life level at present, thereby realize not only can reducing cost but also can satisfy the requirement of use with 10wt% cobalt content alloy.
In addition, suitably adjust the prescription of hydrogen storage material of the present invention, can satisfy different application requirements.
For example, for the electrochemistry capacitance of having relatively high expectations, serviceabilities such as activity function and cycle life, in the application that needs again suitably to reduce cost, the value of x and y should satisfy 0＜x+y＜0.4.For further improving its serviceability, can in prescription, add an amount of dysprosium (0＜z≤0.039).As shown in table 4, when cobalt content was reduced to 6-8wt%, hydrogen storage material of the present invention had kept activity function and the electrochemistry capacitance suitable with prior art, and cycle life is higher than or is equivalent at least prior art simultaneously.For example, when chill roll surface of revolution linear velocity is 2m/s, cobalt content be the activity function of the hydrogen storage material of the present invention between the 6-8wt% and electrochemistry capacitance a little less than or be equivalent to prior art, but cycle life reaches more than 900 times, and is more high (as MmNi than prior art
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3, MmNi
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3, Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.2Cu
0.1Mn
0.4Al
0.3, Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.3Mn
0.4Al
0.3Deng).And cobalt content is when being higher than 8wt%, and cycle life can be up to more than 1000 times.
For another example, significantly reduce cost for requiring, and electrochemistry capacitance, in the application that the satisfied use of serviceabilities such as activity function and cycle life needs get final product, the value of x and y should satisfy 0.4≤x+y≤0.7.Under the prerequisite that significantly reduces cost, for further improving its serviceability, contain dysprosium in the preferred cathode hydrogen storage material of the present invention, promptly satisfy 0＜z≤0.039; And reduce cost and keep in the another kind of mode of better serviceability taking into account, x and y satisfy 0.4≤x+y≤0.5 in the preferred cathode hydrogen storage material of the present invention.As shown in table 4, when cobalt content is reduced to 5wt% when following, in hydrogen storage material, add an amount of dysprosium, still can obtain to satisfy the hydrogen storage material of performance requirement.For example, when being reduced to cobalt content between the 3-5wt% when adding iron and/or copper, by adding an amount of dysprosium and/or regulating chill roll surface of revolution linear velocity is 2m/s, activity function that is obtained and electrochemistry capacitance be a little less than prior art, and cycle life and prior art are quite or even be higher than prior art (as Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.3Cu
0.2Mn
0.4Al
0.3, Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3, MmNi
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3).Even be reduced to 2wt% or when lower when cobalt content, by adding an amount of dysprosium and/or regulating chill roll surface of revolution linear velocity is 2m/s, activity function that is obtained and electrochemistry capacitance are a little less than prior art, and cycle life satisfies instructions for use (as MmNi still greater than 400 times
3.55Co
0.15Fe
0.4Cu
0.2Mn
0.4Al
0.3, Mm
0.961Dy
0.039Ni
3.55Co
0.05Fe
0.4Cu
0.3Mn
0.4Al
0.3Deng).
Claims (16)
1. AB
5The type cathode hydrogen storage material is that 1-3m/s and product thickness are the rapid hardening thin strip process preparation of 0.2～0.5mm by control chill roll surface of revolution linear velocity, this AB
5The atomic ratio composition of type cathode hydrogen storage material consists of Mm
1-zDy
zNi
3.55Co
0.75-x-yFe
xCu
yMn
0.4Al
0.30＜x+y≤0.7 wherein; 0≤z≤0.039; Mm is the lucium of being made up of La, Ce, Pr, Nd element, and is benchmark with the weight of lucium Mm, and the content of La is 64.5-67.5%, and the content of Ce is 22.0-24.0%, and the content of Pr is 2.5-3.5%, and the content of Nd is 7.0-9.0%.
2. AB according to claim 1
5The type cathode hydrogen storage material is characterized in that, described chill roll surface of revolution linear velocity is 2m/s.
3. AB according to claim 1 and 2
5The type cathode hydrogen storage material is characterized in that, 0＜x+y＜0.4.
4. AB according to claim 3
5The type cathode hydrogen storage material is characterized in that, 0＜z≤0.039.
5. AB according to claim 3
5The type cathode hydrogen storage material is characterized in that, described AB
5The type cathode hydrogen storage material is:
MmNi
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Fe
0.1Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.1Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Fe
0.2Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.2Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.45Fe
0.3Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.3Mn
0.4Al
0.3。
6. AB according to claim 5
5The type cathode hydrogen storage material is characterized in that, described AB
5The type cathode hydrogen storage material is:
MmNi
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.65Fe
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.1Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.1Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.55Fe
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.2Cu
0.1Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.45Fe
0.3Mn
0.4Al
0.3。
7. AB according to claim 1 and 2
5The type cathode hydrogen storage material is characterized in that, 0.4≤x+y≤0.7.
8. AB according to claim 7
5The type cathode hydrogen storage material is characterized in that, 0＜z≤0.039.
9. AB according to claim 7
5The type cathode hydrogen storage material is characterized in that, 0.4≤x+y≤0.5.
10. AB according to claim 7
5The type cathode hydrogen storage material is characterized in that, described AB
5The type cathode hydrogen storage material is:
MmNi
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.3Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.3Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.15Fe
0.3Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.15Fe
0.3Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.4Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.4Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.4Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.4Cu
0.1Mn
0.4Al
0.3；
MmNi
3.55Co
0.15Fe
0.4Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.15Fe
0.4Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.05Fe
0.4Cu
0.3Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.05Fe
0.4Cu
0.3Mn
0.4Al
0.3。
11. AB according to claim 10
5The type cathode hydrogen storage material is characterized in that, described AB
5The type cathode hydrogen storage material is:
MmNi
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.1Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.2Cu
0.2Mn
0.4Al
0.3；
MmNi
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.2Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.3Cu
0.1Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.3Cu
0.2Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.15Fe
0.3Cu
0.3Mn
0.4Al
0.3；
MmNi
3.55Co
0.35Fe
0.4Mn
0.4Al
0.3；
Mm
0.961Dy
0.039Ni
3.55Co
0.35Fe
0.4Mn
0.4Al
0.3Or
Mm
0.961Dy
0.039Ni
3.55Co
0.25Fe
0.4Cu
0.1Mn
0.4Al
0.3。
12. one kind prepares the described AB of claim 1
5The method of type cathode hydrogen storage material, this method are the rapid hardening thin strip process that comprises the following steps:
To mol ratio is Mm: Dy: Ni: Co: Fe: Cu: Mn: Al=(1-z): z: 3.55: (0.75-x-y): x: y: 0.4: 0.3 raw material carries out melting, 0＜x+y≤0.7 wherein, 0≤z≤0.039, Mm is the lucium of being made up of La, Ce, Pr, Nd element, and the weight with lucium Mm is benchmark, and the content of La is 64.5-67.5%, and the content of Ce is 22.0-24.0%, the content of Pr is 2.5-3.5%, and the content of Nd is 7.0-9.0%;
The liquation that melting is obtained is directed to the chill roll surface with the linear resonance surface velocity rotation of 1-3m/s, and this chill roll is with the rapid cool to room temperature of melting liquation and be thrown in the sample divider, obtains the AB that thickness is 0.2～0.5mm
5The type cathode hydrogen storage material.
13. method according to claim 12 is characterized in that, described chill roll is with the linear resonance surface velocity rotation of 2m/s.
14. according to claim 12 or 13 described methods, it is characterized in that, adopt the vaccum sensitive stove that vacuumizes the back and feed argon shield to carry out melting in the described melting step.
15., it is characterized in that adopt bottom opening in the described rapid cooling step and place the crucible of chill roll top to compile the melting liquation, the hole of melting liquation below crucible is directed into the surface of chill roll according to claim 12 or 13 described methods.
16. any described AB of claim 1-11
5The application of type cathode hydrogen storage material in making nickel-hydrogen battery negative pole.
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| CNB2005100998998A CN1319196C (en) | 2005-09-09 | 2005-09-09 | AB5 type negative pole hydrogen-storage material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383413B (en) * | 2008-10-30 | 2010-06-02 | 珠海金峰航电源科技有限公司 | AB5 type negative pole hydrogen storing material |
| CN101376941B (en) * | 2007-08-31 | 2010-11-03 | 比亚迪股份有限公司 | Hydrogen storage alloy, preparation thereof, and cathode and battery using the hydrogen storage alloy |
| CN103259003A (en) * | 2012-02-20 | 2013-08-21 | 株式会社杰士汤浅国际 | Hydrogen storage alloy, electrode, nickel-metal hydride rechargeable battery and method for producing hydrogen storage alloy |
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| CN1061057A (en) * | 1990-10-30 | 1992-05-13 | 四川大学 | The preparation method of mercury iodide monocrystal |
| CN1027762C (en) * | 1992-04-25 | 1995-03-01 | 冶金工业部钢铁研究总院 | Hydrogen storage alloy used in negative pole of secondary battery |
| CN1028882C (en) * | 1992-07-16 | 1995-06-14 | 南开大学 | Store hydrogen alloy electrode material |
| CN1044173C (en) * | 1994-10-20 | 1999-07-14 | 浙江大学 | Hydrogen-storing alloy electrode material |
| JP2000144278A (en) * | 1998-11-16 | 2000-05-26 | Mitsui Mining & Smelting Co Ltd | Hydrogen occlusion alloy and its production |
| JP2001294958A (en) * | 2000-04-11 | 2001-10-26 | Sumitomo Metal Ind Ltd | Hydrogen storage alloy for nickel-hydrogen secondary battery and its producing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376941B (en) * | 2007-08-31 | 2010-11-03 | 比亚迪股份有限公司 | Hydrogen storage alloy, preparation thereof, and cathode and battery using the hydrogen storage alloy |
| CN101383413B (en) * | 2008-10-30 | 2010-06-02 | 珠海金峰航电源科技有限公司 | AB5 type negative pole hydrogen storing material |
| CN103259003A (en) * | 2012-02-20 | 2013-08-21 | 株式会社杰士汤浅国际 | Hydrogen storage alloy, electrode, nickel-metal hydride rechargeable battery and method for producing hydrogen storage alloy |
| CN103259003B (en) * | 2012-02-20 | 2017-03-01 | 株式会社杰士汤浅国际 | The manufacture method of hydrogen-storage alloy, electrode, nickel-hydrogen accumulator and hydrogen-storage alloy |
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