CN1268779C - Method for preparing nano rare earth hydrogen storage alloy and equipment - Google Patents
Method for preparing nano rare earth hydrogen storage alloy and equipment Download PDFInfo
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- CN1268779C CN1268779C CNB2004100269048A CN200410026904A CN1268779C CN 1268779 C CN1268779 C CN 1268779C CN B2004100269048 A CNB2004100269048 A CN B2004100269048A CN 200410026904 A CN200410026904 A CN 200410026904A CN 1268779 C CN1268779 C CN 1268779C
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- tundish
- cooling roller
- spillway
- hydrogen
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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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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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Abstract
The present invention relates to a method and a device thereof for preparing nanometer crystal rare-earth hydrogen storage alloy, which is characterized in that an included angle between an overflow outlet of a tundish and the horizontal diameter of the cross section of a cooling roller is from 90 to 180 degrees, and the surface linear speed of the cooling roller is from 1 to 6 m/s. One side of the tundish facing the cooling roller is provided with an overflow outlet for alloy liquid, and the lower edge of the overflow outlet is higher than the inner bottom surface of the tundish. The grain size of a prepared hydrogen storage alloy sheet is from 1 to 1000 nm. Compared with the traditional process, the present invention has the advantages that the steps of roughly and moderately breaking alloy, thermally processing alloy, etc. are reduced, the process flow is shortened, and the production cost is reduced. The nanometer crystal structure prepared by the method and the device provides abundant diffusion channels for hydrogen atoms, reduces the microcrack and the pulverization of alloy in the course of sucking and releasing hydrogen, improves the dynamic performance of sucking and releasing hydrogen of the alloy, and increases electrochemical performance, particularly the stability of charge and discharge cycles and the charge and discharge performance of high current.
Description
Technical field
The present invention relates to a kind of hydrogen storage preparation method and device, particularly a kind of AB
5 ± x(wherein A is one or more rare earth elements to alloy, comprises lanthanon and yttrium; Among B=Ni, Co, Mn, Ti, Al, Zn, Cu, Sn, W, Mo, Fe, Zr, Cr and non-metallic element Si, B, C, the N one or more, 0≤x≤0.75) nanocrystalline rare-earth hydrogen storage preparation method and device.
Background technology
Traditional preparation process rare earth hydrogen-storage alloy technology is to adopt common medium-frequency induction furnace melting, makes alloy pig, and alloy pig is made powder by coarse breaking, middle fragmentation, last ball milling or airflow milling then by high-temperature heat treatment.This method alloy pig is because cooling performance is poor, and the composition segregation is serious, causes the charge and discharge cycles stability of alloy very poor.In order to improve the cycle life of alloy, Japanese Patent Laid prospectus N0.89066/1985 proposes alloy is heat-treated.Although alloy after heat treatment will grow the more nonheat-treated alloy of cycle life of battery because of its composition segregation ratio is low, because grain-size too big (greater than 20 μ m) causes the chemical property of alloy poor.
Chinese patent publication number 1134046,1190677 and European patent EP 0588310A2 a kind of preparation method all is provided, it is first master alloy melting ingot, remelting mother alloy and adopt tundish bottom or the nozzle of crucible bottom makes alloy liquid make the hydrogen-storage alloy thin slice by spray to the roller rapid solidification from gravity then.Chinese patent publication number 1134046 and European patent EP 0588310A2, all more than 2 μ m, this large current density elctrical stability to alloy is unfavorable for the alloy grain size minimum of its preparation.Publication number 1190677 patents, though can make the alloy of grain-size below 2 μ m, wherein the overwhelming majority is an amorphous, the gained alloy is the mixture of amorphous, nanocrystalline and crystallite.The sheet thickness of above patent preparation depends primarily on the rotating speed of roller and nozzle gap and the nozzle bore size to transfer roller.Because alloy liquid is subjected to the difference that influences of gravity, in preparation process, alloy flow quantity instability, with roller way of contact instability, make the alloy slice thickness evenness that makes poor, grain-size size is uneven, and component segregation in the alloy, cyclical stability is poor, production cost is high, thereby can't obviously improve the over-all properties of material.
Summary of the invention
The objective of the invention is to propose a kind ofly to make that thick consistency is good, the method for the single nanocrystalline hydrogen-storage alloy of grain-size.
Another object of the present invention is to propose a device that guarantees that aforesaid method is implemented.
Purpose of the present invention can specifically realize by following measure: will be by AB
5 ± xThe starting material of proportioning components place in the rapid hardening stove smelting pot 1, the operating frequency of this stove is 800～2000Hz, power is 100～400Kw, melting in rare gas element or vacuum environment, wait to melt directly refining 5～40min of back, alloy liquid is poured in the good tundish of preheating 2 then, tundish 2 preheating temperatures are 800～1300 ℃.Described tundish 2 is at the spillway 3 that is provided with alloy liquid in the face of a side of roller 5, and spillway lower edge 4 is higher than the inner bottom surface of tundish 2, and the spillway width is 5～400mm.Tundish can be an integral body, also can be to be combined by several block of material.Angle theta between tundish spillway 3 and the cooling roller 5 cross section horizontal diameter is 90 °～180 °, and the linear resonance surface velocity of cooling roller 5 is 1～6m/s.Alloy liquid is when covering spillway 3, because the effect of alloy liquid inherent tension force when desire stream does not flow out again, is scraped alloy liquid at this place by the cooling roller 5 of rotation, alloy liquid is cooled off on cooling roller 5 make the hydrogen-storage alloy sheet.Temperature by control tundish 2, make the temperature of alloy liquid keep stable, thereby guarantee that the tension force that alloy liquid forms at contact cooling roller 5 places is consistent, like this under the tension force effect, alloy liquid constantly, equably, is not subjected to influence of gravity ground to flow to cooling roller 5 from the side, by the rotation of cooling roller 5, make that thick consistency is good, the single nanocrystalline hydrogen-storage alloy sheet of grain-size, material property obviously improves.The hydrogen-storage alloy sheet grain-size of this method preparation is 1～1000nm, and thickness is 0.02～1mm.
Fig. 1 is the synoptic diagram of hydrogen-storage alloy sheet preparation facilities.
Fig. 2 is the synoptic diagram of tundish.
Fig. 3 is the A-A sectional view of tundish.
1. rapid hardening stove melting crucible; 2. tundish; 3. spillway; 4. spillway lower edge; 5. cooling roller.
What this inventive method and device obtained is the single nanometer crystal alloy of even grain size, is typical CaCu5The type hexagonal structure, free from admixture phase (comprising amorphous phase) is so the capacity of alloy and large current discharging capability are improved. Simultaneously, owing to nanocrystallinely provide abundant hydrogen atom diffusion admittance, reduced the internal stress that alloy produces in charge and discharge process, alloy sheet pulverization rate in charge and discharge process is effectively controlled, improved the stability of alloy charge and discharge cycles, and the service life of having improved alloy. And, because the alloy sheet uniform ingredients of this rapid condensation method preparation, so alloy has good discharge voltage plateau characteristic. In addition, being organized as of this alloy sheet is single nanocrystalline or micron is brilliant, need not heat treatment, kept the good advantage of cast alloy activity function (only need activation 3 times, capacity reaches more than the 340mAh/g), and technique is simple, good product consistency.
The method that the present invention adopts and tundish structure have reduced the steps such as thick, the middle fragmentation of alloy and heat treatment than traditional handicraft, shortened the technological process of production, have reduced the production cost of alloy. On the other hand, the standby alloy of this legal system is nanocrystalline, and nanocrystalline structure provides abundant diffusion admittance to hydrogen atom, reduce alloy and put fine fisssure and efflorescence in the hydrogen process in suction, improve the alloy suction, put the dynamic performance of hydrogen, thereby greatly carry stability and the high rate during charging-discharging of the charge and discharge cycles of heavy alloyed chemical property, particularly alloy.
Embodiment
Be described in further detail the present invention below in conjunction with embodiment.
Embodiment
Selecting composition for use is AB
5 ± x(wherein A is one or more rare earth elements to alloy, comprises lanthanon and yttrium; B=Ni, Co, Mn, Ti, Al, Zn, Cu, Sn, W, Mo, Fe, Zr, Cr and non-metallic element Si, B, C, among the N one or more, 0≤x≤0.75) starting material place in the vacuum rapid hardening stove, the operating frequency of this stove is 800～2000Hz, power is 100～400Kw, melting in rare gas element or vacuum environment, wait to melt directly refining 5～40min of back, then alloy is poured in the good tundish of preheating 2, the tundish preheating temperature is 800～1300 ℃, the linear velocity of cooling roller 5 is in 1～6m/s scope, angle theta between tundish spillway 3 and cooling roller 5 cross section horizontal diameter is in 90 °～180 ° scopes, the width of tundish spillway 3 is 250mm, make alloy slice, with alloy slice powder process and be assembled into simulated battery and test its performance, the result is as shown in the table.
| Sample | Linear velocity (m/s) | θ (°) | The 60mA/g specific discharge capacity | The 3000mA/g specific discharge capacity | Sheet is thick | Crystal grain | ||
| C 60，Max(mAh/g) | S 60，500(％) | C 3000，Max(mAh/g) | S 3000，500(％) | mm | nm | |||
| 1 | 1 | 90 | 315 | 28.9 | 178 | 36.0 | ～0.8 | 400 |
| 2 | 2 | 150 | 318 | 20.1 | 205 | 25.5 | ～0.2 | 100 |
| 3 | 3 | 100 | 332 | 19.4 | 231 | 20.2 | ～0.4 | 40 |
| 4 | 3 | 120 | 340 | 17.7 | 241 | 20.5 | ～0.3 | 40 |
| 5 | 3 | 150 | 338 | 16.3 | 236 | 18.0 | ～0.2 | 40 |
| 6 | 4 | 120 | 335 | 13.2 | 235 | 17.5 | ～0.3 | 35 |
| 7 | 6 | 120 | 319 | 11.1 | 231 | 16.4 | ～0.3 | 15 |
| 8 | 6 | 150 | 315 | 10.8 | 228 | 14.2 | ～0.2 | 15 |
| 9 | 6 | 180 | 301 | 10.1 | 215 | 13.9 | ～0.1 | 10 |
| 10 | Comparative Examples (1) | 320 | 31.8 | 142 | 100 * | Ingot casting | ＞1μm | |
| 11 | Comparative Examples (2) | 300 | 15.4 | 170 | 100 # | ＜0.1 | Mixed crystal | |
Annotate: it is as follows that this shows employed nomenclature:
*: under the situation of 3000mA/g discharge, the capacity attenuation rate during the 68th discharge just reaches 100%.
#: under the situation of 3000mA/g discharge, the capacity attenuation rate during the 180th discharge just reaches 100%.
C
60, Max: discharging current is the maximum specific discharge capacity of 60mA/g;
S
60,500: the capacity attenuation rate when the 500th time the circulation time discharging current is 60mA/g;
C
3000, Max: discharging current is the maximum specific discharge capacity of 3000mA/g;
S
3000,500: the capacity attenuation rate when the 500th time the circulation time discharging current is 3000mA/g;
Claims (4)
1. a nanocrystalline rare-earth hydrogen storage preparation method comprises induction melting, cast, rapid condensation, it is characterized in that with composition be AB
5 ± x, wherein A is one or more rare earth elements, comprises lanthanon and yttrium; B is one or more among Ni, Co, Mn, Ti, Al, Zn, Cu, Sn, W, Mo, Fe, Zr, Cr and non-metallic element Si, B, C, the N; It is 800～1300 ℃ tundish (2) that the alloy liquid of 0≤x≤0.75 is poured preheating temperature into, be provided with the spillway (3) of alloy liquid in the face of a side of cooling roller (5) and the angle theta between the horizontal diameter of cooling roller (5) cross section is 90 °～180 °, spillway lower edge (4) is higher than the inner bottom surface of tundish (2), the linear resonance surface velocity of cooling roller (5) is 1～6m/s, alloy liquid flows to cooling roller (5) from the side, and the hydrogen-storage alloy sheet is made in cooling.
2. device of implementing the described nanocrystalline rare-earth hydrogen-storage alloy of claim 1 preparation method, comprise rapid hardening stove melting crucible, tundish, cooling roller, it is characterized in that described tundish (2) is provided with the spillway (3) of alloy liquid in the side in the face of cooling roller (5), spillway lower edge (4) is higher than the inner bottom surface of tundish (2), and the angle theta between tundish spillway (3) and cooling roller (5) the cross section horizontal diameter is 90 °～180 °.
3. device according to claim 2, the width that it is characterized in that described spillway (3) is 5～400mm.
4. device according to claim 2 is characterized in that described tundish (2) is an integral body, or is combined by several block of material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100269048A CN1268779C (en) | 2004-04-19 | 2004-04-19 | Method for preparing nano rare earth hydrogen storage alloy and equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100269048A CN1268779C (en) | 2004-04-19 | 2004-04-19 | Method for preparing nano rare earth hydrogen storage alloy and equipment |
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| Publication Number | Publication Date |
|---|---|
| CN1563470A CN1563470A (en) | 2005-01-12 |
| CN1268779C true CN1268779C (en) | 2006-08-09 |
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| CNB2004100269048A Expired - Fee Related CN1268779C (en) | 2004-04-19 | 2004-04-19 | Method for preparing nano rare earth hydrogen storage alloy and equipment |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9234264B2 (en) | 2004-12-07 | 2016-01-12 | Hydrexia Pty Limited | Magnesium alloys for hydrogen storage |
-
2004
- 2004-04-19 CN CNB2004100269048A patent/CN1268779C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9234264B2 (en) | 2004-12-07 | 2016-01-12 | Hydrexia Pty Limited | Magnesium alloys for hydrogen storage |
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| Publication number | Publication date |
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| CN1563470A (en) | 2005-01-12 |
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Effective date of registration: 20180104 Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No. Patentee after: GUANGDONG INSTITUTE OF RARE METALS Address before: Wushan 510651 Guangdong city of Guangzhou Province Patentee before: Guangzhou Research Institute of Non-ferrous Metals |
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Granted publication date: 20060809 Termination date: 20190419 |