CN100352957C - Preparation method of high content rare earth -magnesium base composite hydrogen storage alloy for MH-Ni battery - Google Patents
Preparation method of high content rare earth -magnesium base composite hydrogen storage alloy for MH-Ni battery Download PDFInfo
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- CN100352957C CN100352957C CNB2004100920787A CN200410092078A CN100352957C CN 100352957 C CN100352957 C CN 100352957C CN B2004100920787 A CNB2004100920787 A CN B2004100920787A CN 200410092078 A CN200410092078 A CN 200410092078A CN 100352957 C CN100352957 C CN 100352957C
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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
Abstract
The present invention relates to a method for preparing a high capacity rare earth-magnesium-base composite hydrogen storing alloy electrode material for nickel metal hydride (MH-Ni) batteries, which is characterized in that dibasic lanthanum and magnesium alloy LaMg3 and AB5 type rare earth-base alloy with a CaCu5 phase structure are selected to carry out sintering treatment to prepare AB< 5 >-x mass%LaMg3 composite hydrogen storing alloy, wherein x=0.05 to 10.00. The AB<5 >-x mass%LaMg3 (x=0.05 to 10.00) composite hydrogen storing alloy prepared by the present invention has the characteristics of high discharging capacity and good low temperature discharging performance.
Description
One, technical field:
The invention belongs to battery manufacturing technology field, relate to a kind of preparation method who can be used for the rare-earth and Mg base composite hydrogen storage alloy of nickel metal hydride (MH-Ni) cell high-capacity negative material.
Two, background technology:
At present, commercial nickel metal hydride (MH-Ni) battery mainly uses rare earth based AB
5The type hydrogen-storage alloy is as negative material.Rare earth based AB
5Advantage such as that the type hydrogen-storage alloy has is easily-activated, have extended cycle life and price is low, but its chemical capacity is not high, generally at 300-330mAh/g.Along with developing rapidly of modern portable electronic devices, communication equipment and power truck etc., capacity to the MH-Ni battery that uses as power supply is had higher requirement, and correspondingly also the capacity of the hydrogen-storage alloy that can be used for the MH-Ni cell negative electrode material is also had higher requirement.
With Mg
2Ni has the characteristics of heavy body (can reach more than the 500mAh/g) for the magnesium base hydrogen-storing alloy on basis, but because cycle life is short and comprehensive electrochemical is poor, is very limited in actual applications, therefore, and with AB
5Type rare earth based alloy and magnesium base hydrogen-storing alloy carry out compound, and preparation rare-earth and Mg base hydrogen-storage alloy compensates to overcome the inherent defect of single alloy their advantage mutually, is to improve AB
5An effective way of type rare earth based alloy and magnesium base hydrogen-storing alloy performance.
It is that raw material prepares Mg through sintering processes with nickel powder, magnesium powder and cobalt powder or titanium valve that Chinese invention patent CH1109769C provides a kind of
2The method of Ni type magnesium base hydrogen-storing alloy, the hydrogen-storage alloy that relates in this patent of invention does not contain rare earth composition, and the raw material of use is all different with the present invention with the alloy that obtains.
Chinese invention patent application number 03114234.6 also discloses a kind of nanocrystalline heterogeneous mishmetal-magnesium base hydrogen-storing alloy and preparation method thereof, and this application patent has related to MI
1-xMg
xNi
yAlloy, wherein, MI is rich La mishmetal, 0.02≤y≤0.8,2≤x≤4 will be carried out the high-energy ball milling processing through the He Jindian after melting and the annealing and be made the hydrogen-storage alloy with nanocrystalline structure in this alloy preparation.This application patent is to utilize lanthanum rich mischmetal, MAGNESIUM METAL and metallic nickel to prepare mishmetal one magnesium base hydrogen-storing alloy for raw material through induction melting and anneal, handle through high-energy ball milling and obtain nanocrystalline heterogeneous rare-earth and Mg base hydrogen-storage alloy, raw material, the preparation method who uses with the present invention is all different with the alloy that obtains.
Three, goal of the invention:
The object of the present invention is to provide a kind of rare-earth and Mg base hydrogen storage preparation method of heavy body, by adding LaMg
3Alloy utilizes the agglomerating method to prepare the rare-earth and Mg base composite hydrogen storage alloy, improves to have CaCu
5The AB of phase structure
5The chemical property of type rare earth based alloy, thus a kind of negative material of heavy body is provided for the MH-Ni battery.
Four, technical scheme:
To have CaCu
5The AB of phase structure
5The LaMg of melting preparation in type rare earth based alloy and the vacuum induction furnace
3Binary alloy is a raw material, and they are broken respectively, as to grind to form granularity＜75um powdered alloy is the LaMg of 0.05-10.00% again with mass ratio
3Powdered alloy and mass ratio are the CaCu that has of 90.00-99.95%
5The AB of phase structure
5Type rare earth based powdered alloy mixes; through punching press or isostatic pressing; then; under vacuum state or under rare gas elementes such as argon gas or hydrogen shield, in vacuum sintering furnace, carry out sintering processes; sintering temperature is 600 ℃ to 1000 ℃; sintering time is 1-20h, prepares high-capacity rare earth-magnesium base (AB
5-xmass%LaMg
3, x=0.05-10.00 wherein) and composite hydrogen storage alloy.
The present invention is by adding LaMg
3Alloy and employing sintering place have prepared to remove and have contained AB
5CaCu
5Mutually, also contain La at least
2Ni
7Phase or LaNi
3The rare-earth and Mg base composite hydrogen storage alloy of the specific phase structure of phase.Because AB
5CaCu
5Relative La
2Ni
7Phase or LaNi
3Have katalysis mutually, make La
2Ni
7Phase or LaNi
3Becoming mutually is easy to activation and its hydrogen is increased, thereby makes this composite hydrogen storage alloy show higher loading capacity.Simultaneously, because in the sintering processes process, AB
5Relative La
2Ni
7Phase or LaNi
3Produce little coating effect mutually, thereby make the charge and discharge cycles stability (C of this hydrogen-storage alloy
N/ Cmax) and AB
5Alloy phase does not relatively significantly reduce, and the discharge capacitance of its charge during 200 weeks is all greater than AB
5More than 80% of alloy.
Five, invention effect:
The present invention is owing to use LaMg
3Alloy is as additive, overcome because the fusing point of metal M g and rare earth MI, metal Ni differs greatly (Mg649 ℃, La921 ℃, Ni1453 ℃), the magnesium powder volatile quantity can occur greatly and the uppity problem of composition when directly carrying out sintering processes with metal-powders such as rare earth and nickel.Simultaneously, has CaCu owing to having used
5The AB of phase structure
5The type rare earth based as raw material, has also overcome the incomplete and too much problem of generation dephasign of diffusion when directly utilizing metal-powder to carry out sintering with golden.
Rare-earth and Mg base composite hydrogen storage alloy involved in the present invention is through Mechanical Crushing, grinding, make the alloy powder of 10 μ m～150 μ m granularities after, can be used for the negative material of MH-Ni battery, with AB
5The mixed rare earths-based alloy phase of type relatively has the high and low temperature performance of loading capacity and characteristics such as has a few.The present invention is simple, is fit to produce in enormous quantities.
Six, embodiment:
Below in conjunction with embodiment and comparative example the present invention is further specified.
Embodiment one
The block MINi of commodity that selection is produced with Inner Mongol AudioCodes in seventy years of age hydrogen-storage alloy company limited
3.55Co
0.75AI
0.30Mn
0.40(wherein MI is a lanthanum rich mischmetal, and below brief note is MIB
5) the lanthanum magnesium binary alloy LaMg of alloy and induction melting preparation
3Be raw material; Earlier with MIB
5Alloy and LaMg
3Alloy is Mechanical Crushing in air, and mechanical mill to granularity is the powdered alloy below the 75um again; The accurate weighing MIB of mass ratio by 9.90: 0.10
5And LaMg
3Powdered alloy mixes, and coldmoulding on powder compressing machine (pressure is 25MPa) obtains diameter 15mm, and the thin rounded flakes of the about 5mm of thickness is put into vacuum sintering furnace.It is 2.5 * 10 that vacuum sintering furnace is evacuated to vacuum tightness
-3Below the Pa, charge into high-purity Ar gas again and protect, pressure is 0.06Mpa; Then, under 800 ℃ of temperature, carry out sintering processes, sintering time 16h.After sintering finished, sample cooled to room temperature with the furnace.
With the alloy slice fragmentation that sinters, pulverize, more ground alloy powder is collected and will be by 100 order boltings, undersized alloy powder promptly can be used as the heavy body negative material of MH-Ni battery.
The electrochemical discharge capacity test method of hydrogen-storage alloy is: the powdered alloy for preparing and the conductive agent nickel powder mass ratio with 1: 4 is mixed, and the electrode slice that is pressed into diameter and is 10mm under 15MPa pressure is as negative pole.The anodal commodity sintering nickel hydroxide (Ni (OH) that adopts
2) electrode slice.Electrolytic solution is the 6mol/LKOH aqueous solution.Barrier film adopts the special-purpose commodity of import.Barrier film is arranged between positive pole and the negative pole, and they tightly are intertwined insert in the electrolytic solution, make opening two-electrode system half-cell.In order to guarantee the stable of negative electricity chemical property, in Experimental cell, the anodal Capacity design is become to be higher than negative pole far away.Adopt continuous current charge/discharge method, testing tool is the DC-5 type cell tester that the square Electronics Co., Ltd in Shanghai produces, and is controlled automatically and record test data by robot calculator.With the current density is to carry out complete charge/discharge experiment under the 60ma/g condition, and getting the highest discharge capacity is the electrochemical discharge capacity of hydrogen-storage alloy.
The method of stable circulation property testing is: the alloy electrode after will activating fully is with 300mAg
-1Electric current carries out charge, after 50 circulations, uses 60mAg instead
-1Electric current carries out complete charge/discharge, measures the loading capacity of alloy electrode this moment, thereby determines the relation of alloy electrode loading capacity and cycle index, with the ratio (C of the loading capacity after the 200th circulation with maximum discharge capacity
200/ C
Max), be called the capability retention after this electrode circulates for 200 times.Discharge is 1.000V by voltage, and charge/discharge is spaced apart 10min, and test process all carries out under the greenhouse.Test result sees Table 1.
Embodiment two
The block MmNi of commodity that selection is produced with Inner Mongol AudioCodes in seventy years of age hydrogen-storage alloy company limited
3.55Co
0.75Al
0.30Mn
0.40(wherein Mm is a cerium-rich mischmetal, and below brief note is MmB
5) the lanthanum magnesium binary alloy LaMg of alloy and induction melting preparation
3Be raw material.Broken respectively, grind to form alloy powder after, again with MmB
5And LaMg
3Powdered alloy is pressed 9.70: 0.30 the accurate weighing of mass ratio, prepares burden, and carries out sintering again, and sintering temperature is 850 ℃, and sintering time is 10h.Its preparation method and testing method are with embodiment 1.Test result sees Table 1.
Embodiment three
The commodity bulk alloy MmNi that selection is produced with Inner Mongol AudioCodes in seventy years of age hydrogen-storage alloy company limited
3.55Co
0.75Al
0.30Mn
0.40(wherein Ml is a lanthanum rich mischmetal, and below brief note is MlB
5) and the lanthanum magnesium binary alloy LaMg of induction melting preparation
3Be raw material.The accurate weighing MlB of mass ratio by 9.50: 0.50
5And LaMg
3Powdered alloy is prepared burden, and sintering temperature is 900 ℃, and sintering time is 6h.Its preparation method and testing method are with embodiment 1.Test result sees Table 1.
Embodiment four
The commodity bulk alloy MmNi that selection is produced with Inner Mongol AudioCodes in seventy years of age hydrogen-storage alloy company limited
3.55Co
0.75Al
0.30Mn
0.40(wherein Ml is a cerium-rich mischmetal, and below brief note is MlB
5) and the lanthanum magnesium binary alloy LaMg of induction melting preparation
3Be raw material.The accurate weighing MmB of mass ratio by 9.40: 0.60
5And LaMg
3Powdered alloy is prepared burden, and sintering temperature is 650 ℃, and sintering time is 20h.Its preparation method and testing method are with embodiment 1.Test result sees Table 1.
Embodiment five
The commodity bulk alloy MmNi that selection is produced with Inner Mongol AudioCodes in seventy years of age hydrogen-storage alloy company limited
3.55Co
0.75Al
0.30Mn
0.40(wherein Ml is a cerium-rich mischmetal, and below brief note is MlB
5) and the lanthanum magnesium binary alloy LaMg of induction melting preparation
3Be raw material.The accurate weighing MlB of mass ratio by 9.20: 0.80
5And LaMg
3Powdered alloy is prepared burden, and sintering temperature is 750 ℃, and sintering time is 18h.Its preparation method and testing method are with embodiment 1.Test result sees Table 1.
Embodiment six
The commodity bulk alloy MmNi that selection is produced with Inner Mongol AudioCodes in seventy years of age hydrogen-storage alloy company limited
3.55Co
0.75Al
0.30Mn
0.40(wherein Mm is a cerium-rich mischmetal, and below brief note is MmB
5) and the lanthanum magnesium binary alloy LaMg of induction melting preparation
3Be raw material.By 9.05: 0.95 accurate weighing of mass ratio and powdered alloy, to prepare burden, sintering temperature is 1000 ℃, sintering time is 3h.Its preparation method and testing method are with embodiment 1.Test result sees Table 1.
Comparative example one
The commodity bulk alloy MmNi that selection is produced with Inner Mongol AudioCodes in seventy years of age hydrogen-storage alloy company limited
3.55Co
0.75Al
0.30Mn
0.40(wherein Ml is a cerium-rich mischmetal) hydrogen-storage alloy carries out electrochemical property test as a comparative example, and its method is with embodiment 1.Test result sees Table 1.
The loading capacity and the capability retention of subordinate list 1 embodiment and comparative example hydrogen-storage alloy
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Loading capacity mAh/g | 358 | 352 | 368 | 360 | 354 | 352 | 332 |
| C 200/C mn | 78 | 78 | 76 | 72 | 70 | 65 | 80 |
Claims (5)
1. a MH-Ni battery is with the preparation method of rare-earth and Mg base composite hydrogen storage alloy, and it is characterized in that: composite hydrogen storage alloy is by binary lanthanum magnesium alloy LaMg
3And have CaCu
5The AB of phase structure
5Type rare earth based alloy grinds to form＜after the alloy powder of 75 μ m mixes, and through the sintering processes preparation, binary lanthanum magnesium alloy LaMg wherein
3Quality accounts for the 0.05-10.00% of composite hydrogen storage alloy quality.
2. by the preparation method of the described a kind of MH-Ni battery of claim 1 with the rare-earth and Mg base composite hydrogen storage alloy, it is characterized in that: preparing the employed raw material of this alloy is LaMg
3Alloy and have a CaCu
5The AB of phase structure
5Type rare earth based alloy.
3. use the preparation method of rare-earth and Mg base composite hydrogen storage alloy by claim 1 or 2 described a kind of MH-Ni batteries, it is characterized in that: have CaCu
5The AB of phase structure
5Type rare earth based alloy is meant lanthanum rich mixed rare earth soil matrix AB
5Type or cerium-rich mischmetal base AB
5The type alloy.
4. by the preparation method of the described a kind of MH-Ni battery of claim 1, it is characterized in that: at first respectively with AB with the rare-earth and Mg base composite hydrogen storage alloy
5Rare earth based alloy and LaMg
3Alloy is through Mechanical Crushing and be ground to the following granularity of 75 μ m, by the different quality proportion speed weighing AB that form
5And LaMg
3Powdered alloy mixes, and through punching press or isostatic pressing, then, carries out sintering processes under vacuum state or under rare gas element or hydrogen shield, and sintering temperature is 600 ℃ to 1000 ℃, and sintering time is 1-20h.
5. by the preparation method of the described a kind of MH-Ni battery of claim 1 with the rare-earth and Mg base composite hydrogen storage alloy, it is characterized in that: the composite hydrogen storage alloy of sintering processes is through Mechanical Crushing, grinding, cross 100 order vibratory screening apparatuss, make the alloy powder of 10 μ m-150 μ m granularities, be used for the negative material of battery.
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| CNB2004100920787A CN100352957C (en) | 2004-11-02 | 2004-11-02 | Preparation method of high content rare earth -magnesium base composite hydrogen storage alloy for MH-Ni battery |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE554193T1 (en) | 2004-12-07 | 2012-05-15 | Univ Queensland | MAGNESIUM ALLOYS FOR HYDROGEN STORAGE |
| CN100432249C (en) * | 2006-06-27 | 2008-11-12 | 上海大学 | Production of magnesium-based hydrogen-storage material under equalized strong magnetic field and its producer |
| CA2790561C (en) | 2010-02-24 | 2018-08-28 | Hydrexia Pty Ltd | Hydrogen release system |
| JP2018527459A (en) | 2015-07-23 | 2018-09-20 | ハイドレキシア ピーティーワイ リミテッド | Mg-based alloys for hydrogen storage |
| CN108326290B (en) * | 2018-04-26 | 2021-01-22 | 包头昊明稀土新电源科技有限公司 | Hydrogen storage alloy for rare earth new power supply and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000265229A (en) * | 1999-03-16 | 2000-09-26 | Toshiba Corp | Hydrogen storage alloy and secondary battery |
| CN1363962A (en) * | 2001-12-26 | 2002-08-14 | 浙江大学 | Rare-earth alloys for hydrogen-bearing electrode and its preparing process |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000265229A (en) * | 1999-03-16 | 2000-09-26 | Toshiba Corp | Hydrogen storage alloy and secondary battery |
| CN1363962A (en) * | 2001-12-26 | 2002-08-14 | 浙江大学 | Rare-earth alloys for hydrogen-bearing electrode and its preparing process |
Non-Patent Citations (2)
| Title |
|---|
| MH-Ni电池用储氢合金的研究进展 李汉军，孙杰，何国荣等.材料导报，第16卷第3期 2002 * |
| 稀土镁基贮氢电极合金的结构与电化学性能研究 刘永锋，潘洪革，高明霞等.金属学报，第39卷第6期 2003 * |
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