CN100467640C - AB3.5 type hydrogen-storing negative pole material and its prepn process and use - Google Patents
AB3.5 type hydrogen-storing negative pole material and its prepn process and use Download PDFInfo
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Abstract
The process of preparing AB3.5 type hydrogen-storing negative pole material includes: setting the material inside crucible in a vacuum inducing furnace, vacuuming before introducing Ar in the pressure of 0.2-3 atm, smelting and casting. There is one pipe with one end stretched over the crucible inside the furnace and the other end connected to the vacuum pump outside the furnace, and one valve connected to the pipe outside the furnace to control vacuuming rate, so that the Mg vapor may be pumped out from the furnace. The cast ingot is homogenizing treated in a vacuum heat treating furnace at 850-1020 deg.c for 6-15 hr before being cooled inside the furnace to room temperature. The AB3.5 type hydrogen-storing negative pole material is used in metal hydride-nickel cell.
Description
Technical field
The present invention relates to a kind of can preparation of industrialization AB
3.5The method of type cathode hydrogen storage material also relates to the AB by this method preparation
3.5Type battery cathode hydrogen storage material, and the purposes in the negative pole of preparation heavy body metal hydride-nickel cell.
Technical background
Metal hydride-nickel cell 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, share of market is more and more higher, cell types is also developed to other broad varietys by AA, AAA common batteries, and product is widely used in power tool, household electrical appliance, computer, space flight, communication and vehicle using motor etc., develops very rapid.Along with the increase of metal hydride-nickel cell Application Areas, also more and more higher to the requirement of battery performance.The development of particularly wireless in recent years chargeable power tool and electromobile is had higher requirement to the capacity of metal hydride-nickel cell.
The capacity of battery mainly is to be determined by the capacity of the positive and negative electrode of battery, and the capacity of raising battery plus-negative plate is the main approach that improves cell container, and the electrochemistry capacitance that therefore improves the battery cathode hydrogen storage material just becomes particularly important.AB
5The type hydrogen storage material through years of researches, has been developed a series of AB at present since the commercialization of phase at the end of the eighties in last century
5Type hydrogen storage alloy, product performance also are greatly improved, the electrochemistry capacitance of hydrogen storage material is brought up to greater than 330mAh/g by initial 260mAh/g, the capacity of metal hydride-nickel cell (in AA) is also brought up to 2700mAh from about initial 1000mAh, one of reason that though the raising of positive electrode material capacity and the change of battery structure also are cell containeies to improve, but the raising of cathode hydrogen storage material capacity also plays an important role, therefore to further improve the capacity of battery, just must further improve the capacity of negative or positive electrode, because the capacity of the employed anodal nickel hydroxide of metal hydride-nickel cell improves limited at present, therefore people just have been placed on the research emphasis that improves the metal hydride-nickel cell capacity above the research of cathode hydrogen storage material, for LaNi
5The type hydrogen storage material, experiment shows that it is 6 hydrogen atoms that the maximum of common every unit cell is inhaled number of hydrogen atoms, thus according to Theoretical Calculation as can be known its theoretical electrochemistry capacity be 372mAh/g, for the hydrogen storage material of commerce usefulness, for the performance of improving product is used needs, LaNi to satisfy
5In the mixed rare earth Mm of Rare Earth Lanthanum (La) substitute, nickel (Ni) is by cobalt (Co), manganese (Mn) and aluminium (Al) part are alternative, typical composition is MmNi
3.55Co
0.75Mn
0.4Al
0.3, this electrochemistry capacitance that will make material inevitably that substitutes descends, and its theoretical capacity is considered to 348mAh/g, thereby makes people recognize further raising AB
5Therefore the electrochemistry capacitance potentiality of type hydrogen storage material are little, the exploitation of high power capacity storage hydrogen material concentrated on the product of other types, and people begin one's study one after another and have the more hydrogen storage material of heavy body, as with ZrMn
2AB for representative
2Type Laves phase alloy is the AB type of representative and with Mg with TiFe
2Ni is the A of representative
2B Magnuminium, but up to now, these materials be owing to exist the problem (still unresolved as problems such as activation performance and life-spans) of all respects, thereby still be in conceptual phase, still untappedly goes out practical product, and add the AB of Mg
3.5Type La
1-xMg
xNi
3.5Hydrogen storage material is because theoretical capacity surpasses 400mAh/g, and good activation characteristic is arranged, and becomes the Recent study hot of research and development, but because Mg has very high boiling characteristics, if in preparation process, adopt and AB
5The vacuum induction furnace smelting method that hydrogen storage alloy is identical is difficult to the volatilization of control Mg, and what therefore people mainly adopted aspect preparing at alloy in recent years is dual mode:
First kind is to adopt mechanical alloying method; promptly La and Ni make the LaNi alloy of suitable component in elder generation by smelting; be broken into powder; mix by the composition requirement with the Mg powder then, and add the steel ball of proper ratio, be placed on a vacuum-pumping and can feed in the jar of shielding gas; make this jar vibration and rotation; by the ball milling of steel ball, make LaNi alloy and Mg that mechanical alloying take place, obtain the alloy of required composition.
Second kind is earlier La and Ni to be made the LaNi alloy of suitable component by smelting, is broken into fine powder, mixes by the composition requirement with the Mg powder then, heats in vacuum oven, obtains the alloy of required composition by the diffusion of Mg under the high temperature in the LaNi alloy.
Though above-mentioned two kinds of methods all successfully synthesize the cathode hydrogen storage material that high-performance metal hydride-nickel-based battery uses, because Mg is volatile in building-up process, the Composition Control difficulty, therefore complicated process of preparation is difficult to realize industrialization.
For forming mass production, we have found out the method for directly smelting with vacuum induction furnace and have produced the AB that contains Mg through a large amount of experimental studies
3.5Type La
1-xMg
xNi
3.5The technology of hydrogen storage material, and the capacity of producing that utilizes this technology success is greater than 380mAh/g, and the AB with good activation characteristic and cycle life
3.5Type La
1-xMg
xNi
3.5-yAl
yHydrogen storage material, thus a kind of heavy body AB has been proposed
3.5Type La
1-xMg
xNi
3.5-yAl
yThe preparation method of hydrogen storage material.
Summary of the invention
The present invention obtains the much higher novel cathode hydrogen storage material-AB of the present commercially available prod of a kind of ratio electrochemical discharge capacity by starting material and preparation technology's improvement
3.5Type La
1-xMg
xNi
3.5-yAl
yHydrogen storage material is to satisfy the demand of heavy body metal hydride-nickel cell product.
For AB
3.5Shaped metal hydride-nickel-based battery hydrogen storage alloy, the preparation method who adopts mainly is mechanical alloying method and the sintering process that the front is introduced, in the present invention at present, by preparation technology's improvement, thereby obtain a kind of AB that the heavy body metal hydride-nickel cell uses that satisfies
3.5Type La
1-xMg
xNi
3.5-yAl
yCathode hydrogen storage material.
First purpose of the present invention provides a kind of preparation AB
3.5The method of type cathode hydrogen storage material, this preparation method comprises:
(a) be La:Mg:Ni:Al=(1-x) with mol ratio: x:(3.5-y): the raw material of y is inserted in the crucible of vacuum induction furnace, vacuumizes the back and feeds argon gas, and the pressure range of institute's applying argon gas is 0.2atm～3atm, and high pressure can reduce the volatilization of Mg.Then, under argon gas atmosphere, carry out melting to be cast into ingot casting; When induction furnace melting, because the volatilization of Mg, be difficult to see the melting state, connect a pipe to stove for this reason, one of pipe places stove crucible top, the other end of pipe connects a vacuum pump outside stove, on the stove outer tube body, also be connected with valve,, the Mg that volatilizes in the stove can be taken away by this device with the speed that control vacuumizes, the Mg steam of the rate-controlling that vacuumizes in making stove does not influence to be observed the smelting state, owing to the volatilization of Mg, Mg need be excessive when preparation of raw material in addition, and excessive value is to guarantee that final composition reaches design mix and is as the criterion, during smelting the pressure that guarantees argon gas in the stove, argon gas keeps feeding always in the whole smelting process, and by the under meter dominant discharge, during smelting, by the melted state that vision slit is observed alloy, the power of stove need be increased to and make alloy reach whole fusings.
Smelting is foundation with the melted state, can adjust the operating voltage and the electromagnetic intensity of induction furnace according to the difference of institute's melt material quantity.
(b) ingot casting after the smelting carries out the homogenizing processing under the argon shield in vacuum heat treatment furnace, and treatment temp is 850～1020 ℃, and soaking time is 6～15 hours, and furnace cooling takes out alloy pig to room temperature.
Following three kinds of distributions when preparing burden, raw alloy are arranged:
1) prepares burden by the prescription requirement with pure La, pure Mg, pure Ni and pure Al;
2) prepare burden by the prescription requirement with pure La, pure LaMg alloy, pure Ni and pure Al;
3) prepare burden by the prescription requirement with pure La, pure NiMg alloy, pure Ni and pure Al.
Wherein, La is selected from pure La (purity〉99.7%) and LaMg alloy, and (wherein Mg content is at least a among the Mg≤60wt%), Ni is selected from pure Ni (purity〉99.7%) and NiMg alloy, and (wherein Mg content is at least a among the Mg≤40wt%), Mg is selected from pure Mg (purity〉99.7%), LaMg alloy, and (wherein Mg content is that (wherein Mg content is at least a among the Mg≤40wt%), and Al is selected from pure Al (purity〉99.7%) for Mg≤60wt%) and NiMg alloy.
Benefit with LaMg and NiMg alloy is to reduce the volatilization of Mg, helps smelting.
Second purpose of the present invention provides a kind of AB that is obtained by method for preparing
3.5Type La
1-xMg
xNi
3.5-yAl
yHydrogen storage material, it has the high electrochemical loading capacity, this AB
3.5The atomic ratio composition of type cathode hydrogen storage material consists of La
1-xMg
xNi
3.55-yAl
y, 0＜x≤0.3,0≤y≤0.3 wherein.As AB of the present invention
3.5The example of type cathode hydrogen storage material, atomic ratio one-tenth is grouped into and can be:
La
0.80Mg
0.20Ni
3.5；
La
0.80Mg
0.20Ni
3.45Al
0.05；
La
0.80Mg
0.20Ni
3.40Al
0.10；
La
0.80Mg
0.20Ni
3.30Al
0.2；
La
0.80Mg
0.20Ni
3.20Al
0.3；
La
0.80Mg
0.10Ni
3.40Al
0.10Or
La
0.70Mg
0.30Ni
3.40Al
0.10。
Wherein, most preferred AB
3.5The type cathode hydrogen storage material is La
0.80Mg
0.20Ni
3.40Al
0.10
AB
3.5Hydrogen storage alloy is that (as La, Mg) intermetallic compound of forming with other element B (as Ni, Al, Mn, Cu, Co etc.) belongs to Ce by the elements A of easy generation stable hydride
2Ni
7The type hexagonal structure, its electrochemical discharge capacity and AB
5Type hydrogen storage alloy is the same, mainly comes to inhale to put in the hydrogen process, and the transfer transport in the redox processes takes place on hydrogen-bearing alloy electrode the hydrogen ion in the electrolytic solution, and the charge discharge reaction ordinary representation of ni-MH battery is as follows:
The charging reaction:
At negative pole, when applying an electromotive force to negative potential, the water in the electrolytic solution is broken down into hydrogen ion and hydroxide ion, and hydrogen ion becomes hydrogen atom at cathode hydrogen storage material surface electron gain, is inhaled in the alloy, and hydroxide ion is left in the electrolytic solution:
Alloy+H
2O+e
-→Alloy[H]+OH
-
Alloy represents hydrogen storage alloy (1) in the formula
At positive pole, two valency nickel in the nickel hydroxide lose an electronics and are oxidized to nickelic and combine with hydroxide ion in the electrolytic solution and become nickel hydroxide:
Ni(OH)
2+OH
-→NiOOH+H
2O+e
- (2)
Exoelectrical reaction:
At negative pole, be absorbed in that hydrogen in the hydrogen storage alloy is released and be combined into water with hydroxide ion in the electrolytic solution, contribute an electronics simultaneously and form electric current.
Alloy[H]+OH
-→Alloy+H
2O+e
- (3)
At positive pole, nickel hydroxide obtains an electronics and is reduced into the lower valency nickel hydroxide and discharges hydroxide ion and enter in the electrolytic solution.
NiOOH+H
2O+e
-→Ni(OH)
2+OH
- (4)
AB of the present invention
3.5The type hydrogen storage material can be used for preparing the negative pole of metal hydride-nickel cell.Adopt AB of the present invention
3.5The type cathode hydrogen storage material has very high electrochemical discharge capacity as the metal hydride-nickel cell of negative pole.
With the AB that sells in the market
5The type hydrogen storage material is (as the traditional cathode hydrogen storage material MmNi for preparing with identical melting technology
3.55Co
0.75Mn
0.4Al
0.3) compare AB of the present invention
3.5Type cathode hydrogen storage material La
1-xMg
xNi
3.5-yAl
yThe charge/discharge capacity of (0＜x≤0.3,0≤y≤0.3) significantly improves.Correspondingly, adopt AB of the present invention
3.5The electrochemical discharge capacity that metal hydride-nickel cell had that the type cathode hydrogen storage material prepares is higher than commercial metals hydride-nickel-based battery far away.
Description of drawings
Fig. 1 shows the The cyclic lifetime test results of hydrogen storage alloy of the present invention under 30 ℃, 300mA/g charging and discharging currents density.
Embodiment
Below in conjunction with embodiment the present invention is launched further description.But should be appreciated that following embodiment only is used for the present invention is illustrated and is not in order to limit scope of the present invention.
According to table 1 interalloy AB
3.5The weight percent of each element is prepared burden; the alloy raw material for preparing is carried out the melting casting according to the method that provides above in the induction furnace that vacuumizes afterwards and feed argon shield; then ingot casting being carried out homogenizing in the heat treatment furnace that vacuumizes back feeding argon shield handles; treatment temp is 850～1020 ℃; soaking time is 6～15 hours, and furnace cooling takes out to room temperature.
The composition of table 1 embodiment of the invention and prior art is (wt%) relatively
Lm represents lanthanum rich mischmetal in the table.
Embodiment 1
Hydrogen storage alloy 1-7 according to the 1st kind of distribution batching, is the volatilization of compensation Mg respectively, and the excessive of Mg is 20%, and experiment condition is: argon pressure 1.5atm, 1020 ℃ of homogenizing treatment temps are incubated 6 hours.
Embodiment 2
Hydrogen storage alloy 1-7 according to the 2nd kind of distribution batching, is the volatilization of compensation Mg respectively, and the excessive of Mg is 20%, and experiment condition is: argon pressure 1.5atm, 1020 ℃ of homogenizing treatment temps are incubated 6 hours.
Embodiment 3
Hydrogen storage alloy 1-7 according to the 3rd kind of distribution batching, is the volatilization of compensation Mg respectively, and the excessive of Mg is 20%, and experiment condition is: argon pressure 1.5atm, 1020 ℃ of homogenizing treatment temps are incubated 6 hours.
Embodiment 4
Hydrogen storage alloy 1-7 according to the 3rd kind of distribution batching, is the volatilization of compensation Mg respectively, and the excessive of Mg is 20%, and experiment condition is: argon pressure 1.5atm, 850 ℃ of homogenizing treatment temps are incubated 15 hours.
In the foregoing description, LaMg alloy (wherein Mg content is Mg=58wt%) and NiMg alloy (wherein Mg content is Mg=38wt%) have been adopted.
But also can adopt commercially available other LaMg alloys and NiMg alloy, wherein, Mg content is Mg≤60wt% in the LaMg alloy, and Mg content is Mg≤40wt% in the NiMg alloy.
The testing method of electrochemistry capacitance is as follows: the hydrogen storage alloy ingot after at first homogenizing being handled at room temperature grinds to form less than 200 purpose alloy powders, the mixed that to press 1:4 less than 200 purpose negative alloy powder 0.25g and nickel powder then, be cold-pressed into diameter and use [the Ni (OH) that used positive electricity is very identical with metal hydride-nickel cell as negative potential for the cake of (d=15mm)
2-NiOOH] electrode, the Capacity design of positive electrode is the capacity far above negative potential, so that negative electrode material reaches fully saturated when charging, [Hg/HgO/6M KOH] is reference electrode.In the electrode performance test process, at first storage hydrogen negative material is fully activated 30 ℃ of current densities with 60mA/g, the activation system is as follows: the current charges 400min that adopts 60mA/g, paused 15 minutes in the charging back, till being-0.5 volt to the negative potential current potential with respect to the electropotential of reference electrode with the current discharge of 60mA/g then, carry out the next round charge and discharge cycle again.Along with the increase of activation number of times, capacity of negative plates will progressively increase and after reaching a maximum value relatively stable down, this moment, activation finished, and this maximum value is decided to be the hydrogen storage capability of material under 30 ℃.
For ease of relatively, with the AB that makes among the embodiment 1
3.5Traditional AB of type hydrogen storage material and prior art
5The electrochemistry capacitance of type hydrogen storage material under 30 ℃, 60mA/g charging and discharging currents density listed in the table 2.
The loading capacity (mAh/g) of table 2 hydrogen storage alloy under 30 ℃, 60mA/g charging and discharging currents density
By the data of table 2 as can be known: the AB that produces with this smelting process
3.5Type La
1-xMg
xNi
3.5-yAl
y(0＜x≤0.3,0≤y≤0.3) cathode hydrogen storage material, the change with Mg, Al content all has a maximum value, wherein with La
0.80Mg
0.20Ni
3.40Al
0.10Electrochemistry capacitance the highest, be 386mAh/g, far above the AB that sells in the market
5The type hydrogen storage material.
Test for cycle life, in order to shorten the test duration, charging and discharging currents density is chosen as 300mA/g, testing method is as follows: at first adopt the current density of 60mA/g to activate by the method for above-mentioned 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 potential current potential with respect to the electropotential of reference electrode for till-0.5 volt, carrying out next round again fills, discharge cycles, in order to contrast conveniently, the cycle life of sample is defined as cycle index when its capacity under this experiment condition drops to 160mAh/g, and its test result all is given among Fig. 1.
Fig. 1 provided these alloying constituents at 30 ℃, the The cyclic lifetime test results that discharges and recharges with the 300mA/g current density.As seen from the figure, at AB
3.5In the research of type hydrogen storage material,, can obtain ideal and have heavy body and long-life AB if by composition replacement with adopt suitable preparation technology
3.5Shaped metal hydride-nickel-based battery cathode hydrogen storage material is wherein with La
0.80Mg
0.20Ni
3.40Al
0.10Electrochemistry capacitance the highest, be 386mAh/g, and the longest cycle life arranged, its cycle life and the AB that sells in the market
5Type is used the approaching of hydrogen storage alloy always.
In sum, by selecting appropriate ingredients and being aided with suitable smelting technology, can successfully produce AB in the technical scheme of the present invention with the induction furnace smelting process
3.5Type Mg based hydrogen storage material, and the material that is obtained has the electrochemical discharge capacity above 380mAh/g, and can with AB
5Type is used the comparable cycle life of hydrogen storage alloy always, and this material can satisfy the rechargeable Ni-H 2 battery applications fully.
Claims (6)
1. one kind prepares AB
3.5The method of type cathode hydrogen storage material, this method comprises:
(a) with mol ratio be La:Mg:Ni:Al=(1-x): x:(3.5-y): the raw material of y is inserted in the crucible of vacuum induction furnace, vacuumize the back and feed argon gas, the pressure range of institute's applying argon gas is 0.2atm～3atm, under argon gas atmosphere, carry out melting then to be cast into ingot casting, in the induction furnace melting process, connect a pipe to stove, one of pipe places stove crucible top, the other end of pipe connects a vacuum pump outside stove, on the stove outer tube body, also be connected with valve, with the speed that control vacuumizes, by said apparatus the Mg that volatilizes in the stove is taken away, thereby guarantee smelting the observation of state;
(b) ingot casting after the melting carries out the homogenizing processing under the argon shield in vacuum heat treatment furnace, and treatment temp is 850～1020 ℃, and soaking time is 6～15 hours, and furnace cooling takes out ingot casting to room temperature;
Wherein raw material has following 2 kinds of distributions:
1) prepares burden with La, LaMg alloy, Ni and Al; Or
2) prepare burden with La, NiMg alloy, Ni and Al.
2. method according to claim 1 is characterized in that used La purity〉99.7%, the purity of Ni〉99.7%, the purity of Al〉99.7%, Mg content is Mg≤60wt% in the LaMg alloy, Mg content is Mg≤40wt% in the NiMg alloy.
3. the AB for preparing of claim 1 or 2 described methods
3.5The type cathode hydrogen storage material, its atomic ratio composition consists of La
1-xMg
xNi
3.5-yAl
y, wherein 0＜x≤0.3,0≤y≤0.3.
4. AB according to claim 3
3.5The type cathode hydrogen storage material is characterized in that the atomic ratio composition of described material consists of:
La
0.80Mg
0.20Ni
3.5；
La
0.80Mg
0.20Ni
3.45Al
0.05；
La
0.80Mg
0.20Ni
3.40Al
0.10；
La
0.80Mg
0.20Ni
3.30Al
0.2；
La
0.80Mg
0.20Ni
3.20Al
0.3Or
La
0.70Mg
0.30Ni
3.40Al
0.10。
5. AB according to claim 4
3.5The type cathode hydrogen storage material is characterized in that described AB
3.5The atomic ratio composition of type cathode hydrogen storage material consists of:
La
0.80Mg
0.20Ni
3.40Al
0.10。
6. any described AB of claim 3～5
3.5The application of type cathode hydrogen storage material in preparation metal hydride-nickel cell negative pole.
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| CN102104146B (en) * | 2010-12-31 | 2014-03-26 | 北京浩运金能科技有限公司 | Cobalt-free AB3.5-type hydrogen storage alloy anode material used for nickel-hydrogen battery and preparation method thereof |
| CN105514399A (en) * | 2015-12-21 | 2016-04-20 | 宁波高新区锦众信息科技有限公司 | Magnesium-based hydrogen storage alloy for Ni-MH secondary batteries and preparation method of magnesium-based hydrogen storage alloy |
| CN106119652B (en) * | 2016-06-21 | 2019-01-15 | 安泰科技股份有限公司 | Use for nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloy and preparation method thereof |
| WO2020195543A1 (en) * | 2019-03-26 | 2020-10-01 | 日本重化学工業株式会社 | Hydrogen storage alloy for alkaline storage battery, alkaline storage battery using the same in negative electrode, and vehicle |
| CN111509196A (en) * | 2020-04-20 | 2020-08-07 | 深圳市量能科技有限公司 | Novel nickel-metal hydride battery negative plate and manufacturing method thereof |
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