CN1121648A - Hydrogen-storage alloy material used for negative electrode of alkaline cell and making method thereof - Google Patents
Hydrogen-storage alloy material used for negative electrode of alkaline cell and making method thereof Download PDFInfo
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Abstract
The composition of the invented hydrogen storage alloy is Ml1-XMl'x (or LaX) Ni5-y-z-uAly CuZ Mu, M1 is La-rich mixed rare earth metal, Ml' is mixed rare earth metal whose La content is more higher than Ml, M=Co, Si, Cr, X is greater than 0 and less than 1, g is greater than 0.5 and less than 0.8, Z is greater than 0.5 and less than 1, u is greater than 0 and less than 0.4. Said hydrogen storage alloy possesses of high chemical capacity, good electrochemical circulation property and large current discharging property. The invented method features simple process, short productive period and low product cost.
Description
The present invention relates to alkaline storage battery used alloy material storing hydrogen and manufacture method thereof,
Because the MH-Ni secondary cell is compared with Ni-Cd battery commonly used, it has higher specific energy, and it is higher to discharge and recharge number of times, and environment is not polluted; And as a kind of green battery that can replace the Ni-Cd battery, advancing just at a terrific speed, in the battery industry of the world today and hydrogen bearing alloy field, formed focus, the hydrogen storage material that the MH-Ni battery cathode is used is one of key technology of whole M H-Ni battery, AB5 type hydrogen storage alloy Mm (NiMnCoAl) the 5th, one of a large amount of hydrogen bearing alloy series of using at present, in this a series of hydrogen bearing alloy, metallic cobalt is one of most important alloying element wherein, in order to guarantee this class hydrogen bearing alloy stability in use, metallic cobalt in this class hydrogen bearing alloy contained percentage composition mostly about 10% (percetage by weight), almost account for whole hydrogen bearing alloy cost of material about half, make the holding at high price of this class hydrogen bearing alloy, because the fluctuation of world's metallic cobalt market price greatly, certainly will influence the production of this class alloy material storing hydrogen, in order to reduce the MH-Ni battery cost, many researchers attempt to reduce the content of cobalt in this class hydrogen bearing alloy always or simply seek a kind of other metallic elements and come the substituted metal cobalt.
Application number is that 92108396.3 Chinese patent literature has been reported the Ml1NiwAlySixZnz alloy material storing hydrogen, 0＜W＜4.8 wherein, 0＜y＜0.6,0＜x＜0.5,0＜z＜0.5,4＜w+y+x+y＜5.5, Ml is commercially available lanthanum rich norium (La＞40%), its maximum electrochemistry capacitance can reach 270mAh/g, but do not see the report of electrochemistry cycling life test, moreover, because zinc is volatile when melting, burning, so zinc, aluminium, silicon must be smelted into intermediate alloy in advance, to guarantee the stability of its composition.
Chinese patent literature CN1075380A has reported the alloy material storing hydrogen of MmNi5-x-y-zZnxQyRz, wherein Mm is a lanthanum rich mischmetal, and it contains lanthanum amount＞85%, does not contain heavy rare earth, Q=Al.Ca, Sr, R=Li, Na, K, 0＜x≤1,0＜y≤0.8,0＜z≤1, its maximum electrochemistry capacitance can reach 288mAh/g, but, reach preferable performance in order to make this kind alloy, need coat the Ni-P composite bed of one deck 2-3 μ m on its surface with the method for chemical plating, vacuumize under 80-100 ℃ temperature, be incubated 15-20 hour, be warming up to 150 ℃ again, be incubated 15 hours and carry out diffusion annealing.
Though more than two kinds of alloy material storing hydrogens reduced cost of material because their manufacturing process is comparatively complicated, improved manufacturing cost to a certain extent.
F.Meli etc. [Journal of Alloys and compoumds 202 (1993) 81-88] have developed the alloy material storing hydrogen of Lm0.5Mm0.5Ni4.2Mn0.2Al0.3Si0.3, Mm is for containing the cerium mischmetal metal, Lm is a lanthanum-rich rare-earth metal, its maximum electrochemistry capacitance can reach 270mAh/g, average per 100 loop attenuation 8.3% after 400 circulations.
Purpose of the present invention just be to work out a kind of new used for negative electrode of alkaline cell, have the alloy material storing hydrogen that high electrochemistry capacitance has good electric chemical cycle performance and heavy-current discharge performance again, and it is cheap for manufacturing cost.
Another object of the present invention is to develop the method for the alloy material storing hydrogen of producing above-mentioned a kind of new used for negative electrode of alkaline cell, makes its technology easy, and low production cost is with short production cycle.
The alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of the present invention, its chemical composition are Ml
1-xMl ' x (or Lax) Ni5-y-z-uAly Cuz Mu, wherein Ml is a lanthanum rich norium, Ml ' contains the higher norium of lanthanum amount for another kind of its contains the lanthanum amount than Ml, M=Co.Si.Cr, 0≤x≤1,0.5≤y≤0.8,0.5≤z≤1.0,0≤u≤0.4
Silicon, copper have been studied to the hydrogen storage alloy electrochemical Effect on Performance.People's such as SaKai [J, Less-Common Metals 172-174 (1990) 1175-1184] its maximum electrochemistry capacitance of MmNi4.2Al0.8 that studies show that can reach 260mAh/g, decay 64% after 300 electrochemistry circulations, behind the Ni that replaces with a certain amount of silicon wherein, the electrochemistry cycle performance of the 1# alloy MlNi4.0Al0.8Si0.2 that obtains has obtained bigger improvement, after 330 electrochemistry circulations, only decay 17%, but its maximum electrochemistry capacitance is then reduced to 216.7mAh/g, and activation increased frequency, after 60 circulations, can reach heap(ed) capacity.
In order to improve the electrochemistry capacitance of hydrogen bearing alloy, replace aluminium with part Mn and obtain 2# alloy MlNi4.0Al0.3Si0.3Mn0.4, the maximum electrochemistry capacitance of this alloy can reach 231.7mAh/g, MlNi4.0Al0.8Si0.2 has raising slightly than the 1# alloy, activation is accelerated, can reach high electrochemistry capacitance through 10 circulations, but its electrochemistry cycle stability but has decline by a relatively large margin, decay 42% after 330 circulations, replace Al with a small amount of Mn and obtain 3# alloy MlNi3.9Al0.7Si0.2Mn0.2, its maximum electrochemistry capacitance is identical with MlNi4.0Al0.8Si0.2, without any rising, though its activation is accelerated, but its electrochemistry cycle stability rapid deterioration, through 300 circulation back capacity attenuations 32%, thus with Mn for the method that Al improves the electrochemistry capacitance of hydrogen bearing alloy, as if can not realize satisfactory results.
Obtain 4# alloy MlNi3.5Al0.7Cu0.8 when replacing Ni with part copper, its electrochemistry capacitance can reach 256mAh/g, after 300 circulations, and decay 54%, suitable with the electrochemistry capacitance of alloy MmNi4.2Al0.8, but the electrochemistry cycle stability improves.
Studied of the influence of elements such as Si, Co, Cr to hydrogen bearing alloy.Resulting quinary alloy MlNi3.4Al0.6Cu0.8Si0.2 (5# alloy) after replacing Ni with a small amount of Si, compare with corresponding quaternary alloy MlNi3.5Al0.7Cu0.8, capacity has reduction slightly, but its peak capacity and 1# alloy MlNi4.0Al0.8Si0.2 and 3# alloy MlNi3.9Al0.7Si0.2Mn0.2 are suitable, be 220mAh/g, decay 17% after 330 charge discharge circulations, its stability is better than the 3# alloy, and work as with the 1# alloy phase, but its electrochemical activation performance is better than the 1# alloy, can reach peak capacity through about 20 times.Because Cu is to the bigger replacement of Ni, its cost greatly reduces than 1#, 3# alloy, and therefore this alloy perhaps relatively is suitable for low energy consumption, requires to leave standstill in the device cheaply.
Resulting 6# alloy MlNi3.3Al0.7Cu0.8Co0.2 compares with 4# alloy MlNi3.5Al0.7Cu0.8 after replacing Ni with a small amount of Co, electrochemistry capacitance slightly improves, be 260mAh/g, can reach peak capacity through about about 10 times circulations, and the electrochemistry cyclical stability increases substantially, decay 20.5% after 300 charge discharge circulations, though this alloy has added a small amount of Co, but because Cu has reduced the content of Ni to the bigger replacement of Ni, therefore the cost of this alloy still with Chinese patent literature CN1098268A, CN1075380A and J.Alloys and Compound 202 (1993) 81-88, the cost of material of several no cobalt Langaloy of being reported is close, but its technological process is simple, and the technology cost greatly reduces.
In order further to improve the electrochemistry capacitance of alloy, select the another kind of higher lanthanum rich norium of La amount that contains (to contain lanthanum 80%, atomic percentage), the Ml that has replaced a part of original use (contains lanthanum 52%, atomic percentage) obtains 7# alloy Ml ' 0.7Ml0.3Ni3.3Al0.7Cu0.8Co0.2, its electrochemistry capacitance increases, reach as high as the 270mAh/g (see figure 1), and electrochemical activation performance and electrochemistry stable circulation performance are still close with MlNi3.3Al0.7Cu0.8Co0.2, decay 21% after 300 charge discharge circulations, average per 100 decay 7%, the performance of this alloy can reach the practical requirement of cell negative electrode material, so 6#, the 7# alloy is a kind of battery cathode hydrogen bearing alloy that can satisfy the battery performance requirement cheaply.
Resulting 8# alloy Ml ' 0.7Ml0.3Ni3.3Al0.7Cu0.8Cr0.2 and 9# alloy Ml ' 0.7Ml0.3Ni3.1Al0.7Cu0.8Cr0.4 after replacing part Ni with Cr, it activates increased frequency, capacity reduces, raising along with the chromium amount, capacity descends, the peak capacity of 8# alloy is 233.4mAh/g, and the peak capacity of 9# alloy only is 200mAh/g, though Cr has improved the electrochemical stability performance to a certain extent to the replacement of Ni, but its effect compares Co, Si is poor, further improve the replacement amount of Cr, more effectively do not improve electrochemistry stable circulation performance, so the M among its chemical composition Ml1-xMl ' x (or Lax) Ni5-y-z-uAly Cuz Mu is with Co yet, Si is good.
The chemical property preface composition Cmax Cmax-C of several hydrogen bearing alloys of table 1
200 *Max-C
300 *Number (mAh/g) Cmax Cmax4# MlNi
3.5Al
0.7Cu
0.6256.0 33.6% 54.4%5# MlNi
3.4Al
0.8Cu
0.8Si
0.2220.0 12.3% 13.9%6# MlNi
3.3Al
0.7Cu
0.8Co
0.2260.0 10.3% 20.5%7# Ml '
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.8Co
0.2270.0 9.9% 21.0%8# Ml '
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.8Cr
0.2233.4 24.6%9# Ml '
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.3Cr
0.4200.0 20.1%
* C
200Be the capacity after 200 circulations, * * C
300Be the capacity after 300 circulations.
As can be seen from Table 1, substituted element is pressed following sequence arrangement Cr＜Co＜Si for the effect that improves the electrochemistry cyclical stability, and the arrangement of this order order of cubical expansivity when putting hydrogen with its suction is identical, therefore reduce hydrogen bearing alloy and inhale volumetric expansion when putting hydrogen, to reduce its efflorescence tendency, be still raising hydrogen storage alloy electrochemical cyclical stability main path.
Studied the high-rate discharge ability of various hydrogen bearing alloys.People such as F.Meli [J .Alloys and Compounds.202 (1993) 81-88] research hydrogen bearing alloy Lm
0.5Mm
0.5Ni
3.3CuMn
0.2Si
0.3Al
0.2The time, find that the activation of this kind alloy is slower, and its high-rate discharge ability is very poor, and when discharging with 15mA/g, its peak capacity is 230mAh/g, and when discharging with 150mA/g, its peak capacity only is 195mAh/g, and the 4# that the present invention studied, 5#, 6# alloy all have higher copper content (Cu0.8), and the above-mentioned alloy of being studied with F.MeLi (Cu1.0) is close, but has high-rate discharge ability preferably, as shown in Figure 2.When with the constant current charge-discharge of 800mA/g, the 5# hydrogen bearing alloy can reach 156.7mAh/g, and 4#, 6# hydrogen bearing alloy still remain on about 210mAh/g.
Several hydrogen bearing alloy performance comparison of table 2 preface composition Cmax Cmax-C
300C
300*Cost colon (mAh/g) Cmax C
1005# MlNi
3.4Al
0.8Cu
0.8Si
0.2220.0 13.9% 72.2% 0.576# MlNi
3.3Al
0.7Cu
0.8Co
0.2260.0 20.5% 81.2% 0.667# Ml '
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.8Co
0.2270.0 21.0% 0.68-MmNi
3.5Co
0.8Mn
0.4Al
0.3280 40% 79.6%* 1-Lm
0.5Mml
0.5Ni
4.2Mn
0.2Al
0.3Si
0.3270 27.8% 55.5% 0.59*C
800/ C
100The ratio of the discharge capacity when discharge capacity is with discharging current 100mA/g when being 800mA/g for discharging current, this value of * * is C
700/ C
90
As seen from Table 2, the 4# standard hydrogen bearing alloy MmNi that the 6# that the present invention studied, its peak capacity of 7# alloy and a large amount of at present IBA that use recommend
3.5Co
0.8Mn
0.4Al
0.3And Lm
0.5Mm
0.5Ni
4.2Mn
0.2Al
0.3Si
0.3Close, but its electrochemistry cyclical stability and heavy-current discharge performance all are better than above-mentioned two kinds of hydrogen bearing alloys, 5# hydrogen bearing alloy capacity level is low slightly, but has goodish electrochemistry cyclical stability, and heavy-current discharge performance is also better.If with MmNi
3.5Co
0.8Mn
0.4Al
0.7Cost of material be 1 to calculate, then other several alloy materials costs change about 0.60, especially be low with 5# hydrogen bearing alloy cost, thereby the earth has reduced the cost of hydrogen bearing alloy, so the 5#-7# hydrogen bearing alloy have the Ni-MH battery cathode hydrogen bearing alloy likely of superior performance price ratio.
The preparation method of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of the present invention, press the composition of chemical general formula Ml1-xMl ' x (or Lax) Ni5-y-z-uAly Cuz Mu, (wherein Ml is a lanthanum rich norium, Ml ' contains the higher lanthanum rich norium of lanthanum amount for another kind of its contains the lanthanum amount than Ml, M=Co.Si.Cr, 0≤x≤1,0.5≤y≤0.8,0.5≤z≤1.0,0≤u≤0.4), with each metallic element of requirement, in the smelting furnace of packing into, vacuumize, feed inert gas, under 1400-1700 ℃ temperature, heat melting, after melting fully to all metallic elements, be incubated the suitable time again, make alloy pig, used lanthanum-rich rare-earth metal Ml, it contains the lanthanum amount is 45-＜80% (atomic percent), another kind of for to contain the lanthanum amount lanthanum rich norium Ml ' higher than the lanthanum amount that contains of Ml, it contains the lanthanum amount is 80-90% (atomic percent).
Used smelting furnace is vaccum sensitive stove or arc furnace, is evacuated to 1Pa-1x10
-2Pa is for well, the inert gas that is fed, with argon gas is good, when feeding argon gas, argon pressure remains on 0.05-0.1Mpa, after the heating melting, the time of insulation along with the total weight of raw material what and change, the time of the big insulation of raw material total weight is just long, measures little then temperature retention time and just can shorten, and temperature retention time was generally 0.3-120 minute.Being smelted into and can adopting behind the alloy pig mechanical crushing method or hydrogenization method that alloy pig is crushed to hydrogen storing alloy powder less than 74 μ m (particle diameter), is good to be crushed to 20-70 μ m again.
With the arc melting of non-consumable formula the time, even for guaranteeing alloy compositions, the button ingot need be climbed over remelting more than three times.
Hydrogen storing alloy powder is mixed the garden sheet test electrode that is pressed into φ 15 mutually with copper powder less than 40 μ m in the ratio of 1: 4 (weight ratio), with this electrode is negative pole, the sintering oxidation nickel electrode is anodal, the centre imposes barrier film, constitute the sandwich style open cell, electrolyte is the KOH aqueous solution of 30% (percetage by weight), the method that the mensuration of discharge capacity adopts constant current (200mA/g) to discharge and recharge is carried out, charging interval is 2 hours, and the discharge stopping potential is 1.0V, with the constant current charge-discharge of 200mA/g, make the mensuration of electrochemistry cycle performance, depth of discharge is 100%, with the constant current charge-discharge of 50-800mA/g, measures the various rate charge-discharge performances of electrode.
The advantage of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of the present invention is:
1. the alloy material storing hydrogen of used for negative electrode of alkaline cell of the present invention has high electrochemistry capacitance, has good electrochemistry cycle performance and heavy-current discharge performance again, and manufacturing process is simple, and product cost is low.
2. the technology of producing the hydrogen bearing alloy of used for negative electrode of alkaline cell of the present invention does not need through intermediate alloy, and directly carries out melting, more do not need to reach tens hours diffusion annealing, so it is its manufacturing process is simple, with short production cycle, product cost is low, is easy to large-scale production.The electrochemistry cycle performance curve 6# MlNi of Figure 16 #-7# hydrogen bearing alloy
3.3Al
0.7Cu
0.8Co
0.27# Ml
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.8Co
0.2Ordinate is electrochemistry capacitance C (Capacity) mAh/g, and abscissa is electric cycle-index (n/cycles).The discharge performance 4# MlNi of the various multiplying powers of Figure 24 #-6# hydrogen bearing alloy
3.5Al
0.7Cu
0.85# MlNi
3.4Al
0.8Cu
0.8 Si
0.26# MlNi
3.3Al
0.7Cu
0.8Co
0.2Ordinate is electrochemistry capacitance C (Capacity) mAh/g, and abscissa is discharging current I, mA/g
More specifically at length describe the present invention with following non-limiting examples, will help the understanding to the present invention and advantage thereof, the protection range of this moon is not subjected to the qualification of these embodiment, and protection scope of the present invention is decided by claim.
Embodiment 1
The chemical composition of the alloy material storing hydrogen of the used for negative electrode of alkaline cell of present embodiment is Ml '
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.3Co
0.2
Its manufacture method is for pressing above-mentioned chemical formula, each metallic element with requirement, pack in the non-consumable stove, be evacuated to 0.1pa, feed argon gas, the pressure of argon gas is 0.08Mpa, after melting fully, all metals are incubated 10 minutes in heating melting under 1550 ℃ ± 50 ℃ the temperature again, for guaranteeing the even of composition, climb over the back remelting more than three times, with Mechanical Crushing hydrogen bearing alloy ingot, it is worn into＜the hydrogen bearing alloy powder of 74 μ m, the hydrogen storing alloy powder made is mixed the garden sheet sample that is pressed into φ 15 mutually with copper powder less than 40 μ m in the ratio of 1: 4 (weight), with this sample is negative pole, with the sintering oxidation nickel block is positive pole, is electrolyte with the KOH aqueous solution of 30% (percetage by weight), puts into H type electrolysis tank, constitute open cell, the method that the mensuration of discharge capacity adopts constant current (200mA/g) to discharge and recharge is carried out, and the charging interval is 2 hours, and the discharge stopping potential is 1.0V; Constant current charge-discharge with 200mA/g, make the mensuration of electrochemistry cycle performance, depth of discharge is 100%, and the maximum electrochemistry capacitance of this alloy material storing hydrogen can reach 270mA/g, after discharging and recharging chemical cycle entirely through 330 times, decay 21%, average per 100 decay 7%, a large amount of at present alloy material storing hydrogen MmNi3.5Co0.8Mn0.4Al0.3 that use, its initial electrochemistry capacitance is 280mAh/g, after 300 circulations, its capacity attenuation 40%, and alloy material storing hydrogen Ml ' of the present invention
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.3Co
0.2, cost of material only be 68% of MmNi3.5Co0.8Mn0.4Al0.3, with the hydrogen bearing alloy Lm of people such as MeLi research
0.5Mm
0.5Ni
4.2Mn
0.2Al
0.3Si
0.3Relatively, its capacity is suitable, and the electrochemistry cycle performance is better than Lm
0.5Mm
0.5Ni
4.2Mn
0.2Al
0.3Si
0.3
The performance comparison of several hydrogen bearing alloys of table 3
Composition
CmaxCmax-C
300Cost is than (mAh/g) CmaxMl '
0.7Ml
0.3Ni
3.3Al
0.7Cu
0.8Co
0.2270 21% 0.68MmNi
3.5Co
0.8Mn
0.4Al
0.3280 40% 1Lm
0.5Mm
0.5Ni
4.2Mn
0.2Al
0.3Si
0.3270 27.8% 0.59MlNi
3.3Ai
0.7Cu
0.2Co
0.2280 20.5% 0.68
Embodiment 2
The chemical composition of the alloy material storing hydrogen of present embodiment is MlNi
3.3Al
0.7Cu
0.8Co
0.2Melting in the non-consumable vacuum melting furnace, its smelting technology is identical with embodiment 1, adopt with embodiment 1 in identical method make negative plate, and test out various chemical properties, maximum electrochemistry capacitance is 260mAh/g, after 300 full charge and discharge cycles, decay 20.5%, its performance and alloy MlNi
3.5Mn
0.4Al
0.3Cu
0.3And Lm
0.5Mm
0.5Ni
4.2Mn
0.2Al
0.3Si
0.3relatively see Table 3.
Claims (6)
1. the alloy material storing hydrogen of a used for negative electrode of alkaline cell is characterized in that, its chemical composition is Ml
1-xMl ' x (or Lax) Ni5-y-z-u Aly Cuz Mu, wherein Ml is a lanthanum rich norium, Ml ' contains the higher norium of lanthanum amount for another kind of lanthanum content than Ml, M=Co.Si.Cr, 0≤x≤1,0.5≤y≤0.8,0.5≤z≤1.0,0≤u≤0.4.
2. according to the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 1, it is characterized in that M is Co.Si.
3. the preparation method of the alloy material storing hydrogen of a used for negative electrode of alkaline cell is characterized in that,
(1) presses chemical general formula Ml
1The composition of-xMl ' x (or Lax) Ni5-y-z-u Aly Cuz Mu, (wherein Ml is a lanthanum rich norium, Ml ' contains the higher lanthanum rich norium of lanthanum for another kind of its contains the lanthanum amount than Ml, M=Co.Si.Cr, 0≤x≤1,0.5≤y≤0.8,0.5≤z≤1.0,0≤u≤0.4), with each metallic element of requirement, in the smelting furnace of packing into;
(2) vacuumize, feed inert gas, under 1400-1700 ℃ temperature, heat melting, after melting fully to all metallic elements, be incubated the suitable time again; Make alloy pig,
(3) used lanthanum-rich rare-earth metal Ml, it contains the lanthanum amount is 45-＜80% (atomic percent), and another kind contains the lanthanum amount lanthanum rich norium Ml ' higher than the lanthanum amount that contains of Ml, and it contains the lanthanum amount is 80-90% (atomic percent).
4. according to the preparation method of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 3, it is characterized in that, be evacuated to 1Pa～1 * 10
-2Pa.
5. according to the preparation method of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 3, it is characterized in that the inert gas that is fed is an argon gas, the pressure of argon gas is 0.05-0.1Mpa.
6. according to the preparation method of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 3, it is characterized in that temperature retention time is 0.3-120 minute.
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|---|---|---|---|
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|---|---|---|---|
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| CN1056018C CN1056018C (en) | 2000-08-30 |
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| CN1028882C (en) * | 1992-07-16 | 1995-06-14 | 南开大学 | Store hydrogen alloy electrode material |
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