CN1056017C - Hydrogen-storage alloy material for negative electrode of alkaline accumulator and mfg. process thereof - Google Patents
Hydrogen-storage alloy material for negative electrode of alkaline accumulator and mfg. process thereof Download PDFInfo
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Abstract
The present invention relates to a hydrogen storage alloy material for negative electrodes of alkaline accumulators, and a manufacturing method thereof. The hydrogen storage alloy is M1<1-x>Mmx (NiyCozMnu) 5Cw alloy which is formed by one of mixtures of misch metal (M1) with rich lanthanum, and misch metal (mm) with rich cerium, or the mixtures with the lanthanum and the misch metal (mm) with rich cerium, wherein x is greater than or equal to 0, and is less than or equal to l; y is greater than or equal to 0.6, and is less than or equal to 0.9; z is greater than or equal to 0, and is less than or equal to 0.2; u is greater than 0 and is less than 0.15, and y + z + u =1; C is Co and Ti, and W is greater than 0 and is less than 0.2. The accumulators manufactured with the hydrogen storage alloy have the advantages of high electrochemical capacitance, stable electrochemical performance and long electrochemical cycle life. The manufacturing method of the hydrogen storage alloy has the advantages of simple manufacturing process and stabilization.
Description
The present invention relates to the alloy material storing hydrogen that electrode is used, alkaline storage battery used more precisely alloy material storing hydrogen.
In recent years, the MH-Ni battery was with its electrochemistry capacitance height, and was pollution-free, can heavy-current discharge, and characteristic surfaces such as memory-less effect cause researchers' very big concern.And its selection as the alloy material storing hydrogen of negative electrode active material is one of key technology.
At present, mainly containing titanium system and rare earth in the alloy material storing hydrogen of having developed is two big classes.Has CaCu
5The AB of type structure
5Type rare earth based material is one of hydrogen storage material the most widely of using.The LaNi5 alloy material storing hydrogen of Ying Yonging the earliest, its initial capacity is higher, but decline is too fast, after 100 charge and discharge cycles, has just decayed 40%.In order to improve its chemical cycle stability, J.J.Gwillesns[J.Less-Common Met.129 (1987) 13], replace the part lanthanum with Nd, replace some of nickel with cobalt, silicon or aluminium and form the alloy material storing hydrogen of La0.8Nd0.2Co0.4Si0.1Ni2.5 and La0.8Nd0.2Co2.4Al0.1Ni2.5, and greatly improved electrochemistry cycle life.After 1000 electrochemistry circulations, only decay 30%.But because the employed raw material of alloy material storing hydrogen is pure lanthanum, pure neodymium, the content of cobalt is also high, thereby cost is increased greatly, has limited in industrial possibility of its application.[Power Sources 12 (1988) for people such as H.Ogawa, 383], (Mm) comes the instead of pure lanthanum with cerium-rich mischmetal, developed the alloy material storing hydrogen of MmNi3.55Co0.75Mn0.4Al0.3, reduced its manufacturing cost widely, made its industrialization become possibility.People such as Lei Yongquan (novel hydrogen storage material and application scientific seminar paper compilation 1990.12 thereof, Tianjin P24) have adopted lanthanum rich mischmetal to substitute the polynary storage alloy material for hydrogen that pure lanthanum has formed MlNi3.45 (CoMnTi) 1.55.
Chinese patent literature CN1078827A has introduced the hydrogen-storing alloy as electrode material that a kind of Ni-H cell is used, it is a kind ofly to replace lanthanum among the LaNi5 with a certain proportion of lanthanum rich mischmetal (Ml) and a certain proportion of cerium-rich mischmetal (Mm), forms Ml with copper, cobalt, aluminium, manganese rice replacement part of nickel
1The hydrogen-storing alloy as electrode material of-xMmxNi5-y (CoAlMn) yCuz (Ml) is lanthanum rich mischmetal, and wherein lanthanum 47.4%, cerium 3.3%, and neodymium 37.7%, samarium＜0.2%, all the other are other rare earths.(Mm) be cerium-rich mischmetal, wherein lanthanum 25%, cerium 48-50%, neodymium 18%, praseodymium 7-8%, remainder is other rare earths, X=0.2-0.8, y=Co+Mn+Al=0.5-3.0, cobalt≤0.8 Z=0.3-1.3 wherein, its electrode capacity (mAh/g) is 250-274.
At present, in mishmetal manufacturer, because the restriction of some condition, (Ml is a lanthanum rich mischmetal for Mm, Ml that the different lot numbers of different manufacturers or same producer are produced, Mm is a cerium-rich rare earth) in four main rare-earth elements Las, Ce, Pr, the atomic percent of Nd bigger fluctuation is all arranged, owing to having caused, the fluctuation of these compositions the instability of hydrogen storage material chemical property hindered the development of its suitability for industrialized production.
When the electrochemistry of research AB5 type hydrogen storage alloy material circulates fail machine-processed, find that alloy material storing hydrogen when electrochemical hydrogenation and dehydrogenation, volumetric expansion and contraction takes place, make the further efflorescence of alloy material storing hydrogen.Because the efflorescence of alloy material storing hydrogen has aggravated the corrosion of electrode surface, and causes the decline of electrode capacity.
Purpose of the present invention just is to work out a kind of alloy material storing hydrogen of new used for negative electrode of alkaline cell, make four the main rare-earth elements of lanthanum of this alloy material storing hydrogen in its raw material (Mm), (Ml), cerium, praseodymium, when neodymium atom percentage has bigger fluctuation and do not cause the instability of alloy material storing hydrogen chemical property, promote its direction to develop to suitability for industrialized production.
Another object of the present invention is exactly to make the alloy material storing hydrogen of producing be difficult for efflorescence, is of value to the electrochemistry cycle performance that improves alloy material storing hydrogen.
A further object of the present invention is exactly to develop the method for the alloy material storing hydrogen of preparation used for negative electrode of alkaline cell of the present invention, makes this method simple, and product cost is low.
The alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of the present invention, the Ml that forms by the mixture of the mixture of the mixture of lanthanum rich mischmetal (Ml) and cerium-rich mischmetal (Mm), lanthanum rich mischmetal (Ml) and another kind of lanthanum rich mischmetal Ml ', lanthanum rich mischmetal (Ml) and lanthanoid metal La, cerium-rich mischmetal (Mm) and mixture a kind of mixture wherein of lanthanoid metal La
1-xMmx (Niy CozMnu)
5Cw, Ml
1-xMl ' x (Niy Coz Mnu)
5Cw, Ml
1-xLax (Niy Coz Mnu)
5Cw or Mm
1-xLax (Niy Coz Mnu)
5The alloy of Cw, 0＜x＜1,0.6≤y≤0.9,0≤z≤0.2,0＜u＜0.15 wherein, y+z+u=1, C are Co, V, Cr, Al, Fe, Ti, Zr or the intermediate alloy be made up of these elements, 0＜w＜0.2.
The hydrogen bearing alloy of a kind of used for negative electrode of alkaline cell of the present invention no longer is the stoichiometric of AB5, but the non-stoichiometry proportioning of AB5Cx, owing to adopted the non-stoichiometry proportioning, alloy material of the present invention is outside the principal phase divided by the CaCu5 structure, second phase has also appearred, this second separates out at crystal boundary, because the existence of this crystal boundary second phase has improved the performance of alloy material high current charge-discharge.
When (Ml), (Ml '), (Mm) and metal La when making the hydrogen bearing alloy raw material of used for negative electrode of alkaline cell of the present invention, when adopting different proportioning alloyages, La/ (Ml wherein
1-xMmx) or (Ml
1-xMl ' x) or (Mm
1-xLax) or (Ml
1-xLax) can change.For following narration conveniently makes La/ (Ml
1-xMmx) or (Ml
1-xMl ' x) or (Mm
1-xLax) or (Ml
1-xLax) be E, said E is during for the hydrogen bearing alloy of preparation used for negative electrode of alkaline cell, with various rare earths materials (wherein the atomic percentage sum of La, Ce, Pr, Nd the is 100%) atomic percent of lanthanum in the new mishmetal of gained according to a certain ratio.Experiment shows, increase along with the E value, the electrochemistry capacitance of its alloy material storing hydrogen increases significantly, when the E value when 42.6% increases to 49.98%, its corresponding electrochemistry capacitance Cmax (mAh/g) rises to 271.7 from 213.0, and the E value increases to after 49.98%, along with the increase of E value, has not had remarkable influence for its chemical capacity.So work as the E value in the scope of 42.60%-49.98%, the minor variations of E just can cause the marked change of hydrogen storage alloy electrochemical capacity.In the mishmetal raw material of actual production, the fluctuation of lanthanum atomic percent in the scope of 42.60-49.98% often is visible, if therefore use single mishmetal, be difficult to guarantee the stable of hydrogen bearing alloy performance, produce probably electrochemistry capacitance than great fluctuation process, so the E value at 49.98-81.48 for well, its E value again with 50.55-62.96% for better.In order to suppress the efflorescence of hydrogen bearing alloy, the intermediate alloy that in alloy material storing hydrogen, has added Co, V, Cr, Al, Fe, Ti, Zr or formed by these elements.Experiment shows, adds The addition of C o, V
4, Fe, Ti or Zr, do not cause the bigger decline of hydrogen storage alloy electrochemical capacity, add the remarkable decline that Cr, Al have then caused the hydrogen storage alloy electrochemical capacity, thus in alloy material storing hydrogen, be good to add Co, V4, Fe, Ti or Zr, again to add Co or Ti for better.
The preparation method of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of the present invention presses chemical general formula Ml
1-xMmx (Niy Coz Mnu)
5Cw, Ml
1-xMl ' x (Niy Coz Mnu)
5Cw, Ml
1-xLax (Niy Coz Mnu)
5Cw or Mm
1-xLax (Niy Coz Mnu)
5The alloy composition of Cw, wherein 0＜x＜1,0.6≤y≤0.9,0≤z≤0.2,0＜u＜0.15, y+z+u=1, C is Co, V, Cr, Al, Fe, Ti or Zr or the intermediate alloy be made up of these elements, packs each metallic element of requirement in the smelting furnace in 0＜w＜0.2, vacuumize, feed inert gas, under 1400-1700 ℃ temperature, heat melting, after melting fully to all metallic elements, be incubated 0.3～120 minute again, make alloy pig; Its composition of used lanthanum rich mischmetal (atomic percent) is La45-85%, Ce4-30%; Pr5-20%; Nd10-40%, its composition of cerium-rich mischmetal (atomic percent) is La25-30%, Ce45-55%, Pr5-20%, Nd10-20%.
Used smelting furnace is vaccum sensitive stove or arc furnace, is evacuated to 1Pa-1 * 10
-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.
Hydrogen storing alloy powder is mixed the block test electrode that is pressed into 19 millimeters * 14 millimeters * 0.7 millimeter mutually with copper powder less than 40 μ m in the ratio of 1: 4 (weight ratio).
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.
The present invention has adopted three kinds of mishmetals in experiment in these three kinds of mishmetals, the shared therein atomic percent of its main rare earth element is listed in the table 1 as the raw material (also using this three kinds of raw materials among the embodiment) of alloyage.
The atomic percent of main rare earth element in table 1 mishmetal
| The mishmetal kind | The atomic percent % of main rare earth element | |||
| Ml Ml’ (Mm) | La | Ce | Pr | Nd |
| 52.87 47.08 27.22 | 27.26 4.31 50.52 | 5.45 11.35 5.75 | 14.41 37.26 16.51 | |
Electrochemical property test carries out in the glass three electrode Experimental cell systems of routine, sintered type nickel hydroxide electrode just very, and anodal excessive, reference electrode is Hg/HgO, electrolyte is 30% (percetage by weight) potassium hydroxide aqueous solution.
The project of electrochemical property test comprises: discharge capacity, charge discharge cycle performance, various rate charge-discharge performances.The method that the mensuration of discharge capacity adopts constant current (100mA/g) to discharge and recharge is carried out, the discharge stopping potential is-0.6V (Hg/HgO relatively), constant current charge-discharge with 200mA/g, carry out the mensuration of electrochemistry cycle performance, depth of discharge is 100%, with the constant current charge-discharge of 100-800mA/g, measure 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. owing to adopted two kinds of mishmetals to carry out suitable proportioning, can reach the best fit of alloy electrochemistry capacitance and electrochemistry cyclical stability, and maintenance hydrogen storage alloy electrochemical performance is stable, when keeping the E value constant, both made when adopting different mishmetal alloyages, the variation of Ce, Pr, Nd content can not cause the bigger variation of alloy property yet in the alloy.The battery made from alloy material storing hydrogen of the present invention has high electrochemistry capacitance, maximum electrochemistry capacitance can reach 300-320mAh/g, dress up AA type battery capacity and can reach 1350mAh, AAA type battery capacity can reach 490mAh, and be packaged into the rectangular cell of 35Ah, the battery made from alloy material storing hydrogen of the present invention has long electrochemistry cycle life, after discharging and recharging 400 times entirely, capacity attenuation＜10%, dress up AA type battery, press the IEC standard detection life-span greater than 1000 times, and the battery made from alloy material storing hydrogen of the present invention, have good heavy-current discharge performance, have the good low-temperature performance again.
2. in non-stoichiometric hydrogen bearing alloy of the present invention, add elements such as Co, V, Fe, Ti, Zr in right amount, do not caused the bigger decline of capacity, the increase that has also caused capacity that has, and suppressed the efflorescence of alloy, improved the hydrogen storage alloy electrochemical cycle performance.
The method for preparing hydrogen bearing alloy of the present invention, technology is simple, and is easy to operate, process stabilizing, the product hydrogen bearing alloy stable performance of producing.
Fig. 1 Ml
0.6Ml '
0.4(Ni
0.74Co
0.18Mn
0.08)
5Co
0.1The electrochemistry cycle performance.
Abscissa is cycle-index (n/cycles), and ordinate is electrochemistry capacitance C (capacity) MAh/g.
Fig. 2 Ml
0.6Ml '
0.4(Ni
0.74Co
0.18Mn
0.08)
5Co
0.1With the discharge performance of the various multiplying powers of MmNi3.5Co0.8Mn0.4Al0.3, abscissa is discharging current I, mA/g, and 1,0 is Ml0.6Ml ' 0.4 (Ni
0.74Co
0.18Mn
0.08)
5Co0.1,2, ▲ be MmNi3.5Co0.8Mn0.4Al0.3, ordinate electrochemistry capacitance C (capacity) mAh/g.
Fig. 3 Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5The electrochemistry cycle performance of Ti0.05.
Abscissa is cycle-index (n/cycles), and ordinate is electrochemistry capacitance C (Capacity) and the ratio C/Cmax (%) of maximum electrochemistry capacitance Cmax.
Fig. 4 Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5The different multiplying discharge performance of Ti0.05 and MmNi3.5Co0.8Mn0.4Al0.3, abscissa are discharging current I, mA/g.3,0 is Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Ti0.05,4, ▲ be MmNi3.5Co0.8Mn0.4Al0.3; Ordinate is electrochemistry capacitance C (capacity) mAh/g.
More specifically at length describe the present invention with following indefiniteness embodiment, will help the understanding to the present invention and advantage thereof, protection scope of the present invention 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
0.6Ml '
0.4(Ni
0.74Co
0.18Mn
0.08)
5Co0.1.
Its manufacture method with each metallic element of requirement, in the vaccum sensitive stove of packing into, is evacuated to 1 * 10 for to press chemical formula
-2Pa, feed argon gas, the pressure of argon gas is 0.07Mpa, is incubated 10 minutes in heating melting under 1500 ℃ ± 50 ℃ the temperature again after all metals melt fully, pour into alloy pig, melted hydrogen bearing alloy is worn into＜alloy powder of 74 μ m with vibrating ball-mill.The hydrogen storing alloy powder made is mixed the block sample that is pressed into 19mm * 14mm * 0.7mm mutually with copper powder less than 40 μ m in the ratio of 1: 4 (weight), with this block sample as negative pole, with sintering hydroxide nickel block is positive pole, the potassium hydroxide aqueous solution of 30% (percetage by weight) is an electrolyte, put into H type electrolysis tank, constitute open cell, the method that the mensuration of discharge capacity adopts constant current (100mA/g) to discharge and recharge is carried out, the discharge stopping potential is-0.6V (with respect to Hg/HgO), constant current charge-discharge with 200mA/g, make the mensuration of electrochemistry cycle performance, depth of discharge is 100%, with the constant current charge-discharge of 100-800mA/g, measure the various rate charge-discharge performances of electrode, its initial electrochemistry capacitance can reach 313.4mA/g, after discharging and recharging entirely through 330 times, its capacity attenuation rate was 11% (as shown in Figure 1), and average each full charge and discharge cycles capacity rate of descent is 0.033%, a large amount of at present hydrogen bearing alloy MmNi3.5Co0.8Mn0.4Al0.3 that use; Its initial electrochemistry capacitance is 280mAh/g, and after 300 circulations, its capacity attenuation is 40%, and average each full charge and discharge cycles capacity rate of descent is 0.133%, Ml
0.6Ml '
0.4(Ni
0.74Co
0.18Mn
0.08)
5The contrast of the various performance index of Co0.1 and MmNi3.5Co0.8Mn0.4Al0.3 is as shown in table 2.
Table 2 Ml
0.6Ml '
0.4(Ni
0.74Co
0.18Mn
0.08)
5Co
0.1With the MmNi3.5Co0.8Mn0.4Al0.3 property comparison
* C
800/ C
100Discharge volume to weight ratio when being respectively 800mA/g and 100mA/g for charging and discharging currents.This value of * is C
700/ C
95The ratio.
| Hydrogen bearing alloy | Cmax(mAh/g) | C 300/Cmax | C 800/C 100* |
| Ml 0.5Ml’ 0.4(Ni 0.74Co 0.18Mn 0.08) 5Co0.1 | 313.4 | 89％ | 85％ |
| MmNi3.5Co0.8Mn0.4Al0.3 | 280 | 60％ | 79％** |
Ml
0.6Ml '
0.4(Ni
0.74Co
0.18Mn
0.08)
5Co
0.1High-rate charge-discharge capability be greatly improved Ml
0.6Ml '
0.4(Ni
0.74Co
0.18Mn
0.08)
5Co
0.1C
800/ C
100Be 85%, and MmNi
3.5Co
0.8Mn
0.4Al
0.3C
700/ C
95Be 79%, as shown in Figure 2.
Embodiment 2
The chemical composition of the alloy material storing hydrogen of the used for negative electrode of alkaline cell of present embodiment is Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Ti0.05.Its manufacture method is substantially the same manner as Example 1, and only different is to heat melting under 1550 ℃ ± 20 ℃ temperature, is incubated 7 minutes again.Its initial electrochemistry capacitance is 310.78mAh/g, through after 215 full charge and discharge cycles, only decays 7%, as shown in Figure 3.Average each full charge and discharge cycles capacity rate of descent is 0.032%, and this hydrogen bearing alloy also has high-rate discharge ability preferably, C
800/ C
100Be 78%, suitable with MmNi3.5Co0.8Mn0.4Al0.3, as shown in Figure 4.Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Ti0.05 and MmNi
3.5Co
0.8Mn
0.4Al
0.3The contrast of various performance index as shown in table 3.
Table 3 Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Ti0.05 and MmNi
3.5Co
0.8Mn
0.4Al
0.3Performance comparison:
* this value is C
700/ C
95
| Hydrogen bearing alloy | Cmax(mAh/g) | C 200/Cmax | C 800/C 100 |
| Ml 0.5Ml’ 0.5(Ni 0.78Co 0.14Mn 0.08) 5Ti0.05 | 310.78 | 93％ | 78％ |
| MmNi 3.5Co 0.8Mn 0.4Al 0.3 | 280 | 70％ | 79％* |
Its method for making is identical with embodiment 1 with method of testing, and only different is adopts same apparent atomic ratio, make two kinds of hydrogen bearing alloys, and performance is different, so when making hydrogen bearing alloy, should note the variation of composition in the raw material mishmetal.
Table 4 adopts the performance of the hydrogen bearing alloy of same apparent atomic ratio preparation for different mishmetals
| Hydrogen bearing alloy | E | Cmax(mAh/g) | C100/Cmax* |
| Ml 0.6Mm 0.4(Ni 0.76Co 0.16Mn 0.08) 5Co0.1 | 42.6 | 213.0 | 97％ |
| Ml 0.8Ml’ 0.4(Ni 0.74Co 0.18Mn 0.08) 5Co0.1 | 50.6 | 313.4 | 95％ |
* C100/Cmax is the ratio of unit weight and heap(ed) capacity after the charge discharge circulation 100 times
Its method for making is identical with embodiment 1 with method of testing, only different is adopts the E value maintenance of the hydrogen bearing alloy that different mishmetals make constant, its maximum electrochemistry capacitance value and after the circulation of 100 charge discharges the capacity attenuation rate all extremely close, in other words as long as keep the E value constant, the variation of Ce, Pr, Nd content will can not cause the bigger variation of hydrogen bearing alloy performance in the alloy, see Table 5.
Table 5 adopts the performance of two kinds of hydrogen bearing alloys that constant E value makes with different mishmetals
| Composition | E | Cmax(mAh/g) | C100/Cmax* |
| Ml 0.6Ml’ 0.4(Ni 0.76Co 0.16Mn 0.08) 5Co 0.1 | 50.55 | 313.4 | 94.0％ |
| Ml 0.91Mm 0.09(Ni 0.76Co 0.16Mn 0.08) 5Co 0.1 | 50.55 | 318.4 | 95.0％ |
The hydrogen bearing alloy Ml that makes
0.6Ml '
0.4(Ni
0.76Co
0.16Mn
0.08)
5C
0.01Has electrochemistry combination property preferably, its initial electrochemistry capacitance is 313.4mAh/g, discharge and recharge chemical cycle entirely through 215 times after, its capacity attenuation rate is 14%, average each full charge and discharge cycles capacity rate of descent is 0.065%, and a large amount of at present hydrogen bearing alloy MmNi that uses
3.5Co
0.8Mn
0.4Al
0.3Its initial electrochemistry capacitance only is 280mAh/g, and after 200 circulations, its capacity attenuation rate is 16%, and average each full charge and discharge cycles capacity rate of descent is 0.08%, Ml
0.6Ml '
0.4(Ni
0.78Co
0.18Mn
0.08)
5Co
0.1With MmNi
3.5Co
0.8Mn
0.4Al
0.3The contrast of various performance index as shown in table 6.
Table 6 Ml
0.6Ml '
0.4(Ni
0.76Co
0.16Mn
0.08)
5Co
0.1With MmNi
3.5Co
0.8Mn
0.4Al
0.3Performance comparison
* C
800/ C
100Discharge capacity is C than this value of * * when being respectively 800mAh/g with 100mAh/g for charging and discharging currents
700/ C
95The ratio.
| Hydrogen bearing alloy | Cmax(mAh/g) | C200/Cmax | C 800/C 100* |
| Ml 0.6Ml’ 0.4(Ni 0.76Co 0.16Mn 0.08) 5Co 0.1 | 313.4 | 86％ | 85％ |
| MmNi 3.5Co 0.8Mn 0.4Al 0.3 | 230 | 70％ | 79％** |
Embodiment 5,6,7,8,9,10,11,12,13,14,15
Its method for making is identical with embodiment 1 with method of testing, and only different is that the E value is different, the results are shown in Table 7
Table 7 E value is to the influence of hydrogen storage alloy electrochemical capacity
Hydrogen bearing alloy Ec
Max (mAh/g)Ml
0.8Ml '
0.4(Ni
0.76Co
0.16Mn
0.08)
5Co
0.142.60 213.0Ml
0.3Ml '
0.7(Ni
0.76Co
0.16Mn
0.08)
5Co
0.148.82 213.4Ml
0.4Ml '
0.6(Ni
0.76Co
0.16Mn
0.08)
5Co
0.149.40 263.4Ml
0.5Ml '
0.5(Ni
0.76Co
0.16Mn
0.08)
5Co
0.149.98 271.7M1
0.6Ml '
0.4(Ni
0.76Co
0.16Mn
0.08)
5Co
0.150.55 313.4Ml
0.7Ml '
0.3(Ni
0.76Co
0.16Mn
0.08)
5Co
0.151.11 315.2Ml
0.95Ml '
0.05(Ni
0.76Co
0.16Mn
0.08)
5Co
0.152.60 314.3La
0.2Ml '
0.8(Ni
0.76Co
0.16Mn
0.08)
5Co
0.157.66 318.2La
0.3Ml '
0.7(Ni
0.76Co
0.16Mn
0.08)
5Co
0.162.96 304.2La
0.5M1 '
0.5(Ni
0.76Co
0.16Mn
0.08)
5Co
0.173.54 303.5La
0.65Ml '
0.35(Ni
0.76Co
0.16Mn
0.08)
5Co
0.181.48 305.7
Embodiment 16,17,18,19,20,21,22,23,24
Component by chemical general formula is measured each metallic element on demand, place non-consumable arc furnace, and make the E value be 49.98, be evacuated to 1Pa, feed argon gas, the pressure of argon gas is 0.08Mpa, heats melting to all metals and melt fully under 1600 ℃ ± 20 ℃ temperature, is incubated 0.3 minute again.In order to guarantee the even of alloy compositions, the button ingot to be climbed over remelting three times, with mechanical crushing method the hydrogen bearing alloy ingot is crushed to less than 74 μ m alloyed powders, adopt with embodiment 1 in identical method make negative plate, with sintering hydroxide nickel block is positive pole, potassium hydroxide aqueous solution with 30% (percentage by weight) is an electrolyte, adopt the electric current constant current charge-discharge of 100mA/g, the discharge stopping potential is-0.6V (Hg/HgO electrode relatively), has listed the influence of various interpolation elements to the hydrogen storage alloy electrochemical capacity in the table 8.
The various interpolation elements of table 8 are to the influence of hydrogen storage alloy electrochemical capacity
Hydrogen bearing alloy Cmax (mAh/g) Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Co
0.1271.7Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5(V
4Fe)
0.08285.32Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08Cr
0.02)
5Cr
0.1216.67Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08Al
0.02)
5Al
0.1233.55Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Ti
0.05310.78Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Ti
0.1273.39Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Zr
0.05260.38Ml
0.5Ml '
0.5(Ni
0.78Co
0.14Mn
0.08)
5Zr
0.1255.05MmNi
3.5Co
0.8Mn
0.4Al
0.3280.0
Claims (8)
1. the alloy material storing hydrogen of a used for negative electrode of alkaline cell, it is characterized in that the Ml that forms by the mixture of the mixture of the mixture of lanthanum rich mischmetal (Ml) and cerium-rich mischmetal (Mm), lanthanum rich mischmetal (Ml) and another kind of lanthanum rich mischmetal Ml ', lanthanum rich mischmetal (Ml) and lanthanoid metal La, cerium-rich mischmetal (Mm) and mixture a kind of mixture wherein of lanthanoid metal La
1-xMmx (NiyCoz Mnu)
5Cw, Ml
1-xMl ' x (Niy Coz Mnu)
5Cw, Ml
1-xLax (Niy Coz Mnu)
5Cw or Mm
1-xLax (Niy Coz Mnu)
5The alloy of Cw, 0＜x＜1,0.6≤y≤0.9,0≤z≤0.2,0＜u＜0.15 wherein, y+z+u=1, C are Co, V, Cr, Al, Fe, Ti, Zr or the intermediate alloy be made up of these elements, 0＜w＜0.2.
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, make La/ (Ml
1-xMmx) or (Ml
1-xMl ' x) or (Mm
1-xLax) or (Ml
1-xLax) be E, when said E is the hydrogen bearing alloy of preparation used for negative electrode of alkaline cell, use various rare earths materials, wherein the atomic percentage sum of La, Ce, Pr, Nd is 100%, the atomic percent of lanthanum in the new mishmetal of gained according to a certain ratio, its E is 49.98～81.48%.
3. according to the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 2, it is characterized in that the E value is 50.55-62.96%.
4. 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 C is Co, V
4Fe, Ti or Zr.
5. according to the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 4, it is characterized in that C is Co or Ti.
6. the preparation method of the alloy material storing hydrogen of a used for negative electrode of alkaline cell is characterized in that, comprises step:
(1) presses chemical general formula Ml
1-xMmx (Niy Coz Mnu)
5Cw, Ml
1-xMl ' x (Niy CozMnu)
5Cw, Ml
1-xLax (Niy Coz Mnu)
5Cw or Mm
1-xLax (Niy Coz Mnu)
5The alloy composition of Cw, wherein 0＜x＜1,0.6≤y≤0.9,0≤z≤0.2,0＜u＜0.15, y+z+u=1, C are Co, V, Cr, Al, Fe, Ti, Zr or the intermediate alloy be made up of these elements, 0＜w＜0.2 is 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 0.3～120 minute again; Make alloy pig;
(3) used its composition of lanthanum rich mischmetal (atomic percent) is La45-85%, Ce4-30%, Pr5-20%; Nd10-40%, its composition of cerium-rich mischmetal (atomic percent) is La25-30%, Ce45-55%, Pr5-20%, Nd10-20%.
7. according to the preparation method of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 6, it is characterized in that, be evacuated to 1Pa-1 * 10
-2Pa.
8. according to the preparation method of the alloy material storing hydrogen of a kind of used for negative electrode of alkaline cell of claim 6, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108085A CN1056017C (en) | 1994-08-10 | 1994-08-10 | Hydrogen-storage alloy material for negative electrode of alkaline accumulator and mfg. process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108085A CN1056017C (en) | 1994-08-10 | 1994-08-10 | Hydrogen-storage alloy material for negative electrode of alkaline accumulator and mfg. process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1116777A CN1116777A (en) | 1996-02-14 |
| CN1056017C true CN1056017C (en) | 2000-08-30 |
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ID=5033345
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108085A Expired - Lifetime CN1056017C (en) | 1994-08-10 | 1994-08-10 | Hydrogen-storage alloy material for negative electrode of alkaline accumulator and mfg. process thereof |
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| Country | Link |
|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03294444A (en) * | 1990-04-11 | 1991-12-25 | Agency Of Ind Science & Technol | Hydrogen occluding electrode |
| CN1078827A (en) * | 1992-05-16 | 1993-11-24 | 上海工业大学 | A kind of hydrogen-storing alloy as electrode |
-
1994
- 1994-08-10 CN CN94108085A patent/CN1056017C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03294444A (en) * | 1990-04-11 | 1991-12-25 | Agency Of Ind Science & Technol | Hydrogen occluding electrode |
| CN1078827A (en) * | 1992-05-16 | 1993-11-24 | 上海工业大学 | A kind of hydrogen-storing alloy as electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1116777A (en) | 1996-02-14 |
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