CN1285621A - Hydroyen stored alloy for megative electrode of high power nickel metal hydride cell - Google Patents
Hydroyen stored alloy for megative electrode of high power nickel metal hydride cell Download PDFInfo
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- CN1285621A CN1285621A CN00125368A CN00125368A CN1285621A CN 1285621 A CN1285621 A CN 1285621A CN 00125368 A CN00125368 A CN 00125368A CN 00125368 A CN00125368 A CN 00125368A CN 1285621 A CN1285621 A CN 1285621A
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- Y02E60/10—Energy storage using batteries
Abstract
The chemical formula of hydrogen storage alloy for negative pole of high-power nickel metal hydride cell is RENixCoyMnzAluBv, where RE is rare earth element, y=0.1-1.0, z=0.3-0.5, u=0.1-0.4, v=0.05-0.5 and x is the rest, and x+y+z+u+v is greater than or equal to 4.8 or less than or equal to 5.5, in the alloy there is CeCo4B type second phase, it does not change main phase CaCu5 type hexagon structure in the alloy, and the addition of boron can adopt simple substance or boron-nickel alloy, and they can be formed into AB5 type rare-earth system hydrogen storage alloy with non-chemical metering ratio, and the optimization matching of the rare earth elements of La, Ce, Pr and Nd and raise the heavy current discharge property of alloy.
Description
The present invention relates to a kind of high power type nickel metal hydride battery negative pole hydrogen-storage alloy, this alloy has the performance that excellent high speed absorbs and emit hydrogen, when as nickel metal hydride battery negative pole, can obtain excellent initial activation performance and high rate capability, belong to the hydrogen-storage alloy field.
Since nineteen ninety adopt hydrogen-storage alloy as the nickel metal hydride battery of negative material at first since Japanese industrialization, nickel metal hydride battery is because of having high-energy-density (be nickel-cadmium cell 1.5～2 times), memory-less effect, no cadmium pollution is replacing nickel-cadmium cell rapidly.Present small-sized nickel metal hydride battery and cathode hydrogen storing alloy powder thereof be all industrialization on a large scale at home and abroad.
Special place application of nickel metal hydride batteries such as suitable high power are subjected to people's favor just day by day.Environmental pollution and energy crisis have promoted the research and development of various countries' electric motor cars.At present, international electric motor car developing direction turns to development hybrid electric vehicle (HEV) just gradually.HEV need adopt the high power energy that auxiliary power is provided when starting, quickening and climbing, and transforms its regenerated energy of absorption when car deceleration and brake fast.HEV with the main performance requirement of high-power battery is: high power density, high-specific-power, high-power energy ratio and high charge capacity etc.From environmental angle and performance and price characteristic, the high power type nickel metal hydride battery is one of best candidate of HEV battery, must research and develop as early as possible.In addition, the high power type nickel metal hydride battery also has huge development space on electric tool market.Though, abroad, released HEV and electric tool high power type nickel metal hydride battery, adopt that prior art produces hydrogen-storage alloy can not satisfy the instructions for use of (more than or equal to the 5C multiplying power) under the big current condition well.The key problem in technology of exploitation high power type nickel metal hydride battery is Hydrogen storage alloy materials for negative electrodes.
The electro catalytic activity and the diffusion velocity of hydrogen in the hydrogen-storage alloy body that depend on electrode surface in the nickel metal hydride battery on the rate charge-discharge characteristic dynamics of hydrogen-occlussion alloy electrode.Philips once reported in the laboratory, added a small amount of molybdenum and made the alloy of two-phase and can make AB
5The electrochemical kinetics performance of type hydrogen-storage alloy is obviously improved, and makes it be easy to activation, the second phase MoNi of formation
3Has forceful electric power chemical catalysis ability [J.Electrochem.Soc., 183 (1991) 1877].In addition, second-phase dispersion is distributed in and can be hydrogen atom in the body diffusion admittance is provided, and quickens the diffusion velocity of hydrogen in alloy body.Adopt methods such as element replacement or surface treatment also can improve the electrochemical kinetics performance of hydrogen-storage alloy, use at low discharging current (less than the 5C multiplying power) with nickel metal hydride but said method all is a limitation.The negative pole that is fit to high power type nickel metal hydride battery (discharging current is more than or equal to the 5C multiplying power) is used the hydrogen-storage alloy bibliographical information seldom.The domestic market demand amount is big, does not still have report but production at present is fit to the producer of the cathode hydrogen storing alloy powder of high power type nickel metal hydride battery.
Purpose of the present invention just is to provide a kind of superior cathode hydrogen storing alloy of high rate capability that is used for the high power type nickel metal hydride battery.Also promptly, the present invention relates to a kind of high power type nickel metal hydride battery negative pole hydrogen-storage alloy, this alloy has absorption (being equivalent to " charging ") fast and emits hydrogen (being equivalent to " discharge ") speed.
The objective of the invention is to add boron element, utilize boron in the alloy melting process, to be easy to cyrystal boundary segregation and to form second realize mutually by adopting when the hydrogen-storage alloy melting.Add the existing report of boron document in the hydrogen-storage alloy, but its adding purpose has nothing in common with each other, and addition is controlled also lowlyer (≤0.2).Adopt stoichiometric proportion AB such as a spot of boron (≤0.1) part replacement as CN1124411
5Ni in the type rare earth based hydrogen storage alloy to be improving its fast charging and discharging performance, and thinks that the replacement amount makes the alloy self-discharge rate increase too greatly.And for example CN1128413 adopts 0.05～0.15 stoichiometric proportion AB such as boron portion replacement
5Ni in the type rare earth based hydrogen storage alloy, the bridged ring network structure that makes the hydride that forms behind the absorption hydrogen have part has lower self discharge to reduce nickel metal hydride battery.CN1065353 is at AB for another example
5Add 0.005～0.2 boron in the type rare earth based hydrogen storage alloy and come reinforced alloys, reduce pulverization rate; Suppress the surface segregation that rare-earth elements La etc. puts in the hydrogen process in suction simultaneously and take place, improve the decay resistance of alloy.The present inventor finds to add the CeCo that a certain amount of boron can form high catalytic activity in rare earth based hydrogen storage alloy
4Type B second phase, the existence of second phase obviously improves the fast charging and discharging performance of alloy.Boron addition scope is 0.05≤v≤0.5, adds boron amount (＜0.05) very little, and second phase content that forms in the alloy is also few, and the alloy high rate capability improves little; Add boron amount too many (＞0.5), second phase content that forms in the alloy is too high, though the alloy high rate capability is fabulous, the discharge capacity of alloy is low excessively, can not satisfy the capacity requirement of high power type nickel metal hydride battery.
Hydrogen-storage alloy employing non-stoichiometric of the present invention especially over-stoichiometric ratio makes easier formation boracic second phase in the alloy.Adopt X-ray diffraction to detect and show, have CeCo in the hydrogen-storage alloy of the present invention
4Type B second phase, electrochemical test studies show that, this second is a kind of high catalytic activity phase mutually, and the existence of second phase has improved the diffusion velocity of hydrogen in the hydrogen-storage alloy body.In the hydrogen-storage alloy of the present invention second do not change principal phase CaCu mutually
5The type hexagonal structure is inhaled principal phase and to be put the hydrogen capacity properties influence seldom, and second itself can not inhale mutually and put hydrogen, but has improved the suction hydrogen releasing efficient of principal phase.The hydrogen-storage alloy that the present invention proposes is more recommended to adopt the additive of nickel boron alloy as boron except that adopting pure boron, can further improve the homogeneity of ingredients of hydrogen-storage alloy, and reduces the cost of raw material significantly, because the pure boron price is extremely expensive.In the hydrogen-storage alloy of the present invention by the distributing rationally of rare earth constituent element La, Ce, Pr and Nd, the thermodynamic property of improving hydrogen-storage alloy can further strengthen hydrogen in hydrogen-storage alloy absorption and emit speed.Simultaneously, the activity function of hydrogen-storage alloy of the present invention, inhale hydrogen desorption plateau pressure, charge and discharge circulation life, anti-oxidant, prevent that performance such as micronizing from also can satisfy the requirement of high power type nickel metal hydride battery.
A kind of high power type nickel metal hydride battery negative pole hydrogen-storage alloy provided by the invention, the chemical formula of its alloy is: RENi
xCo
yMn
zAl
uB
v, y=0.1～1.0, z=0.3～0.5, u=0.1～0.4, v=0.05～0.5, x is a surplus, and 4.8≤x+y+z+v≤5.5.Wherein RE is a rare earth element, can be La, Ce, Pr, Nd, rich La mishmetal, the alloy of a kind of or two or more the described metal in the rich Ce mishmetal.
Hydrogen-storage alloy provided by the invention adopt purity be higher than 99% Ni, Co, Mn, Al and purity be higher than 99% La, Ce, Pr, Nd and purity greater than 96% pure boron or nickel boron alloy as adding constituent element, press the chemical formula of alloy: RENi
xCo
yMn
zAl
uB
vThe proportioning copper crucible of packing into adopts radio-frequency magnetic levitation melting under argon shield, after the ingot casting remelting 3 times, again 950 ℃ down annealing made in 6 hours.That is alloy provided by the invention, production technology and production equipment all are common equipments, production cost is low, the huge market demand.
Compared with prior art, the present invention has following advantage:
(1) high power type nickel metal hydride battery negative pole hydrogen-storage alloy of the present invention, owing to add boron, adopt the composition proportion of non-stoichiometric, in alloy, formed second phase with high electrocatalytic active, improve the high-rate charge-discharge capability of the negative pole that adopts hydrogen-storage alloy preparation of the present invention greatly, designed a kind of cathode hydrogen storing alloy that satisfies the requirement of high power type nickel metal hydride battery high-multiplying power discharge (more than or equal to the 5C multiplying power).
(2) hydrogen-storage alloy of the present invention is easily-activated, and discharge capacity can reach maximum for the 1st～2 time, has solved the difficult problem that the opening of nickel metal hydride battery changes into.
(3) hydrogen-storage alloy of the present invention, production technology is identical with the prior art condition with equipment, and production cost is low, and the market demand is big.
The ratio of the discharge capacity the when high-rate discharge ability of hydrogen-storage alloy is meant the discharge capacity of alloy when big electric current with 60mA/g alloy discharging current.The high rate capability specimen is hydrogen-storage alloy mechanical crushing to 200～400 orders that will make, and adopting hydrogen-storage alloy powder and nickel powder weight ratio is to be pressed into sequin as metal hydride cathode sheet at 1: 4.Test is carried out in standard three-electrode system (work electrode is a metal hydride cathode, and auxiliary electrode is the nickel hydroxide positive plate sheet, and reference electrode is the Hg/HgO electrode, and electrolyte is the KOH solution of 6M), and the test environment temperature is 20 ℃.
High rate capability test system is: test after 60mA/g alloy electric current charge and discharge cycles 10 times and 300mA/g alloy charge and discharge cycles 30 times, charging was filled 1.2 hours with the 300mA/g alloy during test, after shelving 10 minutes, put to stopping potential with different discharging currents respectively again; When discharging current was 60mA/g alloy, 300mA/g alloy, 900mA/g alloy, 1500mA/g alloy and 3000mA/g alloy, corresponding respectively stopping potential be-0.6V ,-0.6V ,-0.5V ,-0.4V ,-the relative and Hg/HgO reference electrode of 0.3V.
Fig. 1 is the high-rate discharge ability and the discharging current graph of a relation of hydrogen-storage alloy provided by the invention and comparative alloy.Abscissa is discharging current (a mA/g alloy), and ordinate is discharge high rate capability (%).1～6 corresponds respectively to table 1 embodiment 1～5 and Comparative Examples 6 among the figure.
Fig. 2 hydrogen-storage alloy provided by the invention and comparative alloy X-ray diffractogram.1～6 corresponds respectively to table 1 embodiment 1～5 and Comparative Examples 6 among the figure.
Further specify the outstanding feature and the marked improvement of hydrogen-storage alloy provided by the invention below by embodiment, for more manifesting the invention, special the Comparative Examples alloy property is listed in the lump.But the present invention never is limited to listed embodiment.
The embodiment that embodiment provides is the example 1～5 shown in the table 1.Wherein embodiment 1～3 and embodiment 5 adopt pure boron for adding constituent element, and it is 18.86% that embodiment 4 adopts boron content, and impurity content is less than 1.6% nickel boron alloy for adding constituent element.What Comparative Examples 6 adopted is common in the market a kind of hydrogen-storage alloy composition.Embodiment 1～4 rare earth elements RE adopts purity to be higher than 99% La, Ce, Pr, Nd.It is the percentage by weight 24.59% of La that embodiment 5 rare earth elements adopt composition, the percentage by weight 52.90% of Ce, the percentage by weight 5.52% of Pr, the percentage by weight 16.91% of Nd and the commercially available cerium-rich mischmetal of a small amount of inevitable impurity.
Because added the boron of different amounts in the alloy of embodiment and adopted non-stoichiometric, the alloy heavy-current discharge performance obviously improves.The embodiment 1～5 that the present embodiment provides and the heavy-current discharge performance of Comparative Examples 6 are listed in table 2.By table 2 as seen, during more than or equal to the 900mA/g alloy, its discharge capacity is all greater than No. 6 alloys of Comparative Examples at discharging current for embodiment 1～5 alloy.Comparing embodiment 3 and 4 adopts the alloy (embodiment 4) of nickel boron alloy form interpolation boron to have better heavy-current discharge performance as can be seen.Comparing embodiment 3 and 5 as can be seen, adopt the good heavy current of cerium-rich mischmetal (embodiment 5) than the hydrogen-storage alloy that adopts lanthanum rich rare earth component (embodiment 3) gained, the proportioning that rare earth component La, Ce, Pr, Nd are optimized in this explanation can improve the heavy-current discharge performance of alloy.
The high-rate discharge ability of embodiment 1～5 and Comparative Examples 6 alloys is shown in Fig. 1.As seen from Figure 1, when the discharge capacity of Comparative Examples 6 alloys when 3000mA/g alloy electric current (near the 10C multiplying power) only is 60mA/g alloy electric current (near the 0.2C multiplying power) 14.9% of discharge capacity, and embodiment 4 and the 5 alloys discharge capacity when 3000mA/g alloy electric current (near the 13C multiplying power) can reach 60mA/g alloy electric current (near the 0.25C multiplying power) respectively the time discharge capacity 83.3% and 92.4%.Adopt hydrogen-storage alloy of the present invention can satisfy performance requirements such as battery high power density, high-specific-power, high-power energy ratio and high charge capacity as the high power type nickel metal hydride battery negative pole.The composition (stoichiometric number) of table 1 embodiment 1～5 and Comparative Examples 6 alloys
Table 2 embodiment 1～5 and the discharge capacity of Comparative Examples 6 alloys under different discharging current conditions
| Sequence number La Ce Pr Nd Ni Co Mn Al B |
| ?1???0.62??0.27??0.03??0.08??3.55??0.75???0.4???0.3???0.05 |
| ?2???0.62??0.27??0.03??0.08??3.55??0.75???0.4???0.3???0.2 |
| ?3???0.62??0.27??0.03??0.08??3.55??0.75???0.4???0.3???0.3 |
| ?4???0.62??0.27??0.03??0.08??3.55??0.75???0.4???0.3???0.3 |
| ?5???0.25??0.53??0.06??0.16??3.55??0.75???0.4???0.3???0.3 |
| ?6???0.62??0.27??0.03??0.08??3.55??0.75???0.4???0.3????- |
| Discharging current (mA/g alloy) | Discharge capacity (mAh/g alloy) | |||||
| Embodiment 1 | | | Embodiment 4 | Embodiment 5 | Comparative Examples | |
| ????60 | ?312.9 | ?258.8 | ?243.3 | ?230.6 | ?212.1 | ?327.8 |
| ????300 | ?303.3 | ?256.6 | ?230.1 | ?226.8 | ?215.0 | ?294.5 |
| ????900 | ?247.4 | ?230.8 | ?213.4 | ?220.1 | ?210.5 | ?168.4 |
| ????1500 | ?177.5 | ?202.8 | ?196.0 | ?215.0 | ?208.0 | ?108.3 |
| ????3000 | ?81.8 | ?114.0 | ?133.7 | ?192.1 | ?196.0 | ?49.0 |
Claims (8)
1, a kind of high power type nickel metal hydride battery negative pole hydrogen-storage alloy is characterized in that:
(1) chemical formula of alloy is: RENi
xCo
yMn
zAl
uB
v, wherein RE is a rare earth element, y=0.1～1.0, and z=0.3～0.5, u=0.1～0.4, v=0.05～0.5, x is a surplus, and 4.8≤x+y+z+u+v≤5.5;
(2) interpolation by boron forms the AB of non-stoichiometric
5The type rare earth based hydrogen storage alloy;
(3) there is high catalytic activity phase CeCo in the alloy
4Type B second phase, it does not change principal phase CaCu in the alloy
5The type hexagonal structure is inhaled hydrogen releasing efficient but improve principal phase.
2, by the described hydrogen-storage alloy of claim 1, it is characterized in that adding constituent element boron or with simple substance form, or add with nickel boron alloy, addition is 0.05～0.5.
3, by the described hydrogen-storage alloy of claim 1, it is characterized in that RE is La, Ce, Pr, Nd, rich La mishmetal, the alloy of a kind of or two or more the described metal in the rich Ce mishmetal.
4,, it is characterized in that the optimization of described rare-earth elements La, Ce, Pr, Nd cooperates the heavy-current discharge performance that can improve alloy by claim 1 or 3 described hydrogen-storage alloys; The mishmetal good heavy current that adopts rich cerium is in the mishmetal of rich lanthanum.
5, by the described hydrogen-storage alloy of claim 1, it is characterized in that: x=3.55, y=0.75, z=0.4, u=0.3, v=0.05.
6, by the described hydrogen-storage alloy of claim 1, it is characterized in that: x=3.55, y=0.75, z=0.4, u=0.3, v=0.2.
7, by the described hydrogen-storage alloy of claim 1, it is characterized in that: x=3.55, y=0.75, z=0.4, u=0.3, v=0.3.
8, by the described hydrogen-storage alloy of claim 1, it is characterized in that by chemical formula RENi
xCo
yMnzAl
uB
vThe hydrogen-storage alloy of preparation is used for the negative pole of high magnification type nickel metal hydride battery, and discharge-rate reaches 5C or higher.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492873A (en) * | 2011-12-13 | 2012-06-13 | 广州有色金属研究院 | Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy |
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2000
- 2000-09-22 CN CN00125368A patent/CN1285621A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492873A (en) * | 2011-12-13 | 2012-06-13 | 广州有色金属研究院 | Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy |
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