CN100400691C - Hydrogen storage alloy and hydrogen storage alloy powder, method for production thereof, and negative electrode for nickel-hydrogen secondary cell - Google Patents
Hydrogen storage alloy and hydrogen storage alloy powder, method for production thereof, and negative electrode for nickel-hydrogen secondary cell Download PDFInfo
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- CN100400691C CN100400691C CNB02824754XA CN02824754A CN100400691C CN 100400691 C CN100400691 C CN 100400691C CN B02824754X A CNB02824754X A CN B02824754XA CN 02824754 A CN02824754 A CN 02824754A CN 100400691 C CN100400691 C CN 100400691C
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- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
A hydrogen storage alloy which is useful as an electrode material for a secondary cell has achieved the reduction of a cobalt content, and also offers a good balance of a level of activities such as initial activity and discharge characteristics, corrosion resistance, and life characteristics, and further is excellent in recyclability, has a composition represented by the formula (1): RNiaCobAlcMndMe, wherein R represents a rare earth element including Y, or the like, M represents Mg, Fe or the like, and 3.50 <= a <= 4.95, 0.10 <= b <= 0.50, 0.35 <= c <= 0.55, 0.10 <= d <= 0.45 and 0 <= e <= 0.10, provided that 5.10 <= a+b+c+d+e <= 5.50, and has a particle diameter of 10 mu m or less and, at a grain boundary and within a grain of the base phase constituting the alloy, a second phase having an Al content and a Mn content greater than those of the base phase.
Description
Technical field
The present invention relates to be suitable for as the electrode materials of nickel-hydrogen secondary cell etc., especially by being used for the secondary battery cathode material, and the balanced hydrogen-storage alloy that has excellent activity degree, erosion resistance and life characteristic well, its powder, their method for making and negative electrode for nickel-hydrogen secondary cell.
Background technology
In metal oxide-hydrogen battery, the battery that constitutes hydrogen negative pole form with hydrogen-storage alloy is subjected to extensive concern at present.This battery has its original high-energy-density, the volumetric efficiency excellence, and can trouble-free service, the reliability of its characteristic is also fine.The AB that mainly uses as this cell negative electrode material
5In the type hydrogen-storage alloy,, require to have various characteristics such as flatness as high hydrogen storage amount, low equilibrium pressure, erosion resistance, platform usually in order to improve the characteristic of battery.Some characteristics among these characteristics are characteristics of mutual exclusion, are therefore extensively carrying out about neither sacrificing side's characteristic at present, can improve the opposing party's The Characteristic Study again, and part research has reached the practicability stage.
The erosion resistance of hydrogen-storage alloy is to improve the key element of battery cycle characteristics, and aspect the erosion resistance that improves hydrogen-storage alloy, the method for adding cobalt can improve effect, and has reached the practicability stage.But cobalt is invaluable metal, so the price of alloy is also very high.So studying the addition that reduces cobalt at present, and keeping the technology of alloy corrosion resistance.
For example studying when using cobalt, using multiple other to add the method for element.But in this method, increase owing to constitute the number of elements of alloy, it is difficult that the utilization again of battery becomes, so occurred utilizing the new problem of cost increase again again.Simultaneously also to studying based on the method for the B lateral element ratio of Ni with respect to A lateral element increase based on rare earth element.In the method, be difficult to make alloy structure even, the inclination of terrace part becomes too big in the PCT curve, increases the tendency that forms the multistage platform, so the cell container reduction occurred, problems such as inner pressure of battery characteristic reduction.
The activity degree of hydrogen-storage alloy is the key element that improves the battery activity degree, aspect the activity degree that improves hydrogen-storage alloy, at alloy, has attempted being undertaken by bronsted lowry acids and bases bronsted lowry the method for surface-treated method, increase A lateral element ratio.But activity degree and aforementioned erosion resistance are the key elements of mutual exclusion, so these improve the method for activity degree, also have the problem that reduces erosion resistance simultaneously.
Particularly nearest, need in the battery of deep discharge in power-driven tool application etc., also used nickel-hydrogen secondary cell, therefore just require further to improve the characteristic of the hydrogen-storage alloy that is used for this battery.
Disclosure of the Invention
The object of the present invention is to provide electrode materials to be suitable for as nickel-hydrogen secondary cell, by using as negative material, equilibrium possesses good initial activity, deep discharge characteristic isoreactivity degree well under the few situation of the consumption of cobalt, erosion resistance and life characteristic, and utilize the also good hydrogen-storage alloy of characteristic, its powder, their manufacture method and the negative electrode for nickel-hydrogen secondary cell that uses this hydrogen-storage alloy powder again.
In order to solve above-mentioned problem, the present inventor has carried out research with keen determination to the composition of alloy and the mutual relationship of tissue, erosion resistance and activity degree, the result recognizes by using when the B lateral element with alloy is limited in the specified range, the amount that makes Al and Mn in the B lateral element is in specified range, and make the 2nd fine hydrogen-storage alloy of in whole parent phase, evenly separating out just can solve above-mentioned problem, thereby finished the present invention.
If just according to the present invention, hydrogen-storage alloy can be provided, it is to have the alloy of forming shown in the formula (1), contain the 2nd mutually on the parent grain border that constitutes alloy with intragranular, the content of the 2nd middle mutually Al and Mn is higher than Al and the Mn content in the parent phase, and the particle diameter of the 2nd phase is at 10 μ m or following.
RNi
aCo
bAl
cMn
dM
e (1)
(in the formula, R represents to contain the rare earth element of yttrium or their complex element, and M represents Mg, Fe, Cu, Zr, Ti, Mo, W, B or their mixture.A is that 3.50≤a≤4.95, b are that 0.10≤b≤0.50, c are that 0.35≤c≤0.55, d are that 0.10≤d≤0.45, e are 0≤e≤0.10,5.10≤a+b+c+d+e≤5.50)
If according to the present invention, hydrogen-storage alloy powder can be provided, it is to have a composition shown in the above-mentioned formula (1), particle diameter is at 10 μ m or above powdered alloy, and alloy particle inside contain the grain boundary with at least one the 2nd mutually.
If according to the present invention, hydrogen-storage alloy powder can also be provided, it is that median size is the powdered alloy of 5～100 μ m, and contains above-mentioned powdered alloy.
If according to the present invention, the manufacture method of above-mentioned hydrogen-storage alloy can also be provided, after it is characterized in that the alloy raw material of forming shown in the above-mentioned formula (1) carried out fusion, with this molten alloy cooled and solidified, obtaining mean thickness is the casting sheet of 0.05～0.5mm, under 900～1100 ℃ gained casting sheet is carried out 30 minutes～10 hours thermal treatment.
If according to the present invention, the manufacture method of above-mentioned powdered alloy can also be provided, after it is characterized in that the alloy raw material of forming shown in the above-mentioned formula (1) carried out fusion, with this molten alloy cooled and solidified, obtaining mean thickness is the casting sheet of 0.05～0.5mm, under 900～1100 ℃, gained casting sheet is carried out 30 minutes～10 hours thermal treatment, and then pulverize.
If according to the present invention, can also provide and contain above-mentioned powdered alloy and electro-conductive material negative electrode for nickel-hydrogen secondary cell as negative material.
The simple declaration of accompanying drawing
Fig. 1 is the copy pattern of expression with the electron micrograph of the fractography of the synthetic hydrogen storage alloy casting strip of embodiment 1-1.
Fig. 2 is the copy pattern of expression with the electron micrograph of the fractography of the synthetic hydrogen-storage alloy powder of embodiment 2-1.
Preferred implementation
Below describe situation of the present invention in detail.
Hydrogen-storage alloy of the present invention has the composition shown in the above-mentioned formula (1).R in the formula (1) represents to contain the complex element of the rare earth element of yttrium or 2 kinds or above these elements.When for example using as the negative electrode active material of nickel-hydrogen secondary cell, consider from the angle that improves erosion resistance, mainly contain a kind, 2 kinds or above element from La, Ce, Pr and Nd, selecting, perhaps preferably constitute by a kind that from La, Ce, Pr and Nd, selects, 2 kinds or above element.At this moment the preferred La of the ratio of each rare earth element is that 40～100 quality %, Ce are that 0～50 quality %, Pr are that 0～50 quality %, Nd are 0～50 quality %.
In the formula (1), a of expression Ni amount is 3.50≤a≤4.95, preferred 3.90≤a≤4.75.The b of expression Co amount is 0.10≤b≤0.50, preferred 0.20≤b≤0.50.If b surpasses 0.50, then the price of alloy raises; If be lower than 0.10, then to reduce erosion resistance inevitably.The c of expression Al amount is 0.35≤c≤0.55, preferred 0.35≤c≤0.50.The d of expression Mn amount is 0.10≤d≤0.45, preferred 0.15≤d≤0.30.The amount of Al and Mn is good in aforementioned range, but in order to reach the object of the invention better, adjusts when forming, especially preferably make expression Al and Mn exist the c/d of ratio reach 0.7 or more than.
M in the formula (1) is the interpolation element for the purposes such as hydrogen storage property of adjusting alloy, the mixture of expression Mg, Fe, Cu, Zr, Ti, Mo, W, B or 2 kinds or above this dvielement.The e of expression M amount is 0≤e≤0.10.If e surpasses 0.10, then can not get improving with the corresponding characteristic of addition, may make and utilize the difficulty that becomes again.
The value of the a+b+c+d+e of expression B side element ratio is 5.10～5.50 in the alloy of the present invention, preferred 5.20～5.40.If this value is lower than 5.10, then be difficult to make the fine the 2nd in alloy structure, to disperse; If surpass 5.50, the capacity in the time of then can reducing as battery material inevitably.
Hydrogen-storage alloy of the present invention has above-mentioned composition, in order to obtain needed characteristic, grain boundary and intragranular that it is organized in the parent phase that constitutes alloy contain the 2nd phase, the Al of the 2nd phase and Mn amount are more than Al in the parent phase and Mn amount, and its particle diameter is at 10 μ m or following.The form of the 2nd phase, with the contained the 2nd mutually different in the hydrogen-storage alloy in past, majority presents sphere or elliposoidal.In order to make the 2nd uniform distribution in powdered alloy of being on good terms, the 2nd phase is preferably dimensioned to be 0.05～10 μ m, preferred especially 0.05～5 μ m, the more preferably scope of 0.05～2 μ m.The 2nd phase minimum interval each other that exists in hydrogen-storage alloy is preferably in 10 μ m or following, particularly preferably in 5 μ m or following, more preferably at 2 μ m or following, the 2nd also can not exist at interval mutually each other, the existence of the 2nd phase can be confirmed by electron microscope and EPMA.
The above-mentioned the 2nd mutually in, so-called Al and Mn amount more than the connotation of Al in the parent phase and Mn amount be meant the 2nd mutually in the amount of contained Al and Mn more than the mean value of Al contained in the parent phase and Mn amount, have heterodyne arranged.For example, the Al of preferred the 2nd phase and Mn the amount than the mean value in the parent phase Duo 2% or more than.In addition, if when representing the composition of the 2nd phase with ABx, the ideal range of x is 6～10.
In order to make hydrogen-storage alloy of the present invention,, then be not particularly limited so long as the composition of gained alloy and particle diameter, shape and the dispersion state etc. of the 2nd phase can be controlled at aforesaid method.But preferred following manufacture method of the present invention.
The feature of hydrogen-storage alloy manufacture method of the present invention is that the alloy raw material of forming shown in the above-mentioned formula (1) is carried out fusion, makes this molten alloy cooled and solidified then, obtains the casting sheet of specific mean thickness, with specified conditions gained casting sheet is heat-treated.
In manufacture method of the present invention,,, then be not particularly limited so long as the gained alloy composition satisfies the metal of formula (1) requirement and the mixture of alloy as the alloy raw material of forming shown in the formula (1).Usually can use each metal mixture of composition shown in the formula that to form (1) etc.The molten alloy of this alloy raw material for example can use alumina crucible in inert gas atmosphere, obtains by currently known methodss such as high-frequency meltings.
In the manufacture method of the present invention, then be that above-mentioned molten alloy is carried out cooled and solidified, obtaining mean thickness is the casting sheet of 0.05～0.5mm.In this course, if speed of cooling is fast, then the crystallization particle diameter becomes fine; If speed of cooling is slow, then the crystallization particle diameter becomes thick.When this casting sheet was made, the crystallization particle diameter was inhomogeneous, and the shape of then above-mentioned the 2nd phase and precipitation state are also inhomogeneous, so in subsequent handling, heat-treat with specified conditions.Therefore if speed of cooling is too slow when making the casting sheet, then during aftermentioned thermal treatment, the crystallization particle diameter is thick, is difficult to make the dispersion state of the 2nd phase even, is not preferred.If opposite speed of cooling is too fast, though crystallization is fine, dispersion state is good, heat-treat condition becomes and is difficult to control, and productivity reduces, and also is not preferred.If speed of cooling is further accelerated, when forming noncrystalline state,, the back makes its crystallization even also heat-treating, and also be difficult in intragranular and separate out the 2nd phase, remain not preferred.
According to above situation, when making above-mentioned casting sheet, preferably by can obtaining band teeming practice (ス ト リ Star プ キ ヤ ス ト) suitable speed of cooling, that adopt single roller or two rollers, centrifugal casting, rotating-disk teeming practice etc. carries out.Cooling conditions normally with about 10～3000 ℃/second, preferred 10～500 ℃/second, more preferably 10～200 ℃/second speed is cooled off.
In order to eliminate the size deviation of casting sheet section direction crystallization particle diameter, make the crystallization particle diameter after the aftermentioned thermal treatment even, gained must be cast the gauge control of sheet usually in the scope of 0.05～0.5mm.At this moment, by adopting above-mentioned method of cooling, column crystallization is grown on the thickness direction of gained casting sheet.In the single face cooling headed by single roller strap material cast, the crystallization particle diameter minimum of the face that contacts with heat-eliminating medium, the crystallization particle diameter is along more becoming big towards opposite sides.In the two-sided cooling headed by two roller strap material cast, the crystallization particle diameter on the surface that contacts with heat-eliminating medium is little, and the crystallization particle diameter is along more becoming big towards casting sheet centre.If casting sheet thickness surpasses 0.5mm, then part that the crystallization particle diameter is little and big part particle diameter difference are too big, even carry out thermal treatment described later, also are difficult to obtain the tissues needed structure of having narrated the front.
In the manufacture method of the present invention, by to carrying out specific thermal treatment, obtain hydrogen-storage alloy of the present invention then with the above-mentioned casting sheet that obtains.Generally speaking, improve thermal treatment temp, prolong heat treatment time, it is poor to dwindle interior each the crystalline particle diameter of casting sheet more, too big but the crystallization particle diameter becomes, and also might can not get needed characteristic.Therefore in the manufacture method of the present invention, must be defined as heat-treat condition under 900～1100 ℃, handle 30 minutes～10 hours.
Hydrogen-storage alloy powder of the present invention is to have the composition shown in the above-mentioned formula (1), particle diameter at 10 μ m or above powdered alloy, and be in alloy particle inside, contain the grain boundary with at least the 2 mutually powdered alloy (below, this powdered alloy is called the 1st powdered alloy), and median size is the powdered alloy of 5～100 μ m, and is the powdered alloy that contains above-mentioned the 1st powder (following this powdered alloy is called the 2nd powder).
In the 1st powder, as form with the 2nd mutually, preferably enumerate composition and 2nd phase identical with narrating content in the invention described above hydrogen-storage alloy.Contain a plurality of the 2nd phase times, the 2nd mutually each other minimum interval all at 10 μ m or following, preferred especially 5 μ m or following, more preferably 2 μ m or following also can be not at interval.
The composition of the 2nd powder preferably all has the composition shown in the formula (1), other powder in the 2nd powder except that the 1st powder, also preferably contain in alloy particle inside the grain boundary with at least the 2 mutually.
In the present invention the 1st and the 2nd powder, the crystallization particle diameter preferably 5 μ m or more than, more preferably at 5～50 μ m, when particularly using as electrode, the crystallization particle diameter preferably used powdered alloy median size 1/2 or below.
In the present invention the 1st and the 2nd powder, for example when using as electrode materials, in order further to reach the purpose that improves the electrode various characteristics, can also carry out the surface with coating or high molecular polymer etc. and coat, perhaps known processing such as surface treatment are carried out in enforcement with solution such as acid, alkali.
The present invention the 1st and the 2nd powder for example can be by after making hydrogen-storage alloy of the present invention, and the manufacture method of the present invention that the casting sheet after the gained thermal treatment is pulverized obtains.
Operation to the casting sheet after the aforementioned hot processing is pulverized can adopt known method to pulverize, so long as when the casting sheet is pulverized, do not produce alloy oxidation, and can obtain the method for specified particle size, then there is no particular limitation.For example can preferably enumerate the case of wet attrition method that adopts hypoxemia water, dry type comminuting methods such as ピ Application formula grinding machine, disc type grinding machine, the hydrogen comminuting method of use hydrogen.
Negative electrode for nickel-hydrogen secondary cell of the present invention so long as contain the 1st or the 2nd powder and electro-conductive material as negative material, then is not particularly limited, and in order further to reach needed purpose, and for reaching other purpose, also can contain other material.
Negative electrode for nickel-hydrogen secondary cell of the present invention for example can be ground into the 1st or the 2nd powder and electro-conductive material of specified particle size by use, by currently known methods, modulates with the method for mixed together such as tackiness agent, conductive auxiliary agent, moulding.For employed electro-conductive material, tackiness agent, conductive auxiliary agent etc. in this process, also there is no particular limitation, can use known substances.
Hydrogen-storage alloy of the present invention and powder thereof have specific composition and specific tissue, so the electrode materials as nickel-hydrogen secondary cell is suitable for, by using as this negative material, can balancedly obtain to have good initial activity, deep discharge characteristic, erosion resistance and life characteristic well, and just can obtain these characteristics with a spot of Co, also consider its usability again, so its practicality is fine.In addition, if adopt manufacture method of the present invention, can be easy to obtain this hydrogen-storage alloy and powder thereof in industrial mode.
Negative electrode for nickel-hydrogen secondary cell of the present invention, the hydrogen-storage alloy powder that uses the invention described above be as active substance, so the effect can obtain as secondary battery cathode the time is rich in practicality.
Embodiment
By the following examples and comparative example, illustrate in greater detail situation of the present invention, but the present invention is not subjected to the qualification of these embodiment.
Embodiment 1-1～1-6 and comparative example 1-1～1-2
With the rare earth metal (cerium mischmetal that embodiment 1-1～1-4 uses Three Tak Co., Ltd to make) formed shown in the table 1 as the A side, by being 1 o'clock with this A side, make the atomic ratio of Ni, Co, Mn, Al and the x of ABx reach the value shown in the table 1, the mixing raw material metal or alloy, use alumina crucible, in argon atmospher, carry out high-frequency melting, the modulation molten alloy.Then by tundish the gained molten alloy is supplied with single roller continuously, adopt the band teeming practice, with 100 ℃/second speed of cooling chilling, making thickness is the casting sheet of 0.2mm.In argon gas atmosphere, the condition shown in the use table 1 is heat-treated gained casting sheet, the modulation hydrogen-storage alloy.
With x-ray fluorescence analysis (of science electric machine industry society system SMX-10) composition of the hydrogen-storage alloy of gained is carried out quantitative analysis, the result can confirm that with mixing composition be identical.And with scanning electronic microscope alloy structure is observed, determine to have or not the particle diameter and the 2nd each other minimum interval mutually of form, the 2nd phase of the 2nd phase, the 2nd phase respectively.Also from above-mentioned observed alloy structure, by EPMA (NEC system JXL8800) quantitative analysis, measure Al and the Mn amount of parent phase and the 2nd in mutually, and by calculating obtain the 2nd in mutually Al and the total amount (s) of Mn with respect to the increase mark of Al in the parent phase and the average total amount of Mn (b), the result is shown in table 1.
Along perpendicular to cutting section, the copy pattern of the electron micrograph of this fractography of expression is shown in Fig. 1 with the synthetic hydrogen storage alloy casting strip thickness direction of embodiment 1-1.
Embodiment 2-1～2-6 and comparative example 2-1～2-2
To carrying out mechanical disintegration, modulate the hydrogen-storage alloy powder of median size below 60 μ m respectively with embodiment 1-1～1-6 or the synthetic hydrogen-storage alloy of comparative example 1-1～1-2.
Employing x-ray fluorescence analysis (the electric machine industry system SMX-10 of society of science) is carried out quantitative analysis to the composition of gained hydrogen-storage alloy powder, and the result can confirm that it is identical forming with embodiment 1-1～1-6 and the synthetic hydrogen-storage alloy of comparative example 1-1～1-2.By scanning electronic microscope the tissue of powdered alloy is observed simultaneously, determined to have or not the 2nd to reach the grain boundary mutually, and measure the crystal size of crystal grain short-axis direction in the powdered alloy.Also adopt hondrometer to measure the minimum grain size and the median size of powdered alloy respectively, the result is shown in table 2.
The copy pattern of expression with the electron micrograph of the synthetic hydrogen-storage alloy powder fractography of embodiment 2-1 shown in Fig. 2.
Table 2
| Have or not the 2nd phase, grain boundary | Crystal size (μ m) | Powder minimum grain size (μ m) | Powder median size (μ m) | |
| Embodiment 2-1 | Have | 5.0 | 1.9～2.8 | 50.15 |
| Embodiment 2-2 | Have | 5.5 | 2.8～3.9 | 50.65 |
| Embodiment 2-3 | Have | 9.1 | 2.8～3.9 | 49.86 |
| Embodiment 2-4 | Have | 6.4 | 2.8～3.9 | 50.58 |
| Embodiment 2-5 | Have | 7.2 | 1.9～2.8 | 50.17 |
| Embodiment 2-6 | Have | 10.2 | 1.9～2.8 | 50.15 |
| Comparative example 2-1 | Do not have | 120 | - | - |
| Comparative example 2-2 | Do not have | 8.4 | - | - |
Embodiment 3-1～3-6 and comparative example 3-1～3-2
Take by weighing respectively with embodiment 2-1～2-6 or the synthetic hydrogen-storage alloy powder 1.2g of comparative example 2-1～2-2, and mix, modulate fibrous material respectively as the nickle carbonoxide 1g of electro-conductive material with as the fluororesin powder 0.2g of adhesives.With nickel screen the fibrous material of gained is wrapped in the inside, use 2.8ton/cm
2Pressure carry out extrusion forming, make negative electrode for nickel-hydrogen secondary cell.In 5 atmospheric pressurizing vessels, in 30% KOH, each electrode is discharged and recharged test, initial activity as follows, deep discharge characteristic and erosion resistance are evaluated, the result is shown in table 3.
Initial activity is that the discharging current with 0.2C carries out 10 circulations, and the 3rd round-robin loading capacity carry out by evaluating with respect to the 10th round-robin loading capacity.
The deep discharge characteristic is in the 11st circulation, discharges with 1C, measures the capability value of this moment, evaluates the ratio of this value with respect to the 10th cyclic discharge capacity.
Erosion resistance is that the discharging current with 0.2C discharges again after the 12nd circulation, evaluates the 600th round-robin loading capacity conservation rate with respect to the 10th cyclic discharge capacity.
Table 3
| Initial activity (%) | Deep discharge characteristic (%) | Erosion resistance (%) | |
| Embodiment 3-1 | 98.2 | 95.3 | 95.7 |
| Embodiment 3-2 | 97.8 | 94.8 | 96.1 |
| Embodiment 3-3 | 95.5 | 92.8 | 94.2 |
| Embodiment 3-4 | 97.0 | 93.2 | 96.0 |
| Embodiment 3-5 | 96.6 | 93.0 | 92.2 |
| Embodiment 3-6 | 93.4 | 91.4 | 90.9 |
| Comparative example 3-1 | 89.4 | 84.2 | 95.5 |
| Comparative example 3-2 | 96.2 | 82.2 | 82.2 |
Claims (4)
1. hydrogen-storage alloy powder, it is to have the composition shown in the formula (1), particle diameter is at 10 μ m or above powdered alloy, contain the crystallization of particle diameter 5～50 μ m, and in powdered alloy inside, contain the grain boundary with at least one the 2nd mutually, and the 2nd phase minimum interval each other is all below 10 μ m
RNi
aCo
bAl
cMn
dM
e (1)
In the formula, R represents to contain the rare earth element of yttrium or their complex element, M represents Mg, Fe, Cu, Zr, Ti, Mo, W, B or their mixture, a is that 3.50≤a≤4.95, b are that 0.10≤b≤0.50, c are that 0.35≤c≤0.55, d are that 0.10≤d≤0.45, e are 0≤e≤0.10,5.10≤a+b+c+d+e≤5.50.
2. hydrogen-storage alloy powder, it is that median size is the powdered alloy of 5～100 μ m, and contains the hydrogen-storage alloy powder of claim 1.
3. the manufacture method of the hydrogen-storage alloy powder of claim 1, it is after the alloy raw material of forming shown in the formula (1) is carried out fusion, adopt the band teeming practice that this molten alloy is carried out cooled and solidified, obtaining mean thickness is the casting sheet of 0.05～0.5mm, and by under 900～1100 ℃, the casting sheet of gained carried out 30 minutes～10 hours thermal treatment, generation contains the crystallization of particle diameter 5～50 μ m, and in powdered alloy inside, contain grain boundary and at least one the 2nd mutually powdered alloy, pulverize afterwards.
4. negative electrode for nickel-hydrogen secondary cell, it contains the hydrogen-storage alloy powder described in the claim 1 and electro-conductive material as negative material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001380048 | 2001-12-13 | ||
| JP380048/2001 | 2001-12-13 |
Publications (2)
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| JP (1) | JP4647910B2 (en) |
| CN (1) | CN100400691C (en) |
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| EP1652947A4 (en) * | 2003-08-08 | 2008-06-25 | Mitsui Mining & Smelting Co | LOW Co HYDROGEN OCCLUSION ALLOY |
| CN1297021C (en) * | 2005-05-31 | 2007-01-24 | 钢铁研究总院 | Cathode material in use for nickel-hydrogen battery in high capacity |
| WO2007040277A1 (en) * | 2005-10-06 | 2007-04-12 | Mitsui Mining & Smelting Co., Ltd. | LOW-Co HYDROGEN ABSORBING ALLOY |
| JP2010182684A (en) * | 2006-07-25 | 2010-08-19 | Panasonic Corp | Processing method of anode active material for nickel hydrogen battery, anode active material for nickel hydrogen battery, and nickel hydrogen battery |
| JP5169050B2 (en) * | 2006-07-25 | 2013-03-27 | パナソニック株式会社 | Negative electrode active material for nickel metal hydride battery, nickel metal hydride battery, and method for treating negative electrode active material for nickel metal hydride battery |
| JP3992075B1 (en) | 2007-01-30 | 2007-10-17 | 中央電気工業株式会社 | Hydrogen storage alloy and electrode for nickel-hydrogen battery |
| CN100467168C (en) * | 2007-02-02 | 2009-03-11 | 厦门钨业股份有限公司 | Method for preparing hydrogen storing alloy powder |
| JP5179777B2 (en) * | 2007-03-30 | 2013-04-10 | 株式会社三徳 | Hydrogen storage alloy, negative electrode for nickel metal hydride secondary battery, nickel metal hydride secondary battery |
| JP2011127185A (en) * | 2009-12-18 | 2011-06-30 | Santoku Corp | Hydrogen storage alloy, method for producing the same, negative electrode for nickel hydrogen secondary battery and nickel hydrogen secondary battery |
| CN102181751B (en) * | 2011-01-28 | 2013-01-09 | 厦门钨业股份有限公司 | Low-self-discharge hydrogen storage alloy and preparation method thereof |
| JP6935613B2 (en) * | 2019-08-19 | 2021-09-15 | 株式会社三徳 | Hydrogen storage material, hydrogen storage container and hydrogen supply device |
| EP4129535A1 (en) | 2021-08-03 | 2023-02-08 | GRZ Technologies SA | Ab2 type-based hydrogen storage alloys, methods of preparation and uses thereof |
| EP4129534A1 (en) | 2021-08-03 | 2023-02-08 | GRZ Technologies SA | Ab5-type based hydrogen storage alloys, methods of preparation and uses thereof |
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| JPH10261413A (en) * | 1997-03-19 | 1998-09-29 | Japan Metals & Chem Co Ltd | Hydrogen storage alloy for secondary battery |
| JP2000219928A (en) * | 1999-02-01 | 2000-08-08 | Mitsui Mining & Smelting Co Ltd | Hydrogen storage alloy and its production |
| EP1055740A1 (en) * | 1998-12-15 | 2000-11-29 | Mitsui Mining & Smelting Co., Ltd. | Hydrogen storage alloy and method for preparation thereof |
| JP2001040442A (en) * | 1999-05-26 | 2001-02-13 | Mitsui Mining & Smelting Co Ltd | Hydrogen storage alloy |
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| US6261517B1 (en) * | 1996-09-06 | 2001-07-17 | Santoku Metal Industry Co., Ltd. | Rare earth metal-nickel hydrogen storage alloy, a method for producing the same, and anode for nickel-hydrogen rechargeable battery |
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| JP2001126724A (en) * | 1999-10-25 | 2001-05-11 | Shin Etsu Chem Co Ltd | Method for manufacturing hydrogen-occlusion alloy powder |
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- 2002-12-13 WO PCT/JP2002/013062 patent/WO2003054240A1/en active Application Filing
- 2002-12-13 JP JP2003554939A patent/JP4647910B2/en not_active Expired - Lifetime
- 2002-12-13 CN CNB02824754XA patent/CN100400691C/en not_active Expired - Lifetime
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Patent Citations (5)
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| JPH10261413A (en) * | 1997-03-19 | 1998-09-29 | Japan Metals & Chem Co Ltd | Hydrogen storage alloy for secondary battery |
| EP1055740A1 (en) * | 1998-12-15 | 2000-11-29 | Mitsui Mining & Smelting Co., Ltd. | Hydrogen storage alloy and method for preparation thereof |
| JP2000219928A (en) * | 1999-02-01 | 2000-08-08 | Mitsui Mining & Smelting Co Ltd | Hydrogen storage alloy and its production |
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| AB5型贮氢合金研究进展. 李相哲.电池工业，第6卷第1期. 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003054240A1 (en) | 2003-07-03 |
| CN1602366A (en) | 2005-03-30 |
| JPWO2003054240A1 (en) | 2005-04-28 |
| JP4647910B2 (en) | 2011-03-09 |
| AU2002354479A1 (en) | 2003-07-09 |
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