CN102181751A - Low-self-discharge hydrogen storage alloy and preparation method thereof - Google Patents
Low-self-discharge hydrogen storage alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydrogen storage alloy, particularly a low-self-discharge hydrogen storage alloy and a preparation method thereof. The low-self-discharge hydrogen storage alloy has the advantages of high charge retention rate, favorable activation property, high discharge capacity and long service life. The low-self-discharge hydrogen storage alloy is an AB5-tye alloy of which the general formula is La[a]Ce[1-a]Ni[b]Co[c]Mn[d]Al[e], wherein the elements of the hydrogen storage part only include La and Ce alloys; and a, b, c, d and e represent mol ratios, 0.81<=a<=0.85, 3.72<=b<=3.92, 0.58<=c<=0.72, 0.3<=d<=0.4, 0.15<=e<=0.25, and 4.9<=b+c+d+e<=5.1. Under the protection of inert gas, raw materials, which satisfy the low-self-discharge hydrogen storage alloy of which the general formula is La[a]Ce[1-a]Ni[b]Co[c]Mn[d]Al[e], is smelted, and cooled by a solidifying method, thereby obtaining the low-self-discharge hydrogen storage alloy.
Description
Technical field
The present invention relates to a kind of hydrogen-storage alloy, especially relate to a kind of low self-discharge hydrogen-storage alloy and preparation method thereof.
Background technology
Along with the raising of human environmental consciousness, because ni-mh has characteristics such as environment friendly and pollution-free, security preferably, so secondary cell Ni/MH has obtained using widely aspect civilian.But because primary alkaline battery has and promptly buys the i.e. characteristics of usefulness, and nickel metal hydride battery is often because hang tag in reasons such as supermarket, convenience stores for a long time, the carried charge that dispatches from the factory is exhausted substantially, needing again, charging re-uses, become the restriction nickel metal hydride battery and substitute the once main factor of civilian battery, therefore develop the low self-discharge nickel metal hydride battery, make battery can promptly buy i.e. usefulness, become the market mainstream in recent years.Hydrogen-storage alloy is the critical material of decision Ni/MH battery performance.Hydrogen-storage alloy is a kind of new-type functional material, and hydrogen atom can be stored in its crystalline space, and this storage has reversibility, therefore is widely used in secondary cell.The hydrogen atom that hydrogen-storage alloy can be stored, if synthetic at normal temperatures and pressures hydrogen, its volume is more than 1000 times of this hydrogen-storage alloy, that is to say that its suction hydrogen density surpasses liquid hydrogen and solid-state hydrogen density, both light, safety demonstrates incomparable superiority again.
That be used widely in nickel metal hydride battery at present, is rare earth AB
5The type alloy, representing composition is MmNi
3.55Al
0.4Mn
0.3Co
0.75, wherein Mm contains La, and Ce, Pr, Nd, this alloy have advantages such as activation is fast, high-rate discharge ability is good, the life-span is long.Studies show that, La in the alloy is the strongest element of hydrogen storage capacity, simultaneously also be to reduce the fastest element of equilibrium hydrogen pressure, but its life-span is the poorest, Ce then is a best element of life-span, and Pr, Nd is between the two, now in the commercialization in order to be in harmonious proportion La, the performance of Ce alloy, what show extremely is to carry out Pr, and Nd doses, but after these two kinds of elements dose, the reduction effect of putting the hydrogen platform to hydrogen-storage alloy is obvious not as La, cause the alloy equilibrium hydrogen pressure in the present commercialization alloy under 45 ℃, all to be higher than 0.22 (atH/M=0.4dehydrogenation), caused being made into battery year self-discharge rate generally than higher, be not suitable as the low self-discharge pond.
Publication number is that to disclose a kind of low self-discharge electrode metal be AB in the patent application of CN1073046A
2V-Ti, it comprises: based on atomic percent, 14%～22% vanadium, 28%～39% nickel, 7%～15% titanium, 15%～34% zirconium, with at least a element that is selected from following group, comprise: 0.01%～3.6% manganese and 0.01%～2.7% aluminium, wherein the atomic ratio of vanadium and zirconium is 1: in the scope of (2.26～0.68).Though this alloy is a kind of electrochemical hydrogen storage alloy that reduces self-discharge rate that has, and owing to vanadium titanium zirconium all is the expensive element of price comparison, adds AB
2The alloy activation is slow, and this alloy does not obtain the real marketization now.
Publication number is that the patent application of CN1015188A discloses a kind of low self-discharge battery hydrogen-storage alloy, is not traditional AB
5Structure, this alloy contains A
2B
7Structure, chemical general formula are Nd
1-xMg
xNi
yAl
z, x wherein, y, z are atomic ratio, x: y: z=0.1～0.25: 3.1～3.6: 0.1～0.3 is though this alloy also has low characteristics of putting the hydrogen platform, because this alloy contains volatile Mg, production control is extremely difficult, and performance is comparatively unstable, and therefore the difficulty of the marketization is very high.
Summary of the invention
The object of the present invention is to provide a kind of charged conservation rate height, and have the low self-discharge hydrogen-storage alloy in good activation performance, high discharge capacity and life-span and preparation method thereof.
Low self-discharge hydrogen-storage alloy of the present invention is AB
5Type alloy, general formula are La
A,Ce
1-aNi
bCo
cMn
dAl
e, in the formula, storage hydrogen partial element only contains La, two kinds of alloys of Ce alloy, a, b, c, d, e represent mol ratio, and its numerical range is: 0.81≤a≤0.85,3.72≤b≤3.92,0.58≤c≤0.72,0.3≤d≤0.4,0.15≤e≤0.25,4.9≤b+c+d+e≤5.1.
Described low self-discharge hydrogen-storage alloy has high discharge capacity and low equilibrium hydrogen pressure.
Low self-discharge hydrogen storage preparation method of the present invention may further comprise the steps:
Under protection of inert gas, the general formula that will meet described low self-discharge hydrogen-storage alloy is La
A,Ce
1-aNi
bCo
cMn
dAl
eThe raw material melting after, adopt clotting method to cool off, the low self-discharge hydrogen-storage alloy.
The temperature of described melting can be 940～1000 ℃, and the time of melting can be 6～7h.Described cooling, controlled refrigeration roller linear velocity 〉=2m/s makes the thickness≤0.3mm of the low self-discharge hydrogen-storage alloy of gained; Resulting low self-discharge hydrogen-storage alloy is to have under 45 ℃, and putting the hydrogen balance pressure is the hydrogen-storage alloy of 0.12～0.22atm (at H/M=0.4dehydrogenation).
Described low self-discharge hydrogen-storage alloy has CaCu
5The type structure is traditional AB
5Alloy, the stoichiometric ratio of B: A is 4.9～5.1 simultaneously; In the general formula of described low self-discharge hydrogen-storage alloy, A side element only contains La, two kinds of alloys of Ce, and do not contain alloys such as Pr, Nd, Pm, Sm, Dy, Y, Zr and Ti.The scope of La is 0.81≤a≤0.85, if the content of La is lower than 0.81, then the equilibrium hydrogen pressure of alloy is too high, and capacity is low; If the content of La is higher than 0.85, then the life-span has largely and reduces.
In the general formula of described low self-discharge hydrogen-storage alloy, the scope of Ni is 3.72≤b≤3.92, if the content of Ni then can reduce the electrochemical activation performance of alloy smaller or equal to 3.72, and the reduction capacity; If Ni content is higher than 3.92, consider 4.95≤b+c+d+e≤5.1, then can have influence on the adding of falling the more tangible element of equilibrium pressure, as the adding of Co, what be difficult to guarantee hydrogen-storage alloy like this puts hydrogen balance pressure≤0.22atm (at H/M=0.4dehydrogenation).
In the general formula of described low self-discharge hydrogen-storage alloy, the scope of Co is 0.58≤c≤0.72, if Co is lower than 0.58, then the cycle performance of alloy can worsen, and puts hydrogen balance and presses higher; If the content of Co is greater than 0.72, then performance boost is few, increases cost of alloy simultaneously, reduces cost performance.
In the general formula of described low self-discharge hydrogen-storage alloy, the scope of Mn is 0.3≤d≤0.4, if the content of Mn is less than 0.3, then the equilibrium hydrogen pressure of alloy can be too high, thereby cause the inner pressure of battery height, and self-discharge is big; If the content of Mn then causes the segregation of making processes easily greater than 0.65, be made into battery Mn and separate out easily, worsen the cycle life of battery.
In the general formula of described low self-discharge hydrogen-storage alloy, the scope of Al is 0.15≤e≤0.25, if the content of Al is lower than 0.15, the capacity of alloy increases, but the obvious variation of cycle life.If the content of Al is higher than 0.25, the capacity of alloy can obviously reduce.
In the general formula of described low self-discharge hydrogen-storage alloy, the scope of alloy metering ratio is 4.9≤b+c+d+e≤5.1, if stoichiometric ratio is lower than 4.9, then the cycle life of alloy can reduce; If stoichiometric ratio is higher than 5.1, then alloy the obvious capacity that influences alloy, also can cause equilibrium hydrogen pressure to uprise simultaneously, self-discharge is big.
The hydrogen balance pressure of putting of hydrogen-storage alloy is that 0.12～0.22atm (at H/M=0.4dehydrogenation) is higher than 0.22atm (at H/M=0.4dehydrogenation) as if equilibrium pressure, and then the self-discharge of alloy is just bigger; If equilibrium pressure is lower than 0.22atm (atH/M=0.4dehydrogenation), then the discharge platform of alloy is on the low side, and loading capacity is less than normal.
With existing AB
5The alloy phase ratio, the present invention is on the basis of other alloy over-all propertieies such as guaranteed capacity and life-span, by rejecting Pr, elements such as Nd are adjusted La, the Ce ratio, optimize melting, annealing process, realized reducing the gordian technique of the equilibrium hydrogen pressure of hydrogen-storage alloy under 45 ℃, achievement battery normal temperature lotus conservation rate makes the competition of nickel metal hydride battery and primary cell seize the first opportunity.Studies show that, be to reduce equilibrium hydrogen pressure under the normal temperature and improve hydrogen storage performance effective elements the most at the B side La of storage protium, and Ce then be a lifting life-span effective elements the most in the B side.Removing Pr, in the time of Nd, adjusting La, the Ce ratio by control hydrogen-storage alloy preparation technology, thereby obtains the alloy of high discharge capacity and low equilibrium hydrogen pressure.
Low self-discharge hydrogen-storage alloy provided by the present invention especially can be used for nickel metal hydride battery, can reduce the self-discharge performance of hydrogen-storage alloy in battery significantly.
Description of drawings
Fig. 1 is that the embodiment of the invention 1, comparative example 1 and comparative example 2 are that hydrogen curve (P-C-T figure) is put in 45 ℃ of suctions under the condition in temperature.In Fig. 1, X-coordinate is H/M, and ordinate zou is equilibrium hydrogen pressure P
H2(atm); Curve a is embodiment 1, and curve b is a comparative example 1, and curve c is a comparative example 2.
Embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1
Design mix is La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21According to shown in the mass percent formed prepare burden; confected materials is placed the vacuum induction quick quenching furnace; after vacuumizing again applying argon gas protect; carry out the induction heating melting then; cool off fast on the high speed rotating cooling roller of logical water coolant in casting in subsequently; cold roller speed line speed 〉=2m/s; obtain the low self-discharge hydrogen-storage alloy sheet of thickness≤0.3mm; the heating smelting temperature that is adopted is 940～1000 ℃, and adopts air-blast device, to guarantee that temperature is even; the heating smelting time is 6～7h, and the low self-discharge hydrogen-storage alloy sheet that obtains is put the hydrogen balance pressure-controlled at 0.15～0.22atm (at H/M=0.4dehydrogenation) under 45 ℃.Then make D
50It is the powdered alloy about 45 μ m.
Comparative example 1
Design mix is La
0.33Ce
0.48Pr
0.05Nd
0.15Ni
3.59Co
0.73Mn
0.31Al
0.17, except that design mix was different from embodiment 1, other were with embodiment 1.
Comparative example 2
Design mix is La
0.64Ce
0.25Pr
0.03Nd
0.08Ni
3.7Co
0.74Mn
0.4Al
0.2, except that design mix was different from embodiment 1, other were with embodiment 1.
Utilize inductively coupled plasma atomic emission spectrometry method (ICP-AES) to measure each component content in embodiment and the comparative example alloy.As shown in table 1, each constituent content is consistent with design in the alloy.
Table 1
| La | Ce | Pr | Nd | Ni | Co | Mn | Al | B/A | |
| Embodiment 1 | 26.88 | 5.61 | / | / | 51.50 | 9.92 | 4.76 | 1.33` | 5.06 |
| Comparative example 1 | 10.94 | 16.12 | 1.67 | 5.09 | 50.72 | 10.27 | 4.1 | 1.09 | 4.79 |
| Comparative example 2 | 20.82 | 8.49 | 0.92 | 2.68 | 50.64 | 10.04 | 5.13 | 1.30 | 4.99 |
The opening gram volume test of gained sample is as follows:
At first hydrogen-storage alloy powder is ground to form less than 140 purpose alloy powders, get the 0.2g hydrogen-storage alloy powder and the 0.8gNi powder mixes, the disk that is pressed into diameter 16mm under 20MPa pressure is as negative pole, again the actual content of hydrogen-storage alloy powder in the disk is calculated in weighing after the disk deflashing by the proportional meter of alloy powder and nickel powder.Electric welding nickel strap on the negative pole disk, the anodal sintering nickel hydroxide that adopts same point to weld.To resemble sandwich intermediate plate mode with two positive poles with the negative plate of barrier film parcel and fit together, and fix with polyvinyl chloride (PVC) plate, and immerse in the KOH electrolytic solution of 6mol/L, the composition negative pole determines the open cell of capacity.
The test of electrochemistry capacitance and cycle performance is carried out holding up on day BS9300 tester, and maximum discharge capacity is specifically tested as follows: probe temperature is 25 ℃ of constant temperature, with 60mA/g charging 450min, leave standstill 5min, be discharged to 1.0V with 60mA/g again, leave standstill 5min, repeat above-mentioned charge and discharge process 2 times then; With 300mA/g charging 80min, leave standstill 5min, be discharged to 1.0V with 300mA/g again, leave standstill 5min after, repeat above-mentioned charge and discharge process then, wherein the maximum value that reaches of loading capacity is designated as the opening gram volume of alloy powder.
All samples self-discharge performance testing method is as follows:
Be made into the battery of AA2000 with the method for the routine battery material that alloy powder is relevant with other, improve because the present invention only relates to alloy, therefore other condition all will keep except the alloy powder model can be changed.
Hydrogen-storage alloy powder ground to form then make D
50Be that alloy powder about 50 μ m is pressed into the alloy powder of 9.8g on the collector of 128mm * 43mm * 0.3mm then, wherein comprised the interpolation of conductive agent and tamanori, in like manner the ball nickel of anodal 7.8g is pressed on the collector of 100mm * 43mm * 0.62mm, reel with sulfonated membrane then and install in the box hat of 50AA, annotate alkali lye 2.55g, seal and change into, charged and discharged for 5 weeks with the 0.2C electric current, write down its 5th capacity and then use 0.2C current charges 6h, with its normal temperature storage 1 year, with the 0.2C electric current it is discharged into 1.0V again, its capacity is removed the capacity that writes down in the year before, promptly get charged conservation rate of its year, 0.2C charged and discharged for 2 weeks then, write down the 2nd all capacity, it is removed in capacity the year before, be designated as the capacity restoration rate; Electric current with 0.5C charges and discharge battery at last, is designated as battery life when the capacity 1200mA when (60%), and electrochemistry capacitance and cycle performance test are carried out holding up on day BS9300 tester, and probe temperature is 25 ℃ of constant temperature.
The P-C-T performance test methods of all samples is as follows:
Adopt U.S. home-made pressure component equitemperature tester, after the intensification vacuum outgas of sample elder generation, inhale again and put hydrogen activation 3 times, test then, probe temperature is 318K, and promptly 45 ℃, the residing temperature of instrument is 298K ± 1K, according to perfect gas formula N=pV/RT, calculate suction, put the hydrogen atoms molar weight then from gas pressure change.Repeat this process, draw pressure-component-isothermal curve.
The equilibrium hydrogen pressure and the self-discharge performance of embodiment 1 and Comparative Examples 1,2 are listed in table 2.
Table 2
Illustrate: it is average that charged conservation rate of year, capacity restoration rate and the life-span in the table 2 is 6 battery institutes.
By table 1 as seen, embodiment 1 (La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21) and comparative example 1 (La
0.33Ce
0.48Pr
0.05Nd
0.15Ni
3.59Co
0.73Mn
0.31Al
0.17) main difference be exactly a value of La of comparative example 1 less than 0.81 value, the Ce value is also up to 0.48, greater than the upper limit 0.19 of the present invention, the value of B/A is 4.80, is 4.90 requirement less than minimum value of the present invention.Comparative example 1 is a rich Ce prescription commonly used on the market now.Can find by table 2, the equilibrium hydrogen pressure of comparative example 1 under 45 ℃ condition is that its charged conservation rate of 1.326atm (at H/M=0.4) is lower, year, charged conservation rate had only 58.97%, and embodiment 1 hydrogen pressure is 0.169atm (at H/M=0.4), and its year, charged conservation rate was up to more than 85%.
Comparative example 2 (La
0.64Ce
0.25Pr
0.03Nd
0.08Ni
3.7Co
0.74Mn
0.4Al
0.2) be common on the market rich La prescription, with embodiment 1 (La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21) mainly be that this product has replaced La and Ce with PrNd, make balance fall 0.15～0.22atm (at H/M=0.4) less than requirement of the present invention, this product Mn value is higher simultaneously, can cause this product that the Mn dissolving takes place in battery like this, has influence on the self-discharge performance of battery.
Embodiment 2
Design mix is La
0.83Ce
0.17Ni
3.75Co
0.72Mn
0.38Al
0.21, annealing temperature is 960 ℃, soaking time is 6.5h.
Comparative example 3
Except that thermal treatment process is that 900 ℃ of insulation 6.5h are different from the embodiment 2, other are with embodiment 2.
Comparative example 4
Except that thermal treatment process is that 1000 ℃ of insulation 6.5h are different from the embodiment 2, other are with embodiment 2.
The hydrogen storage property of embodiment 2 and comparative example 3,4, open cell performance, the year charged conservation rate of enclosed cell is listed in table 3.Table 3 data show, adopt the year charged conservation rate of embodiment 2 of 960 ℃ of insulation 6.5h suitable with embodiment 1, and this is that equilibrium hydrogen pressure owing to this alloy reaches 0.15～0.22atm of the present invention (atH/M=0.4).Comparative example 3,4 adopts 900 ℃ of insulation 6.5h, 1000 ℃ of insulation 6.5h respectively, obtains equilibrium hydrogen pressure all greater than 0.22atm (at H/M=0.4), and therefore a year charged conservation rate all is lower than embodiment 2.Wherein the small portion sintering appears in the product of comparative example 4, is an important factor that descends in its life-span, so the present invention is decided to be upper limit technological temperature with 1000 ℃.
Table 3
Claims (5)
1. a low self-discharge hydrogen-storage alloy is characterized in that being AB
5Type alloy, general formula are La
A,Ce
1-aNi
bCo
cMn
dAl
e, in the formula, storage hydrogen partial element only contains La, two kinds of alloys of Ce alloy, a, b, c, d, e represent mol ratio, and its numerical range is: 0.81≤a≤0.85,3.72≤b≤3.92,0.58≤c≤0.72,0.3≤d≤0.4,0.15≤e≤0.25,4.9≤b+c+d+e≤5.1.
2. a kind of low self-discharge hydrogen storage preparation method as claimed in claim 1 is characterized in that its concrete steps are:
Under protection of inert gas, the general formula that will meet described low self-discharge hydrogen-storage alloy is La
A,Ce
1-aNi
bCo
cMn
dAl
eThe raw material melting after, adopt clotting method to cool off, the low self-discharge hydrogen-storage alloy.
3. a kind of low self-discharge hydrogen storage preparation method as claimed in claim 2, the temperature that it is characterized in that described melting is 940～1000 ℃, the time of melting is 6～7h.
4. a kind of low self-discharge hydrogen storage preparation method as claimed in claim 2 is characterized in that described cooling, is the cold roller linear velocity 〉=2m/s of control, makes the thickness≤0.3mm of the low self-discharge hydrogen-storage alloy of gained.
5. a kind of low self-discharge hydrogen storage preparation method as claimed in claim 2 is characterized in that described low self-discharge hydrogen-storage alloy has CaCu
5Type structure, the stoichiometric ratio of B: A are 4.9～5.1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828069A (en) * | 2012-09-26 | 2012-12-19 | 鞍山鑫普电池材料有限公司 | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof |
| CN102888539A (en) * | 2012-10-25 | 2013-01-23 | 厦门钨业股份有限公司 | Low-cost AB5 type hydrogen storage alloy having ultrahigh capacity characteristic, and preparation method and application thereof |
| CN113881872A (en) * | 2021-10-27 | 2022-01-04 | 厦门钨业股份有限公司 | Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11191412A (en) * | 1997-06-27 | 1999-07-13 | Hitachi Maxell Ltd | Alkaline storage battery |
| JP2000239767A (en) * | 1999-02-22 | 2000-09-05 | Shin Etsu Chem Co Ltd | Hydrogen storage alloy, and hydrogen storage alloy electrode |
| WO2001094653A1 (en) * | 2000-06-09 | 2001-12-13 | Mitsui Mining & Smelting Company, Ltd. | Hydrogen-occluding alloy and process for producing the same |
| JP3369148B2 (en) * | 1997-06-27 | 2003-01-20 | 日立マクセル株式会社 | Alkaline storage battery |
| JP3454780B2 (en) * | 1997-06-27 | 2003-10-06 | 日立マクセル株式会社 | Alkaline storage battery |
| CN1602366A (en) * | 2001-12-13 | 2005-03-30 | 株式会社三德 | Hydrogen storage alloy and hydrogen storage alloy powder, method for production thereof, and negative electrode for nickel-hydrogen secondary cell |
-
2011
- 2011-01-28 CN CN2011100327490A patent/CN102181751B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11191412A (en) * | 1997-06-27 | 1999-07-13 | Hitachi Maxell Ltd | Alkaline storage battery |
| JP3369148B2 (en) * | 1997-06-27 | 2003-01-20 | 日立マクセル株式会社 | Alkaline storage battery |
| JP3454780B2 (en) * | 1997-06-27 | 2003-10-06 | 日立マクセル株式会社 | Alkaline storage battery |
| JP2000239767A (en) * | 1999-02-22 | 2000-09-05 | Shin Etsu Chem Co Ltd | Hydrogen storage alloy, and hydrogen storage alloy electrode |
| WO2001094653A1 (en) * | 2000-06-09 | 2001-12-13 | Mitsui Mining & Smelting Company, Ltd. | Hydrogen-occluding alloy and process for producing the same |
| CN1602366A (en) * | 2001-12-13 | 2005-03-30 | 株式会社三德 | Hydrogen storage alloy and hydrogen storage alloy powder, method for production thereof, and negative electrode for nickel-hydrogen secondary cell |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828069A (en) * | 2012-09-26 | 2012-12-19 | 鞍山鑫普电池材料有限公司 | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof |
| CN102828069B (en) * | 2012-09-26 | 2015-05-20 | 鞍山鑫普电池材料有限公司 | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof |
| CN102888539A (en) * | 2012-10-25 | 2013-01-23 | 厦门钨业股份有限公司 | Low-cost AB5 type hydrogen storage alloy having ultrahigh capacity characteristic, and preparation method and application thereof |
| CN102888539B (en) * | 2012-10-25 | 2015-07-29 | 厦门钨业股份有限公司 | A kind of there is ultra-high capacity characteristic low cost AB5 type hydrogen-storage alloy and method for making and application |
| CN113881872A (en) * | 2021-10-27 | 2022-01-04 | 厦门钨业股份有限公司 | Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof |
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