CN102628125A - AB5 hydrogen storage alloy with high hydrogen diffusion coefficient and preparation method thereof of AB5 hydrogen storage alloy - Google Patents
AB5 hydrogen storage alloy with high hydrogen diffusion coefficient and preparation method thereof of AB5 hydrogen storage alloy Download PDFInfo
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- CN102628125A CN102628125A CN2012100837820A CN201210083782A CN102628125A CN 102628125 A CN102628125 A CN 102628125A CN 2012100837820 A CN2012100837820 A CN 2012100837820A CN 201210083782 A CN201210083782 A CN 201210083782A CN 102628125 A CN102628125 A CN 102628125A
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Abstract
The invention belongs to the field of hydrogen storage alloy electrode materials and particularly relates to an AB5 hydrogen storage alloy with a high hydrogen diffusion coefficient and a preparation method of the AB5 hydrogen storage alloy. According to the invention, the chemical general formula of the components of the hydrogen storage alloy represented in percentage by mass is as follows: (REM) aNib-xCoc-yMndAle (CufPg)x+y, wherein x is not less than 0 and not more than 7.2; y is not less than 1.2 and not more than 8.4; x+y is not less than 1.2 and not more than 8.4; and a, b, c, d, e, f and g are as follows: a is equal to 33 plus or minus 1, b is equal to 50 plus or minus -2, c is equal to 10 plus or minus -1, d is equal to 5 plus or minus -1, e is equal to 1.5 plus or minus -0.5, and g/(f+g) is equal to 0.13 plus or minus 0.02. According to the invention, the hydrogen storage alloy containing P and Cu is prepared by using a rapid solidification method; because part of Co and Ni metals with higher prices are replaced with a cheap phosphorus copper alloy, the diffusion speed of the hydrogen in the alloy is increased and the production cost of the AB5 alloy is reduced; the prepared AB5 alloy has the characteristics of fine crystal particles and uniform components; and element segregation is eliminated. Without reducing the discharge capacity of the alloy, the circulating performance and rate capability of the AB5 alloy are improved.
Description
Technical field
The invention belongs to the hydrogen-adsorped alloy electrode material field, be specifically related to a kind of AB with high hydrogen diffusion coefficient
5Hydrogen storage alloy and preparation method thereof.
Background technology
1984, the breadboard Willems of Dutch philips adopted multi-element alloyed method partly to substitute LaNi with the Co element
5Ni in the alloy makes alloy making a breakthrough aspect the charge and discharge cycles stability, is that the MH/Ni battery of electrode materials begins to get into the practicability stage finally with the hydrogen storage alloy.In order further to improve the comprehensive electrochemical of hydrogen storage alloy, Japan and China adopt cheap mishmetal Ml (rich lanthanum) or Mm (rich cerium) to replace LaNi
5The higher pure La of cost in the alloy carries out multi-element alloyedly simultaneously to the alloy B side, developed multiple AB in succession
5It is disclosed Mm (NiCoMnAl) in 271043 the European patent that type mixed rare-earth alloy, wherein more typical alloy have the patent No.
5And document (J.Less-Common Met, 1991, Vol.1265, pp172-174) Ml (NiCoMnTi) of middle report
5Deng, its maximum discharge capacity can reach 280 ~ 320mAh/g, and has cyclical stability and comprehensive electrochemical preferably, at home and abroad is widely used in the MH/Ni battery at present.
Co is practicability AB at present
5One of indispensable crucial alloy element in the hydrogen-storage alloy; Especially aspect cycle performance, it can reduce alloy microhardness, strengthen alloy snappiness, reduce the volumetric expansion behind the absorption hydrogen and improve the anti-efflorescence ability of alloy, simultaneously; In charge and discharge process; Co can also suppress elements segregation strippings such as La, Mn, Al, reduces the erosion rate of alloy, thereby improves the cyclical stability of alloy.But business-like REMNi
3.55Co
0.75Mn
0.4Al
0.3Hydrogen storage alloy still exists two subject matters to influence its further application: (1) Co costs an arm and a leg, though Co content is generally about 10wt% in the alloy, its cost accounts for 40% ~ 50% of alloy material total cost; (2) increase of Co content is to AB
5Alloy electrode maximum discharge capacity and high-rate discharge ability etc. have disadvantageous effect.Document (J.Alloys and compounds, 1997, Vol. 579, and correlative study pp253-254) proves: Co content x is increased at 1.3 o'clock by 0, alloy MmNi
4.0-xCo
xMn
0.75Al
0.3(the Wasserstoffatoms diffusion coefficient D is by 1.4 * 10 among the x=0-1.3)
-10Cm
2/ s is decreased to 2.1 * 10
-11Cm
2/ s, promptly the alternative spread coefficient of Wasserstoffatoms in alloy that make of Co reduces, and these two shortcomings restrict AB just
5Hydrogen-storage alloy is in the key issue of New-energy electric vehicle widespread use.In order to solve this two problems, the main at present method that adopts is at REM (NiCoMnAl)
5On the basis of alloy, separately or unite the alloy B lateral element is substituted with elements such as Fe, Si, Cr and Ti.Document (J.Alloys and compounds, 2007, Vol.440 pp323-327) is improved its dynamic performance with the Co in the cheap Fe instead of alloy, alloy LaNi
3.55Mn
0.4Al
0.3Co
0.75-xFe
x(x=0.35) hydrogen diffusion coefficient before substitute 6.29 * 10
-11Cm
2After/s is increased to and substitutes 7.62 * 10
-11Cm
2/ s just reaches maximum capacity 194mAh/g but the activation of iron content hydrogen-bearing alloy electrode surpasses 20 all after dates, and five all after dates of iron content electrode activation do not reach maximum capacity 294 mAh/g, and activation performance and loading capacity all weaken along with the increase of the alternative amount of Fe.Document (J.Alloys and compounds, 2003, Vol.354 pp310-314) discloses with Cr, Si and has replaced AB
5Co in the alloy, though reduced cost, and the Cr element substitution can make alloy activation number of times reduce, the Si element substitution improves the cycle performance of hydrogen storage alloy, but makes maximum discharge capacity and high rate performance variation.
Summary of the invention
To the deficiency that above-mentioned prior art exists, the present invention provides a kind of AB with high hydrogen diffusion coefficient
5Hydrogen storage alloy and preparation method thereof, purpose are to improve AB effectively
5The dynamic performance of hydrogen storage alloy reduces production costs, for its application on new-energy automobile provides condition.
Realize that technical scheme of the present invention is:
A kind of AB with high hydrogen diffusion coefficient
5Hydrogen storage alloy, this alloy is at business-like REMNi
3.55Co
0.75Mn
0.4Al
0.3Add Cu, P element in the hydrogen storage alloy, the chemical general formula that its alloy composition is represented by mass percent is: (REM)
aNi
B-xCo
C-yMn
dAl
e(Cu
fP
g)
X+y, in the formula: 0≤x≤7.2,1.2≤y≤8.4,1.2≤x+y≤8.4, the batching error allowed band of described a, b, c, d, e, f, g are a=33 ± 1, b=50 ± 2, c=10 ± 1, d=5 ± 1, e=1.5 ± 0.5, g/ (f+g)=0.13 ± 0.02; Described REM represents the norium of La content>=50wt%, and other rare earth metals wherein comprise known REE except that La at present.
Above-mentioned (REM)
aNi
B-xCo
C-yMn
dAl
e(Cu
fP
g)
X+yThe preparation method of alloy carries out according to following steps:
(1) presses alloy (REM)
aNi
B-xCo
C-yMn
dAl
e(Cu
fPg)
X+yAtom form and excess coefficient; That is: 0≤x≤7.2,1.2≤y≤8.4,1.2≤x+y≤8.4, a=33 ± 1, b=50 ± 2, c=10 ± 1, d=5 ± 1, e=1.5 ± 0.5 and g/ (f+g)=0.13 ± 0.02 preparation raw material of weighing; REM, Ni, Co, Mn and Al are packed in the smelting pot in the vacuum induction furnace, and phosphor copper is packed in the secondary charging device;
(2) the vacuum induction process furnace is evacuated to less than 10Pa, then charges into argon gas, and repeat to vacuumize, applying argon gas process 1～3 time, under the condition of vacuum tightness≤35Pa, start power supply then, be warming up to 400 ~ 500 ℃ and stop insulation 20～30min;
(3) charge into argon gas to vacuum tightness and be at least 0.05MPa, temperature is raised at least 1500 ℃, the metal in the smelting pot is fully melted;
(4) cool the temperature to 1250～1450 ℃, add phosphor copper simultaneously;
The melt that (5) will add behind the phosphor copper waters rapidly on cooling roller, melt on cooling roller with rate of cooling 2m/s～30m/s chilling slabbing metal.
The sheet metal that the present invention obtains, its crystalline structure have structure and the even tiny equiaxed grain structure characteristic of composition.
Creative part of the present invention is to have taked two gordian technique measures, that is:
(1) the present invention's height of being based on the spread coefficient of Wasserstoffatoms in alloy directly influences the high-rate discharge ability of battery; The Cu element has good electrical conductivity and has less action force with Wasserstoffatoms; Under the synergy of P element, can effectively improve the principle of the spread coefficient of Wasserstoffatoms in alloy, at business-like AB
5Adopt Cu, P element to replace partial C o or Ni or Co and Ni in the hydrogen storage alloy, to improve the velocity of diffusion of hydrogen in alloy;
(2) the present invention is adopting conventional teeming practice preparation (REM) in order to solve
aNi
B-xCo
C-yMn
dAl
e(Cu
fPg)
xIn the alloy process, the introducing of P and Cu will make the high melting compound that generates in the melt (like REP
2); The crystallization that causes the founding alloy is thick, composition profiles is inhomogeneous, crystals stress is easy to efflorescence more greatly; The problem that causes its chemical property to descend; The present invention adopts quick setting method, and to make this alloy have a composition even to reach, and crystal grain is tiny characteristics, makes alloy demonstrate the purpose of good comprehensive electrochemical.
In sum, the present invention compared with prior art has following advantage:
(1) the present invention has substituted higher Co and the Ni metal of part price with cheap phosphor copper, has improved the velocity of diffusion of hydrogen in alloy, has reduced AB
5The production cost of alloy;
(2) AB that makes of the present invention
5Alloy has the crystal grain tiny characteristics, and composition is even, has eliminated element segregation.On the basis of the loading capacity that does not reduce alloy, improved AB
5The cycle performance of alloy and high rate performance.
Embodiment
The vacuum induction process furnace model that the present invention adopted is ZG25A;
Electrochemical test device model is: AUTOLAB PGSTAT30;
The raw metal purity 99.5% of the rare earth that adopts among the embodiment, nickel, cobalt, manganese, copper, phosphorus, aluminium adopts block to add.
REM described in the embodiment represents the norium of La content>=50wt%, has comprised described La
56RE
44, La
60RE
40, La
50RE
50, La
69RE
31And La
100RE
0, RE representative other REEs except that La wherein.
In order to further describe the technique effect of technical scheme of the present invention, it is routine as a comparison also to have enumerated hydrogen storage alloy that preparation do not contain P and Cu and preparation method thereof.
Adopt the hydrogen diffusion coefficient under permanent its room temperature of electromotive force step method test test for the hydrogen storage alloy for preparing in part embodiment of the present invention and the Comparative Examples; Concrete grammar is: concrete testing method is: it is even that the hydrogen storing alloy powder about mean particle size 65 μ m and the nickel powder about 3 μ m are pressed the 1:3 mixed; Being pressed into diameter is that 10mm, thickness are the disk shape hydrogen-bearing alloy electrode of 0.6mm, with sintering Ni (OH)
2Be counter electrode, mercuric oxide electrode is a reference electrode, and the KOH of 6M is an electrolytic solution, and three electrode electrolysers that hydrogen-bearing alloy electrode is housed were at room temperature left standstill about 1 hour, treats to test after current potential is stablized; The step electromotive force is 600mV, step time 3000s.
Part embodiment of the present invention and Comparative Examples are also further tested the chemical property of hydrogen storage alloy; Detailed process is: it is even that the hydrogen storing alloy powder about mean particle size 65 μ m and the nickel powder about 3 μ m are pressed the 1:3 mixed, and being pressed into diameter is that 10mm, thickness are the disk shape hydrogen-bearing alloy electrode of 0.6mm; Select sintering Ni (OH) for use
2Be counter electrode, the KOH of 6M is an electrolytic solution, with the synthetic glass clamping plate with hydrogen-bearing alloy electrode negative pole/barrier film/sintering Ni (OH)
2Anodal fixing, the KOH that then immerses 6M soaked 2 hours in the electrolytic solution.The electro-chemical test process is charging current 100mA/g, and in 4 hours duration of charging, charging finishes and left standstill 10 minutes; Begin discharge after electrode potential of alloy is stable; Discharging current is identical with charging current, and the discharge stopping potential is-0.6V (vs. Hg/HgO) that the record maximum discharge capacity is C
MaxWith big current i (300mA/g, 900mA/g, 1500mA/g) and little electric current 100mA/g discharge, it is worth HRD respectively in the high rate capability test
i=C
i/ (C
i+ C
100), its charging and discharging currents of cycle performance test is 100mA/g, and the capacity that writes down after 100 circulations is C
100, the capability retention after its 100 circulations is S
100=C
100/ C
Max
Comparative Examples 1
By (REM)
32.95Ni
49.43Co
10.5Mn
5.2Al
1.92Shown in the mass percent proportioning, take by weighing various raw metals, the hydrogen storage alloy that preparation does not contain P and Cu prepares hydrogen storage alloy then as follows:
(1) raw material is packed into is evacuated to less than 10Pa in the vacuum induction process furnace, then charge into argon gas, and repeat 1～3 time, under the condition of vacuum tightness≤35Pa, start power supply, stop 20～30min when slowly being warming up to 450 ± 50 ℃;
(2) charge into argon gas to vacuum tightness and be at least 0.05MPa, temperature is risen to more than 1500 ℃, metal is fully melted;
(3) alloy melt is watered on cooling roller the sheet metal that obtains with rate of cooling 2m/s chilling rapidly.
With the hydrogen storage alloy of this method preparation example as a comparison, adopt the preceding method test to draw that hydrogen diffusion coefficient is 5.2113 * 10 under the room temperature
-10Cm
2/ s; Its battery performance is C
Max=293.9mAh/g; S
100=70.37%; HRD
300=89.22%, HRD
900=74.63%, HRD
1500=53.23%.
Embodiment 1
By (La
56RE
44)
32.95Ni
49.43Co
9.09Mn
5.21Al
1.92Cu
1.2P
0.2Shown in the mass percent proportioning, the preparation raw material of weighing is packed REM, Ni, Co, Mn and Al in the smelting pot in the vacuum induction furnace into, Cu and P pack into the form of phosphor copper in the secondary charging device;
The vacuum induction process furnace is evacuated to less than 10Pa, then charges into argon gas, and repeat to vacuumize, applying argon gas process 1 time, under the condition of vacuum tightness≤35Pa, start power supply then, be warming up to 400 ℃ and stop insulation 30min;
Charge into argon gas to vacuum tightness when being 0.05MPa, temperature is risen to 1500 ℃, the metal in the smelting pot is fully melted;
Cool the temperature to 1250 ℃, add phosphor copper simultaneously;
The melt that adds behind the phosphor copper is watered rapidly on cooling roller, melt on cooling roller with rate of cooling 30m/s chilling slabbing metal.
According to aforesaid detection method, the hydrogen diffusion coefficient that test obtains under the room temperature is: 1.1424 * 10
-9Cm
2/ s, this result compare hydrogen diffusion coefficient and have increased 2.19 times with Comparative Examples 1.
Embodiment 2
By (La
56RE
44)
32.95Ni
49.43Co
7.69Mn
5.21Al
1.92Cu
2.4P
0.4Shown in the mass percent proportioning, the preparation raw material of weighing is packed REM, Ni, Co, Mn and Al in the smelting pot in the vacuum induction furnace into, Cu and P pack into the form of phosphor copper in the secondary charging device;
The vacuum induction process furnace is evacuated to less than 10Pa, then charges into argon gas, and repeat to vacuumize, applying argon gas process 1 time, under the condition of vacuum tightness≤35Pa, start power supply then, be warming up to 500 ℃ and stop insulation 2min;
Charge into argon gas to vacuum tightness when being 0.05MPa, temperature is risen to 1500 ℃, the metal in the smelting pot is fully melted;
Cool the temperature to 1450 ℃, add phosphor copper simultaneously;
The melt that adds behind the phosphor copper is watered rapidly on cooling roller, melt on cooling roller with rate of cooling 2m/s chilling slabbing metal.
According to aforesaid detection method, the hydrogen diffusion coefficient that test obtains under the room temperature is: hydrogen diffusion coefficient is 1.5176 * 10
-9Cm
2/ s.This result compares with Comparative Examples 1, and hydrogen diffusion coefficient has increased 2.92 times.
Embodiment 3
By (La
56RE
44)
32.95Ni
49.43Co
4.89Mn
5.21Al
1.92Cu
4.8P
0.8Shown in the mass percent proportioning, the preparation raw material of weighing is packed REM, Ni, Co, Mn and Al in the smelting pot in the vacuum induction furnace into, Cu and P pack into the form of phosphor copper in the secondary charging device;
The vacuum induction process furnace is evacuated to less than 10Pa, then charges into argon gas, and repeat to vacuumize, applying argon gas process 1 time, under the condition of vacuum tightness≤35Pa, start power supply then, be warming up to 450 ℃ and stop insulation 25min;
Charge into argon gas to vacuum tightness when being 0.05MPa, temperature is risen to 1500 ℃, the metal in the smelting pot is fully melted;
Cool the temperature to 1300 ℃, add phosphor copper simultaneously;
The melt that adds behind the phosphor copper is watered rapidly on cooling roller, melt on cooling roller with rate of cooling 20m/s chilling slabbing metal.
According to aforesaid detection method, the hydrogen diffusion coefficient that test obtains under the room temperature is: hydrogen diffusion coefficient is 1.9384 * 10
-9Cm
2/ s.This result compares with Comparative Examples 1, and hydrogen diffusion coefficient has increased 3.72 times.
Embodiment 4
By (La
60RE
40)
32.95Ni
49.43Co
2.1Mn
5.2Al
1.92Cu
7.2P
1.2Shown in the mass percent proportioning, take by weighing various raw materials, preparation contains the hydrogen storage alloy of P and Cu, according to embodiment 3 described preparing methods and aforesaid detection method, test the hydrogen diffusion coefficient that obtains under the room temperature and be: hydrogen diffusion coefficient is 2.5782 * 10
-9Cm
2/ s.This result compares with Comparative Examples 1, and hydrogen diffusion coefficient has increased 4.95 times.
Embodiment 5
By (La
50RE
50)
32.95Ni
42.23Co
9.3Mn
5.2Al
1.9Cu
7.2P
1.2Shown in the mass percent proportioning, take by weighing various raw materials, preparation contains the hydrogen storage alloy of P and Cu, according to embodiment 3 described preparing methods and aforesaid detection method, test the hydrogen diffusion coefficient that obtains under the room temperature and be: hydrogen diffusion coefficient is 1.3582 * 10
-9Cm
2/ s, this result compares with Comparative Examples, and hydrogen diffusion coefficient has increased 2.61 times.
Embodiment 6
Press La
32.95Ni
42.23Co
9.3Mn
5.2Al
1.9Cu
7.2P
1.2Shown in the mass percent proportioning; Take by weighing various raw materials; Preparation contains the hydrogen storage alloy of P and Cu, and according to the embodiment of the invention 3 described preparing methods and aforesaid detection method, the hydrogen diffusion coefficient that test obtains under the room temperature is: hydrogen diffusion coefficient is 1.2475 * 10
-9Cm
2/ s, this result compares with Comparative Examples 1, and hydrogen diffusion coefficient has increased 2.39 times.
Embodiment 7
By (La
56RE
44)
32.95Ni
49.43Co
6.29Mn
5.21Al
1.92Cu
3.6P
0.6Shown in the mass percent proportioning, take by weighing various raw materials, preparation contains the hydrogen storage alloy of P and Cu, according to embodiment 3 described preparing methods and aforesaid detection method, testing the hydrogen diffusion coefficient that obtains under the room temperature is 1.7568 * 10
-9Cm
2/ s, this result compares with Comparative Examples 1, and hydrogen diffusion coefficient has increased 3.37 times; Its battery performance is: C
Max=291.7mAh/g; S
100=85.22%; HRD
300=94.68%, HRD
900=84.91%, HRD
1500=68.82%.Compare S with Comparative Examples 1
100Increased by 14.85%, HRD
300Increased by 5.46%, HRD
900Increased by 10.28%, HRD
1500Increased by 15.59%.
Embodiment 8
By (La
69RE
31)
32.95Ni
49.43Co
6.29Mn
5.21Al
1.92Cu
3.6P
0.6Shown in the mass percent proportioning, take by weighing various raw materials, preparation contains the hydrogen storage alloy of P and Cu; According to embodiment 3 described preparing methods; Different is that speed of cooling is 7m/s, and the sheet metal that obtains plays crystalline structure and has structure and the uniform tiny equiaxed grain structure of composition.According to aforesaid detection method, the hydrogen diffusion coefficient that test obtains under the room temperature is: hydrogen diffusion coefficient is 1.6342 * 10
-9Cm
2/ s, this result compares with Comparative Examples 1, and hydrogen diffusion coefficient has increased 3.14 times; Its battery performance is: C
Max=358mAh/g; S
100=90.73%; HRD
300=93.75%, HRD
900=82.85%, HRD
1500=66.34%.Compare C with Comparative Examples 1
MaxIncreased by 64.1 mAh/g, S
100Increased by 20.36%, HRD
300Increased by 4.53%, HRD
900Increased by 8.22%, HRD
1500Increased by 13.11%.
Embodiment 9
Adopt and the identical hydrogen storage alloy of embodiment 7 compositions, according to the described method of the embodiment of technical measures of the present invention, with the sheet metal that rate of cooling 30m/s chilling obtains, its crystalline structure has structure and the uniform tiny equiaxed grain structure characteristic of composition.Adopt foregoing testing method, the hydrogen diffusion coefficient that test obtains under the room temperature is: hydrogen diffusion coefficient is 1.1812 * 10
-9Cm
2/ s, this result compares with Comparative Examples 1, and hydrogen diffusion coefficient has increased 2.27 times; Its battery performance is: C
Max=282.1mAh/g; S
100=90.52%; HRD
300=91.89%, HRD
900=80.65%, HRD
1500=65.71%.Compare S with Comparative Examples 1
100Increased by 20.15%, HRD
300Increased by 2.67%, HRD
900Increased by 6.02%, HRD
1500Increased by 12.48%.
Claims (3)
1. AB with high hydrogen diffusion coefficient
5Hydrogen storage alloy is characterized in that the chemical general formula that alloy composition is represented by mass percent is: (REM)
aNi
B-xCo
C-yMn
dAl
e(Cu
fP
g)
X+y, in the formula: 0≤x≤7.2,1.2≤y≤8.4,1.2≤x+y≤8.4, described a, b, c, d, e, f, g are a=33 ± 1, b=50 ± 2, c=10 ± 1, d=5 ± 1, e=1.5 ± 0.5, g/ (f+g)=0.13 ± 0.02; Described REM represents the norium of La content>=50wt%.
2. a kind of AB as claimed in claim 1 with high hydrogen diffusion coefficient
5The preparation method of hydrogen storage alloy is characterized in that carrying out according to following steps:
(1) presses alloy (REM)
aNi
B-xCo
C-yMn
dAl
e(Cu
fPg)
X+yAtom form and excess coefficient; That is: 0≤x≤7.2,1.2≤y≤8.4,1.2≤x+y≤8.4, a=33 ± 1, b=50 ± 2, c=10 ± 1, d=5 ± 1, e=1.5 ± 0.5 and g/ (f+g)=0.13 ± 0.02 preparation raw material of weighing; REM, Ni, Co, Mn and Al are packed in the smelting pot in the vacuum induction furnace, and phosphor copper is packed in the secondary charging device;
(2) the vacuum induction process furnace is evacuated to less than 10Pa, then charges into argon gas, and repeat to vacuumize, applying argon gas process 1～3 time, under the condition of vacuum tightness≤35Pa, start power supply then, be warming up to 400 ~ 500 ℃ and stop insulation 20～30min;
(3) charge into argon gas to vacuum tightness and be at least 0.05MPa, temperature is raised at least 1500 ℃, the metal in the smelting pot is fully melted;
(4) cool the temperature to 1250～1450 ℃, add phosphor copper simultaneously;
The melt that (5) will add behind the phosphor copper waters rapidly on cooling roller, melt on cooling roller with rate of cooling 2m/s～30m/s chilling slabbing metal.
3. a kind of AB according to claim 2 with high hydrogen diffusion coefficient
5The preparation method of hydrogen storage alloy is characterized in that described REM represents the norium of La content>=50wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104638272A (en) * | 2013-11-14 | 2015-05-20 | 北汽福田汽车股份有限公司 | Positive pole piece for sodium borohydride fuel cell and preparation method of positive pole piece |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000345263A (en) * | 1999-06-03 | 2000-12-12 | Mitsubishi Materials Corp | Hydrogen storage alloy enabling high rate discharge of battery |
| WO2007011572A1 (en) * | 2005-07-19 | 2007-01-25 | Ovonic Battery Company, Inc. | Hydrogen storage alloys having improved cycle life and low temperature operating characteristics |
| CN101613818A (en) * | 2009-07-21 | 2009-12-30 | 厦门钨业股份有限公司 | A kind of low-cost hydrogen storage alloy and its production and application |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000345263A (en) * | 1999-06-03 | 2000-12-12 | Mitsubishi Materials Corp | Hydrogen storage alloy enabling high rate discharge of battery |
| WO2007011572A1 (en) * | 2005-07-19 | 2007-01-25 | Ovonic Battery Company, Inc. | Hydrogen storage alloys having improved cycle life and low temperature operating characteristics |
| CN101613818A (en) * | 2009-07-21 | 2009-12-30 | 厦门钨业股份有限公司 | A kind of low-cost hydrogen storage alloy and its production and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104638272A (en) * | 2013-11-14 | 2015-05-20 | 北汽福田汽车股份有限公司 | Positive pole piece for sodium borohydride fuel cell and preparation method of positive pole piece |
| CN104638272B (en) * | 2013-11-14 | 2017-10-13 | 北汽福田汽车股份有限公司 | Sodium borohydride fuel cell anode pole piece and preparation method thereof |
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