CN102628125B - 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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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 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 Willems in Dutch philips laboratory adopted multi-element alloyed method to substitute LaNi with Co element part
5ni in alloy, is making a breakthrough alloy aspect charge and discharge cycles stability, the MH/Ni battery take hydrogen storage alloy as electrode materials starts to enter practical stage finally.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 alloy, while alloy B side is carried out multi-element alloyed, has in succession developed multiple AB
5type mixed rare-earth alloy, wherein to have the patent No. be disclosed Mm (NiCoMnAl) in 271043 European patent to more typical alloy
5and the Ml (NiCoMnTi) reporting in document (J.Less-Common Met, 1991, Vol.1265, pp172-174)
5deng, its maximum discharge capacity can reach 280 ~ 320mAh/g, and has good cyclical stability and comprehensive electrochemical, now at home and abroad in MH/Ni battery, is widely used.
Co is practical AB at present
5one of indispensable crucial alloy element in hydrogen-storage alloy, especially aspect cycle performance, it can fall low-alloyed microhardness, strengthens the snappiness of alloy, reduce the volumetric expansion after absorption hydrogen and carry heavy alloyed productive technique, simultaneously, in charge and discharge process, Co can also suppress the segregation stripping of the elements such as La, Mn, Al, reduces the erosion rate of alloy, thereby carries heavy alloyed cyclical stability.But business-like REMNi
3.55co
0.75mn
0.4al
0.3hydrogen storage alloy still exists two subject matters to affect its further application: (1) Co's is expensive, although Co content is generally 10wt% left and right, 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.The correlative study of document (J.Alloys and compounds, 1997, Vol. 579, pp253-254) proves: Co content x is increased at 1.3 o'clock by 0, alloy MmNi
4.0-xco
xmn
0.75al
0.3in (x=0-1.3), hydrogen atom diffusion coefficient D is by 1.4 × 10
-10cm
2/ s is decreased to 2.1 × 10
-11cm
2/ s, the alternative spread coefficient of hydrogen atom 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 method adopting is at REM(NiCoMnAl at present)
5on the basis of alloy, with the elements such as Fe, Si, Cr and Ti alone or in combination alloy B lateral element substitute.Document (J.Alloys and compounds, 2007, Vol.440, pp323-327) is improved its dynamic performance with the Co in cheap Fe instead of alloy, alloy LaNi
3.55mn
0.4al
0.3co
0.75-xfe
x(x=0.35) hydrogen diffusion coefficient from 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 iron content hydrogen-bearing alloy electrode activation exceedes 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 alloy, although reduce cost, and Cr element substitution can make alloy activation number of times reduce, and 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
The deficiency existing for above-mentioned prior art, the invention provides a kind of AB with high hydrogen diffusion coefficient
5hydrogen storage alloy and preparation method thereof, object is effectively to improve AB
5the dynamic performance of hydrogen storage alloy, reduces production costs, for its application on new-energy automobile provides condition.
Realizing 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
0.3in hydrogen storage alloy, add Cu, P element, the chemical general formula that its alloy composition represents by mass percent is: (REM)
ani
b-xco
c-ymn
dal
e(Cu
fp
g)
x+yin formula: 0≤x≤7.2,1.2≤y≤8.4,1.2≤x+y≤8.4, the Aggregate Feeding Error allowed band of described a, b, c, d, e, f, g is 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 the known rare earth element except 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) press alloy (REM)
ani
b-xco
c-ymn
dal
e(Cu
fpg)
x+yatom composition 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 vacuum induction furnace, and phosphor copper packs in secondary charging device;
(2) vacuum induction process furnace is evacuated to and is less than 10Pa, be then filled with argon gas, and repeat to vacuumize, applying argon gas process 1～3 time, then under the condition of vacuum tightness≤35Pa, start power supply, be warming up to 400 ~ 500 ℃ and stop insulation 20～30min;
(3) be filled with argon gas to vacuum tightness and be at least 0.05MPa, temperature is raised to at least 1500 ℃, the metal in smelting pot is fully melted;
(4) cool the temperature to 1250～1450 ℃, add phosphor copper simultaneously;
(5) will add the melt after phosphor copper to water 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 has structure and the even tiny equiaxed grain structure feature of composition.
Creative part of the present invention is to have taked two key measures, that is:
(1) the present invention is the high-rate discharge ability that the height of the spread coefficient in alloy based on hydrogen atom directly affects battery, Cu element has good electroconductibility and has less reactive force with hydrogen atom, under the synergy of P element, can effectively improve the principle of the spread coefficient of hydrogen atom in alloy, at business-like AB
5in hydrogen storage alloy, adopt Cu, P element to replace Co or Ni or Co and Ni partly, 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 alloy process, the introducing of P and Cu by the high melting compound that makes to generate in melt (as REP
2), by thick the crystallization that causes founding alloy, composition profiles is inhomogeneous, crystals stress is easy to more greatly efflorescence, the problem that causes its chemical property to decline, the present invention adopts quick setting method, and to reach, to make this alloy have composition even, crystal grain is tiny characteristics, makes alloy present the object of good comprehensive electrochemical.
In sum, the present invention compared with prior art tool have the following advantages:
(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 the present invention makes
5alloy has crystal grain tiny characteristics, and composition is even, has eliminated element segregation.Not falling on the basis of low-alloyed loading capacity, improve AB
5the cycle performance of alloy and high rate performance.
Embodiment
Vacuum induction process furnace model of the present invention is ZG25A;
Electrochemical test device model is: AUTOLAB PGSTAT30;
The raw metal purity 99.5% of the rare earth that adopts in embodiment, nickel, cobalt, manganese, copper, phosphorus, aluminium, adopts block to add.
REM described in 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 wherein represents other rare earth elements except La.
In order to further describe the technique effect of technical scheme of the present invention, also enumerate preparation and do not contained hydrogen storage alloy of P and Cu and preparation method thereof as a comparison case.
In part embodiment of the present invention and comparative example, adopt the hydrogen diffusion coefficient under permanent its room temperature of electromotive force step method test test for the hydrogen storage alloy preparing, concrete grammar is: concrete testing method is: the hydrogen storing alloy powder of mean particle size 65 μ m left and right is mixed in 1:3 ratio with the nickel powder of 3 μ m left and right, being pressed into diameter is the disc-shaped hydrogen-bearing alloy electrode that 10mm, thickness are 0.6mm, with sintering Ni (OH)
2for to electrode, mercuric oxide electrode is reference electrode, and the KOH of 6M is electrolytic solution, and three electrode electrolysers that hydrogen-bearing alloy electrode is housed are at room temperature left standstill to about 1 hour, after current potential is stable, tests; Step electromotive force is 600mV, step time 3000s.
Part embodiment of the present invention and comparative example are also further tested the chemical property of hydrogen storage alloy, detailed process is: the hydrogen storing alloy powder of mean particle size 65 μ m left and right is mixed in 1:3 ratio with the nickel powder of 3 μ m left and right, and being pressed into diameter is the disc-shaped hydrogen-bearing alloy electrode that 10mm, thickness are 0.6mm; Select sintering Ni (OH)
2for to electrode, the KOH of 6M is electrolytic solution, with synthetic glass clamping plate by hydrogen-bearing alloy electrode negative pole/barrier film/sintering Ni (OH)
2anodal fixing, the KOH that then immerses 6M soaks in electrolytic solution 2 hours.Electro-chemical test process is charging current 100mA/g, and in 4 hours duration of charging, charging finishes and leaves standstill 10 minutes, after electrode potential of alloy is stable, start electric discharge, discharging current is identical with charging current, and electric discharge stopping potential is-0.6V(vs. Hg/HgO), recording maximum discharge capacity is C
max; High rate capability test is respectively with large current i (300mA/g, 900mA/g, 1500mA/g) and little electric current 100mA/g electric discharge, and it is worth HRD
i=C
i/ (C
i+ C
100), cycle performance is tested its charging and discharging currents and is 100mA/g, and the capacity recording after 100 circulations is C
100, the capability retention after its 100 circulations is S
100=C
100/ C
max.
Comparative example 1
By (REM)
32.95ni
49.43co
10.5mn
5.2al
1.92shown in mass percent proportioning, take various raw metals, then preparation does not prepare hydrogen storage alloy as follows containing the hydrogen storage alloy of P and Cu:
(1) raw material is packed in vacuum induction process furnace and is evacuated to and is less than 10Pa, be then filled with argon gas, and repeat 1～3 time, under the condition of vacuum tightness≤35Pa, start power supply, while being slowly warming up to 450 ± 50 ℃, stop 20～30min;
(2) be filled with 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 rapidly on cooling roller to the sheet metal obtaining with rate of cooling 2m/s chilling.
The hydrogen storage alloy of preparing with this method as a comparison case, adopts preceding method test to show that under room temperature, hydrogen diffusion coefficient is 5.2113 × 10
-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 mass percent proportioning, the preparation raw material of weighing, packs REM, Ni, Co, Mn and Al in the smelting pot in vacuum induction furnace into, Cu and P pack in secondary charging device with the form of phosphor copper;
Vacuum induction process furnace is evacuated to and is less than 10Pa, be then filled with argon gas, and repeat to vacuumize, applying argon gas process 1 time, then under the condition of vacuum tightness≤35Pa, start power supply, be warming up to 400 ℃ and stop insulation 30min;
When being filled with argon gas to vacuum tightness and being 0.05MPa, temperature is risen to 1500 ℃, the metal in smelting pot is fully melted;
Cool the temperature to 1250 ℃, add phosphor copper simultaneously;
To add the melt after phosphor copper to water 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 under room temperature, test obtains is: 1.1424 × 10
-9cm
2/ s, this result hydrogen diffusion coefficient compared with comparative example 1 has increased 2.19 times.
Embodiment 2
By (La
56rE
44)
32.95ni
49.43co
7.69mn
5.21al
1.92cu
2.4p
0.4shown in mass percent proportioning, the preparation raw material of weighing, packs REM, Ni, Co, Mn and Al in the smelting pot in vacuum induction furnace into, Cu and P pack in secondary charging device with the form of phosphor copper;
Vacuum induction process furnace is evacuated to and is less than 10Pa, be then filled with argon gas, and repeat to vacuumize, applying argon gas process 1 time, then under the condition of vacuum tightness≤35Pa, start power supply, be warming up to 500 ℃ and stop insulation 2min;
When being filled with argon gas to vacuum tightness and being 0.05MPa, temperature is risen to 1500 ℃, the metal in smelting pot is fully melted;
Cool the temperature to 1450 ℃, add phosphor copper simultaneously;
To add the melt after phosphor copper to water 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 under room temperature, test obtains is: hydrogen diffusion coefficient is 1.5176 × 10
-9cm
2/ s.This result is compared with comparative example 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 mass percent proportioning, the preparation raw material of weighing, packs REM, Ni, Co, Mn and Al in the smelting pot in vacuum induction furnace into, Cu and P pack in secondary charging device with the form of phosphor copper;
Vacuum induction process furnace is evacuated to and is less than 10Pa, be then filled with argon gas, and repeat to vacuumize, applying argon gas process 1 time, then under the condition of vacuum tightness≤35Pa, start power supply, be warming up to 450 ℃ and stop insulation 25min;
When being filled with argon gas to vacuum tightness and being 0.05MPa, temperature is risen to 1500 ℃, the metal in smelting pot is fully melted;
Cool the temperature to 1300 ℃, add phosphor copper simultaneously;
To add the melt after phosphor copper to water 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 under room temperature, test obtains is: hydrogen diffusion coefficient is 1.9384 × 10
-9cm
2/ s.This result is compared with comparative example 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 mass percent proportioning, take various raw materials, the hydrogen storage alloy that preparation contains P and Cu, according to the preparation method described in embodiment 3 and aforesaid detection method, under room temperature, the hydrogen diffusion coefficient that obtains of test is: hydrogen diffusion coefficient is 2.5782 × 10
-9cm
2/ s.This result is compared with comparative example 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 mass percent proportioning, take various raw materials, the hydrogen storage alloy that preparation contains P and Cu, according to the preparation method described in embodiment 3 and aforesaid detection method, under room temperature, the hydrogen diffusion coefficient that obtains of test is: hydrogen diffusion coefficient is 1.3582 × 10
-9cm
2/ s, this result is compared with comparative example, 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 mass percent proportioning, take various raw materials, the hydrogen storage alloy that preparation contains P and Cu, according to the preparation method described in the embodiment of the present invention 3 and aforesaid detection method, the hydrogen diffusion coefficient that under room temperature, test obtains is: hydrogen diffusion coefficient is 1.2475 × 10
-9cm
2/ s, this result is compared with comparative example 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 mass percent proportioning, take various raw materials, the hydrogen storage alloy that preparation contains P and Cu, according to the preparation method described in embodiment 3 and aforesaid detection method, under room temperature, the hydrogen diffusion coefficient that obtains of test is 1.7568 × 10
-9cm
2/ s, this result is compared with comparative example 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%.Compared with comparative example 1, S
100increase by 14.85%, HRD
300increase by 5.46%, HRD
900increase by 10.28%, HRD
1500increase by 15.59%.
Embodiment 8
By (La
69rE
31)
32.95ni
49.43co
6.29mn
5.21al
1.92cu
3.6p
0.6shown in mass percent proportioning, take various raw materials, preparation contain P and Cu hydrogen storage alloy, according to the preparation method described in embodiment 3, different is that speed of cooling is 7m/s, and the sheet metal obtaining 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 under room temperature, test obtains is: hydrogen diffusion coefficient is 1.6342 × 10
-9cm
2/ s, this result is compared with comparative example 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%.Compared with comparative example 1, C
maxincrease by 64.1 mAh/g, S
100increase by 20.36%, HRD
300increase by 4.53%, HRD
900increase by 8.22%, HRD
1500increase by 13.11%.
Embodiment 9
Adopt the hydrogen storage alloy identical with embodiment 7 compositions, according to the method described in the embodiment of the technology of the present invention measure, the sheet metal obtaining with rate of cooling 30m/s chilling, its crystalline structure has structure and the uniform tiny equiaxed grain structure feature of composition.Adopt foregoing testing method, the hydrogen diffusion coefficient that under room temperature, test obtains is: hydrogen diffusion coefficient is 1.1812 × 10
-9cm
2/ s, this result is compared with comparative example 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%.Compared with comparative example 1, S
100increase by 20.15%, HRD
300increase by 2.67%, HRD
900increase by 6.02%, HRD
1500increase by 12.48%.
Claims (2)
1. one kind has the AB of high hydrogen diffusion coefficient
5hydrogen storage alloy, is characterized in that the chemical general formula that alloy composition represents by mass percent is: (REM)
ani
b-xco
c-ymn
dal
e(Cu
fp
g)
x+y, in formula: 0≤x≤7.2,1.2≤y≤8.4,1.2≤x+y≤8.4, described a, b, c, d, e, f, g is 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 with high hydrogen diffusion coefficient as claimed in claim 1
5the preparation method of hydrogen storage alloy, is characterized in that carrying out according to following steps:
(1) press alloy (REM)
ani
b-xco
c-ymn
dal
e(Cu
fpg)
x+yelementary composition 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, 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 vacuum induction furnace, and phosphor copper packs in secondary charging device;
(2) vacuum induction process furnace is evacuated to and is less than 10Pa, be then filled with argon gas, and repeat to vacuumize, applying argon gas process 1～3 time, then under the condition of vacuum tightness≤35Pa, start power supply, be warming up to 400～500 ℃ and stop insulation 20～30min;
(3) be filled with argon gas to vacuum tightness and be at least 0.05MPa, temperature is raised to at least 1500 ℃, the metal in smelting pot is fully melted;
(4) cool the temperature to 1250～1450 ℃, add phosphor copper simultaneously;
(5) will add the melt after phosphor copper to water rapidly on cooling roller, melt on cooling roller with rate of cooling 2m/s～30m/s chilling slabbing metal.
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|---|---|---|---|
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