CN103436738B - A kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy - Google Patents

A kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy Download PDF

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CN103436738B
CN103436738B CN201310362901.0A CN201310362901A CN103436738B CN 103436738 B CN103436738 B CN 103436738B CN 201310362901 A CN201310362901 A CN 201310362901A CN 103436738 B CN103436738 B CN 103436738B
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hydrogen storage
storage alloy
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CN103436738A (en
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王常春
姜波
迟新宇
沈欣
柳立
张远
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BAOTOU XINPU NEW MATERIAL Co Ltd
ANSHAN KINGPOWERS ADVANCED MATERIALS Co Ltd
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BAOTOU XINPU NEW MATERIAL Co Ltd
ANSHAN KINGPOWERS ADVANCED MATERIALS Co Ltd
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Abstract

The present invention relates to a kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy, it is characterized in that, chemical formula of its composition is: Mm 1-x-yla xmg yni aal b, Mm 1-x-y-zla xmg ym zni aal b, Mm 1-x-yla xmg yni aal bn cor Mm 1-x-y-zla xmg ym zni aal bn cin one, wherein, Mm is rare earth or norium, at least containing one or more in La, Ce, Y, Sm, Gd; M is one or more in Ti, Zr, Hf; N is one or more in Mn, Sn, Cr, V, W, Mo; X, y, z, a, b, c represent mol ratio.Compared with prior art, advantage of the present invention is: loading capacity is large, cost is low, low self-discharge performance is good.

Description

A kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy
Technical field
The present invention relates to hydrogen storage alloy field, particularly relate to a kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy.
Background technology
Along with the lasting rising of rare earth price, especially the increasing substantially of the rare earth metal such as praseodymium Pr, neodymium Nd, brings great pressure to the production cost of the rare earth such as magneticsubstance, nickel metal hydride battery downstream industry.Especially nickel metal hydride battery industry, owing to facing the competition of other batteries such as lithium ion battery, do not had the advantage on cost, consumption market faces the danger of atrophy gradually, has coverd with shade to the development destiny of industry.
How under the prerequisite keeping hydrogen storage alloy performance, reduce the production cost of hydrogen storage alloy, become the key point of closing series nickel-hydrogen cell industry development destiny.Containing magnesium superlattice hydrogen storage alloy, there is the plurality of advantages such as loading capacity is high, self-discharge is low, thermal adaptability is good, be considered to nickel-hydrogen battery negative pole alloy material storing hydrogen of new generation.But, contain magnesium superlattice hydrogen storage alloy what apply at present, mostly be the component that PrNd content is higher, as CN200310124842.X and CN200610154332.0.Price due to current Pr, Nd is about the 4-6 of the high abundance rare earth prices such as La, Ce doubly, and the cost of the alloy of such formula has very large inferior position, and the loading capacity of such alloy is difficult to improve.Therefore, in the urgent need to develop a kind of without praseodymium neodymium, without the low cost high capacity type of cobalt containing magnesium superlattice hydrogen storage alloy.
Summary of the invention
The object of this invention is to provide a kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy, while the loading capacity improving hydrogen storage alloy, middle Pr, Nd element of alloy and the content of Co element is made to be reduced to 0, farthest reduce production cost, improve the market competitiveness of hydrogen storage alloy.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Without praseodymium neodymium, contain a magnesium superlattice hydrogen storage alloy without the heavy body of cobalt, its chemical formulation becoming to be grouped into is: Mm 1-x-yla xmg yni aal b, wherein, Mm is rare earth or norium, containing one or more in La, Ce, Y, Sm, Gd; X, y, a, b represent mol ratio, and its numerical range is: 0.5≤x≤0.75,0.25 < y < 0.4, a>=2.5,0 < b < 0.2,2.8≤a+b≤4.0.
For improving the performance of alloy further, during described one-tenth is grouped into, also comprise N c, chemical formulation is: Mm 1-x- yla xmg yni aal bn c, N is one or more in Mn, Sn, Cr, V, W, Mo; C represents mol ratio, its numerical range is: 0 < c≤0.1, simultaneously 0.5≤x≤0.75,0.25 < y < 0.4, a>=2.5,0 < b < 0.2,2.8≤a+b+c≤4.0.
Above-mentioned a kind of without praseodymium neodymium, without the heavy body of cobalt containing comprising M in magnesium superlattice hydrogen storage alloy component z, namely the constitutional chemistry formula of alloy is expressed as: Mm 1-x-y-zla xmg ym zni aal b, M is one or more in Ti, Zr, Hf; Z represents mol ratio, its numerical range is: 0 < z≤0.05, meanwhile, 0.5≤x≤0.75,0.25 < y < 0.4, a>=2.5,0 < b < 0.2,2.8≤a+b≤4.0.
For improving the performance of alloy further, during described one-tenth is grouped into, also comprise N c, chemical formulation is: Mm 1-x-y- zla xmg ym zni aal bn c, M is one or more in Ti, Zr, Hf; N is one or more in Mn, Sn, Cr, V, W, Mo; C represents mol ratio, its numerical range is: 0 < c≤0.1, meanwhile, 0.5≤x≤0.75,0.25 < y < 0.4,0 < z≤0.05, a>=2.5,0 < b < 0.2,2.8≤a+b+c≤4.0.
It is 0.01 ~ 0.05MPa that the PCT curve under 45 DEG C of conditions of this hydrogen storage alloy puts hydrogen platform pressure.
Described hydrogen storage alloy is made up of heterogeneous, and at least containing PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type superlattice mutually in one or more, namely the XRD diffractogram of alloy sample is 31.5 ° ~ 34.5 ° in 2 θ angles and has a characteristic diffraction peak at least, and in this strongest characteristic diffraction peak in region and diffracting spectrum, the intensity rate of the strongest characteristic diffraction peak is not less than 0.15.
Compared with prior art, the invention has the beneficial effects as follows: this hydrogen storage alloy has that cost is extremely low, PCT platform pressing reason, feature that the high and low self-discharge performance of loading capacity is good, not containing Pr, Nd and Co element in alloy, the market competitiveness is extremely strong, can be widely used in multiple nickel metal hydride battery Application Areas such as high capacity type nickel metal hydride battery and low self-discharge nickel metal hydride battery.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention 1PCT curve;
Fig. 2 is the embodiment of the present invention 1 discharge curve;
Fig. 3 is embodiment of the present invention 1XRD figure.
Embodiment
Below the specific embodiment of the present invention is described further:
The Comparative of the embodiment of the present invention 1 ~ embodiment 15 is in table 1.
Table 1
In above-described embodiment, Mm is rare earth or norium, containing one or more in La, Ce, Y, Sm, Gd; M is one or more in Ti, Zr, Hf; N is one or more in Mn, Sn, Cr, V, W, Mo; Each compositional purity requires by mass percentage, La purity >=99.5%, Mm total amount of rare earth >=99.5%, Mg purity >=99.9%, Ni purity >=99.95%, Al purity >=99.5%; Hf purity >=99%; Zr purity >=99.5%; Ti purity >=99.5%; Mn purity >=99.5%, Sn >=99.5%; Cr >=99.5%; V >=99.5%; W >=99.5%; Mo >=99.5%.
In above-described embodiment 1 ~ embodiment 15, low cost heavy body is containing the preparation method of magnesium superlattice hydrogen storage alloy, and its concrete operation step is as follows:
1) prepare burden according to chemical formula, the raw material prepared is put into the crucible of vacuum melting furnace;
2) vacuum melting furnace is evacuated to≤0.5Pa, in vacuum induction melting furnace, be filled with rare gas element, and control inflation pressure is-0.09MPa ~-0.06MPa;
3) vacuum melting furnace starts to be heated to 1000 ~ 1600 DEG C, after material melting in stove is even, stops heating;
4) start feeding chamber, joined by metal M g in solution, make melt temperature keep stable, ensure that Mg fully melts, refining, after 3 ~ 5 minutes, stops heating;
5) after liquation reaches 1150 ~ 1350 DEG C, be poured into water cooled mo(u)ld or cooling roller, be cooled to alloy pig or alloy slice;
6) melted alloy block is put into vacuum heat treatment furnace to heat-treat, heat treatment process is carried out under the protection of rare gas element, and thermal treatment temp is 800 ~ 1200 DEG C, and soaking time is 3 ~ 20 hours;
7) alloy block or alloy slice are cooled impact grinding or airflow milling powder through low temperature liquid nitrogen, make the hydrogen storing alloy powder that median size is 30 ~ 80um.
PCT tests Japan Suzuki Co., Ltd. and produces on PCT tester and carry out, and test condition is: 45 DEG C of charge and discharge hydrogen, puts hydrogen pressure force value as PCT platform pressure when getting H/M=3.
The electrochemical test method of hydrogen storing alloy powder is: weigh hydrogen storing alloy powder 0.2g and nickel powder 0.8g by 1:4 mass ratio, load weighted hydrogen storing alloy powder and nickel powder are mixed, pour in mould, the disc electrode of diameter 13mm is pressed into the pressure of 8Mpa, with nickel strap, electrode is clamped, be placed in 6mol/LKOH electrolytic solution, with same Solution H g/HgO for reference electrode, with two panels sintered nickel electrode for supporting electrode forms three-electrode system.On U.S. arbin electrochemical test, under envrionment temperature 20 ± 5 DEG C of conditions, carry out charge-discharge test.
Hydrogen storing alloy powder discharge capacity test method: with 60mA/g current charges 7.5h, have a rest 30 minutes, then with 60mA/g current discharge to-0.74Vvs.Hg/HgO, have a rest 30 minutes, circulate again next time, get the electrochemistry capacitance that most high discharge capacity is the powder of hydrogen storage alloy.
The testing method of hydrogen storing alloy powder cycle life: by the testing method of above-mentioned survey maximum discharge capacity, after determining the maximum discharge capacity of hydrogen storage alloy, with 300mA/g charging 75min, suspend 10min, be discharged to-0.65VVS.Hg/HgO with 300mA/g again, circulation said process, when discharge and recharge parameter cyclic to continuous 3 loading capacities lower than 80% of alloy powder 1C maximum discharge capacity, charge and discharge cycles cycle life when namely loading capacity being reached 80% is considered as cycle life, and test result is as table 2.
Self-discharge performance force test method is: use this alloy powder, is prepared into MH-Ni battery, tests the self-discharge of MH-Ni battery.The MH-Ni battery being full of electricity is held in 45 DEG C of thermostat containers and is incubated 28 days, then MH-Ni battery is taken out, at room temperature discharge, its loading capacity is MH-Ni battery charge retention rate with the volume percent before putting into thermostat container, MH-Ni battery charge retention rate is deducted again with 100, be MH-Ni battery self discharge rate, test result is as table 2.
XRD(X ray diffraction) anode produced in company of science turns on target X-ray diffractometer and carries out, and test condition is: 50KV, 150mA, step-length 0.02 degree, and often walk second integral time 1, test specification is 20-80 degree, and XRD test result is as Fig. 3.Utilize the XRD result of Rietveld method alloy to carry out quantitative analysis, thus determine phase composite and the weight percentage of alloy, as table 3.
Prepare comparative example 1
Conventional high capacity type AB 5hydrogen storing alloy powder, according to chemical formula Pr 0.03nd 0.1la 0.63ce 0.24ni 3.8co 0.65mn 0.4al 0.2prepare burden, La purity>=99.5%, Ce purity>=99.5%, Mm total amount of rare earth>=99.5%, Ni purity>=99.95%; Co purity>=99.95%; Mn purity>=99.95%; Al purity>=99.5%.Alloy, after vacuum induction melting, vacuum heat treatment and low-temperature impact abrasive dust are broken, are crossed 200 eye mesh screens, is made the alloy powder that median size is 35-50um.
Prepare comparative example 2
Conventional commercial power type AB 5hydrogen storing alloy powder, according to chemical formula Pr 0.05nd 0.15la 0.6ce 0.20ni 4.0co 0.45mn 0.4al 0.25prepare burden, La purity>=99.5%, Ce purity>=99.5%, Mm total amount of rare earth>=99.5%, Ni purity>=99.95%; Co purity>=99.95%; Mn purity>=99.95%; Al purity>=99.5%.Alloy, after vacuum induction melting, vacuum heat treatment and low-temperature impact abrasive dust are broken, are crossed 200 eye mesh screens, is made the alloy powder that median size is 35-50um.
Table 2
Table 3
As shown in Table 2, of the present invention have following features without cobalt without the low cost heavy body superlattice type hydrogen storage alloy of praseodymium neodymium: loading capacity is high, and maximum discharge capacity is than conventional commercial AB 5type hydrogen storage alloy is high by about 15%; Cycle life and conventional commercial high capacity type AB 5hydrogen storing alloy powder is close; PCT platform pressure is moderate; Self-discharge rate is low.There is no Pr, Nd and Co element in alloy, reduce costs clearly; Wherein, the alloy that casting technique makes, has higher loading capacity, and the alloy that rejection tablet technique makes has higher cycle life.In sum, this type alloy has high cost performance.
It should be pointed out that the above embodiment can make the present invention of those skilled in the art's comprehend, but do not limit the present invention in any way.Therefore, although this specification sheets is to present invention has been detailed description, it will be appreciated by those skilled in the art that and still can modify to the present invention or equivalent replacement; All do not depart from technical scheme and the improvement thereof of spirit of the present invention, and it all should be encompassed in the middle of protection scope of the present invention.

Claims (9)

1. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.15la 0.5mg 0.35ni 3.2al 0.10, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively Ce 2ni 7type 52%, Ce 5co 19type 25%, Pr 5co 19type 23%.
2. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.11la 0.5mg 0.39ni 2.79al 0.01, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 9%, Ce 2ni 7type 49%, Ce 5co 19type 15%, Pr 5co 19type 27%.
3. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.05la 0.6mg 0.35ni 3.4al 0.10, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 10%, Ce 2ni 7type 48%, Ce 5co 19type 16%, Pr 5co 19type 26%.
4. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.11la 0.5mg 0.39ni 3.2al 0.05sn 0.1, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 5%, Ce 2ni 7type 19%, Ce 5co 19type 9%, Pr 5co 19type 67%.
5. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.11la 0.5mg 0.39ni 3.2al 0.10sn 0.05, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 10%, Ce 2ni 7type 37%, Ce 5co 19type 16%, Pr 5co 19type 37%.
6. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.14la 0.5ti 0.03mg 0.33ni 3.2al 0.15cr 0.05, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, PuNi 3type, Ce 2ni 7type, Pr 5co 19type, described CaC u5type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 8%, PuNi 3type 51%, Ce 2ni 7type 23%, Pr 5co 19type 18%.
7. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.16la 0.5hf 0.01mg 0.33ni 3.2al 0.14w 0.01, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described CaC u5type, PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 12%, PuNi 3type 17%, Ce 2ni 7type 32%, Ce 5co 19type 18%, Pr 5co 19type 21%.
8. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.15la 0.5mg 0.35ni 3.2al 0.09mo 0.01, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described CaC u5type, PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 9%, PuNi 3type 9%, Ce 2ni 7type 42%, Ce 5co 19type 16%, Pr 5co 19type 24%.
9. without praseodymium neodymium, without the heavy body of cobalt containing a magnesium superlattice hydrogen storage alloy, it is characterized in that, its chemical formulation becoming to be grouped into is: Mm 0.1la 0.5mg 0.35ti 0.05ni 3.65al 0.15, each component content is molar ratio, and wherein, Mm is rare earth or norium, containing one or more in Ce, Y, Sm, Gd; Described hydrogen storage alloy is made up of heterogeneous, comprises CaC u5type, PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19type, described CaC u5type, PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19the phase content of type is respectively CaC u5type 10%, PuNi 3type 17%, Ce 2ni 7type 31%, Ce 5co 19type 19%, Pr 5co 19type 23%.
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CN1563453A (en) * 2004-04-01 2005-01-12 桂林电子工业学院 rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method
CN102104145A (en) * 2009-12-17 2011-06-22 三洋电机株式会社 Hydrogen-absorbing alloy, fabrication method thereof and alkaline storage battery

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Publication number Priority date Publication date Assignee Title
CN1563453A (en) * 2004-04-01 2005-01-12 桂林电子工业学院 rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method
CN102104145A (en) * 2009-12-17 2011-06-22 三洋电机株式会社 Hydrogen-absorbing alloy, fabrication method thereof and alkaline storage battery

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