CN103436738A - Praseodymium-free, neodymium-free and cobalt-free high capacity superlattice hydrogen storage alloy containing magnesium - Google Patents
Praseodymium-free, neodymium-free and cobalt-free high capacity superlattice hydrogen storage alloy containing magnesium Download PDFInfo
- Publication number
- CN103436738A CN103436738A CN2013103629010A CN201310362901A CN103436738A CN 103436738 A CN103436738 A CN 103436738A CN 2013103629010 A CN2013103629010 A CN 2013103629010A CN 201310362901 A CN201310362901 A CN 201310362901A CN 103436738 A CN103436738 A CN 103436738A
- Authority
- CN
- China
- Prior art keywords
- hydrogen storage
- storage alloy
- alloy
- free
- superlattice
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to praseodymium-free, neodymium-free and cobalt-free high capacity superlattice hydrogen storage alloy containing magnesium. The alloy is characterized in that a composite chemical formula of the alloy is one of Mm(1-x-y)LaxMgyNiaAlb, Mn(1-x-y-z)LaxMgyMzNiaAlb, Mm(1-x-y)LaxMgyNiaAlbNc or Mm(1-x-y-z)LaxMgyMzNiaAlbNc, wherein Mm is rare earth or misch metal at least containing one or more than one of La, Ce, Y, Sm and Gd; M is one or more than one of Ti, Zr and Hf; N is one or more than one of Mn, Sn, Cr, V, W and Mo; x, y, z, a, b and c represent molar ratios. Compared with the prior art, the alloy has the advantages of large discharge capacity, low cost and good low self discharge property.
Description
Technical field
The present invention relates to the hydrogen storage alloy field, relate in particular to a kind of without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy.
Background technology
Along with the lasting rising of rare earth price, especially increasing substantially of the rare earth metal such as praseodymium Pr, neodymium Nd, brought great pressure to the production cost of the rare earth downstream industries such as magneticsubstance, nickel metal hydride battery.Especially the nickel metal hydride battery industry, due to the competition that faces other batteries such as lithium ion battery, do not had the advantage on cost, and consumption market faces the danger of atrophy gradually, coverd with shade to the development destiny of industry.
How, under the prerequisite that keeps the 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.There is the plurality of advantages such as loading capacity is high, self-discharge is low, thermal adaptability is good containing the magnesium superlattice hydrogen storage alloy, be considered to nickel-hydrogen battery negative pole alloy material storing hydrogen of new generation.Yet, at present application containing the magnesium superlattice hydrogen storage alloy, mostly be the component that PrNd content is higher, as CN200310124842.X and CN200610154332.0.Doubly, the cost of the alloy of such formula has very large inferior position to the 4-6 that is about the high abundance rare earth prices such as La, Ce due to the current price of Pr, Nd, and the loading capacity of such alloy is difficult to improve.Therefore, in the urgent need to develop a kind of without the praseodymium neodymium, without the low-cost high capacity type of cobalt containing the magnesium superlattice hydrogen storage alloy.
Summary of the invention
The purpose of this invention is to provide a kind of without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, in the loading capacity that improves hydrogen storage alloy, make the content of middle Pr, Nd element and the Co element of alloy be reduced to 0, farthest reduce production costs, improve the market competitiveness of hydrogen storage alloy.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, the chemical formulation that its one-tenth is grouped into is: Mm
1-x-yla
xmg
yni
aal
b, wherein, Mm is rare earth or norium, contains one or more in La, Ce, Y, Sm, Gd; X, y, a, b mean 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 further improving the performance of alloy, during being grouped into, described one-tenth also comprises 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 means mol ratio, and its numerical range is: 0<c≤0.1,0.5≤x≤0.75,0.25<y<0.4, a>=2.5,0<b<0.2,2.8≤a+b+c≤4.0 simultaneously.
Above-mentioned a kind of without the praseodymium neodymium, without the heavy body of cobalt, containing in magnesium superlattice hydrogen storage alloy component, can comprise M
z, 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 means mol ratio, and its numerical range is: 0<z≤0.05, simultaneously, 0.5≤x≤0.75,0.25<y<0.4, a>=2.5,0<b<0.2,2.8≤a+b≤4.0.
For further improving the performance of alloy, during being grouped into, described one-tenth also comprises 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 means mol ratio, and its numerical range is: 0<c≤0.1, simultaneously, 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 ℃ of conditions of this hydrogen storage alloy is put hydrogen platform pressure.
Described hydrogen storage alloy is comprised of heterogeneous, and at least contains PuNi
3type, Ce
2ni
7type, Ce
5co
19type, Pr
5co
19one or more in mutually of type superlattice, be that 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 the strongest characteristic diffraction peak in this zone and diffracting spectrum the intensity rate of strong characteristic diffraction peak be 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, the good characteristics of the high and low self-discharge performance of loading capacity, do not contain Pr, Nd and Co element in alloy, the market competitiveness is extremely strong, can be widely used in a plurality of nickel metal hydride battery Application Areass such as high capacity type nickel metal hydride battery and low self-discharge nickel metal hydride battery.
The 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 component contrast 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, contains 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 component 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) prepared burden according to chemical formula, the raw material prepared is put into to the crucible of vacuum melting furnace;
2) be evacuated to≤0.5Pa of vacuum melting furnace is filled with rare gas element in vacuum induction melting furnace, control inflation pressure to be-0.09MPa～-0.06MPa;
3) vacuum melting furnace starts to be heated to 1000～1600 ℃, in stove material melting evenly after, stop heating;
4) start feeding chamber, metal M g is joined in solution, make melt temperature keep stable, guarantee that Mg fully melts, refining, after 3～5 minutes, stops heating;
5) after liquation reaches 1150～1350 ℃, 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 to vacuum heat treatment furnace and heat-treat, heat treatment process is carried out under the protection of rare gas element, and thermal treatment temp is 800～1200 ℃, and soaking time is 3～20 hours;
7) by alloy block or alloy slice through the cooling impact grinding of low temperature liquid nitrogen or airflow milling powder, make the hydrogen storing alloy powder that median size is 30～80um.
PCT test Japan Suzuki Co., Ltd. produces on the PCT tester and carries out, and test condition is: 45 ℃ charge and discharge hydrogen, and the hydrogen pressure value of putting while getting H/M=3 is pressed as the PCT platform.
The electrochemical test method of hydrogen storing alloy powder is: by the 1:4 mass ratio, weigh hydrogen storing alloy powder 0.2g and nickel powder 0.8g, load weighted hydrogen storing alloy powder and nickel powder are mixed, pour in mould, be pressed into the disc electrode of diameter 13mm with the pressure of 8Mpa, with nickel strap, electrode is clamped, be placed in 6mol/L KOH electrolytic solution, take same Solution H g/HgO as reference electrode, take two sintered nickel electrodes as supporting electrode composition three-electrode system.On U.S. arbin electrochemical test, under 20 ± 5 ℃ of conditions of envrionment temperature, 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 the 60mA/g current discharge to-0.74V vs.Hg/HgO, have a rest 30 minutes, circulate again next time, get the electrochemistry capacitance of the powder that high discharge capacity is 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, with be discharged to-0.65V of 300mA/g VS.Hg/HgO, the circulation said process, be circulated to continuous 3 loading capacities lower than 80% of alloy powder 1C maximum discharge capacity when discharging and recharging parameter again, charge and discharge cycles cycle life while loading capacity being reached to 80% is considered as cycle life, and test result is as table 2.
The self-discharge performance force test method is: use this alloy powder, be prepared into the MH-Ni battery, test the self-discharge of MH-Ni battery.To be full of electric MH-Ni battery and be held in 45 ℃ of thermostat containers insulation 28 days, then take out the MH-Ni battery, at room temperature electric discharge, its loading capacity is MH-Ni battery charge retention rate with putting into thermostat container volume percent before, deduct MH-Ni battery charge retention rate with 100 again, be MH-Ni self-discharge of battery rate, test result is as table 2.
The XRD(X ray diffraction) anode of producing in company of science turns on the target X-ray diffractometer and carries out, and test condition is: 50KV, 150mA, step-length 0.02 degree, and every step 1 second of integral time, test specification is the 20-80 degree, the XRD test result is as Fig. 3.Utilize the XRD result of Rietveld method alloy to carry out quantitative analysis, thereby determine phase composite and the weight percentage of alloy, as table 3.
Prepare comparative example 1
Tradition 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
0.2prepared 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, is crossed 200 eye mesh screens, makes 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
0.25prepared 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, is crossed 200 eye mesh screens, makes 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
5high 15% left and right of type hydrogen storage alloy; Cycle life and conventional commercial high capacity type AB
5hydrogen storing alloy powder is close; The PCT platform is pressed moderate; Self-discharge rate is low.There is no Pr, Nd and Co element in alloy, reduce costs very obvious; Wherein, the alloy that casting technique is made, have higher loading capacity, and the alloy that rejection tablet technique is made, have 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 has been described in detail to the present invention,, it will be appreciated by those skilled in the art that still and can modify or be equal to replacement the present invention; All do not break away 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 (6)
- One kind without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, it is characterized in that, the chemical formulation that its one-tenth is grouped into is: Mm 1-x-yla xmg yni aal b, wherein, Mm is rare earth or norium, contains one or more in La, Ce, Y, Sm, Gd; X, y, a, b mean 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.
- According to claim 1 a kind of without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, it is characterized in that, also comprise N during described one-tenth is grouped into 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 means mol ratio, and its numerical range is: 0<c≤0.1,0.5≤x≤0.75,0.25<y<0.4, a>=2.5,0<b<0.2,2.8≤a+b+c≤4.0 simultaneously.
- One kind without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, it is characterized in that, the chemical formulation that its one-tenth is grouped into is: Mm 1-x-y-zla xmg ym zni aal b, M is one or more in Ti, Zr, Hf; Z means mol ratio, and its numerical range is: 0<z≤0.05, simultaneously, 0.5≤x≤0.75,0.25<y<0.4, a>=2.5,0<b<0.2,2.8≤a+b≤4.0.
- According to claim 3 a kind of without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, it is characterized in that, also comprise N during described one-tenth is grouped into 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 means mol ratio, and its numerical range is: 0<c≤0.1, simultaneously, 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.
- According to claim 1,2,3 or 4 described a kind of without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, it is characterized in that, it is 0.01～0.05MPa that the PCT curve under 45 ℃ of conditions of this hydrogen storage alloy puts that the hydrogen platform presses.
- According to claim 1,2,3 or 4 described a kind of without the praseodymium neodymium, without the heavy body of cobalt containing the magnesium superlattice hydrogen storage alloy, it is characterized in that, described hydrogen storage alloy is comprised of heterogeneous, and at least contains PuNi 3type, Ce 2ni 7type, Ce 5co 19type, Pr 5co 19one or more in mutually of type superlattice, be that 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 the strongest characteristic diffraction peak in this zone and diffracting spectrum the intensity rate of strong characteristic diffraction peak be not less than 0.15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310362901.0A CN103436738B (en) | 2013-08-16 | 2013-08-16 | A kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310362901.0A CN103436738B (en) | 2013-08-16 | 2013-08-16 | A kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103436738A true CN103436738A (en) | 2013-12-11 |
| CN103436738B CN103436738B (en) | 2016-04-27 |
Family
ID=49690451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310362901.0A Expired - Fee Related CN103436738B (en) | 2013-08-16 | 2013-08-16 | A kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103436738B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779822A (en) * | 2016-04-06 | 2016-07-20 | 广州有色金属研究院 | Hydrogen storage alloy for nickel-hydrogen power battery |
Citations (2)
| 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 |
-
2013
- 2013-08-16 CN CN201310362901.0A patent/CN103436738B/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105779822A (en) * | 2016-04-06 | 2016-07-20 | 广州有色金属研究院 | Hydrogen storage alloy for nickel-hydrogen power battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103436738B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102828069B (en) | Praseodymium-neodymium-free low-cost superlong life type hydrogen storage alloy and preparation method thereof | |
| CN102226243B (en) | Magnesium-containing superlattice hydrogen storage alloy and preparation method thereof | |
| CN104195372A (en) | Rare earth-magnesium-nickel system heterogeneous hydrogen storage alloys used for nickel-hydrogen batteries and preparing method thereof | |
| CN102104146B (en) | Cobalt-free AB3.5-type hydrogen storage alloy anode material used for nickel-hydrogen battery and preparation method thereof | |
| CN108893656B (en) | La-Mg-Ni system A2B7Hydrogen storage alloy and preparation method thereof | |
| CN102758104A (en) | Low-cobalt and praseodymium-neodymium-free AB5 type hydrogen storage alloy with low cost and preparation method thereof | |
| CN105274395B (en) | La-Mg-Ni hydrogen storage material | |
| CN101613818B (en) | Low cost hydrogen storage alloy, preparation method and application thereof | |
| CN110257649A (en) | A kind of High-performance Single-Phase La0.6R0.15Mg0.25Ni3.5Electrode metal and preparation method thereof | |
| CN111118341B (en) | Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method | |
| CN108511742A (en) | A kind of single-phase A2B7Type superlattices praseodymium-magnesium-nickel-base alloy electrode material and preparation method thereof | |
| CN108149073A (en) | Low-temperature nickel-hydrogen battery La-Mg-Ni base hydrogen storage alloys and preparation method thereof | |
| CN104451219B (en) | A kind of containing A2b7the A of phase5b19the preparation method of type RE-Mg-Ni series hydrogen storage alloy | |
| CN108588495B (en) | AB with high capacity and long service life4.5Hydrogen storage alloy and preparation method thereof | |
| CN104404280A (en) | Preparation method for superlattice RE-Mg-Ni hydrogen storage alloy | |
| CN102383011B (en) | Rare earth magnesium-based hydrogen storage alloy with low cost and long life and applications thereof | |
| CN101899591B (en) | Superlattice hydrogen storage alloy material for nickel hydrogen battery and preparation method thereof | |
| CN106544535B (en) | Preparation method of hydrogen storage alloy containing yttrium and nickel elements | |
| CN104294087B (en) | The preparation method of superlattice hydrogen storage alloy | |
| CN103436738B (en) | A kind of without praseodymium neodymium, without the heavy body of cobalt containing magnesium superlattice hydrogen storage alloy | |
| CN102888539B (en) | A kind of there is ultra-high capacity characteristic low cost AB5 type hydrogen-storage alloy and method for making and application | |
| CN114107740B (en) | Low-cost high-performance rare earth hydrogen storage alloy and preparation method thereof | |
| CN111471893B (en) | Doped A5B19Gadolinium-containing hydrogen storage alloy, electrode, battery and preparation method thereof | |
| CN105463256B (en) | A kind of Hydrogen storage alloy for nickel-metal hydride battery and preparation method thereof | |
| CN111224092B (en) | Zirconium or titanium doped samarium-containing hydrogen storage alloy, negative electrode, battery and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160427 Termination date: 20210816 |