CN1110865C - Hydrogen-storage alloy powder for MH-Ni secondary battery - Google Patents
Hydrogen-storage alloy powder for MH-Ni secondary battery Download PDFInfo
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- CN1110865C CN1110865C CN00123177A CN00123177A CN1110865C CN 1110865 C CN1110865 C CN 1110865C CN 00123177 A CN00123177 A CN 00123177A CN 00123177 A CN00123177 A CN 00123177A CN 1110865 C CN1110865 C CN 1110865C
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- 239000000956 alloy Substances 0.000 title claims abstract description 58
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 58
- 239000000843 powder Substances 0.000 title claims abstract description 32
- 229910017704 MH-Ni Inorganic materials 0.000 title claims abstract description 19
- 229910017739 MH—Ni Inorganic materials 0.000 title claims abstract description 19
- 238000003860 storage Methods 0.000 title abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 230000006698 induction Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000007670 refining Methods 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000001996 bearing alloy Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 5
- 229910052786 argon Inorganic materials 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract 2
- 229910005518 NiaCobMnc Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 238000010998 test method Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- -1 nickel metal hydride Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a high-capacity long-life hydrogen-storage alloy powder for high-performance MH-Ni secondary battery and its preparation method, its chemical structural formula is Mm1-x-y-zLaxPryNdzNiaCobMncAldMeWhere Mm is a mixtureThe rare earth metal Ce is more than or equal to 45 percent, La is more than or equal to 20 percent, M is one or more of Ti, Zr, V, Mo, Fe, B and Sn, and the preparation method comprises the steps of placing raw materials in a vacuum induction melting furnace, vacuumizing, filling argon, refining for 5-30 minutes after complete melting, pouring into a water cooling mold, preserving the heat of an alloy ingot in argon at 900-1200 ℃ for 2-10 hours, and preparing powder by a semi-closed machine of the alloy ingot after heat treatment under the protection of nitrogen. The hydrogen storage alloy powder has the characteristics of high capacity, long service life, moderate PCT curve plateau pressure and low oxygen content, and is particularly suitable for high-performance MH-Ni secondary batteries.
Description
Technical field: the present invention relates to a kind of MH-Ni secondary cell its manufacture method of hydrogen storing alloy powder, this alloyed powder is mainly used in high-performance MH-Ni secondary cell, as negative electrode active material.
Background technology: at present, the MH-Ni secondary cell that countries in the world produce mainly all is to adopt rare earth based AB
5Type hydrogen storage alloy is Mm (NiCoMnAl)
5, wherein Mm be norium (1. US 5,306,583 2. US 5,490,970 3. US 5,537,390 4. the spy open 5. CN 1153404A of flat 8-45505), AB
5The type hydrogen storage alloy combination property is better, especially inhale hydrogen desorption kinetics characteristic and cycle life and be better than the other types hydrogen storing alloy powder, but its electrochemical discharge capacity is not high, generally in the 290-310mAh/g scope.Along with the continuous development of modern portable telecommunication apparatus, electronic equipment, electric tool and electric motor car, the specification requirement of its used MH-Ni secondary cell is also being improved constantly, like this, correspondingly require to have high performance hydrogen storing alloy powder and be complementary with it.
In order to improve the discharge capacity of rare earth based hydrogen storing alloy powder, the researcher has developed a kind of hydrogen bearing alloy that contains more rare earth metal (1. T.Sakai et al., J.Alloys And Compounds., 180 (1992) 37 2. ministry of electronics industry's power supply staff intelligence nets, nickel metal hydride battery, 1994 (5) 1), discharge capacity can improve 10%, but because the increase of content of rare earth, the alkaline-resisting etch ability drop of alloy, the alloy unit cell volume expands and increases, and the alloy pulverization rate improves, and has shortened MH-Ni secondary cell cycle life.Japanese patent laid-open 10-188972 and 10-1022172 propose a kind of AB
xThe non-stoichiometry hydrogen bearing alloy, x is 5.1-5.5, has improved alloy life, but discharge capacity is less than 300mAh/g.
By the hydrogen bearing alloy that the vacuum induction melting casting is produced, though adopt water cooled mo(u)ld cold soon, still there is certain segregation in alloy composition, and this alloy is not corrosion-resistant and inhale and put the easy efflorescence of hydrogen process in alkali lye.By being heat-treated, it can improve the alloy composition uniformity effectively, eliminate crystal lattice stress, suppressed alloy pulverization, thereby prolonged alloy life (1. J.H.Guo et al., J.Alloys AndCompaunds., 293-295 (1999) 821 is ITE Battery Newsletter 2., and 1 (1997) 42).
Summary of the invention: the object of the present invention is to provide a kind of high-performance, high power capacity, long-life MH-Ni secondary cell hydrogen storing alloy powder and manufacture method thereof.
For achieving the above object, the invention provides a kind of high property MH-Ni secondary cell hydrogen storing alloy powder, it is characterized in that: chemical structural formula is Mm
L-x-y-zLa
xPr
yNd
zCi
aCo
bMn
cAl
dM
e, wherein Mm is a norium, Ce content 〉=45%, La content 〉=20%, M is Ti, Zr, V, Mo, Fe, B and Sn a kind of element or multiple element wherein mixes, 0.55≤x≤0.95,0.01≤y≤0.25,0.04≤z≤0.40,3.50≤a≤4.50,0.40≤b≤1.00,0.20≤c≤0.60,0.20≤d≤0.60,5.05≤a+b+c+d+e≤5.50,0≤e≤0.10; Its preferable range is 0.60≤X≤0.90,5.10≤a+b+c+d+e≤5.40,0≤e≤0.05; Its manufacture method is for pressing hydrogen bearing alloy chemical structural formula Mm
L-x-y-zLa
xPr
yNd
zNi
aCo
bMn
cAl
dM
ePrepare burden, the raw material of having joined is packed in magnesium oxide or the alumina crucible, adopt the intermediate frequency vacuum induction melting, vacuum degree reaches 0.01-0.5Pa, charge into inert gas,, melt is poured into cooling fast in the water cooled mo(u)ld through refining in 5-30 minute, cooldown rate 10-100 ℃/s, the thick 20-50mm of alloy pig; Under inert gas shielding, alloy pig was 900-1200 ℃ of insulation 2-10 hour; Alloy pig after the heat treatment is slightly broken to 3-5mm, and through the powder process of semi-enclosed impact grinding machinery, crushing process all adopts inert gas shielding again; If employing vacuum induction melting, alloy pig are cold soon; Alloy pig was 950-1150 ℃ of insulation 4-8 hour under inert gas shielding; Semi-enclosed impact grinding machinery powder process under inert gas shielding.
The present invention is by adjusting the content of La, Ce, Pr and Nd in the alloy, improved alloy electrochemical discharge capacity, adopt non-stoichiometric 1: (5.05-5.50) improved alloy cycle life, two kinds of methods are gone back scalable hydrogen bearing alloy PCT curve plateau pressure simultaneously.The metallic element M that adds forms second phase on the crystal boundary of alloy, improved the caustic corrosion resistance and the anti-efflorescence ability of alloy, has prolonged the MH-Ni battery cycle life.
Description of drawings: accompanying drawing 1 is put the hydrogen curve for the PCT of hydrogen storing alloy powder under 45 ℃.
Accompanying drawing 2 is put the hydrogen curve for heat treatment and the PCT of non-heat treatment hydrogen storing alloy powder under 45 ℃.
Embodiment: be described in more detail the present invention below by embodiment and comparative example:
Embodiment 1
Chemical structural formula Mm by design
0.30La
0.55Pr
0.05Nd
0.10Ni
3.65Co
0.75Mn
0.4Al
0.25(a+b+c+d=5.05) prepare burden, material purity adopts homemade 25kg vacuum induction melting all greater than 99%, is evacuated to 10
-1Pa charges into argon gas, and pressure is-0.05MPa, and raw material all melts back refining 10 minutes, controls certain pouring temperature, with melt cast in water cooled mo(u)ld, the thick 30mm of alloy pig.Ingot casting is incubated 8 hours down at 950 ℃, and protection gas is argon gas in the stove.Alloy pig after the heat treatment adopts U.S.'s import impact grinding semiclosed mechanical powder process under nitrogen protection with jaw crusher is slightly broken then to 3-5mm under nitrogen protection, the alloyed powder of output is by 140 order vibrating screens.The oxygen content of hydrogen storing alloy powder is 0.078%.
The PCT of hydrogen storing alloy powder (pressure-composition-temperature) curve is by the test of U.S. import computer controlled automatic Sieverts reactor, and the theoretical discharge capacity of hydrogen storing alloy powder can be by Q=26800 * H/M
2(mAh/g) obtain, H/M be hydrogen balance when being pressed in 1.0MPa every mole of alloy put the hydrogen molal quantity, M is the molecular weight of alloy.
The electrochemical discharge capacity test method of hydrogen storing alloy powder is: accurately take by weighing hydrogen storing alloy powder 0.200g and nickel powder 0.800g by 1: 4 mass ratio, the hydrogen storing alloy powder and the nickel powder that weigh up are mixed, pour in the mould, pressure with 5MPa is pressed into diameter Ф 13mm garden sheet shape electrode, with nickel strap electrode is clamped, inserting in the KOH electrolyte of 6mol/L, to be reference electrode with Solution H g/HgO, is that auxiliary electrode is formed three-electrode system with two sintered nickel electrodes.On U.S. Maccor battery combined test stand, discharge and recharge, with 60mA/g current charges 7.5h, had a rest 30 minutes, again with the 60mA/g current discharge to-0.74V vs.Hg/HgO, had a rest 30 minutes, circulate, getting high discharge capacity is the electrochemical discharge capacity of hydrogen storing alloy powder next time again.
MH-Ni battery cycle life method of testing is: the anodal Ni (OH) that adopts
2Foam nickel electrode, negative pole adopts the perforation nickel plated steel strip electrode that applies hydrogen storing alloy powder, through reeling, annotate alkali, roll ditch, seal, change into sorting and be made into AA type MH-Ni battery, rated capacity is 1300mAh, the charging of 1C multiplying power ,-Δ V=10mV control, the 1C multiplying power discharging is to 1.0V, each was not had a rest between the step, and 80% o'clock the cycle-index that discharge capacity drops to initial capacity is the cycle life of battery.The results are shown in Table 1 and accompanying drawing 1.
Embodiment 2
Chemical structural formula Mm by design
0.30La
0.55Pr
0.05Nd
0.10Ni
3.65Co
0.75Mn
0.4Al
0.3Prepare burden, its manufacture method and method of testing the results are shown in Table 1 and accompanying drawing 2 with embodiment 1 except that heat treatment temperature and asynchronism(-nization).
Embodiment 3
Chemical structural formula Mm by design
0.10La
0.75Pr
0.05Nd
0.10Ni
3.9Co
0.65Mn
0.35Al
0.3Zr
0.05Prepare burden, its manufacture method and method of testing the results are shown in Table 1 and accompanying drawing 1 with embodiment 1 except that heat treatment temperature and asynchronism(-nization).
Embodiment 4
Chemical structural formula Mm by design
0.15La
0.70Pr
0.05Nd
0.10Ni
3.9Co
0.7Mn
0.3Al
0.3Prepare burden, its manufacture method and method of testing the results are shown in Table 1 and accompanying drawing 1 with embodiment 1 except that heat treatment temperature and asynchronism(-nization).Comparative example 1--3
Respectively by the chemical structural formula Mm that designs
0.50La
0.40Pr
0.05Nd
0.05Ni
3.6Co
0.7Mn
0.4Al
0.3, Mm
0.30La
0.55Pr
0.05Nd
0.10Ni
3.65Co
0.75Mn
0.4Al
0.25And Mm
0.80La
0.10Pr
0.05Nd
0.05Ni
3.55Co
0.75Mn
0.4Al
0.3Prepare burden, its manufacture method and method of testing are with embodiment 1, and wherein comparative example 2 does not adopt Technology for Heating Processing, the results are shown in Table 1, accompanying drawing 1 and accompanying drawing 2.
By above embodiment and comparative example as seen, by hydrogen bearing alloy chemical structural formula of the present invention and the prepared hydrogen storing alloy powder of manufacture method, the electrochemical discharge capacity is greater than 320mAh/g, reach as high as 333mAh/g, cycle life is greater than 550 cycles, PCT curve platform be pressed between the 0.01-0.1Mpa and platform smooth, oxygen content is specially adapted to high-performance MH-Ni secondary cell less than 0.10%.
Claims (4)
1. a MH-Ni secondary cell hydrogen storing alloy powder is characterized in that chemical structural formula is: Mm
L-x-y-zLa
xPr
yNd
zNi
aCo
bMn
cAl
dM
e, wherein Mm is a norium, Ce content 〉=45%, La content 〉=20%, M is Ti, Zr, V, Mo, Fe, B and Sn a kind of element or multiple element wherein mixes, 0.55≤X≤0.95,0.01≤y≤0.25,0.04≤z≤0.40,3.50≤a≤4.50,0.40≤b≤1.00,0.20≤c≤0.60,0.20≤d≤0.60,5.05≤a+b+c+d+e≤5.50,0≤e≤0.10.
2. by the described MH-Ni secondary cell of claim 1 hydrogen storing alloy powder, it is characterized in that 0.60≤X≤0.90,5.10≤a+b+c+d+e≤5.40,0≤e≤0.05.
3. a MH-Ni secondary cell is characterized in the manufacture method of hydrogen storing alloy powder:
(1) described hydrogen bearing alloy chemical structural formula Mm
L-x-y-zLa
xPr
yNd
zNi
aCo
bMn
cAl
dM
ePrepare burden, the raw material of having joined is packed in magnesium oxide or the alumina crucible, adopt the intermediate frequency vacuum induction melting, vacuum degree reaches 0.01-0.5Pa, charge into inert gas,, melt is poured into cooling fast in the water cooled mo(u)ld through refining in 5-30 minute, cooldown rate 10-100 ℃/s, the thick 20-50mm of alloy pig.
(2) under inert gas shielding, alloy pig was 900-1200 ℃ of insulation 2-10 hour.
(3) alloy pig after the heat treatment is slightly broken to 3-5mm, and through the powder process of semi-enclosed impact grinding machinery, crushing process all adopts inert gas shielding again.
4. the MH-Ni secondary cell according to claim 3 manufacture method of hydrogen storing alloy powder is characterized in that: alloy pig was 950-1150 ℃ of insulation 4-8 hour under inert gas shielding.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00123177A CN1110865C (en) | 2000-10-31 | 2000-10-31 | Hydrogen-storage alloy powder for MH-Ni secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00123177A CN1110865C (en) | 2000-10-31 | 2000-10-31 | Hydrogen-storage alloy powder for MH-Ni secondary battery |
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| Publication Number | Publication Date |
|---|---|
| CN1290048A CN1290048A (en) | 2001-04-04 |
| CN1110865C true CN1110865C (en) | 2003-06-04 |
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|---|---|---|---|
| CN00123177A Expired - Fee Related CN1110865C (en) | 2000-10-31 | 2000-10-31 | Hydrogen-storage alloy powder for MH-Ni secondary battery |
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| CN102286678A (en) * | 2011-08-27 | 2011-12-21 | 宁波申江科技股份有限公司 | Non-stoichiometric-ratio LaNi5 base cobalt-free hydrogen storage alloy and preparation method thereof |
| CN106602048B (en) * | 2017-03-02 | 2019-03-22 | 辽宁九夷能源科技有限公司 | A kind of resistance to deep discharge nickel-metal hydride battery and preparation method thereof |
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