CN1173057C - Novel mixed rare earth hydrogen storage electrode alloy for nickel-metal hydride secondary battery - Google Patents
Novel mixed rare earth hydrogen storage electrode alloy for nickel-metal hydride secondary battery Download PDFInfo
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- CN1173057C CN1173057C CNB011318988A CN01131898A CN1173057C CN 1173057 C CN1173057 C CN 1173057C CN B011318988 A CNB011318988 A CN B011318988A CN 01131898 A CN01131898 A CN 01131898A CN 1173057 C CN1173057 C CN 1173057C
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 239000000956 alloy Substances 0.000 title claims abstract description 50
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 title claims abstract description 14
- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000003860 storage Methods 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- GKXJWSZPLIKUPS-IUNAMMOKSA-N N-[(2Z,6Z)-2,6-bis(hydroxyimino)cyclohexylidene]hydroxylamine Chemical compound O\N=C1\CCC\C(=N\O)C1=NO GKXJWSZPLIKUPS-IUNAMMOKSA-N 0.000 claims abstract description 5
- 229910006087 NiCoN Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- -1 hydride-nickel Chemical compound 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 21
- 229910006020 NiCoAl Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019083 Mg-Ni Inorganic materials 0.000 description 1
- 229910019403 Mg—Ni Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 229910010340 TiFe Inorganic materials 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 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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Abstract
本发明公开一种镍-金属氢化物(Ni-MH)二次电池用新型混合稀土系贮氢电极合金。它的成分为：Ml1-yMy(NiCoN)x，Ml为混合稀土，其中稀土元素总含量不低于90(重量)%，La含量不低于30(重量)%，Ce含量不高于70(重量)%，0.01≤y≤0.8；2.0≤x≤4.0；M＝Mg、Ca中的一种或两种成分，N＝Mn、Fe、Mo、Co、Al、Si、Ga、S、Ti、V、Cr、Cu、Zn、Zr、B、Sn中的一种或两种或两种以上成分。应用本发明材料制成的氢化物-镍电池，其活化性能、起始容量、高倍放电性能等项技术性能指标皆大大优于现有传统商用稀土系AB5合金。
The invention discloses a novel mixed rare earth hydrogen storage electrode alloy for a nickel-metal hydride (Ni-MH) secondary battery. Its composition is: Ml 1-y M y (NiCoN) x , Ml is a mixed rare earth, wherein the total content of rare earth elements is not less than 90 (weight)%, the content of La is not less than 30 (weight)%, and the content of Ce is not high At 70 (weight)%, 0.01≤y≤0.8; 2.0≤x≤4.0; M=Mg, Ca or one or two components, N=Mn, Fe, Mo, Co, Al, Si, Ga, S , Ti, V, Cr, Cu, Zn, Zr, B, Sn, one or two or more components. The hydride-nickel battery made of the material of the present invention has technical performance indicators such as activation performance, initial capacity, high-rate discharge performance, etc., which are much better than the existing traditional commercial rare earth AB 5 alloy.
Description
Technical field
The present invention relates to secondary cell, relate in particular to the mixed rare-earth alloys for hydrogen-bearing electrode that nickel-metal hydrides (Ni-MH) secondary cell is used.
Background technology
Since LaNi is found in Dutch Philips laboratory in 1970
5Reversible hydrogen storage property since, hydrogen-storage alloy has obtained widespread use in the accumulating of hydrogen, the purification of hydrogen and the fields such as separation of isotopes of compression, heat pump and refrigeration, hydrogen-burning automobile, nickle-metal hydride secondary battery, fuel cell and hydrogen.Especially on nickle-metal hydride secondary battery, become the focus of lot of domestic and foreign scholar's research owing to advantages such as it have the capacity height, has extended cycle life, memory-less effect, anti-over-charging are crossed the strong and non-environmental-pollution of exoergic power.
The cell reaction of nickel-metal hydrides (Ni-MH) secondary cell can be expressed as:
Anodal reaction:
Negative reaction:
Total reaction:
More than the reaction of expression charging to the right in all formulas, to the left representation exoelectrical reaction.As seen in the charge and discharge process of battery, the quantity of alkaline electrolyte does not change, i.e. additive decrementation electrolytic solution not.
From at present, the hydrogen-storage alloy in the research mainly contains AB
5Type rare earth-based alloy, AB
2Type Zr (Ti) is that Laves phase alloy, AB type TiFe are alloy, A
2Type B Mg-Ni is base types such as alloy and V based solid solution type alloy.Wherein, with LaNi
5AB for prototype
5Solid type rare earth-based alloy is owing to can be under room temperature and normal pressure reversibly inhale in the mode of gas-reaction or electrochemical reaction and put hydrogen, and and have advantage such as easily-activated, that suction hydrogen discharge reaction speed is fast and extremely pay attention to, develop also the fastest.But because rare earth based AB
5The capacity of type alloy lower (about 320mAh/g), this has just impelled people to remove the higher hydrogen-storing alloy as electrode of research and development capacity.
AB
2The type alloy was once once causing people's attention, and it has higher electrochemical discharge capacity and long cycle life, but its large current discharging capability and initial stage activation performance are poor, and cost is higher, so be difficult to practicability.Magnuminium is owing to adopt the comparatively cheap elements of price such as magnesium, nickel as starting material, therefore cost is quite low, and Magnuminium has very high initial electrochemical discharge capacity and good activation performance, but the corrosion of this alloy in alkaline electrolyte is quite serious, caused the rapid decline of capacity, also can't practicability within the short-term.Vanadium radical sosoloid alloy is the same with Magnuminium, also has higher initial electrochemical discharge capacity, but because the precipitation of vanadium in alkaline electrolyte is very serious, also can cause the rapid decline of capacity, and not possess practical value because the price comparison of vanadium is expensive.
New-type hydrogen-storing RE electrode alloy has higher electrochemical discharge capacity.Kohno has studied La
5Mg
2Ni
23The electrochemical discharge capacity of type hydrogen-storing alloy as electrode electrode can reach 400mAh/g, has surmounted rare earth based AB greatly
5The loading capacity of type hydrogen-storing alloy as electrode electrode.And its alloy electrode has good cyclical stability, good high magnification characteristic and advantage such as activation capacity and low price and has demonstrated powerful application prospect in electrolytic solution.Therefore, we have reason to believe that in the near future New-type hydrogen-storing RE electrode alloy will replace traditional AB
5Type hydrogen-storing alloy as electrode and being applied among the production of Ni-MH secondary cell.
Summary of the invention
Purpose of the present invention just is to have proposed a kind of nickle-metal hydride secondary battery mixed rare-earth alloys for hydrogen-bearing electrode.
Its composition is: Ml
1-yM
y(NiCoN)
x, Ml is a mishmetal, and wherein the rare earth element total content is not less than 90 (weight) %, and La content is not less than 30 (weight) %, and Ce content is not higher than 70 (weight) %, 0.01≤y≤0.8; 2.0≤x≤4.0; One or both compositions among M=Mg, the Ca, one or both among N=Mn, Fe, Mo, Co, Al, Si, Ga, S, Ti, V, Cr, Cu, Zn, Zr, B, the Sn or two or more composition.
Designed nickel-metal hydrides (Ni-MH) secondary battery negative pole of the method that adopts the present invention the to propose comprehensive electrochemical of New-type hydrogen-storing RE electrode alloy electrode, comprise that loading capacity and high magnification characteristic etc. and pure rare earth alloy electrode relatively significantly do not descend, cyclical stability increases.Charge and discharge under the condition at little electric current, its performance has substantially exceeded business-like AB
5Hydrogen-storing alloy as electrode.Its cost is cheaper in addition, therefore in the near future, will replace existing traditional AB
5Hydrogen-storing alloy as electrode and become the nickle-metal hydride secondary battery negative pole hydrogen-storing alloy as electrode of a new generation, its cost performance will substantially exceed lithium-ion secondary cell, thus the market competitiveness of raising nickel-metal hydrides (Ni-MH) secondary cell.
Description of drawings
Fig. 1 is according to the Ml of New-type hydrogen-storing RE electrode alloy described in the embodiment
0.7Mg
0.3(NiCoAl)
3.3The loading capacity of electrode and the relation curve between the cycle index;
Fig. 2 is according to Ml described in pure La New-type hydrogen-storing RE electrode alloy and the embodiment described in the comparative example 1
0.7Mg
0.3(NiCoAl)
3.3Relation curve between alloy loading capacity and the cycle index;
Fig. 3 is according to the AB of commercialization rare earth based described in the comparative example 2
5Ml described in hydrogen-storing alloy as electrode electrode and the embodiment
0.7Mg
0.3(NiCoAl)
3.3Relation curve between alloy loading capacity and the cycle index.
Embodiment
Nickel-metal hydrides (Ni-MH) secondary battery negative pole New-type hydrogen-storing RE electrode alloy Ml
0.7Mg
0.3(NiCoN)
3.3Alloy adopts vacuum magnetic suspension stove or arc melting preparation.
Embodiment
According to New-type hydrogen-storing RE electrode alloy Ml
0.7Mg
0.3(NiCoN)
3.3Design mix, adopt vacuum magnetic suspension stove melting preparation.The alloy of institute's melting comprises: Ml
0.7Mg
0.3(NiCo)
x, Ml
0.7Mg
0.3(NiCoMn)
x, Ml
0.7Mg
0.3(NiCoAl)
3.3, Ml
0.7Mg
0.3(NiCoFe)
x, Ml
0.7Mg
0.3(NiCoMnAl)
x, Ml
0.7Mg
0.3(NiCoMo)
x, Ml
0.7Mg
0.3(NiCoS)
x, Ml
0.7Mg
0.3(NiCoSi)
x, Ml
0.7Mg
0.3(NiCoGa)
xWherein, x=3.3, Ml are mishmetal, and wherein the rare earth element total content is not less than 90wt%, and La content is not less than 30wt%, and Ce content is not higher than 70wt%, and the purity of alloy constituent element Mg, Mn, Ni, Fe, Mo, Co, Al, Si, Ga, S is all more than 90%.Respectively get alloy part then and carry out the test of electrochemistry cycle life.This test is to carry out in an open type three-electrode system, and it comprises a working electrode (being hydrogen-occlussion alloy electrode), a sintering Ni (OH)
2/ NiOOH supporting electrode and a Hg/HgO reference electrode.Electrolytic solution adopts the 6N KOH aqueous solution, and probe temperature remains on 303K.All test electrodes all are to form by uniform mixing 100mg hydrogen-storing alloy as electrode powder (300 order) and 400mg carbonyl nickel powder and the electrode slice that is pressed into diameter 10mm, thickness 1mm under the pressure of 20Mpa.Electrode adopts the current charges of 100mA/g, the current discharge of 60mA/g, and wherein the duration of charging is 5 hours, the discharge stopping potential is-0.6V (with respect to the Hg/HgO reference electrode).
Comparative example 1
The Ml of selected part pure rare earth element melting
0.7Mg
0.3(NiCoAl)
3.3Hydrogen-storing alloy as electrode carries out the test of electrochemistry cycle life to it.The system and the condition of test are all identical with embodiment.
Comparative example 2
The business-like rare earth based AB that selected part three general companies produce
5Hydrogen-storing alloy as electrode carries out the test of electrochemistry cycle life to it.The system and the condition of test are all identical with embodiment.
As can be seen from Figure 1, mixed rare-earth alloys for hydrogen-bearing electrode Ml
0.7Mg
0.3(NiCoAl)
3.3Activation performance fine, in 2 circulations, just can activate fully, its high discharge capacity can reach 386mAh/g, loading capacity also can keep 85% after 250 circulations.
As can be seen from Figure 2, after the process mixed rare-earth elements substituted, the loading capacity and the cycle life of alloy electrode did not all decrease drastically.
As can be seen from Figure 3, under the same condition that discharges and recharges, mixed rare-earth alloys for hydrogen-bearing electrode Ml
0.7Mg
0.3(NiCoAl)
3.3Comprehensive electrochemical obviously be better than business-like rare earth based AB
5Hydrogen-storing alloy as electrode, its high discharge capacity is than business-like rare earth based AB
5The peak capacity of hydrogen-storing alloy as electrode exceeds nearly 70mAh/g, and increase rate is about 23%, and cyclical stability is also not second to business-like rare earth based AB
5Hydrogen-storing alloy as electrode.
Claims (1)
1. a nickle-metal hydride secondary battery mixed rare-earth alloys for hydrogen-bearing electrode is characterized in that its composition is: Ml
1-yM
y(NiCoN)
x, Ml is a mishmetal, and wherein the rare earth element total content is not less than 90 (weight) %, and La content is not less than 30 (weight) %, and Ce content is not higher than 70 (weight) %, 0.01≤y≤0.8; 2.0≤x≤4.0; One or both compositions among M=Mg, the Ca, one or both among N=Mn, Fe, Mo, Co, Al, Si, Ga, S, Ti, V, Cr, Cu, Zn, Zr, B, the Sn or two or more composition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011318988A CN1173057C (en) | 2001-12-26 | 2001-12-26 | Novel mixed rare earth hydrogen storage electrode alloy for nickel-metal hydride secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011318988A CN1173057C (en) | 2001-12-26 | 2001-12-26 | Novel mixed rare earth hydrogen storage electrode alloy for nickel-metal hydride secondary battery |
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| CN1173057C true CN1173057C (en) | 2004-10-27 |
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|---|---|---|---|---|
| CN101212047B (en) * | 2006-12-31 | 2010-06-23 | 比亚迪股份有限公司 | Hydrogen storage alloy and its preparation method |
| CN104294087B (en) * | 2014-09-09 | 2016-04-27 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method of superlattice hydrogen storage alloy |
| CN105506382A (en) * | 2015-12-21 | 2016-04-20 | 常熟市梅李合金材料有限公司 | High-resistance electro-thermal alloy wire |
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