CN1027762C - Hydrogen storage alloy used in negative pole of secondary battery - Google Patents
Hydrogen storage alloy used in negative pole of secondary battery Download PDFInfo
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- CN1027762C CN1027762C CN92102795A CN92102795A CN1027762C CN 1027762 C CN1027762 C CN 1027762C CN 92102795 A CN92102795 A CN 92102795A CN 92102795 A CN92102795 A CN 92102795A CN 1027762 C CN1027762 C CN 1027762C
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- hydrogen
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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
The present invention provides the hydrogen-storage alloy of mixed rare earth series for negative electrodes of secondary batteries. The hydrogen-storage alloy comprises the following components (atomic ratios): Mm1-a, Ma, Nib, Mnc, Cod, Ale, and Xf, wherein the Mm is mixed rare earth metal, M is at least one of Ti and Zr, and X is at least one of N and B; a is equal to 0.01 to 0.2, b is equal to 3.5 to 4.6, c is equal to 0.2 to 0.6, d is equal to 0.1 to 0.7, e is equal to 0.1 to 0.5, and f is equal to 0.005 to 0.2; in addition, 4.8 is smaller than the sum of b, c, d, e and f, and the sum of b, c, d, e and f is smaller than 5.4. The pulverization rate of the alloy is low; compared with the prior art, the present invention has the advantages that the specific volumetric dilatation is decreased (by 2.6 to 3.6), and the electric capacity is still kept at a high level of 96.9 to 98.6% after 100 times of hydrogen charging and discharging cycles; the hydrogen-storage alloy is long in service life and cheap and is used for negative electrodes.
Description
The present invention relates to a kind of negative electrode active material of nickel-Hydrogenized compound secondary cell, the mixed rare earth based hydrogen storage alloy that particularly a kind of negative pole is used.
The negative electrode active material of nickel-Hydrogenized compound secondary cell generally is divided into, by Ti
2Ni or TiNi development and the Ni-Zr-Ti system that comes and by LaNi
5Alloy development and two kinds of hydrogen-storage alloys of mixed rare-earth of coming.Hydrogen-storage alloy as secondary battery negative pole should satisfy following requirement: the alkali resistance solution corrosion; Sucking/placing hydrogen amount is big; The hydrogen decomposition pressure is moderate, is generally less than 0.5MPa; The electro catalytic activity height; When putting hydrogen, suction is difficult for efflorescence; Performances such as pollution-free and low cost.The Ni-Zr-Ti cording has good comprehensive performances, and mixed rare-earth is the lower cathode hydrogen storing alloy of a kind of cost.Japanese Patent 63-166147(1988.9.7) and European patent 0206776(1986) disclose two kinds and made the mixed rare earth based hydrogen storage alloy that negative pole is used, though they all have good negative electrode active material characteristic and the low characteristics of cost, but this class rare earth is a cathode hydrogen storing alloy is easy to efflorescence after hydrogen is put in suction, cubical expansivity is up to more than 20%, simultaneously the La element in the mishmetal is because the suction internal stress effect in the hydrogen process of putting is tending towards being segregated in the surface of powdered alloy particle, be subjected to the effect of KOH solution in the battery, corrode, form La(OH)
3, lose to inhale and put Hydrogen Energy power, and the cycle life of alloy is reduced.
The objective of the invention is to overcome above-mentioned mixed rare-earth cathode hydrogen storing alloy for this reason and recycle low shortcoming of life-span, provide a kind of Pulverization ratio further to reduce and the strong long lifetime nickel-Hydrogenized compound secondary battery negative pole mixed rare earth based hydrogen storage alloy of alkali corrosion resistance ability.
The present invention is achieved in that by adding nitrogen N and boron and comes reinforced alloys, reduces Pulverization ratio; Suppress the surface segregation that rare-earth elements La etc. puts in the hydrogen process in suction simultaneously and take place, improve the corrosion resistance nature of alloy, thereby obtain composition (atomic ratio, this paper is following identical) following mixed rare-earth secondary battery negative pole hydrogen-storage alloy: Mm
1-aM
aNi
bMn
cCo
dAl
eX
f, wherein Mm is norium main component (weight %): La
43.1, Ce
3.3, Pr
13.5, Nd
38.9Surplusly can not exempt from impurity＜0.5%; M is at least a in titanium Ti and two kinds of elements of zirconium Zr; X is at least a in metalloid element N and two kinds of elements of B; A=0.01～0.2, b=3.5～4.6, c=0.2～0.6, d=0.1～0.7, e=0.1～0.5, f=0.005～0.2, and 4.8≤b+c+d+e+f≤5.4.
The optimal components of alloy of the present invention is:
Mm
0.9M
0.1Ni
4.2Mn
0.3Co
0.4Al
0.2N
0.05B
0.05。
The present inventor notices that the mixed rare-earth cathode hydrogen storing alloy is a kind of low-cost secondary battery negative pole active substance, but its to recycle the life-span low be a very big shortcoming.Cause the reason of this shortcoming to mainly contain two, the one, to put in the hydrogen process in suction, alloy powder particle is easy to efflorescence, and it significantly indicates to be exactly cubical expansivity (△ V)/(V that experiment obtains
O) very high ((△ V)/(V
O)=(△ V)/(V
O) * 100%, alloy principal phase unit cell volume behind the V---suction hydrogen, V
0-the unit cell volume of alloy principal phase when not inhaling hydrogen); The 2nd, the alloy liquid alkali corrosion-resistant performance is poor, and alloy loses hydrogen storage capacity after the oxidation.For this reason, the present inventor finds to add N and B in this mixed rare earth based hydrogen storage alloy, makes it occupy the interstitial site of main hexagonal structure phase, causes lattice distortion, comes reinforced alloys, stablizes powder particle, makes it to be difficult for efflorescence.Because N and B can form highly stable rare earth compound with rare earth element, prevented rare earth elements such as La by the chance of caustic corrosion, thereby strengthened the alloy corrosion resistance energy simultaneously.Last because the raising of alloy strength and erosion resistance has reached and has increased the purpose that alloy recycles the life-span.
Be described in further detail with regard to each element effect in the present invention in the alloy below.
In the mixed rare earth based hydrogen storage alloy of the present invention, norium Mm is the basic assurance that obtains the storage hydrogen capacity, and principal element La wherein and Nd etc. have stronger avidity with hydrogen, can with hydrogen evolution LaH
2Deng rare earth hydride.Rare earth also can be regulated the hydrogen balance decomposition pressure makes it moderate.Mm content is 0.8～0.99 in the present invention, and when being lower than 0.8, hydrogen obviously reduces, and is higher than at 0.99 o'clock, puts the reactivity that the mechanical stress that causes in the hydrogen process will increase La, the segregation that causes atom to form, formation La(OH inhaling repeatedly)
3, cause negative pole alloy hydrogen storage performance decline in the battery.
It is identical that Ti and Zr act in alloy, all is very strong suction hydrogen agent, forms TiH with H-H reaction
2And ZrH
2Compound, Ti still can improve the intensity of alloy, and Zr can suppress alloy pulverization, and the two all has the effect that the hydrogen balance decomposition pressure is reduced.The total amount of alloy Ti of the present invention and Zr is 0.01～0.2, can distinguish or interpolation jointly.If total content is lower than 0.01, does not have and improve intensity and suppress the atomizing effect; If surpass at 0.2 o'clock, then make the hydrogen balance decomposition pressure too low, reduced effective hydrogen, the electrical capacity of negative pole alloy is reduced.
Mn has the raising alloy corrosion resistance, can improve the sucking/placing hydrogen amount of alloy effectively, reduces the self-discharge of battery amount and improves the active ability of alloy.Alloy Mn content of the present invention is 0.2～0.6, and when being lower than 0.2, the sucking/placing hydrogen amount of alloy reduces; And Mn is higher than at 0.6 o'clock, in basic solution because Mn
2+Ion is separated out, and makes the alloy hydrogen absorption and desorption mis-behave.
Al easily forms compact oxide in alloy, play La and the not oxidized effect of Nd that protection segregates to the surface.Al still can reduce the self-discharge amount and regulate the hydrogen balance decomposition pressure.Alloy A l content of the present invention is 0.1～0.5, if be lower than at 0.1 o'clock, effectively sucking/placing hydrogen amount reduces, and promptly negative pole alloy electrical capacity reduces.
Co has the hydrogen balance of reduction decomposition pressure in alloy, while also can be reduced the coefficient of expansion behind the absorption hydrogen, thereby increase the effect of battery life, alloy Co content of the present invention is 0.1～0.7, if Co content in alloy is lower than 0.1, the above-mentioned effect of Co can not show, and the content of Co is too small greater than the hydrogen balance decomposition pressure that can make alloy at 0.7 o'clock, and the shortcoming that increases the battery cost is arranged.
Ni is one of element that mainly keeps sucking/placing hydrogen amount in alloy, and it makes alloy form stable CaCu easily
5The type hexagonal crystallographic texture keeps the higher hydrogen of alloy, and the effect of regulating the hydrogen balance decomposition pressure is arranged.Ni content is 3.5～4.6 in the alloy of the present invention, is lower than 3.5 and can reduces sucking/placing hydrogen amount significantly, and platform nip territory narrows down simultaneously; Be higher than 4.6, the hydrogen balance decomposition pressure is higher, causes battery efficiency to reduce.
As everyone knows, N and B are the atomic radius smaller elements, and they are that form with moderate metal nitride of fusing point and boride adds in the present invention, they stably are present on the interstitial site of hexagonal structure phase, cause lattice distortion, increase lattice parameter, strengthened alloy.And the B atom still can be enriched in crystal boundary, strengthen the alloy crystal boundary.Alloy strength improves and has reduced Pulverization ratio widely, and promptly the cubical expansivity of powdered alloy obviously descends.Simultaneously because N and B can form stable rare earth compound with rare-earth elements La etc., prevented these rare earth atoms when discharging and recharging to the alloying pellet surface segregation, reduce the chance that they are corroded, thereby strengthened the erosion resistance of alloy, also prolonged life-span that recycles of alloy.The best total content of N and B is 0.005～0.2 among the present invention, and both can add simultaneously, also can add separately.
When hydrogen-storage alloy composition of the present invention is: Mm
0.9M
0.1Ni
4.2Mn
0.3Co
0.4Al
0.2N
0.05B
0.05The time, experimental results show that alloy has minimum cubical expansivity, thereby its Pulverization ratio is minimum.The level that the electrical capacity of alloy keeps after the hydrogen circulation is put in 100 suctions is up to 98.6% simultaneously, shows that alloy not only has very low Pulverization ratio, and best alkali corrosion resistance performance is arranged, so this alloy is the longest alloy in a kind of work-ing life.
Compared with prior art, secondary battery negative pole mixed rare earth based hydrogen storage alloy of the present invention owing to add N and B in alloy, has been strengthened alloy, and has been strengthened the alkali corrosion resistance performance of alloy widely, and the result obtains the very low powdered alloy of a kind of Pulverization ratio.Compare the good result of its cubical expansivity decline 2.6～3.6 with comparative example alloy 12, the electrical capacity of alloy still keeps the level up to 96.9～98.6% after the hydrogen circulation is put in 100 suctions, thereby obtains cheap type negative pole hydrogen-storage alloy of a kind of long lifetime.
Introduce embodiments of the invention below, and further specify the present invention.
The composition of the embodiment of the invention 1～11 and comparative example 12～14 is as shown in table 1.The preparation alloy adopts purity to be higher than 99% norium, and 99% sponge Ti and sponge Zr, 99% electrolysis Mn and electrolysis Ni, 99% metal A l, 99% electrolysis Co, N and B adopt the form of moderate metal nitride of fusing point and boride to add.Starting material are evacuated to 0.5 * 10 earlier by the melting in the common vacuum induction furnace of packing into of the proportioning of table 1
-4KPa, applying argon gas protection refining again, the metal nitride and the boride of the adding composition that requires are cast in the water cooled copper mould at last before the tapping.After the steel ingot cooling, take out and coarse breaking, carry out activation treatment in the withstand voltage stainless steel vessel of packing into then, be evacuated to 0.13 * 10 earlier
-2KPa charges into hydrogen again and inhales the hydrogen activation, and still needing then further is ground to required powder size with ball mill, about general 40 μ m.Common electrochemical method testing capacitor amount is adopted in sampling at last, measures each alloy before inhaling hydrogen and inhale lattice parameter behind the hydrogen with x-ray diffraction method, calculates to inhale cubical expansivity before and after the hydrogen, and it the results are shown in table 2.
By visible 1～No. 11 alloy of the embodiment of composition within the scope of the invention of table 2, with 12～No. 14 alloy phase ratios of comparative example, since added in the alloy different quantities N and (or) B, its cubical expansivity of inhaling behind the hydrogen descends 2.6～3.6 than comparative example 12, wherein No. 5 alloys decline mostly is 3.6 most, this just means that alloy puts in suction that Pulverization ratio significantly descends in the hydrogen process, helps the raising of battery life.Can see also simultaneously that alloy of the present invention is after the hydrogen circulation is put in 100 suctions, specific capacitance still keeps 96.9～98.6% high level, hydrogen is put in the suction that alloy is described, and to recycle the life-span very long, compare it with comparative example and be applied to the prolongation greatly that battery cathode will be brought battery life, comparative example 14 is because the content of N and B has exceeded scope of the present invention, though the cubical expansivity behind the absorption hydrogen is compared decline by a big margin (7.1) with comparative example 12, but effectively sucking/placing hydrogen amount also reduces (this electrical capacity reduces too many) greatly, can not use as the battery cathode hydrogen-storage alloy.
Table 1
The sequence number composition
1 Mm
0.99Ti
0.01- Ni
3.5Mn
0.6Co
0.7Al
0.3N
0.02B
0.03
2 Mm
0.9Ti
0.1- Ni
3.8Mn
0.2Co
0.6Al
0.2N
0.08-
3 Mm
0.9Ti
0.1- Ni
4.2Mn
0.3Co
0.3Al
0.3- B
0.05
4 Mm
0.8Ti
0.2- Ni
4.0Mn
0.3Co
0.3Al
0.5N
0.04B
0.10
5 Mm
0.9Ti
0.1- Ni
4.2Mn
0.3Co
0.4Al
0.2N
0.05B
0.05
These 6 Mm
0.9-Zr
0.1Ni
4.2Mn
0.3Co
0.3Al
0.3N
0.05B
0.05
Send out
7 Mm
0.9- Zr
0.1Ni
4.0Mn
0.4Co
0.4Al
0.3N
0.06-
Bright
8 Mm
0.99- Zr
0.01Ni
4.2Mn
0.3Co
0.5Al
0.1- B
0.05
Example
9 Mm
0.9- Zr
0.1Ni
4.6Mn
0.4Co
0.1Al
0.2N
0.03B
0.07
10 Mm
0.8- Zr
0.2Ni
3.8Mn
0.4Co
0.6Al
0.2N
0.05B
0.15
11 Mm
0.8Ti
0.1Zr
0.1Ni
4.2Mn
0.3Co
0.3Al
0.3N
0.02B
0.05
Than 12 Mm
1.0--Ni
4.2Mn
0.3Co
0.3Al
0.3--
Than 13 Mm
1.0--Ni
4.0Mn
0.4Co
0.4Al
0.2--
Example 14 Mm
0.7Ti
0.2Zr
0.1Ni
4.2Mn
0.3Co
0.3Al
0.3N
0.08B
0.2
Table 2
Inhale before the hydrogen and suction hydrogen
The 5th circulation 100 circulations of the 100th circulation just with
Back cubical expansivity
Specific capacitance initial stage electrical capacity behind the sequence number phase specific capacitance
(mAh/g) ratio (%) ((△ V)/(V (mAh/g)
O) %)
1 285 277 97.2 18.8
2 280 274 97.9 18.4
3 280 272 97.1 19.0
4 275 271 98.5 18.2
5 287 283 98.6 18.0
These are 6 289 285 98.6 18.1 years old
Send out
7 289 284 98.3 18.6
Bright
8 282 274 97.1 19.0
Example
9 288 282 98.0 18.3
10 270 266 98.5 18.2
11 288 279 96.9 18.5
12 275 250 90.9 21.6
Ratio
13 270 246 91.1 20.7
{。##.##1},
Example 14 183--14.5
Claims (2)
1, a kind of mixed rare earth based hydrogen storage alloy that is used for secondary battery negative pole is characterized in that, composition range (atomic ratio) is: Mm
1-aM
aNi
bMn
cCo
dAl
eX
f, wherein Mm is a norium, main component (weight %) is: La
43.1, Ce
3.3, Pr
13.5, Nd
38.9, the surplus impurity that can not exempt from＜0.5%; M is at least a in titanium Ti and two kinds of elements of zirconium Zr; X is at least a in metalloid element nitrogen N and two kinds of elements of boron; A=0.01～0.2, b=3.5～4.6, c=0.2～0.6, d=0.1～0.7, e=0.1～0.5, f=0.005～0.2, and 4.8≤b+c+d+e+f≤5.4.
2, hydrogen-storage alloy according to claim 1 is characterized in that, alloying constituent (atomic ratio) is: Mm
0.9M
0.1Ni
4.2Mn
0.3Co
0.4Al
0.2N
0.05B
0.05
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92102795A CN1027762C (en) | 1992-04-25 | 1992-04-25 | Hydrogen storage alloy used in negative pole of secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92102795A CN1027762C (en) | 1992-04-25 | 1992-04-25 | Hydrogen storage alloy used in negative pole of secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065353A CN1065353A (en) | 1992-10-14 |
| CN1027762C true CN1027762C (en) | 1995-03-01 |
Family
ID=4939855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92102795A Expired - Fee Related CN1027762C (en) | 1992-04-25 | 1992-04-25 | Hydrogen storage alloy used in negative pole of secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027762C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2698881B1 (en) * | 1992-12-04 | 1995-01-13 | Accumulateurs Fixes | Hydrurable material for negative electrode of nickel-hydride accumulator. |
| US6074783A (en) * | 1996-12-19 | 2000-06-13 | Duracell Inc. | Hydrogen storage alloys for use in rechargeable electrochemical cells, and methods of producing them |
| CN1297021C (en) * | 2005-05-31 | 2007-01-24 | 钢铁研究总院 | Cathode material in use for nickel-hydrogen battery in high capacity |
| CN1319196C (en) * | 2005-09-09 | 2007-05-30 | 珠海金峰航电源科技有限公司 | AB5 type negative pole hydrogen-storage material |
| WO2014118846A1 (en) * | 2013-01-29 | 2014-08-07 | パナソニック株式会社 | Alloy powder for electrode, negative electrode for alkali storage battery using same, and alkali storage battery |
-
1992
- 1992-04-25 CN CN92102795A patent/CN1027762C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1065353A (en) | 1992-10-14 |
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