CN1119791A - Cheap rare-earth hydrogen storage electrode alloy containing copper and low cobalt - Google Patents
Cheap rare-earth hydrogen storage electrode alloy containing copper and low cobalt Download PDFInfo
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- CN1119791A CN1119791A CN94115249A CN94115249A CN1119791A CN 1119791 A CN1119791 A CN 1119791A CN 94115249 A CN94115249 A CN 94115249A CN 94115249 A CN94115249 A CN 94115249A CN 1119791 A CN1119791 A CN 1119791A
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- 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
Abstract
The present invention belongs to a cheap rare-earth based hydrogen storage electrode alloy containing copper and low cobalt used for manufacturing hydrogen storage type chargeable cell. Its selected chemical composition is RNia-x-y-z CuxCoyMz, in whichy R is mixed rare earth or combination of it and other rare earth elements, M=Al, Mn, Si, Fe, Cr, V and Zn, and a is greater than 4.5 and less than 5.5, x is greater than 0.05 and less than 0.8, y is greater than 0.05 and less than 0.8, z is greater than 0.2 and less than 1.0, but x+y is greater than 0.1 and less than 1. It is characterized by adding cheap substitutive element Cu as main element to stabilize behaviour at the same time of multi-component alloying so as to reduce the demand of noble element Co in the alloy and the material cost.
Description
The invention belongs to the cheap hydrogen storage electrode alloy material that can be applicable to make the hydrogen storage type negative electrode of rechargeable batteries.
Utilize hydrogen bearing alloy can be under certain pressure and temperature conditions reversible absorption and the characteristic that discharges hydrogen, thereby use it to make the long-standing (P.A.Boter of effort that negative electrode is made alkaline hydrogen-bearing formula rechargeable battery, US Patent 4,004,943 (1977)).The seventies, promptly the someone attempted using binary AB5 type rare earth alloy (A is rare earth element, and B is a transition element) LaNi5 to make hydrogen storage battery, but because the electrochemistry cyclical stability of LaNi5 bianry alloy is poor, this effort is baffled once.Simultaneously, simple single element Cu, the trial (as LaNi4Cu or LaNi4.5Al0.5) that Al etc. substitute also fails to change this situation (T.Sakai et al, J.Less-Comm.Met., 161 (1990) 193).
The mid-80, it is the polynary hydrogen storage material series of representative with La0.8Nd0.2Ni2.5-Co2.4Si0.1 that Holland Philips company has successfully developed, be characterized in adopting a large amount of noble element Co to carry out the method for element substitution as the essential element of stable performanceization, make the electrochemistry cyclical stability of rare-earth hydrogen storage electrode alloy material obtain significantly improving, promoted the research and development (J.J.G.Willems of hydrogen storage battery, Philips J.Res., 39 (1984) 1).But what follow this performance improvement is increasing substantially owing to the cost of raw material of having used noble element cobalt (account for weight alloy 30%) to cause in a large number.
The end of the eighties is to the beginning of the nineties, on the basis of big quantity research, extensively adopted the method for using the alternative single rare earth element La of cheap mishmetal Mm (or rich La mishmetal Ml) again with the World Battery industry headed by Japanese industry circle, develop that with MmNi3.5Co0.7Al0.8 or MmNi3.5Co0.8Mn0.4Al0.3 be alloy series (T.Sakai el al, the J.Alloys ﹠amp of representative; Compounds, 180 (1992) 37), and then SANYO GS company has developed Mm (Ni again on the basis of this alloy, Co, Mn, Al) the so-called non-stoichiometric alloy series of x (4.5＜x＜4.8) is as Mm (Ni0.64Co0.2Mn0.12Al0.04) x alloy (M.Tadokoroet al, J.Alloys and Compounds, 192 (1993) 179).Above-mentioned this class alloy generally all has good cyclical stability and is higher than the electrochemistry capacitance of 250mAh/g, thereby becomes present widely used alloy series.Because this alloy has reduced the Co amount that contains of alloy material to a certain extent, thereby makes the cost of material obtain reduction to a certain degree.But both made so, the Co content in the hydrogen storage electrode alloy material still reaches percentage by weight about 10%, makes the cost of Co still account for 40% of alloy raw material cost.Obviously, further reduce containing Co amount and will helping saving a large amount of noble element Co of alloy, thereby further reduce material cost, have bigger real economy meaning.
In recent years, at industrial requirement, some researchs have been carried out in the world to cheap hydrogen storage electrode alloy.Document (P.H.L.Notton et al, Z.Phys.Chem.183 (1993)) utilize the Cu element can impel AB5 type alloy to form AB5+x (x＞0 of non-stoichiometric, as AB6) characteristics of type alloy, proposed is the non-stoichiometric cheap alloy series of representative with LaNi5Cu, be characterized in that to form non-stoichiometric AB5+x alloy be means, improve AB5 bianry alloy electrochemical stability.The shortcoming one of this method is to be higher than atmospheric pressure because the hydrogen balance pressure is put in the suction of this non-stoichiometric alloy, thereby at room temperature its electrochemistry capacitance is lower, add Al when using, the method of the alloy element that Mn etc. are common is put after the decline of hydrogen balance pressure its suction, and its electrochemical stability will be affected again.And because this alloy need use the pure rare earth element La of price far above mishmetal, thereby it also will use the alloy of mishmetal to be short of to some extent aspect cost.Though at above-mentioned situation, document (F.Meli et al, J.Alloys ﹠amp; Compounds, 202 (1993) 81) reported when still using mishmetal as primary raw material, utilize Si, Al, Mn, the trial that the compound alternative method of Cu multielement is developed no Co Cheap rare-earth hydrogen storage electrode alloy, but the alloy of its research or owing to do not contain the Elements C o that makes the alloy property stabilisation, its cyclical stability is relatively poor, reach 20% as the Mm0.5Ml0.5Ni4.2-Mn0.2Al0.3Si0.3 alloy at 200 circulation back capacity attenuations, or because a large amount of addings of substitute element have caused the electrochemistry capacitance of alloy too on the low side, electrochemistry capacitance as the Mm0.5Ml0.5Ni2.4-Cu2.0Mn0.25Si0.35 alloy has only 195mAh/g, and activity function and the rapid deterioration of fast charging and discharging performance generation.Therefore, the hydrogen storage electrode alloy of present industrial employing still belong to above-mentioned contain a great deal of Co with Mm (Ni, Co, Al, Mn) (x approximates 5 to x, Co content accounts for weight alloy percentage about 10%) be the alloy series of representative, the cheap electrode alloy material of the low Co of development is still pressing for of this material development now.
The present invention proposes a kind of cheapness and contains Cu low co hydrogen storage alloys composition series, reduces the Co amount that contains of rare-earth hydrogen storage electrode alloy, thereby reduces the cost of this alloy; Simultaneously, keep high electrochemistry capacitance of such alloy and stability, promote the application and the popularization of such material.
The chemical composition that the cheapness that the present invention proposes contains Cu low co hydrogen storage electrode metal can be written as RNia-x-y-zCuxCoyMz, wherein R can be mishmetal Mm, the combination of rich La mishmetal Ml or itself and other rare earth elements, M is in order to reach the required element of the purpose of adjusting alloy hydrogen absorption and desorption pressure and other performances, as Al, and Mn, Si, Fe, Cr, V, Zn, 4.5≤a≤5.5,0.05≤x≤0.8,0.05≤y≤0.8,0.2≤z≤1.0, and 0.1≤x+y≤1.0. is in alloy, the one of the chief elements of the cyclical stability of Cu when improving hydrogen storage electrode alloy and use, and its addition depends on the addition of another stabilizing element Co of alloy property.
The viewpoint that It is generally accepted is thought, forms the non-stoichiometric structure (as AB6) except promoting alloy, and cheap element Cu does not possess the positive role that makes stable performanceization substantially in rare-earth hydrogen storage electrode alloy.The reason that forms this viewpoint mainly is aforesaidly to studies show that in early days, and simple Cu element substitution does not improve effect substantially to the performance of LaNi5 bianry alloy.And the present invention finds, under polynary alternative situation, especially under the condition that has an amount of stable performance Elements C o to exist, Cu has significantly performance improvement effect.Experiment showed, that Cu can reduce the microhardness of alloy material and the anti-efflorescence ability of raising alloy.Use The addition of C u to substitute noble element Co, not only can not cause the decline of alloy electrochemistry capacitance and cyclical stability, but also can improve the fast charging and discharging performance of alloy to a certain extent.This just provides a kind of possibility, makes us substitute part noble element Co with cheap element Cu under the prerequisite of not damaging alloy electrochemical performance, reduces alloy and contains the Co amount, thereby reach the purpose that reduces cost of alloy.
In sum, the characteristics of alloy of the present invention are, on the basis of ABx (x approximates 5) type rare earth hydrogen storage alloy commonly used, the method that cooperates multiple elements chemical to substitute, in alloy, add cheap Cu element as one of main substitute element of stable alloy chemical property, reduce the addition of stable performance Elements C o, constituted a kind of rare earth based hydrogen bearing alloy that can be used for making hydrogen storage battery negative pole and hydrogen storage battery of cheapness, and this alloy has had high electrochemical performance.
The invention has the advantages that, owing to used cheap element Cu as one of main stabilizing element of hydrogen storage electrode alloy performance, thereby reduced such alloy is the needed Co of the containing amount of stable alloy performance, thereby make the alloy raw material cost obtain the reduction of certain degree, and can save a large amount of noble element Co.Simultaneously, this alloy material has good every chemical property, can substitute the alloy material of the noble element Co that contains percentage by weight about 10% of industrial employing now fully.
Embodiment one is with norium Mm and other metals Ni of commercially available technical purity, Cu, Co, Al press the composition proportion batching of MmNi3.5Cu0.4Co0.35Al0.75, and the method for vacuum arc furnace ignition or vaccum sensitive stove of using is smelted into uniform alloy and is cast into ingot.The method that will adopt Mechanical Crushing or high pressure to inhale the hydrogen fragmentation with the alloy pig that said method obtains is pulverized it to the alloy powder that becomes 200-300 order granularity.Get above-mentioned alloy powder 7 grams, it is equipped with its percentage by weight is about 5% PTFE solution and modulates it and become even pastel, 150 ℃ of temperature, be pressed under the condition that pressure is 2 tons/square centimeter as on the nickel substrate of the bubble of conducting base end and the collector electrode of burn-oning make the negative electrode of hydrogen storage battery.With this electrode is battery cathode, is positive pole with the sintering oxidation nickel electrode, and the 6M sodium hydroxide solution is an electrolyte, and nylon nonwoven fabrics is the AA type hydrogen storage battery A that diaphragm material is assembled into nominal 1000mAh.Other gets the battery B that relatively is assembled into same model with alloy MmNi3.5Co0.7-Al0.8 by same technology.Behind two kinds of cell activation several to method for preparing, its electrochemistry capacitance of test under the 0.5C condition, test result is as shown in table 1.
The discharge of the AA type battery that table 1. is made with the hydrogen bearing alloy of two kinds of compositions
Capacity Ratio is than battery alloy composition electrochemistry capacitance (mAh) A (the present invention) MmNi3.5Cu0.4Co0.35Al0.75 1060B (comparative example) MmNi3.5Co0.7Al0.8 1062
Obviously, the hydrogen storage battery that uses the noble element Co in a considerable amount of cheap element Cu instead of alloy to make has the same high capacity of the battery of the alloy manufacturing that contains more Co with not containing Cu.
Adopt the 0.5C discharging condition to test its cycle life performance to above-mentioned battery, its test result is shown among Fig. 1.As seen from the figure, the battery made from the Cu of containing hydrogen bearing alloy of the present invention have with comparative example in the suitable lower capacity attenuation rate of battery made of high Co alloy.
Fig. 2 is the discharge capacity change curve of battery under different discharge rate conditions that above-mentioned two kinds of materials are made.By data among the figure as can be seen, the battery made from the Cu of containing alloy of the present invention has the discharge capacity high slightly than the battery of comparative example under higher discharge rate.
Table 2 is comparisons of above-mentioned two kinds of hydrogen bearing alloy costs of raw material.
The cost of raw material of the storage oxygen alloy of two kinds of compositions of table 2. is the alloy alloying component cost of raw material (unit/kilogram) A (the present invention) MmNi3.5Cu0.4Co0.35Al0.75 74B (comparative example) MmNi3.5Co0.7Al0.8 98 relatively
Obviously, the alloy that uses the part noble element Co in the cheap element Cu instead of alloy to make contains the alloy phase ratio of more Co with not containing Cu, have suitable price advantage.
The alloy A of embodiment two uses MmNi3.5Cu0.32Co0.48Mn0.4Al0.3 composition of the present invention and the MmNi3.5Co0.8Mn0.4Al0.3 alloy B of comparative example are made the AA type battery of nominal 1000mAh separately by embodiment one described method, and testing its electrochemistry capacitance and cycle life curve, its result is as shown in Figure 3.As seen from the figure, the battery that alloy of the present invention is made has good electrochemistry capacitance and good cyclical stability, and its performance level can be compared with the battery that the alloy of comparative example is made fully.
Embodiment three adopts the alloy A of MlNi3.5Cu0.48Co0.28Al0.74 composition of the present invention and MlNi3.5Co0.7Al0.8 alloy B is as a comparative example made nominal 1000mAh separately according to embodiment one described method AA type battery, and test its discharge capacity and cycle life curve, it the results are shown among Fig. 4.As seen from the figure, cheapness of the present invention contains the battery that the Cu alloy makes and has battery suitable discharge capacity and the cyclical stability made with the alloy of comparative example.Description of drawings
Fig. 1. the discharge life test of the AA type battery of two kinds of different hydrogen storage electrode alloys manufacturings
Curve
A---MmNi3.5Cu0.4Co0.35Al0.75 (the present invention)
B---MmNi3.5Co0.7Al0.8 (comparative example)
Fig. 2. the discharge capacity of the AA type battery of two kinds of different hydrogen storage electrode alloy manufacturings is with putting
The change curve of electricity electric current
A---MmNi3.5Cu0.4Co0.35Al0.75 (the present invention)
B---MmNi3.5Co.07Al0.8 (comparative example)
Fig. 3. the discharge life test of the AA type battery of two kinds of different hydrogen storage electrode alloys manufacturings
Curve
A---MmNi3.5Cu0.32Co0.48Mn0.4Al0.3 (the present invention)
B---MmNi3.5Co0.8Mn0.4Al0.3 (comparative example)
Fig. 4. the discharge life test of the AA type battery of two kinds of different hydrogen storage electrode alloys manufacturings
Curve
A---MlNi3.5Cu0.48Co0.28Al0.74 (the present invention)
B---MlNi3.5Co0.7Al0.8 (comparative example)
Claims (1)
1. a hydrogen storage electrode alloy is characterized in that chemical composition is RNia-x-y-zCuxCoyMz, and wherein R is the combination of mishmetal or itself and other rare earth elements, M=Al, Mn, Si, Fe, Cr, V, Zn, and 4.5≤a≤5.5,0.05≤x≤0.8,0.05≤y≤0.8,0.2≤z≤1.0, and 0.1≤x+y≤1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115249A CN1039611C (en) | 1994-09-30 | 1994-09-30 | Cheap rare-earth hydrogen storage electrode alloy containing copper and low cobalt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115249A CN1039611C (en) | 1994-09-30 | 1994-09-30 | Cheap rare-earth hydrogen storage electrode alloy containing copper and low cobalt |
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| Publication Number | Publication Date |
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| CN1119791A true CN1119791A (en) | 1996-04-03 |
| CN1039611C CN1039611C (en) | 1998-08-26 |
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| CN94115249A Expired - Fee Related CN1039611C (en) | 1994-09-30 | 1994-09-30 | Cheap rare-earth hydrogen storage electrode alloy containing copper and low cobalt |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093692C (en) * | 1999-09-28 | 2002-10-30 | 四川大学 | Hydrogen-storage alloy electrode material of low-Co lanthanum-praseodymium-cerium-nickel series |
| CN100362130C (en) * | 2005-12-15 | 2008-01-16 | 哈尔滨工程大学 | Method of chemical copper plating on hydregen storage alloy surface |
| CN102492873A (en) * | 2011-12-13 | 2012-06-13 | 广州有色金属研究院 | Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy |
| CN109524628A (en) * | 2017-09-18 | 2019-03-26 | 上海杉杉科技有限公司 | The method and lithium ion battery that technique preparation aoxidizes sub- silicium cathode material are broken using hydrogen |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62249358A (en) * | 1986-04-19 | 1987-10-30 | Sanyo Electric Co Ltd | Hydrogen storage electrode |
| JPH04293746A (en) * | 1991-03-22 | 1992-10-19 | Toshiba Corp | Hydrogen storage alloy for secondary battery |
-
1994
- 1994-09-30 CN CN94115249A patent/CN1039611C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093692C (en) * | 1999-09-28 | 2002-10-30 | 四川大学 | Hydrogen-storage alloy electrode material of low-Co lanthanum-praseodymium-cerium-nickel series |
| CN100362130C (en) * | 2005-12-15 | 2008-01-16 | 哈尔滨工程大学 | Method of chemical copper plating on hydregen storage alloy surface |
| CN102492873A (en) * | 2011-12-13 | 2012-06-13 | 广州有色金属研究院 | Praseodymium-and-neodymium-free nickel AB5 type hydrogen storage alloy |
| CN109524628A (en) * | 2017-09-18 | 2019-03-26 | 上海杉杉科技有限公司 | The method and lithium ion battery that technique preparation aoxidizes sub- silicium cathode material are broken using hydrogen |
| CN109524628B (en) * | 2017-09-18 | 2021-06-04 | 上海杉杉科技有限公司 | Method for preparing silicon monoxide negative electrode material by adopting hydrogen cracking process and lithium ion battery |
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| CN1039611C (en) | 1998-08-26 |
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