CN1271734C - Metal negative electrode material for nickel-hydrogen battery and preparing process - Google Patents
Metal negative electrode material for nickel-hydrogen battery and preparing process Download PDFInfo
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- CN1271734C CN1271734C CNB2004100247763A CN200410024776A CN1271734C CN 1271734 C CN1271734 C CN 1271734C CN B2004100247763 A CNB2004100247763 A CN B2004100247763A CN 200410024776 A CN200410024776 A CN 200410024776A CN 1271734 C CN1271734 C CN 1271734C
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- nickel
- alloy
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- metal hydrogen
- storing
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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
Abstract
The present invention relates to a negative material of metal hydrogen storage/ nickel batteries and a preparation method thereof. The negative material is characterized in that the structure of the provided negative material is that the anode material for metal hydrogen storage/ nickel batteries with long life and large capacity belongs to a non-cobalt material with Ce2Ni7 type crystal structures, the general formula of the non-cobalt material is (MmxMg<1-x>) (NiyCozAlmR<1-y-z-m>) n, wherein x is more than or equal to 0.4 and less than 1, y is more than or equal to 0.5 and less than or equal to 1, m is more than or equal to 0 and less than or equal to 0.2, z is more than 0 and less than or equal to 0.3, and n is more than or equal to 3.3 and less than or equal to 3.7; Mm is at least one rare earth element or a mixture of the rare earth elements, wherein La is more than or equal to 25 percent by weight, and R is one of the elements, such as Mn, Ti, Zr, Cr, V, Si, Sn, etc. or a mixture of the elements. The main phase structure Ce2Ni7 of the alloy has much more theoretical capacity than an AB5 (LaNi5 structure) material. The addition of light metal magnesium is favorable to the increase of capacity and the form of Ce2Ni7 structure in the alloy materials. The life and the discharge capacity of materials can be increased by adjusting the proportioning and the ingredients of elements at the B side.
Description
Affiliated field
The present invention relates to a kind of Metal hydrogen-storing/nickel (MH/Ni) battery, particularly a kind of Metal hydrogen-storing/nickel (MH/Ni) negative electrode battery material and preparation method.Belong to the battery electrode material field.
Background technology
Traditional energies such as current oil are exhausted day by day, and because give off a large amount of carbon dioxide in using, produce greenhouse effect, cause serious threat and destruction for the biological environment of the earth.People are above the novel clean energy resource hydrogen of the numerous and confused trend of purchasing of eye.The MH battery is because have a specific capacity height, the characteristics of cleanliness without any pollution and obtain to produce widely and use, and widely used cell negative electrode material is with CaCu
5AB for principal phase
5The type rare earth alloy and is a principal phase with Laves mutually, the AB that is made of Ti, Zr, V and Ni
2The type titanium-base alloy.AB
5Its capacity of type rare earth alloy is near its theoretical limit, AB
2Though the type titanium-base alloy has high capacity, activation is difficulty, and cost is also higher, so people are at the novel MH cell negative electrode material of the cheap high power capacity of active development.There is report to study the LaMg that replaces the rare earth in rare earth-Ni alloy with Mg the earliest
2Ni
9System [K.Kadir, J.of Alloys and compounds 284 (1999) 145], this system is to belong to PuNi
3The system of type has the LaNi of ratio
5High hydrogen.The patent [JP11 264041A+ (TOSHIBA CORP), 28 September 1999] of Toshiba's application has afterwards been mentioned AB
3And AB
3.5The rare earth of type-Ni system alloy has high capacity and multiplying power discharging characteristic preferably, and that study in the patent of Panasonic is AB
3.5And AB
5Rare earth-Ni system that type mixes has higher capacity and good cyclical stability.But the Mg-Ni-rare earth-based alloy exists also that reversible to put hydrogen low, and cyclical stability is poor, composition and structure problem more rambunctious.
Summary of the invention
The hydrogen storage material and the preparation method that the purpose of this invention is to provide a kind of new construction, with the negative material of using in metal current storage hydrogen/nickel (MH/Ni) battery mutually the specific capacity high life long.
For realizing purpose of the present invention, a kind of Metal hydrogen-storing/nickel provided by the invention (MH/Ni) negative electrode battery material is A
2B
7Type or AB
3.5Type (Ce
2Ni
7Type crystal structure) material, the composition general formula of negative material is (Mm
xMg
(1-x)) (Ni
yCo
zAl
mR
(1-y-z-m))
n, 0.4≤x＜1 wherein; 0.5≤y≤1; 0≤m≤0.2,0＜z≤0.3; 3.3≤n≤3.7, main component are rare-earth and Mg-transition metal.A
2B
7The type hydrogen-storage alloy is than AB
5The type alloy has higher theoretical capacity, and the raising that is added with the capacity of being beneficial to and the Ce of light metal magnesium
2Ni
7The formation of type structure.Magnesium corrodes in the alkaline solution of battery easily, improves the cycle life of alloy by the addition of restriction magnesium, the proportioning of adjustment B side element (Ni, Co, Al etc.), mixes middle rare earth La 〉=25wt%.
Because the fusing point of Mg is low, the fusing point of other elements differs bigger in vapour pressure height and the system, if with the direct melting of Mg simple substance, the inevitable a large amount of evaporations of Mg make alloying component be difficult to control.Use MgNi in the present invention
2Intermediate alloy, about 1143 ℃ of its fusing point, can better controlled in melting the evaporation of Mg.
Generate Ce
2Ni
7The reaction of type crystal structure is a peritectic reaction.In generative process, may produce AB
3Type and AB
5The dephasign of type is so melted alloy must obtain purer single phase by heat treatment.
Mg corrodes in alkaline solution easily, by adding elements such as Co, Al; The ratio of adjusting each rare earth composition in the rare earth of A side improves cyclical stability, prevents that the Mg corrosion from causing structural damage, and causes the very fast decline of capacity.
Below technical scheme of the present invention is described in further detail:
The Mg hydrogen is very big, but because generate stable hydride with hydrogen, is difficult to emit hydrogen at normal temperatures and pressures, so reversible hydrogen storage amount is very little under the normal temperature and pressure.Alloy among the present invention is the alloy of Mg-Ni-rare earth system, and its principal phase structure is Ce
2Ni
7Type, the alloy with this structure just has higher reversible hydrogen at normal temperatures and pressures, theoretical electrochemistry capacity height.Mg is in the stable structure, so more generally be difficult to corrosion; Add other as elements such as Co, Al after, form the coating of protectiveness at alloy surface, also can protect Mg not to be corroded.
The fusing point of Mg is low, and vapour pressure is very high, thus with high-melting-point alloy such as Ni together directly during melting, evaporation is violent, be difficult to control composition accurately, and Mg is very active, directly and other compositions together during melting, easily generation is splashed because reaction is violent.So melting the time to adopt the intermediate alloy of Mg.MgNi
2Stable in properties, fusing point have more than 1040 ℃, are more or less the same with the fusing point of other compositions in the alloy, evaporation that can better controlled Mg.
According to 1: 2 mixed Mg powder of amount of substance and Ni powder.At 0.5-2T/cm
2It is 10mm that the powder that following of the pressure of ton mixes is pressed into diameter, and thickness is about the disk of 5mm, puts into the airtight stainless steel tube that is filled with the 0.6MPa argon gas, 960 ℃ of following sintering 6 hours, and the back proves that with the XRD detection that obtain is MgNi
2
, concrete with the foundry alloy of Mg and Ni and rare earth and other composition elements by forming general formula (Mm by the proportioning weighing
xMg
(1-x)) (Ni
yCo
zAl
mR
(1-y-z-m))
n, 0.4≤x＜1 wherein; 0.5≤y≤1; 0≤m≤0.2,0＜z≤0.3; 3.3≤n≤3.7.Behind the batching mixing, the water jacketed copper crucible melting of under argon shield, putting into the high frequency suspension smelting furnace.Smelting temperature is controlled at 1700 ℃-2200 ℃, and the upset melting makes it even for 2 times.
The alloy that obtains after the melting contains many CaCu
5Equate dephasign, for obtaining the purer Ce that contains
2Ni
7The alloy of principal phase must be heat-treated.Mg volatilizees easily, and the easy oxidation of rare earth, so must control heat-treat condition well.Be evacuated down to 1 * 10 earlier during annealing
-5Pa, be warmed up to 300 ℃ after the insulation 0.3-1.2 hour.After charge into an atmospheric argon gas, be warmed up to the temperature that needs again, generally be 600 ℃-1300 ℃.Be incubated 0.5-10 hour.Temperature and temperature retention time are lacked very much and are oversize all bad, and too short diffusion is incomplete, can't obtain the phase of needs, long Mg evaporation, and composition changes, and rare-earth oxidation influences performance.
Description of drawings
Fig. 1 is AB
5Crystal structure figure
Fig. 2 is A
2B
7Crystal structure figure
Fig. 3 is the X diffraction pattern of comparative example of the present invention and embodiment 1
The cycle life curve of Fig. 4 embodiment 1,2,3 and comparative example.Abscissa is a cycle-index among the figure, and ordinate is a discharge capacity, and unit is (mA h/g)
Embodiment
The negative material composition formula that embodiment 1 provides is: (Mg
0.24Mm
0.75) (Ni
0.92Co
0.08)
3.5
It is commercial AB that comparative example uses
5Type SM1 alloy
Mm consists of La70wt%, Ce8wt%, Pr5wt%, Nd17wt%
Alloy is used MgNi by forming proportioning
2After alloy and element (purity is greater than 99.9%) prepare, on the suspension smelting furnace under the argon shield 1800 ℃ to turn over molten secondary evenly melted, be evacuated down to 1 * 10 earlier during annealing
-5Pa is warmed up to 300 ℃ of insulations 0.3-1.2 hour, then under argon shield, under 960 ℃ of the alloys that melting is obtained, anneals 6 hours.Alloyed powder is broken into below 200 orders, makes simulated battery and on DC-5, carry out electrochemistry capacitance and life test.
It is new A that XRD result's (as shown in Figure 3) confirms to obtain
2B
7The material of structure
As can be seen from Figure 4, the capacity of embodiment 1 alloy under 300mA/g is greater than comparative example, by adjust the alloy B side composition proportion, cycle life is improved, the capacity of 300 circulation back embodiment 1 still more than 300mAh/g, is higher than comparative example.Capacity all greater than or be equivalent to comparative example.
Its composition general formula of the negative material that embodiment 2-6 provides is respectively:
(Mg
0.22La
0.63Ce
0.15)(Ni
0.92Co
0.05Al
0.03)
3.4
(Mg
0.22Mm
0.78)(Ni
0.9Co
0.05Al
0.03Ti
0.02)
3.6
(Mg
0.4Mm
0.6)(Ni
0.9Co
0.1)
3.4
(Mg
0.3Mm
0.7)(Ni
0.9Co
0.05Zr
0.05)
3.5
(Mg
0.3La
0.35Ce
0.35)(Ni
0.86Co
0.04Sn
0.1)
3.5
Wherein, comparative example is identical with embodiment 1 with Mm.
With with embodiment 1 corresponding mode batch mixing, melt temperature is 1700-2200 ℃, and fusion is turned over for 2 times, is evacuated down to 1 * 10 earlier during annealing
-5Pa is warmed up to 300 ℃ of insulations 0.3-1.2 hour, then under 600-1200 ℃ of argon atmospher, annealed 6 hours, its performance test condition is with embodiment 1, implement 2,3 and record the cycle life curve and also list in Fig. 4, the discharge capacity that can find out embodiment 2,3 from figure all greater than or suitable with comparative example.The discharge cycles class of a curve of embodiment 4-6 is similar to embodiment 1.
Claims (6)
1. the preparation method of the negative material used of a Metal hydrogen-storing/nickel-based battery is characterized in that processing step is:
(1) presses content composition (Mm
xMg
(1-x)) (Ni
yCo
zAl
mR
(1-y-z-m))
nBatching, wherein 0.4≤x＜1; 0.5≤y≤1; 0≤m≤0.2,0＜z≤0.3; 3.3≤n≤3.7; Mm is at least a rare earth element or their mixing; R is a kind of or their mixing in Mn, Ti, Zr, Cr, V, Si, the Sn element, La 〉=25wt% in the mishmetal;
(2) put into the copper crucible melting of high frequency suspension smelting furnace under the argon shield, 1700 ℃-2200 ℃ of smelting temperatures;
(3) the alloy heat treatment of step (2) gained, condition is a vacuum degree 1 * 10
-5Pa is warming up to 300 ℃ of insulations, charges into an atmospheric argon gas then, is warming up to 600-1300 ℃ again, is incubated 0.5-10 hour and obtains containing Ce
2Ni
7The alloy of principal crystalline phase.
2. the cathode material preparation method of using by the described Metal hydrogen-storing/nickel-based battery of claim 1, its feature metal M g in alloy is with MgNi
2Intermediate alloy adds.
3. the cathode material preparation method of using by the described Metal hydrogen-storing/nickel-based battery of claim 2 is characterized in that MgNi
2Intermediate alloy preparation is to be 1: 2 mixed with the Mg/Ni mass ratio, at 0.5-2T/cm
2Ton pressure depresses to disk, puts into the sealing stainless steel tube that is filled with the 0.6MPa argon gas then, and 960 ℃ of sintering synthesized in 6 hours, pulverized then.
4. the cathode material preparation method of using by the Metal hydrogen-storing/nickel-based battery described in the claim 1 when it is characterized in that heat treatment, is incubated 0.3-1.2 hour under 300 ℃ of conditions.
5. the cathode material preparation method of using by the described Metal hydrogen-storing/nickel-based battery of claim 1 is characterized in that described copper crucible water cooling.
6. the cathode material preparation method of using by the described Metal hydrogen-storing/nickel-based battery of claim 1 is characterized in that in the described copper crucible melting upset melting 2 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100247763A CN1271734C (en) | 2004-05-28 | 2004-05-28 | Metal negative electrode material for nickel-hydrogen battery and preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100247763A CN1271734C (en) | 2004-05-28 | 2004-05-28 | Metal negative electrode material for nickel-hydrogen battery and preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1591937A CN1591937A (en) | 2005-03-09 |
| CN1271734C true CN1271734C (en) | 2006-08-23 |
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845563B (en) * | 2010-03-23 | 2011-06-01 | 广西大学 | Preparation method for improving hydrogen storage performance of AB2C9 La-Mg-Ni-based alloy |
| CN102832380A (en) * | 2012-08-29 | 2012-12-19 | 上海锦众信息科技有限公司 | Preparation method of cathode hydrogen storage material of power battery |
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Granted publication date: 20060823 |