CN1291510C - Non-cobalt negative material of metal hydrogen storage/nickel battery and preparing method thereof - Google Patents
Non-cobalt negative material of metal hydrogen storage/nickel battery and preparing method thereof Download PDFInfo
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- CN1291510C CN1291510C CNB2004100247759A CN200410024775A CN1291510C CN 1291510 C CN1291510 C CN 1291510C CN B2004100247759 A CNB2004100247759 A CN B2004100247759A CN 200410024775 A CN200410024775 A CN 200410024775A CN 1291510 C CN1291510 C CN 1291510C
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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 relates to a non-cobalt negative material of metal hydrogen storage /nickel batteries and a preparation method thereof. The negative material is characterized in that the provided negative material is a negative material of metal hydrogen storage /nickel batteries with long life and large capacity, and belongs to a non-cobalt material of a Ce2Ni7 type crystal structure. The general formula of components of the non-cobalt material is (MmxMg<1-x>) (NiyAlmR<1-y-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 0 and less than or equal to 0.2, 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, and R is one of the elements, such as Mn, Ti, Zr, Cr, V, Si, Sn, etc. or a mixture of the elements. The alloy doesn't comprise the cobalt, which reduces the cost. 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 a Ce2Ni7 structure in the alloy materials. The life and the discharge capacity of materials can be increased by adjusting the proportioning of elements and ingredients at the B side.
Description
Technical field
The present invention relates to the negative material that a kind of Metal hydrogen-storing/nickel (MH/Ni) battery is used, relate to the no cobalt negative material of a kind of Metal hydrogen-storing/nickel (MH/Ni) battery or rather.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 Metal hydrogen-storing 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 compounds284 (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 September1999] 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 non-cobalt 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 longer, and do not add cobalt, material price is cheap.
For realizing purpose of the present invention, a kind of cheap metal storage hydrogen/nickel (MH/Ni) negative electrode battery material that does not contain cobalt provided by the invention is A
2B
7Type or belong to Ce
2Ni
7Type crystal structure material, main component are rare-earth and Mg-transition metal.It forms general formula: (Mm
xMg
(1-x)) (Ni
yAl
mR
(1-y-m))
n, 0.4≤x＜1 wherein; 0.5≤y≤1; 0≤m≤0.2; 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 the elements such as Mn, Ti, Zr, Cr, V, Si, Sn.A
2B
7A, B atomic ratio n are between 3.3-3.7 in the type structure.A
2B
7Hydrogen-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, Al etc.)
Because the fusing point of Mg is low, the vapour pressure height differs bigger with the fusing point of other elements in 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.
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 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 are more than 1143 ℃.Be more or less the same the evaporation of energy better controlled Mg with the fusing point of other compositions in the alloy.
According to 1: 2 mixed Mg powder of amount of substance and Ni powder.At 2T/cm
2The powder that mixes of following of pressure to be pressed into diameter be 10mm, 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, that the back detects that proof obtains with XRD is MgNi
2
With the foundry alloy of Mg and Ni and rare earth and other composition elements by (Mm
xMg
(1-x)) (Ni
yAl
mR
(1-y-m))
n, 0.4≤x＜1 wherein; 0.5≤y≤1; 0＜m≤0.2; 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 the elements such as Mn, Ti, Zr, Cr, V, Si, Sn.The proportioning weighing is good, puts into the water jacketed copper crucible melting of high frequency suspension smelting furnace under the argon shield.Smelting temperature is 1700 ℃-2200 ℃.
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.Charging into an atmospheric argon gas then, be warmed up to the temperature that needs again, generally is 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.
The invention will be further described below in conjunction with drawings and Examples
Description of drawings
Figure 1A B
5Crystal structure figure
Fig. 2 A
2B
7Crystal structure figure
Fig. 3 AB
5Compare with the XRD figure of embodiment
The cycle life curve ratio of Fig. 4 embodiment, comparative example, abscissa is a cycle-index, ordinate is discharge capacity (mA/g).
Embodiment
More further illustrate substantive distinguishing features of the present invention and obvious improvement below by 6 embodiment introductions and Comparative Examples.
6 embodiment compositions are listed in table 1
Table 1
| Embodiment | Form | x | y | m | n | R |
| 1 | (Mg 0.24Mm 0.76)(Ni 0.95Al 0.05) 3.5 | 0.76 | 0.95 | 0.05 | 3.5 | / |
| 2 | (Mg 0.3La 0.35Ce 0.35)(Ni 0.95Al 0.05) 3.5 | 0.7 | 0.95 | 0.05 | 3.5 | / |
| 3 | (Mg 0.22La 0.6Ce 0.1Nd 0.08)(Ni 0.95Al 0.02Sn 0.03) 3.5 | 0.78 | 0.95 | 0.02 | 3.5 | Sn |
| 4 | (Mg 0.22Mm 0.78)(Ni 0.92Al 0.04Sn 0.04) 3.4 | 0.78 | 0.92 | 0.04 | 3.4 | Sn |
| 5 | (Mg 0.22Mm 0.78)(Ni 0.96Al 0.02Mn 0.02) 3.6 | 0.78 | 0.96 | 0.02 | 3.6 | Mn |
| 6 | (Mg 0.24Mm 0.76)(Ni 0.95Al 0.03Mn 0.02) 3.45 | 0.76 | 0.95 | 0.03 | 3.45 | Mn |
| Comparative Examples | (Mg 0.24Mm 0.76)(Ni 0.95Al 0.05) 3 | 0.76 | 0.95 | 0.05 | 3 | / |
Mm consists of La70wt% in the table 1, Ce8wt%, Pr5wt%; Nd17wt% embodiment alloy is pressed table 1 composition proportion, and melted on the suspension smelting furnace of argon shield after preparing with each element simple substance, the back is under argon shield; under 960 ℃ of the alloys that melting is obtained, annealed 6 hours.Alloyed powder is broken into below 200 orders, makes simulated battery and on DC-5, carry out electrochemistry capacitance and life test.Comparative example processing and the method for testing identical with embodiment.
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, all capacity of embodiment alloy under 300mA/g are greater than comparative example, and cycle life is also better, reaches instructions for use.
Claims (4)
1. the no cobalt electrode preparation methods of a Metal hydrogen-storing/nickel-based battery is characterized in that processing step is:
(1) by (Mm
xMg
(1-x)) (Ni
yAl
mR
(1-y-m))
n, 0.4≤x in the formula＜1; 0.5≤y≤1; 0＜m≤0.2; 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;
(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;
Metal M g is with MgNi in the described alloy
2Intermediate alloy adds.
2. by the no cobalt electrode material preparation method of the described Metal hydrogen-storing/nickel-based battery of claim 1, it is characterized in that MgNi
2Intermediate alloy preparation is that the ratio with the Mg/Ni amount of substance is 1: 2 a mixed, at 2T/cm
2Pressure 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.
3. by the no cobalt electrode material preparation method of the Metal hydrogen-storing/nickel-based battery described in the claim 1, when it is characterized in that heat treatment, insulation is 0.3-1.2 hour under 300 ℃ of conditions.
4. by the no cobalt electrode material preparation method of the described Metal hydrogen-storing/nickel-based battery of claim 1, it is characterized in that described copper crucible water cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100247759A CN1291510C (en) | 2004-05-28 | 2004-05-28 | Non-cobalt negative material of metal hydrogen storage/nickel battery and preparing method thereof |
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|---|---|---|---|
| CNB2004100247759A CN1291510C (en) | 2004-05-28 | 2004-05-28 | Non-cobalt negative material of metal hydrogen storage/nickel battery and preparing method thereof |
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|---|---|
| CN1585165A CN1585165A (en) | 2005-02-23 |
| CN1291510C true CN1291510C (en) | 2006-12-20 |
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|---|---|---|---|---|
| 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 |
| CN102383011B (en) * | 2011-10-19 | 2015-02-11 | 厦门钨业股份有限公司 | Rare earth magnesium-based hydrogen storage alloy with low cost and long life and applications thereof |
| CN106111997B (en) * | 2016-06-28 | 2018-01-19 | 湘潭大学 | A kind of preparation method of porous nickel alloy electrolysis liberation of hydrogen composite cathode material |
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Assignee: Ningbo Shenjiang Technology Co., Ltd. Assignor: Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences Contract fulfillment period: 2008.6.26 to 2013.6.25 contract change Contract record no.: 2008330000185 Denomination of invention: Non-cobalt negative material of metal hydrogen storage/nickel battery and preparing method thereof Granted publication date: 20061220 License type: Exclusive license Record date: 2008.8.18 |
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Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.6.26 TO 2013.6.25 Name of requester: NINGBO SHENJIANG TECHNOLOGY CO., LTD. Effective date: 20080818 |
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