CN1050230C - Compounded hydrogen-storage alloy electrode material - Google Patents
Compounded hydrogen-storage alloy electrode material Download PDFInfo
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- CN1050230C CN1050230C CN97119425A CN97119425A CN1050230C CN 1050230 C CN1050230 C CN 1050230C CN 97119425 A CN97119425 A CN 97119425A CN 97119425 A CN97119425 A CN 97119425A CN 1050230 C CN1050230 C CN 1050230C
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- hydrogen
- alloy
- storage alloy
- hydrogen storage
- electrode
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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 belongs to the preparation and the preparation of a hydrogen storage alloy electrode material. The present invention respectively compounds a binary alloy MN3 (wherein M=M0 and W; N = Co and Ni) with a rare earth series hydrogen storage alloy, a titanium-nickel series hydrogen storage alloy or a zirconium series Laves phase hydrogen storage alloy to obtain the hydrogen storage alloy electrode material in which the weight of the binary alloy is 1.0% to 20.0% of that of the hydrogen storage alloy. The present invention utilizes good electrocatalytic property of the binary alloy MN3 to enhance the electrochemical reaction activity and hydrogen-oxygen compounding power of the electrode, and the compounded hydrogen storage alloy electrode has the advantages of high activation speed, high capacity and high multiplying power; the discharge performance of the electrode is obviously improved, and the resistance value of the electrochemical reaction of the electrode is lowered.
Description
The invention belongs to the preparation and the application of hydrogen-adsorped alloy electrode material.
It is negative material as nickle/metal hydrides secondary batteries that current hydrogen bearing alloy has the application of economic worth most.The Ni/MH battery has high energy density, long circulation life, and advantages such as memory-less effect and non-environmental-pollution have many countries to be devoted to the commercialization of Ni-MH battery at present.
M.M.Jaksic, 1nt.J.Hydrogen Energy, 11 (1987) 727 discussed by the reasonable combination of selecting transition metal realize " cooperative effect ", the alloy that obtains possessing the high degree of electrical catalytic activity is significantly improved the dynamic performance of evolving hydrogen reaction.According to the BrewelEngel valence bond theory, point out that " cooperative effect " may be achieved in following situation: when having the transition metal of empty d track and having the transition metal formation alloy of paired d electronics, the result of these two kinds of component interactions will form the optimized electronic structure that is fit to generate H-H reaction, it will be above the electro catalytic activity of single metal component, even may surpass the electro catalytic activity of noble metal such as Pd, Pt in some cases.Some bianry alloys such as MoCo
3, MoNi
3And WCo
3Deng being pointed out to be very suitable element combinations, but in metal smelt control its as phase-splitting relatively difficulty appears, and the extremely difficult pulverizing of above-mentioned alloy that makes with fusion method.
The purpose of this invention is to provide a kind of compounded hydrogen-storage alloy electrode material and preparation method thereof, the present invention is other alloy compositions of admixture in hydrogen storing alloy powder, it can prepare the Compositional type hydrogen-storage electrode, hydrogen-bearing alloy electrode activation after composite is fast, capacity is high, high-rate discharge ability is significantly improved, and the electrode reaction resistance value of electrode reduces.
The Compositional type hydrogen-adsorped alloy electrode material is divided into two classes substantially, and a class is that two or more hydrogen bearing alloys are composite, and another kind of is that a kind of hydrogen bearing alloy and other alloy compositions that does not possess hydrogen storage property are composite.The present invention selects bianry alloy MN
3(M=Mo wherein, W; N=Co, Ni) to be that the Laves phase hydrogen storage alloy carries out composite with lanthanon hydrogen storage alloy, nickel titante series hydrogen bearing alloy or zirconium respectively, and its weight accounts for 1.0%～20.0% of hydrogen bearing alloy weight.The present invention adopts the synthetic high active powder shape bianry alloy MN with Large ratio surface of chemical method
3, be used as composite component, utilize its good catalytic action to come the active and hydrogen-oxygen compound ability of electrochemical reaction of intensifier electrode.
MoCo
3The preparation method be: take by weighing a certain amount of ammonium molybdate and cobalt nitrate by stoicheiometry, ground 400 mesh sieves, mixing; under hydrogen shield, be heated to 400～500 ℃, constant temperature 0.5～2 hour; be warming up to 900～1200 ℃ then, constant temperature 2～6 hours makes MoCo after the cooling
3Alloy powder.Also can prepare WCo with similar method
3Take by weighing a certain amount of hydrogen bearing alloy, take by weighing 1.0%～20.0% the composite alloy that is equivalent to hydrogen bearing alloy weight again, mix being placed in the ball mill under noble gas (as argon gas) protection ball milling 0.5～6 hour, promptly obtain composite good hydrogen storing alloy powder after the taking-up.
MoNi
3The preparation method be: nickel nitrate is soluble in water, and titration goes out nickel concentration.Nickel nitrate solution is heated to 80～100 ℃, stirs and splash into sodium carbonate liquor, the control terminal point is in pH=10～13,3～5 filtering and washing repeatedly, and last suction filtration drying grinds, and obtains basic nickel carbonate.Take by weighing ammonium molybdate and basic nickel carbonate in Mo and 1: 3 ratio of Ni atomic ratio, under hydrogen atmosphere, heat behind the mixing, progressively heat up, 80～120 ℃ of constant temperature 0.5～1 hour, 170～230 ℃ of constant temperature 0.5～1 hour is warming up to 1000～1300 ℃, keeps 1-6 hour, reduce to 400 ℃ and change argon gas into, obtain MoNi after the cooling
3Alloy powder.Also can prepare WNi with similar method
3
With the MoCo that makes
3Deng composite with hydrogen storing alloy powder; process is as follows: take by weighing a certain amount of hydrogen bearing alloy; take by weighing 1.0%～20.0% the composite alloy that is equivalent to hydrogen bearing alloy weight again; mix to be placed in the ball mill under noble gas (as argon gas) protection ball milling 0.5～6 hour, obtain composite good hydrogen storing alloy powder after the taking-up.
Composite good hydrogen storing alloy powder is made electrode.Because powder metallurgy MoCo
3Deng having a higher electro catalytic activity, the electrode activation after composite is fast, capacity is high, and high-rate discharge ability is significantly improved, and the electrode reaction resistance value of electrode reduces.
Embodiment 1.
Take by weighing 55 gram ammonium molybdates and 20 gram cobalt nitrates by stoicheiometry, grind, cross 400 mesh sieves, mixing under the nitrogen atmosphere protection, is heated to 450 ℃, and constant temperature 1 hour is warming up to 1050 ℃ then, and constant temperature 5 hours makes 26 gram MoCo after the cooling
3With the MoCo that makes
3Carry out diffraction analysis, Fig. 1 is MoCo
3Powder diagram, the result shows and MoCo
3Standard powder diffraction card in full accord.With similar approach preparation 26 gram WCo
3, Fig. 2 is WCo
3Powder diagram.
With the MoCo that makes
3With MLNi
3.8Co
0.5Mn
0.4Al
0.2Li
0.1Hydrogen storing alloy powder is composite, and process is as follows: take by weighing the 50.0g hydrogen bearing alloy, take by weighing 5.0gMoCo again
3, mix to be placed in the ball mill under noble gas (as argon gas) protection ball milling 4 hours, obtain composite good hydrogen storing alloy powder after the taking-up.Prepare the composite WCo of 55.0g again with similar approach
3MLNi
3.8Co
0.5Mn
0.4Al
0.2Li
0.1Hydrogen storing alloy powder.
Electrode preparation, is coated with into 2.0 * 2.0cm with PVA solution mixing for the composite back of 0.55g alloyed powder (containing the former powder of 0.50g)
2Foaming nickel substrate, dry back compression moulding.As a comparison, with former powder by making electrode with quadrat method.Three electrode galvanostatic methods are adopted in the discharge capacity test of electrode.Electrolyte is 5NKOH solution, Ni (OH)
2Electrode is made auxiliary electrode, and Hg/HgO (5NKOH) electrode is a reference electrode, measures under the room temperature.General discharging current is that 25mA (about 0.2C) final voltage is-0.740Vvs.Hg/HgO, charges and discharge repeatedly.Heavy-current discharge stops current potential.
Fig. 3 is activation number of times and discharge capacity graph of a relation (wherein, B: former powder, C: former powder+MoCo
3, D: former powder+WCo
3), as can be seen from Figure 3, the composite MoCo of hydrogen storing alloy powder
3And WCo
3Back performance has had obvious improvement, and discharge capacity is brought up to 300mAh/g from 250mAh/g, and the period 1 discharge capacity promptly reached high level, has superior activity function.
The composite MoCo of hydrogen storing alloy powder
3, WCo
3Discharge platform is milder before more composite during latter made electrode 25mA discharge, and discharge platform is high, also milder before more composite during the 125mA discharge.With C
1C/ C
0.2CThe high-rate discharge capacity of expression alloyed powder, table 1 are multiplying power discharging storage power, can find out from table 1, and composite back high-rate discharge capacity significantly improves.Embodiment 2.
With the composite MoCo of 0.11g
3MLNi
3.8Co
0.5Mn
0.4Al
0.2Li
0.1Alloyed powder is coated with into 1 * 1cm
2Foaming nickel substrate, dry back compression moulding; Equally the former powder of 0.10g is made electrode, will carry out ac impedance measurement after 5 cycles of two electrode activations.The ac impedance measurement data are handled with computer applied algorithm, the spectrogram that can draw, and obtain its electrode reaction resistance value.Table 2. is AC impedance values, can find out: the electrode reaction resistance value of composite rear electrode reduces, and the reactivity that helps electrode improves.
Table 1
| Alloyed powder | C 1C/C 0.2C |
| Former powder | 0.885 |
| Former powder+MoCo 3 | 0.944 |
| Former powder+WCo 3 | 0.944 |
Table 2
| Alloyed powder | Rr(ohm.g) |
| Former powder | 0.484 |
| Former powder+MoCo 3 | 0.182 |
Claims (4)
1. a compounded hydrogen-storage alloy electrode material is characterized in that it is bianry alloy MN
3With lanthanon hydrogen storage alloy, nickel titante series hydrogen bearing alloy or zirconium be that the Laves phase hydrogen storage alloy carries out composite forming; Wherein, M=Mo, W, N=Co, Ni, bianry alloy MN
3Weight accounts for 1.0%～20.0% of hydrogen bearing alloy weight.
2. a manufacture method for preparing the described compounded hydrogen-storage alloy electrode material of claim 1 is characterized in that it is to adopt chemical synthesis process directly to prepare bianry alloy MN
3Alloy powder is the Laves phase hydrogen storage alloy with lanthanon hydrogen storage alloy, nickel titante series hydrogen bearing alloy or zirconium respectively again, mixes to be placed in the ball mill under the noble gas protection ball milling 0.5～6 hour, promptly obtains composite good hydrogen storing alloy powder.
3. according to the manufacture method of the described compounded hydrogen-storage alloy electrode material of claim 2, it is characterized in that MoCo
3Or WCo
3Be through the following steps preparation:
Press stoicheiometry ammonium molybdate or ammonium tungstate are mixed with cobalt nitrate, ground 400 mesh sieves, mixing; under the nitrogen atmosphere protection, be heated to 400～500 ℃, constant temperature 0.5～2 hour; be warming up to 900～1200 ℃ then, constant temperature 2～6 hours makes the bianry alloy powder after the cooling.
4. according to the manufacture method of the described compounded hydrogen-storage alloy electrode material of claim 2, it is characterized in that MoNi
3Or WNi
3Be through the following steps preparation:
The nickel nitrate solution of metering is heated to 80～100 ℃, stirs and splash into sodium carbonate liquor, the control terminal point is in pH=10～13,3～5 filtering and washing repeatedly, and drying grinds, and obtains basic nickel carbonate.Take by weighing ammonium molybdate or ammonium tungstate and basic nickel carbonate in Mo or W and 1: 3 ratio of Ni atomic ratio, under hydrogen atmosphere, heat behind the mixing, progressively heat up, 80～120 ℃ of constant temperature 0.5～1 hour, 170～230 ℃ of constant temperature 0.5～1 hour is warming up to 1000～1300 ℃, keeps 1～6 hour, reduce to 400 ℃ and change argon gas into, obtain the bianry alloy powder after the cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119425A CN1050230C (en) | 1997-10-17 | 1997-10-17 | Compounded hydrogen-storage alloy electrode material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119425A CN1050230C (en) | 1997-10-17 | 1997-10-17 | Compounded hydrogen-storage alloy electrode material |
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| Publication Number | Publication Date |
|---|---|
| CN1177845A CN1177845A (en) | 1998-04-01 |
| CN1050230C true CN1050230C (en) | 2000-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97119425A Expired - Fee Related CN1050230C (en) | 1997-10-17 | 1997-10-17 | Compounded hydrogen-storage alloy electrode material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100566A (en) * | 1994-06-28 | 1995-03-22 | 北京大学 | Lattice-defective metal and hydrogen-storing alloy composite, its preparation and usage thereof |
| CN1119349A (en) * | 1995-07-03 | 1996-03-27 | 陈有孝 | Hydrogen storing alloy material for large-size nickel-hydride secondary battery |
-
1997
- 1997-10-17 CN CN97119425A patent/CN1050230C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100566A (en) * | 1994-06-28 | 1995-03-22 | 北京大学 | Lattice-defective metal and hydrogen-storing alloy composite, its preparation and usage thereof |
| CN1119349A (en) * | 1995-07-03 | 1996-03-27 | 陈有孝 | Hydrogen storing alloy material for large-size nickel-hydride secondary battery |
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| Publication number | Publication date |
|---|---|
| CN1177845A (en) | 1998-04-01 |
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