CN102810665A - Method for improving electrochemical performance of hydrogen storing alloy by using polypyrrole - Google Patents
Method for improving electrochemical performance of hydrogen storing alloy by using polypyrrole Download PDFInfo
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- CN102810665A CN102810665A CN2012102644786A CN201210264478A CN102810665A CN 102810665 A CN102810665 A CN 102810665A CN 2012102644786 A CN2012102644786 A CN 2012102644786A CN 201210264478 A CN201210264478 A CN 201210264478A CN 102810665 A CN102810665 A CN 102810665A
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- hydrogen
- alloy powder
- hydrogen storing
- storing alloy
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for improving electrochemical performance of hydrogen storing alloy by using polypyrrole. The method mainly comprises the steps of: preparing mixed solution from pyrrole, oxidant and water; soaking 100-400 meshes of hydrogen storing alloy powder into the mixed solution; agitating for 3-20 minutes under the condition that the agitating speed is 120-300 r/min; putting the reacted hydrogen storing alloy powder into a vacuum drying box to dry in vacuum after washing and extracting, and forming a conductive polypyrrole film with a sponge fiber structure oxidized and attached to the surface of the hydrogen storing alloy powder. The method is simple in process condition, easy to obtain the material, free of poison and pollution and suitable for being used as the hydrogen storing alloy of a nickel-metal hydride battery cathode material, and the combination degree and uniformity of the polypyrrole and the surface of the hydrogen storing alloy powder can be improved, thereby improving high-rate discharge capability and circulating stability of a hydrogen storing alloy electrode.
Description
Technical field:
The present invention relates to a kind of battery material, particularly the hydrogen-storage alloy process for treating surface.
Background technology:
Advantages such as Ni-MH battery (MH-Ni battery) is novel high-performance, free of contamination secondary cell, has the energy density height, has extended cycle life, and environment compatibility is good are used widely in fields such as electric motor car (EV) and various portable Military Electronic Equipment.Along with improving constantly of productive life level, energy demand increases day by day, and as the main negative material of MH-Ni battery, hydrogen-storage alloy is expressed more and more high expectation.Therefore, searching can improve the method for hydrogen-storage alloy performance, becomes to enlarge MH-Ni Battery Market competitiveness and the key point of widening its range of application.
1992, Japanese scientist's clothes portion great [TOHKEMY is put down 4-259762A] disclosed a kind of polyaniline that utilizes and has been plated on the method that its self-discharge performance is improved on the hydrogen-storage alloy surface, and the polyaniline plating amount that this method is announced is less, and it is very limited to improve effect.2007; The Xu Fen of the Chinese Academy of Sciences (China application (patent) number: 200710011049.7) disclose a kind of with mode and the hydrogen-storage alloy composite methods of macromolecule (polyaniline, polypyrrole, polythiophene) through ball milling; Process nickel-hydrogen battery negative pole material, improve its cyclical stability.But can obviously find, add, be difficult to make macromolecule and alloy fully to mix, and very easily generate amorphous phase, be prone to the body alloy is had side effects through ball milling method.In order to improve the action effect of conductive polymer polyanilinc to the hydrogen-storage alloy performance impact; 200910227963.4), ((the China's application (patent) number: 201110158364.9) of " utilizing the electropolymerization polyaniline to improve the method for electrochemical properties of hydrogen storage alloy powder " patent of invention we are respectively at declaring (the China's application (patent) number: of " a kind of method of improving electrochemical properties of hydrogen storage alloy powder by using polyaniline " patent of invention in 2009 and 2011; The mode through chemical deposition and electropolymerization more than applied for a patent respectively is at the coralloid polyaniline rete of hydrogen-storage alloy coating surface one deck; Through being different from [TOHKEMY is put down 4-259762A] described plating polyaniline form and plating amount, improved the high-rate discharge ability and the cyclical stability of hydrogen-storage alloy significantly.But above patent can find that aniline monomer required in the polyaniline building-up process has toxicity, with the direct or indirect operating environment that influences to a certain extent, causes chemical contamination.
Summary of the invention:
The object of the present invention is to provide that a kind of technology is simple, the application polypyrrole of nontoxic pollution-free, conjugation and good uniformity improves the method for hydrogen-storage alloy chemical property.The present invention utilizes the auto polymerization of pyrroles's nothing electricity to be reflected at the hydrogen-storage alloy powder surface to form the polypyrrole coating film with spongy fibre structure conductivity and corrosion resistance.
Method of the present invention is following:
1, by the pyrroles: oxidant: the mol ratio of water=1.25～25 * 10
-3: 0.9～9 * 10
-3: 1, pyrroles, oxidant and water are mixed with mixed solution; Above-mentioned oxidant is ammonium persulfate, potassium bichromate or hydrogen peroxide.
2, press the mass ratio=0.2～1.5:1 of hydrogen-storage alloy powder and above-mentioned mixed solution, 100-400 purpose hydrogen-storage alloy powder is immersed in the above-mentioned mixed solution, low whipping speed is to stir 3～20min under 120～300 rev/mins the condition.
3, with above-mentioned reacted hydrogen-storage alloy powder through the washing, suction filtration, place vacuum drying chamber vacuumize.
The present invention compared with prior art has following advantage:
1, operating process and technology are simple, need not to add organic solvent in the polypyrrole generative process, and production cost is low.
2, nontoxic pollution-free only has a spot of pyrroles's oligomer in the waste liquid, can be through simple mechanical filter recycling.
3, improve the conjugation and the uniformity on polypyrrole and alloy powder surface, thereby improved the high-rate discharge ability and the cyclical stability of hydrogen-storage alloy.
Description of drawings:
Fig. 1 is AB before and after handling among the embodiment 1
5Type (MlNi
4.20Mn
0.30Co
0.42Al
0.23) the field emission scanning electron microscope figure of hydrogen-storage alloy powder.(a) being untreated hydrogen-storage alloy powder, (b) is the hydrogen-storage alloy powder after handling.
Fig. 2 is AB before and after handling among the embodiment 1
5Type (MlNi
4.20Mn
0.30Co
0.42Al
0.23) the FFIR curve of hydrogen-storage alloy powder.(a) being untreated hydrogen-storage alloy powder, (b) is the hydrogen-storage alloy powder after handling.
Fig. 3 is AB before and after handling among the embodiment 1
5Type (MlNi
4.20Mn
0.30Co
0.42Al
0.23) the multiplying power discharging property curve of hydrogen-occlussion alloy electrode.(a) being untreated hydrogen-occlussion alloy electrode, (b) is the hydrogen-occlussion alloy electrode after handling.
Fig. 4 is AB before and after handling among the embodiment 1
5Type (MlNi
4.20Mn
0.30Co
0.42Al
0.23) the stable circulation linearity curve of hydrogen-occlussion alloy electrode.(a) being untreated hydrogen-occlussion alloy electrode, (b) is the hydrogen-occlussion alloy electrode after handling.
Embodiment:
Embodiment 1
Preparation 100ml contains the mixed aqueous solution of pyrroles 1ml, hydrogen peroxide 1ml; In above-mentioned mixed solution, add 100-200 order 20g AB
5Type (MlNi
4.20Mn
0.30Co
0.42Al
0.23) hydrogen-storage alloy powder, low whipping speed is to stir 8min under the 180 commentaries on classics/min conditions; Above-mentioned reacted hydrogen-storage alloy powder through washing, suction filtration, is placed vacuum drying chamber vacuumize.
As shown in Figure 1, handle the back alloy surface and generate spongy fibre structure polypyrrole rete.
As shown in Figure 2, handle the pyrrole ring characteristic peak 1560cm that polypyrrole appears in the back alloy in the fourier-transform infrared collection of illustrative plates
-1, 1480cm
-1, the out-of-plane vibration characteristic peak 1160cm of C-N stretching vibration and C-C
-1And 906cm
-1, and the in-plane deformation vibration peak of C-H and N-H is 1041cm
-1To sum up, provable polypyrrole rete plating is in the alloying pellet surface.
Like Fig. 3 and shown in Figure 4, alloy powder is processed the hydrogen storage electrode negative pole before and after will handling, and uses Ni (OH)
2(capacity is more than 4 times of negative material capacity to/NiOOH electrode as positive pole; To guarantee accurately to test the performance of negative material); Form the half-cell test macro with the KOH aqueous solution of 6M as electrolyte, use the chemical property of DC-5 cell tester test negative pole.Test condition is under 25 ℃, and multiplying power discharging test charging current is 45mA/g, and discharging current is respectively 9mA/g, 45mA/g, 90mA/g, 135mA/g, 180mA/g and 225mA/g; Stable circulation property testing charging current is 45mA/g, and discharging current is 9mA/g, 100 weeks of repeated charge-discharge cycles.The charge and discharge cycles test result shows: hydrogen-occlussion alloy electrode high-rate discharge ability HRD (HRD=C
i/ C
Max* 100%; C
iBe discharge capacity under the different discharge current densities, C
MaxBe big discharge capacity.) bring up to 30.9%, cyclical stability S from 17.6%
100(S
100=C
100/ C
Max* 100%; C
100For discharging and recharging discharge capacity under the 100th week.) bring up to 94.4% from 92.8%.
Embodiment 2
Preparation 100ml contains the mixed aqueous solution of pyrroles 0.25ml, ammonium persulfate 0.25g; In above-mentioned mixed solution, add 200-400 order 30g AB
3Type (La
0.88Mg
0.12Ni
2.95Mn
0.10Co
0.55Al
0.10) hydrogen-storage alloy powder, low whipping speed is to stir 13min under the 120 commentaries on classics/min conditions; Above-mentioned reacted hydrogen-storage alloy powder through washing, suction filtration, is placed vacuum drying chamber vacuumize.
Alloy powder is processed electrode and is carried out electro-chemical test before and after will handling, and experiment condition is with embodiment 1.Experimental result shows: hydrogen-occlussion alloy electrode high-rate discharge ability HRD brings up to 28.5%, cyclical stability S from 13%
100Bring up to 93.4% from 89.2%.
Embodiment 3
Preparation 100ml contains the mixed aqueous solution of pyrroles 5ml, potassium bichromate 1g; In above-mentioned mixed solution, add 100-300 order 150g AB
5Type (La
0.60Ce
0.28Pr
0.03Nd
0.09Ni
3.94Mn
0.31Co
0.45Al
0.26) hydrogen-storage alloy powder, low whipping speed is to stir 3min under the 220 commentaries on classics/min conditions; Above-mentioned reacted hydrogen-storage alloy powder through washing, suction filtration, is placed vacuum drying chamber vacuumize.
Alloy powder is processed electrode and is carried out electro-chemical test before and after will handling, and experiment condition is with embodiment 1.Experimental result shows: hydrogen-occlussion alloy electrode high-rate discharge ability HRD brings up to 28.5%, cyclical stability S from 13%
100Bring up to 93.4% from 89.2%.
Embodiment 4
Preparation 100ml contains the mixed aqueous solution of pyrroles 1.25ml, hydrogen peroxide 1.25ml; In above-mentioned mixed solution, add 100-200 order 80g AB
2Type (Zr
0.9Ti
0.1Ni
1.2Mn
0.6V
0.2) hydrogen-storage alloy powder, low whipping speed is to stir 20min under the 300 commentaries on classics/min conditions; Above-mentioned reacted hydrogen-storage alloy powder through washing, suction filtration, is placed vacuum drying chamber vacuumize.
Alloy powder is processed electrode and is carried out electro-chemical test before and after will handling, and experiment condition is with embodiment 1.Experimental result shows: hydrogen-occlussion alloy electrode high-rate discharge ability HRD brings up to 28.5%, cyclical stability S from 13%
100Bring up to 93.4% from 89.2%.
Embodiment 5
Preparation 100ml contains the mixed aqueous solution of pyrroles 0.5ml, ammonium persulfate 0.25g; In above-mentioned mixed solution, add 300-400 order 25g AB
3Type (La
0.85Mg
0.15Ni
2.90Mn
0.20Co
0.55Al
0.05) hydrogen-storage alloy powder, low whipping speed is to stir 17min under the 160 commentaries on classics/min conditions; Above-mentioned reacted hydrogen-storage alloy powder through washing, suction filtration, is placed vacuum drying chamber vacuumize.
Alloy powder is processed electrode and is carried out electro-chemical test before and after will handling, and experiment condition is with embodiment 1.Experimental result shows: hydrogen-occlussion alloy electrode high-rate discharge ability HRD brings up to 28.5%, cyclical stability S from 13%
100Bring up to 93.4% from 89.2%.
Claims (1)
1. use the method that polypyrrole improves electrochemical properties of hydrogen storage alloy powder for one kind, it is characterized in that:
(1) by the pyrroles: oxidant: the mol ratio of water=1.25～25 * 10
-3: 0.9～9 * 10
-3: 1, pyrroles, oxidant and water are mixed with mixed solution, above-mentioned oxidant is ammonium persulfate, potassium bichromate or hydrogen peroxide;
(2) press the mass ratio=0.2～1.5:1 of hydrogen-storage alloy powder and above-mentioned mixed solution, 100-400 purpose hydrogen-storage alloy powder is immersed in the above-mentioned mixed solution, low whipping speed is to stir 3～20min under 120～300 rev/mins the condition;
(3) with above-mentioned reacted hydrogen-storage alloy powder through the washing, suction filtration, place vacuum drying chamber vacuumize.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078093A (en) * | 2012-12-20 | 2013-05-01 | 燕山大学 | Method for modifying electrochemical performance of hydrogen storing alloy by applying nickel/polyaniline |
| CN103904308A (en) * | 2014-03-06 | 2014-07-02 | 燕山大学 | Method for improving electrochemical performance of hydrogen storage alloy through application of nickel/polypyrrole |
| CN107293752A (en) * | 2017-06-20 | 2017-10-24 | 燕山大学 | A kind of plating polyaniline that evaporates improves the method for negative plate of nickel-hydrogen battery chemical property |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10261409A (en) * | 1997-03-18 | 1998-09-29 | Sanyo Electric Co Ltd | Hydrogen storage alloy electrode and manufacture thereof |
| CN101289576A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Composite material of conducting high polymers/alloy for nickel-hydrogen battery and preparation thereof |
| CN101728527A (en) * | 2009-12-01 | 2010-06-09 | 燕山大学 | Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline |
-
2012
- 2012-07-30 CN CN2012102644786A patent/CN102810665A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10261409A (en) * | 1997-03-18 | 1998-09-29 | Sanyo Electric Co Ltd | Hydrogen storage alloy electrode and manufacture thereof |
| CN101289576A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Composite material of conducting high polymers/alloy for nickel-hydrogen battery and preparation thereof |
| CN101728527A (en) * | 2009-12-01 | 2010-06-09 | 燕山大学 | Method for improving electrochemical properties of hydrogen storage alloy powder by using polyaniline |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078093A (en) * | 2012-12-20 | 2013-05-01 | 燕山大学 | Method for modifying electrochemical performance of hydrogen storing alloy by applying nickel/polyaniline |
| CN103078093B (en) * | 2012-12-20 | 2015-09-16 | 燕山大学 | A kind of application of nickel/polyaniline improves the method for Electrochemical Performance of Hydrogen Storage Alloy |
| CN103904308A (en) * | 2014-03-06 | 2014-07-02 | 燕山大学 | Method for improving electrochemical performance of hydrogen storage alloy through application of nickel/polypyrrole |
| CN107293752A (en) * | 2017-06-20 | 2017-10-24 | 燕山大学 | A kind of plating polyaniline that evaporates improves the method for negative plate of nickel-hydrogen battery chemical property |
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Application publication date: 20121205 |