CN102315460A - Zinc-air cell air electrode catalyst and preparation method thereof - Google Patents
Zinc-air cell air electrode catalyst and preparation method thereof Download PDFInfo
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- CN102315460A CN102315460A CN201110254606A CN201110254606A CN102315460A CN 102315460 A CN102315460 A CN 102315460A CN 201110254606 A CN201110254606 A CN 201110254606A CN 201110254606 A CN201110254606 A CN 201110254606A CN 102315460 A CN102315460 A CN 102315460A
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- electrode catalyst
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a zinc-air cell air electrode catalyst and a preparation method thereof. The general formula for the air electrode catalyst is NixAl1-xMn2O4, wherein, x is no less than 0 and no more than 1. The preparation method comprises the following steps: weighing a mixture of nickel nitrate and aluminum nitrate according to a mol ratio of Ni to Al of x to 1-x and ammonium oxalate, and respectively dissolving the above-mentioned components in deionized water; mixing prepared solutions, and allowing the mixture to react to produce precipitate, wherein, a pH value in the reaction process is controlled to be in a range of 4.0 to 7.0; rinsing, filtering and drying the prepared precipitate, uniformly grinding the precipitate in manganese nitrate, and carrying out calcining at a temperature of 500 DEG C for three hours; pressing a calcined mixture into a sheet, calcining the sheet at a temperature of 950 to 1050 DEG C for four hours, annealing the sheet at a temperature of 500 DEG C for five hours, and cooling the sheet to room temperature. According to the invention, NixAl1-xMn2O4 with a spinel crystalline structure is prepared by using the method of oxalic acid coprecipitation; raw materials for preparing the air electrode catalyst are cheap, and the prepared air electrode catalyst has the advantages of high catalytic activity, good chemical stability, etc.
Description
Technical field
The present invention relates to technical field of chemical power, particularly air electrode catalyst of a kind of zinc-air cell and preparation method thereof.
Background technology
In zinc and air cell, the catalyst of the catalytic performance of raising air electrode, searching Cheap highly effective is the focus of zinc and air cell research.Catalyst as air electrode mainly contains traditional active carbon, electrolysis MnO at present
2Deng, noble metal and alloy thereof, like Pt, Ag and Pt alloy etc., and some metal oxides, like the green stone type of Jiao oxide, perofskite type oxide and spinel oxides etc.Wherein traditional active carbon, electrolysis MnO that adopts
2Catalytic activity Deng catalyst is lower, makes the reaction speed of oxygen on electrochemical interface slower, thereby has limited the discharge current density of zinc-air cell, makes it can only be applied to low-power equipment; Noble metal and alloy thereof, like catalyst such as Pt, Ag and Pt alloys than active carbon, electrolysis MnO
2Catalytic activity Deng catalyst increases, but noble metal costs an arm and a leg, and has still satisfied not the instructions for use of home electronics with its discharge current density as catalyst cell, thereby also can not get large-scale application; Catalyst such as burnt green stone type oxide, perofskite type oxide and spinel oxides have catalytic activity height, conductivity advantages of higher; Be very promising novel air electrode catalyst system, transition metal spinel oxides wherein especially receives much concern because of its good conductivity and electro catalytic activity.Chinese patent 01104488.4 discloses a kind of catalyst of air electrode of zinc-air cell, and its chemical structural formula is LiMn
2-xCo
xO
4, x=0～0.5 mol ratio wherein, the discharge current density of zinc-air cell of making catalyst with this material is with electrolysis MnO
2Improve for the discharge current density of the zinc-air cell of catalyst has had significantly, its optimal discharge current density can reach 150mA/ ㎝
2More than; Chinese patent 200510032676.x discloses a kind of preparation method of zinc-air cell eelctro-catalyst, adopts the synthetic LiMn of solwution method
2-xCo
xO
4Metal oxide can be up to 258 mA/ ㎝ in the optimum polarization current density the under-0.6V polarization potential with the zinc-air cell of the catalyst assembling of this method preparation
2Chinese patent 200710028839.6 discloses eelctro-catalyst of a kind of zinc-air cell and preparation method thereof, and the general formula of this eelctro-catalyst is LiNi
xCo
yFe
zMn
2-x-y-zO
4, be that the salt with transition metal such as Mn, Ni, Fe, Co is a base-material, adopt Prepared by Sol Gel Method and; Use the heat treatment temperature of this method lower, heat treatment time is shorter; The microstructure of course of reaction and collosol and gel all is easy to control, and side reaction is less, and the conversion ratio of product is higher.Yet still there is following problem in above-mentioned technology:
1, the price of Co material is high, thereby makes the business-like cost of its material also higher;
2, in alkaline electrolyte, the chemical stability of metal Co element is relatively poor, thereby has influenced the useful life of battery.
Summary of the invention
The objective of the invention is to provide the air electrode catalyst of the zinc-air cell that a kind of prices of raw and semifnished materials are cheap, catalytic activity is high, chemical stability is good to the existing problem of above-mentioned existing zinc-air cell.
Another object of the present invention is the preparation method who is to provide the air electrode catalyst of above-mentioned zinc-air cell, and this preparation method adopts oxalic acid coprecipitation to prepare the Ni with spinel-type crystalline structure
xAl
1-xMn
2O
4
The object of the invention is realized through following technical proposals:
The air electrode catalyst of zinc-air cell of the present invention, its general formula are Ni
xAl
1-xMn
2O
4, wherein, 0≤x≤1.
Preferably, the general formula of said air electrode catalyst is Ni
xAl
1-xMn
2O
4, wherein, 0≤x≤0.35.
The preparation method of the air electrode catalyst of above-mentioned zinc-air cell may further comprise the steps:
The first step: mixture and ammonium oxalate by the mol ratio Ni:Al=x:1-x of material takes by weighing nickel nitrate, aluminum nitrate are dissolved in the deionized water respectively;
In second step, the solution that the first step is prepared evenly splashes in the reactor of continuous stirring simultaneously, makes it hybrid reaction until reacting completely, and generates oxalate precipitation, controls PH=4.0～7.0 in the course of reaction;
The 3rd step went on foot the precipitate with deionized water that makes with second and washs, filters, dries, and the deposition powder after the oven dry grinds in manganese nitrate evenly, calcines 3h down at 500 ℃;
In the 4th step, the mixture that calcining in the 3rd step is obtained is pressed into sheet, and again at 500 ℃ of annealing 5h, cool to room temperature promptly gets the air electrode catalyst of zinc-air cell behind 950～1050 ℃ of calcining 4h.
Compared with prior art, air electrode of zinc-air cell catalyst of the present invention has good catalytic action to air electrode, can obviously reduce the polarization of hydrogen reduction process; Compare with the eelctro-catalyst of other spinel structures that adopt the Co material simultaneously, catalysagen material price of the present invention is cheap, chemical stability good.
Description of drawings
Fig. 1 is the Ni of embodiment 2 gained
0.35Al
0.65Mn
2O
4XRD spectra;
Fig. 2 is the Ni of embodiment 3 gained
0.5Al
0.5Mn
2O
4XRD spectra;
Fig. 3 is the Ni of embodiment 1 gained
0.2Al
0.8Mn
2O
415000 multiplying powers under SEM figure;
Fig. 4 is the Ni of embodiment 1 gained
0.2Al
0.8Mn
2O
45000 multiplying powers under SEM figure;
Fig. 5 is the Ni of embodiment 4 gained
0.7Al
0.3Mn
2O
415000 multiplying powers under SEM figure;
Fig. 6 is the Ni of embodiment 4 gained
0.7Al
0.3Mn
2O
45000 multiplying powers under SEM figure;
Fig. 7 is the cathodic polarization curve figure of the different catalysts among the embodiment 10;
Wherein, 1:Ni
0.2Al
0.8Mn
2O
4, 2:Ni
0.35Al
0.65Mn
2O
4, 3:Ni
0.5Al
0.5Mn
2O
4, 4:Ni
0.7Al
0.3Mn
2O
4, 5:Ni
0.8Al
0.2Mn
2O
4, 6:AlMn
2O
4, 7:NiMn
2O
4
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further specified.Should be understood that following examples only are used to the present invention is described but not are used to limit scope of the present invention.
Embodiment 1
The mol ratio of getting Ni ion and Al ion is the nickel nitrate (Ni (NO of 0.2:0.8
3)
2.6H
2O analyzes pure) and aluminum nitrate (Al (NO
3)
3, analyze pure) mixture and ammonium oxalate ((NH
4)
2C
2O
4.H
2O; Analyze pure) be dissolved in respectively in the deionized water, ammonium oxalate solution and mixed solution are side by side evenly splashed in the reactor of continuous stirring, make it hybrid reaction till two kinds of solution complete reactions; Generate oxalate precipitation, control PH=4.0～7.0 in the course of reaction; The precipitate with deionized water washing that obtains is filtered oven dry for several times; The deposition powder of oven dry grinds in a certain amount of manganese nitrate evenly; Calcine 3h down at 500 ℃, make oxalate coprecipitation and manganese nitrate accomplish and be decomposed into oxide, the mixed oxide that obtains after decomposing is pressed into sheet; It is fully contacted; Behind 950～1050 ℃ of calcining 4h, at 500 ℃ of annealing 5h, cool to room temperature promptly gets Ni again
0.2Al
0.8Mn
2O
4
Embodiment 2
Present embodiment is with embodiment 1, and institute's difference is: the mol ratio of Ni ion and Al ion is 0.35:0.65 in the mixture of nickel nitrate and aluminum nitrate; That obtain is Ni
0.35Al
0.65Mn
2O
4
Embodiment 3
Present embodiment is with embodiment 1, and institute's difference is: the mol ratio of Ni ion and Al ion is 0.5:0.5 in the mixture of nickel nitrate and aluminum nitrate, and that obtain is Ni
0.5Al
0.5Mn
2O
4
Embodiment 4
Present embodiment is with embodiment 1, and institute's difference is: the mol ratio of Ni ion and Al ion is 0.7:0.3 in the mixture of nickel nitrate and aluminum nitrate, and that obtain is Ni
0.7Al
0.3Mn
2O
4
Embodiment 5
Present embodiment is with embodiment 1, and institute's difference is: the mol ratio of Ni ion and Al ion is 0.8:0.2 in the mixture of nickel nitrate and aluminum nitrate, and that obtain is Ni
0.8Al
0.2Mn
2O
4
Embodiment 6
Present embodiment is with embodiment 1, and institute's difference is: the mol ratio of Ni ion and Al ion is 0:1 in the mixture of nickel nitrate and aluminum nitrate, does not promptly contain nickel nitrate; That obtain is AlMn
2O
4
Embodiment 7
Present embodiment is with embodiment 1, and institute's difference is: the mol ratio of Ni ion and Al ion is 1:0 in the mixture of nickel nitrate and aluminum nitrate, does not promptly contain aluminum nitrate; That obtain is NiMn
2O
4
Embodiment 8
To resulting Ni in embodiment 2 and 3
0.35Al
0.65Mn
2O
4And Ni
0.5Al
0.5Mn
2O
4Sample adopts X-ray diffractometer to carry out structure and material phase analysis, its powder diffraction XRD spectra respectively like Fig. 1, shown in 2, from figure, can judge: two samples are spinel-type, and its cell parameter is 0.83725nm.
Embodiment 9
To resulting Ni in embodiment 1 and 4
0.2Al
0.8Mn
2O
4And Ni
0.7Al
0.3Mn
2O
4Sample adopts the morphology change of scanning electron microscopic observation material, shown in Fig. 3～6, can find out: particle is the cube crystalline of rule, and particle size distribution range is narrower, Ni
0.2Al
0.8Mn
2O
4Particle compare Ni
0.7Al
0.3Mn
2O
4Particle thinner.Well known to a person skilled in the art it is that particle is thinner, distribution is more even, the particle agglomeration phenomenon is just not obvious more, catalytic active center is more, and catalytic performance is better.
Catalyst with 15% and 85% graphite and active carbon (wherein, the mass ratio of graphite and active carbon is 8:1) ball mill mixing is even.Cross 200 mesh sieves, add polytetrafluoroethylsolution solution, stir into pasty state, be coated in uniformly on the currect collecting net, 110 ℃ of dry 12h were with 15Mpa compacting 3 minutes; (7mol/L KOH) makes reference electrode with the Hg/HgO electrode, and nickel electrode is made auxiliary electrode, forms three-electrode system, carries out the measurement of polarization curve with electrochemical workstation, and probe temperature is 25 ℃.Said catalyst adopts embodiment 1～7 resulting Ni respectively
0.2Al
0.8Mn
2O
4, Ni
0.35Al
0.65Mn
2O
4, Ni
0.5Al
0.5Mn
2O
4, Ni
0.7Al
0.3Mn
2O
4, Ni
0.8Al
0.2Mn
2O
4, AlMn
2O
4And NiMn
2O
4The result is as shown in Figure 7: curve 1～7 all has slope preferably, further illustrates the Ni of spinel structure
xAl
1-xMn
2O
4Air electrode there is good catalytic action, can obviously reduces the polarization of hydrogen reduction process; Wherein curve 2 has greatest gradient, and curve 1 is only second to curve 2, and curve 6 is only second to curve 1, and is bigger than the slope of curve 3,4,5,7; Shown that the polarization of electrode hydrogen reduction is less when 0≤x≤0.35, the catalytic effect of catalyst is better.In addition, compare with the eelctro-catalyst of other spinel structures that adopt the Co material, catalysagen material price of the present invention is cheap, chemical stability good.
Claims (3)
1. the air electrode catalyst of a zinc-air cell is characterized in that, the general formula of said air electrode catalyst is Ni
xAl
1-xMn
2O
4, wherein, 0≤x≤1.
2. the air electrode catalyst of zinc-air cell according to claim 1 is characterized in that, said air electrode catalyst general formula Ni
xAl
1-xMn
2O
4In 0≤x≤0.35.
3. the preparation method of the air electrode catalyst of a zinc-air cell according to claim 1 is characterized in that, may further comprise the steps:
The first step: mixture and ammonium oxalate by the mol ratio Ni:Al=x:1-x of material takes by weighing nickel nitrate, aluminum nitrate are dissolved in the deionized water respectively;
In second step, the solution that the first step is prepared evenly splashes in the reactor of continuous stirring simultaneously, makes it hybrid reaction until reacting completely, and generates oxalate precipitation, controls PH=4.0～7.0 in the course of reaction;
The 3rd step went on foot the precipitate with deionized water that makes with second and washs, filters, dries, and the deposition powder after the oven dry grinds in manganese nitrate evenly, calcines 3h down at 500 ℃;
In the 4th step, the mixture that calcining in the 3rd step is obtained is pressed into sheet, and again at 500 ℃ of annealing 5h, cool to room temperature promptly gets the air electrode catalyst of zinc-air cell behind 950～1050 ℃ of calcining 4h.
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| CN201110254606A CN102315460A (en) | 2011-08-31 | 2011-08-31 | Zinc-air cell air electrode catalyst and preparation method thereof |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579638A (en) * | 2013-11-11 | 2014-02-12 | 上海中聚佳华电池科技有限公司 | Air electrode catalyst of lithium air battery and preparation method of air electrode catalyst |
| CN105609794A (en) * | 2016-01-18 | 2016-05-25 | 湖南众麒能源科技有限责任公司 | Air electrode catalyst for zinc-air battery and preparation method of air electrode catalyst |
| CN114917921A (en) * | 2022-06-08 | 2022-08-19 | 珠海格力电器股份有限公司 | NiMnAl hydrotalcite-like catalyst and preparation method and application thereof |
-
2011
- 2011-08-31 CN CN201110254606A patent/CN102315460A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579638A (en) * | 2013-11-11 | 2014-02-12 | 上海中聚佳华电池科技有限公司 | Air electrode catalyst of lithium air battery and preparation method of air electrode catalyst |
| CN103579638B (en) * | 2013-11-11 | 2016-04-27 | 上海中聚佳华电池科技有限公司 | Air electrode catalyst of lithium-air battery and preparation method thereof |
| CN105609794A (en) * | 2016-01-18 | 2016-05-25 | 湖南众麒能源科技有限责任公司 | Air electrode catalyst for zinc-air battery and preparation method of air electrode catalyst |
| CN105609794B (en) * | 2016-01-18 | 2018-12-21 | 长沙锦锋新能源科技有限公司 | A kind of air electrode catalyst of zinc-air battery and preparation method thereof |
| CN114917921A (en) * | 2022-06-08 | 2022-08-19 | 珠海格力电器股份有限公司 | NiMnAl hydrotalcite-like catalyst and preparation method and application thereof |
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Application publication date: 20120111 |