CN100431210C - Air electrode catalyst of zn air cell added with lead oxide - Google Patents
Air electrode catalyst of zn air cell added with lead oxide Download PDFInfo
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- CN100431210C CN100431210C CNB2004100136313A CN200410013631A CN100431210C CN 100431210 C CN100431210 C CN 100431210C CN B2004100136313 A CNB2004100136313 A CN B2004100136313A CN 200410013631 A CN200410013631 A CN 200410013631A CN 100431210 C CN100431210 C CN 100431210C
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to an air electrode catalyst of a Zn-air cell added with lead oxide, which is a carbon carried catalyst, wherein the carbon carried catalyst comprises MnO2 and lead oxide, and is manufactured by that lead acetate is added in active carbon and manganous nitrate by a solid phase calcination method. The present invention has the advantages of simple technology for manufacturing the catalyst, low price and high catalytic activity. Compared with MnO2 catalysts without adding the lead oxide, the present invention can enhance the discharge voltage of the catalyst under the same density of discharging current. The present invention can be totally used for air electrodes of Zn-air cells.
Description
Technical field
The present invention relates to a kind of air electrode of zinc-air cell catalyst that adds lead oxides of electrochemical field.
Background technology
Zinc-air cell is to be the negative electrode active material of battery with zinc, is the battery of positive active material with airborne oxygen.Because airborne oxygen is desirable at any time, do not take battery space again, therefore in equal volume, under the identical weight, zinc-air cell can store reactive material more, compare with other traditional batteries, have specific energy height (can reach 1350Wh/kg in theory), capacity is big, discharge performance is stable, cost is low and characteristics such as safe, is a kind of chemical power source with great market prospect.But the discharge current density of the air electrode of zinc and air cell is on the low side, is not suitable for the discharge of high current density, has limited it and has been widely used.Therefore numerous scientific and technical personnel have proposed several different methods for the current density that improves zinc-air cell, a kind ofly be to use noble metal (Pt, Ag etc.) as the catalyst of its air electrode, its shortcoming is that catalyst costs an arm and a leg, and makes the battery cost too high; At present general zinc-air cell adopts cheap MnO
2Make the catalyst of air electrode, but its current density is still lower, in order to improve its current density, a kind of method is to set about from improving technology or preparation method, prepares MnO as using collosol and gel
2Catalyst is though make MnO
2Performance increases, but its preparation process complexity improves preparation cost; Another kind method is at MnO
2The middle auxiliary substance that adds, as Co .Li or rare earth element, it is more expensive that its shortcoming is still price, makes the battery cost very high.Can be referring to documents: on September 12 calendar year 2001, application number be 01107488.4, people's such as Zhou Zhentao patent of invention " catalyst of air electrode of zinc-air cell ".
Summary of the invention
The present invention adopts the method for solid phase calcination to pass through at MnO
2Middle method of adding plumbous oxide reaches the purpose of the air electrode discharge current density that improves zinc-air cell.
Metallic lead and compound thereof are generally thought the material poisonous to catalyst by the people, avoid using in catalyst.Lead oxides plays and stablizes MnO in the present invention
2The effect of structure by adding the oxide of an amount of lead, makes MnO
2In catalytic process, keep its favourable structure and composition, thereby improved with MnO
2Discharge current density for the air electrode of main catalyst.
Air electrode of zinc-air cell of the present invention adds the MnO of lead oxides
2The Preparation of catalysts method is as follows:
At first get the active carbon of certain mass, disperse the back to add the manganese nitrate solution and the lead acetate solution of certain mass with ethanol, its mass ratio is manganese nitrate: C=7～8%; Lead acetate: C=5～15% stirs it, and heating boils off ethanol, oven dry, puts into crucible after grinding, and 260～280 ℃ of temperature lower calcinations 1 hour, treats to grind after it reduces to room temperature, makes carbon and carries MnO
2With the lead oxides catalyst.
Next is to use the present invention to add the MnO of lead oxides
2Catalyst is made binding agent with ptfe emulsion, is rolled into the thick catalytic membrane of 0.1～0.2mm on roll forming machine, and wherein polytetrafluoroethylene weight is 12%.Sequence arrangement by catalytic membrane, conduction nickel screen, breathing waterproof film is pressed into air electrode on forcing press, making thickness of electrode is 0.4～0.5mm.
Adopt the constant current method of testing that the air electrode made from catalyst of the present invention is tested then, the polarization curve of measuring is seen accompanying drawing 1.Curve 2 representatives in the accompanying drawing 1 do not contain the MnO of lead oxides
2The polarization curve of the air electrode of making for catalyst; Curve 1 representative in the accompanying drawing 1 contains the MnO of lead oxides
2The polarization curve of the air electrode that catalyst is made; Abscissa is the polarized current density of air electrode among the figure, and unit is mA/cm
2, ordinate is the electrode potential [with respect to Hg/HgO (7MKOH) reference electrode] of air electrode after polarization under the different current densities.
Through repetition test, polarizing electrode current potential during by the comparison same current density, the performance of air electrode when investigating the lead tolerance difference, the content that adds lead oxides in different proportionings is 8～9% o'clock, the performance of air electrode is best.With the MnO that does not add lead oxides
2For the air electrode of catalyst is compared, when current density is 20～50mA/cm
2The time, can improve current potential 30～50mV, at 150mA/cm
2The time, can improve 118mV, can find out that from accompanying drawing 1 current density is 150mA/cm
2The time electrode only polarize about 560mV, the catalyst that is better than being provided in this paper documents is made the performance of air electrode, promptly under 1.0V (1000mV) polarization potential, current density is about 150mA/cm
2
By the foregoing explanation, it is simple that the present invention has preparation technology, the advantage that cost of material is low; And the air electrode chemical property with Preparation of Catalyst of the present invention is good, can be used in the zinc-air cell fully.
Description of drawings
Fig. 1 is to use the polarization curve of the air electrode that catalyst of the present invention makes.
Embodiment
Get the active carbon of certain mass, disperse with small amount of ethanol, manganese nitrate solution (the manganese nitrate: C=8%) that adds certain mass, lead acetate solution (the lead acetate: C=8%), stir, heat and boil off ethanol, oven dry, grinding, put into crucible again that adds certain mass again, 270 ℃ of temperature lower calcinations 1 hour, treat that it reduces to room temperature, grind, make catalyst.
Using above-mentioned catalyst, is binding agent with the ptfe emulsion, is rolled into the thick catalytic membrane of 0.1～0.2mm on roll forming machine, (wherein the polytetrafluoroethylene quality accounts for 12%).Sequence arrangement by catalytic membrane, conduction nickel screen, breathing waterproof film is pressed into air electrode on forcing press, making thickness of electrode is 0.4～0.5mm.The electrode polarization test result is shown in the curve in the accompanying drawing 11.Compare at 20～50mA/cm with the curve 2 that does not contain lead oxides
2The time, can improve electrode potential 30～54mV; At 150mA/cm
2The time can improve 118mV.From accompanying drawing 1, as seen, be 0mA/cm from current density
2The time electrode potential be about 0 volt, current density is 150mA/cm
2The time, electrode potential is-560mV about, i.e. electrode potential about 560mV that polarized.Current density can reach 150mA/cm
2, be better than in the documents electrode potential polarization 1.0V (1000mV) current density and be about 150mA/cm
2Performance.
The present invention has the advantage that technology is simple, cost is low, and in the zinc-air battery with this catalyst preparation Its chemical property of air electrode good.
Claims (1)
1. air electrode of zinc-air cell catalyst that adds lead oxides is characterized in that adopting the preparation of solid phase calcination method:
Get the activated carbon of certain mass, disperse with ethanol, add manganese nitrate solution and lead acetate solution, wherein manganese nitrate and lead acetate with the mass percent of activated carbon are respectively: manganese nitrate: activated carbon=7～8%; Lead acetate: activated carbon=5～15%, stir, heating boils off ethanol, oven dry, puts into crucible again after grinding, and 260～280 ℃ of temperature lower calcinations 1 hour, reduces to grind after the room temperature and makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100136313A CN100431210C (en) | 2004-03-18 | 2004-03-18 | Air electrode catalyst of zn air cell added with lead oxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100136313A CN100431210C (en) | 2004-03-18 | 2004-03-18 | Air electrode catalyst of zn air cell added with lead oxide |
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| Publication Number | Publication Date |
|---|---|
| CN1564357A CN1564357A (en) | 2005-01-12 |
| CN100431210C true CN100431210C (en) | 2008-11-05 |
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| CNB2004100136313A Expired - Fee Related CN100431210C (en) | 2004-03-18 | 2004-03-18 | Air electrode catalyst of zn air cell added with lead oxide |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124539A (en) * | 1977-12-02 | 1978-11-07 | Exxon Research & Engineering Co. | Pb2 [M2-x Pbx ]O7-y compounds wherein M is Ru, Ir or mixtures thereof, and method of preparation |
| CN1312595A (en) * | 2001-01-21 | 2001-09-12 | 华南理工大学 | Catalyst for air electrode of zinc-air cell |
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2004
- 2004-03-18 CN CNB2004100136313A patent/CN100431210C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124539A (en) * | 1977-12-02 | 1978-11-07 | Exxon Research & Engineering Co. | Pb2 [M2-x Pbx ]O7-y compounds wherein M is Ru, Ir or mixtures thereof, and method of preparation |
| CN1312595A (en) * | 2001-01-21 | 2001-09-12 | 华南理工大学 | Catalyst for air electrode of zinc-air cell |
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| CN1564357A (en) | 2005-01-12 |
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