CN1758469A - Air electrode catalyst containing strontium oxide and process thereof - Google Patents
Air electrode catalyst containing strontium oxide and process thereof Download PDFInfo
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- CN1758469A CN1758469A CNA2005100103028A CN200510010302A CN1758469A CN 1758469 A CN1758469 A CN 1758469A CN A2005100103028 A CNA2005100103028 A CN A2005100103028A CN 200510010302 A CN200510010302 A CN 200510010302A CN 1758469 A CN1758469 A CN 1758469A
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Abstract
The invention relates to an air electrode catalyst containing strontium oxide and a process thereof, wherein the catalyst is MnO supported by carbon 2 、La 2 O 3 And SrO. The preparation process comprises the steps of adding a manganese nitrate solution into carbon powder, uniformly dispersing, adding nitrates of rare earth lanthanum and alkaline earth strontium, evaporating to dryness, and then adopting a solid phase calcination method to prepare the rare earth lanthanum strontium nitrate. The catalyst has the advantages of simple preparation process, high electrocatalytic activity and stable performance. Catalyst and carbon-supported MnO of the present invention 2 Compared with the catalyst, the catalyst can reduce the polarization of the air electrode and improve the working electricity of the zinc-air batteryPressure and battery capacity.
Description
Technical Field
The invention relates to an air electrode catalyst containing strontium oxide and a process thereof, which are used for a zinc-air battery in the field of electrochemistry.
Background
The zinc-air battery is a battery which takes air as a positive active material and takes metal zinc as a negative active material. It has the advantages of large capacity, high specific energy, low cost, stable discharge performance, no pollution, etc. and is one kind of chemical power source with great market foreground. However, the air electrode of the zinc-air battery has low discharge current density and working voltage, large electrode polarization and wide involved potential range, which all limit the wide application of the zinc-air battery. Therefore, it is very important to select a catalyst for the air electrode to improve the polarization characteristics of the air electrode and to increase the operating voltage and open circuit voltage of the battery. For a long time, research on air electrode catalysts has been mainly conducted around noble metals and alloys thereof, metal chelates, metal oxides, and the like. When noble metals and alloys thereof are used as catalysts, the catalytic effect is good, but the cost of the battery is high, and the battery is difficult to commercialize; although the metal chelate, spinel-type and perovskite-type catalysts have good catalytic effect, the preparation process is complex and the additional cost is high. See the references: the invention patent of 2001, 9/12/01107488.4, zhou Otao et al, "catalyst for air electrode of zinc-air battery".
MnO 2 Has certain oxygen reduction and hydrogen peroxide decomposition activity, low price and simple preparation, but still has lower discharge current density and working voltage and is to be further improved. The rare earth oxide has Lewis acid property, active chemical property and catalytic action, and is suitable for being used as a catalyst in an alkaline medium. It is thus considered to prepare a mixed catalyst to improve catalytic performance.
Disclosure of Invention
The invention adds manganese nitrate solution into carbon powder, adds rare earth lanthanum and alkaline earth strontium nitrate after uniform dispersion, and then prepares an air electrode catalyst by adopting a solid-phase calcination method to improve catalytic activity and achieve the purpose of improving the working voltage and discharge current density of a zinc-air battery.
The catalyst of the invention is MnO supported by carbon 2 、La 2 O 3 The SrO consists of the following components in percentage by weight: mnO 2 Accounting for 10-15% of the mass of the carbon powder, the molar ratio of the three metal elements is Mn: la: sr = 1: 0.3-0.5: 0.5-0.7.
The preparation process of the invention is as follows:
weighing activated carbon and acetylene black in a mass ratio of 9: 1, dispersing the activated carbon and the acetylene black in ethanol, adding a certain mass of manganese nitrate solution, then adding lanthanum nitrate and strontium nitrate solution according to a certain molar ratio, uniformly stirring, heating to evaporate ethanol, drying, grinding, putting the mixture into a crucible, calcining for 1 hour at 260-280 ℃, cooling to room temperature, and grinding into powder to obtain the air electrode catalyst.
The steps of preparing the air electrode by using the catalyst of the invention are as follows:
dispersing the catalyst powder with ethanol, adding 12-15% of polytetrafluoroethylene emulsion, heating and stirring to form a dough, and rolling the dough into a film with the thickness of about 0.20mm on a double-roll film pressing machine to obtain the catalyst layer. The air electrode is formed by cold pressing a catalyst layer, a conductive framework (a nickel net) and a waterproof breathable layer on an oil press, and the thickness of the electrode is 0.4-0.5 mm.
The air electrode prepared by the catalyst of the invention is used for performance test, and the specific steps are as follows:
the steady-state polarization test adopts a three-electrode constant current steady-state polarization method, the reference electrode is Hg/HgO (7 mol/L KOH), the auxiliary electrode is a nickel sheet, and the electrolyte is 7mol/LKOH. The polarization curves are shown in FIG. 1. Curve 1 in FIG. 1 represents MnO supported on carbon 2 Polarization curves for air electrodes made with catalysts;curve 2 represents the polarization curve of an air electrode made with the catalyst of the present invention. It can be seen from the figure that the electrode performance of curve 2 is significantly better than that of curve 1, at a polarization current density of 2mA cm -2 ～150mA·cm -2 When the electrode polarization potential of the curve 2 is shifted by 32mV to 226mV more than that of the curve 1, the air electrode has good electrocatalytic activity whether the air electrode works under low current density or high current density.
At a polarization current density of 150mA cm -2 The air electrode prepared by the catalyst of the invention has polarization of about 530mV, which is superior to that of 1.0V (1000 mV) polarized electrode potential in the reference, and the current density is about 150mA cm -2 The performance of (c).
An AA type external oxygen type cylindrical zinc-air battery is assembled by using an air electrode prepared by the catalyst, and the battery adopts a 10 omega constant resistance continuous discharge mode (the discharge resistance is implemented according to GB/T-LR4, the national standard stipulates that the AA type alkaline zinc-manganese battery discharges with 10 omega resistance, one hour of discharge is carried out every day, and twelve days of discharge are qualified). The discharge test result shows that the average working voltage and the discharge capacity of the battery made of the catalyst are 1.221V and 4762mAh respectively, the discharge time is as long as 39 hours, and the discharge voltage is stable.
In conclusion, the catalyst has the advantages of simple preparation process and excellent electrochemical performance, and can be completely used in zinc-air batteries.
Drawings
FIG. 1 shows an air electrode made using the catalyst of the present invention and MnO supported on carbon 2 A comparison of polarization curves for air electrodes made with the catalyst.
Detailed Description
Active carbon and acetylene black in the mass ratio of 9 to 1 are weighed, dispersed by ethanol and added with certain mass of manganese nitrate solution, and the proportion of the manganese nitrate solution is MnO generated 2 The catalyst is prepared by adding lanthanum nitrate and strontium nitrate solution according to a certain molar ratio, wherein the molar ratio of the three metal elements is Mn: la: sr = 1: 0.4: 0.6, uniformly stirring, heating to evaporate ethanol, drying, grinding, calcining in a crucible at 270 ℃ for 1 hour, cooling to room temperature, and grinding into powder. Dispersing the catalyst powder with ethanol, adding 15% of polytetrafluoroethylene emulsion, heating and stirring to form a cluster, and rolling the cluster into a film with the thickness of about 0.20mm on a double-roller film pressing machine to obtain the catalyst layer. The air electrode is formed by cold pressing on an oil press by adopting a structure comprising a catalyst layer, a conductive framework (a nickel net) and a waterproof breathable layer from inside to outside in turn, and the thickness of the electrode is 0.4-0.5 mm. The results of the electrode polarization test are shown in FIG. 1, curve 2, and MnO supported by carbon 2 Polarization current density of 2mA cm in comparison with polarization curve 1 of air electrode as catalyst -2 To150mA·cm -2 The electrode polarization potential is positively shifted by 32mV to 226mV. At a polarization current density of 150mA cm -2 The air electrode prepared by the catalyst of the invention has polarization of about 530mV, which is superior to the electrode potential polarization of 1.0V (1000 mV) in the comparative literature, and the current density is about 150mA cm -2 The performance of (c).
The invention has the characteristics of simple preparation process and excellent electrochemical performance, and can be completely used in zinc-air batteries.
Claims (2)
1. An air electrode catalyst containing strontium oxide and its preparation method are characterized in that the catalyst comprises MnO supported by carbon 2 、La 2 O 3 SrO; the proportion is MnO 2 Accounting for mass of carbon powder10 to 15 percent, and the mol ratio of the three metal elements is Mn to La to Sr =1 to 0.3 to 0.5 to 0.7.
2. The air electrode catalyst containing strontium oxide and process thereof according to claim 1, characterized in that the process comprises: weighing activated carbon and acetylene black in a mass ratio of 9: 1, dispersing the activated carbon and the acetylene black with ethanol, adding a certain mass of manganese nitrate solution, then adding lanthanum nitrate and strontium nitrate solution according to the molar ratio of claim 1, uniformly stirring, heating to evaporate ethanol, drying, grinding, putting the mixture into a crucible, calcining at 260-280 ℃ for 1 hour, cooling to room temperature, and grinding to obtain the activated carbon and acetylene black.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2005100103028A CN1758469A (en) | 2005-09-05 | 2005-09-05 | Air electrode catalyst containing strontium oxide and process thereof |
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| CNA2005100103028A CN1758469A (en) | 2005-09-05 | 2005-09-05 | Air electrode catalyst containing strontium oxide and process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101683613A (en) * | 2008-09-22 | 2010-03-31 | 北京长力联合能源技术有限公司 | Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode |
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2005
- 2005-09-05 CN CNA2005100103028A patent/CN1758469A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101683613A (en) * | 2008-09-22 | 2010-03-31 | 北京长力联合能源技术有限公司 | Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode |
| CN101683613B (en) * | 2008-09-22 | 2014-07-30 | 北京中航长力能源科技有限公司 | Catalytic agent for air electrode and novel air electrode manufactured by catalytic agent and manufacturing method of air electrode |
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