CN1529374A - Zinc-air battery electrocatalyst and preparation method thereof - Google Patents
Zinc-air battery electrocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an electrocatalyst of a zinc-air battery, which has a general formula A 1－x B x C 1－y DyO 3 Wherein A is a rare earth metal element; b is an alkaline earth metal element; c and D represent different or same transition metal elements; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and the structure of the electrocatalyst is a perovskite crystalline structure. The invention adopts a sol-gel method to synthesize the metal composite oxide electrocatalyst with a perovskite crystalline structure; the obtained electrocatalyst has high electrocatalytic activity, good chemical stability and long service life, has high electrocatalytic activity for not only oxygen reduction but also oxygen precipitation, and is a bifunctional electrocatalyst.
Description
1. Field of the invention
The invention relates to a metal composite oxide with a perovskite crystalline structure used as an electrocatalyst of a zinc-air battery and a preparation method thereof, belonging to the field of chemical power sources.
2. Background of the invention
The zinc-air battery is a battery which takes oxygen in the air as a positive active material and metal zinc as a negative active material, and the oxygen and the zinc react to release electric energy under the catalytic action of an electrocatalyst. Because the air does not occupy the volume and the weight of the battery, the battery has very high specific energy (3-4 times of that of an alkaline zinc-manganese battery with the same type and 7-8 times of that of a zinc-manganese dry battery with the same type), can utilize zinc resources to the maximum extent, and meets the requirements of sustainable development strategies in China. The zinc-air battery has the characteristics of large capacity, high specific energy, stable discharge performance, cheap and easily-obtained raw materials, no environmental pollution in the production and use processes and the like, and is called as a green power supply facing the 21 st century. As an advanced power supply product, the zinc-air battery has high cost performance, is expected to become the best matching power supply for rapidly developing portable electronic and electrical equipment, and has wide market prospect.
However, the lack of suitable air diffusion electrode electrocatalysts has led to a decrease in the discharge current density of zinc-air batteries, which has greatly limited the application area and the pace of practical use of zinc-air batteries. The materials that have been studied as electrocatalysts for air diffusion electrodes of zinc-air batteries are mainly noble metals Pt (see us 4379772 for details), ag, metal chelates, manganese oxides (see us 6368365 for details), spinel type metal oxides (see chinese 01107488.4 for details), etc. However, the above-mentioned background art has the following problems:
1. the noble metals Pt and Ag as the air diffusion electrode electrocatalyst have high electrocatalytic activity, but the noble metals have fewer resources, are expensive, have lower cost performance, and are not suitable for large-scale industrial production.
2. Manganese oxide (mainly manganese dioxide) is low in price, abundant and easily available, and is the only electrocatalyst used by button zinc-air batteries which are practically produced in batches at present. However, the catalytic activity is too low, the discharge current density per unit area is too small, and the requirement of working current of common high-power electronic appliances cannot be met.
3. Although the spinel-type crystalline structure metal oxide electrocatalyst has high initial catalytic activity, the chemical stability is not good, and the polarization degree of discharge is obviously increased after the obtained battery is stored for a period of time, so that the service life is short.
4. Although the metal chelate has higher electrocatalytic activity, the preparation process is more complex, and the structure and the quality are difficult to control, so the metal chelate is difficult to be applied to the large-scale industrial production of the zinc-air battery.
5. All other electrocatalysts of the above background art, except for the noble metal Pt, have a relatively low catalytic activity for the oxygen evolution reaction and the bifunctional air diffusion electrodes made with them as bifunctional electrocatalysts have a relatively short lifetime.
3. Summary of the invention
The invention aims to provide a zinc-air battery electrocatalyst aiming at the problems existing in the prior background technology of the zinc-air battery.
The invention also aims to provide a preparation method of the zinc-air battery electrocatalyst.
The general formula of the zinc-air battery electrocatalyst is A 1-x B x C 1-y D y O 3 In the formula, A represents a rare earth metal element; b represents an alkaline earth metal element; c and D represent different or same transition metal elements; x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1. The crystalline structure of the electrocatalyst is a perovskite crystalline structure.
The electrocatalyst of the zinc-air battery is synthesized by adopting a sol-gel method to form a metal composite oxide electrocatalyst with a perovskite crystalline structure. The preparation method comprises the following specific steps:
according to the stoichiometric molar ratio of A: B: C: D = 0-1.00: 1.00-0: 0-1.00: 1.00-0 of perovskite type crystalline structure metal composite oxide, soluble metal salt (injecting one or a mixture of more than one of nitrate, acetate or oxalate) of each metal element is weighed, and deionized water is added to prepare a saturated aqueous solution. Wherein the rare earth metal element A is lanthanum (La), cerium (Ce) or praseodymium (Pr); the alkaline earth metal element B is calcium (Ca), strontium (Sr) or barium (Ba); the transition metal element C is iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn) or copper (Cu); the transition metal element D is iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn) or copper (Cu).
Adding organic acid (one or more of tartaric acid, citric acid, malic acid and ethylene diamine tetraacetic acid) and polyalcohol (one or more of ethylene glycol and glycerol) into the reaction system, and adjusting the pH of the reaction system to 1-6 by ammonia water. Wherein the molar ratio of the organic acid to the total of the polyhydric alcohol and the metal ions is 1.5-2.5: 3.5-4.5: 1.0.
Placing the reaction system in a constant-temperature water bath, dehydrating at 50-90 ℃ to obtain sol, continuously dehydrating to form wet gel, heating and drying the wet gel at 100-200 ℃ for 1-10 hours to obtain honeycomb-shaped gel, finally performing heat treatment on the dried gel at 400-1000 ℃ in an air atmosphere for 0.5-10 hours, and then cooling to room temperature along with a furnace to obtain the electrocatalyst with a perovskite crystalline structure.
Structural analysis: the crystalline structure of the prepared catalyst was analyzed by a Japan-produced C.O./Max-IIIA X-ray diffraction (XRD) apparatus, cuK a The target, voltage 30Kv, current 30mA, scan range 2 θ =10 ° to 75 °. The analysis result shows that the obtained electrocatalyst has a perovskite crystalline structure.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof and breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring to disperse, coagulating and rolling to obtain the catalyst film. And (3) superposing the waterproof breathable film, the catalytic film and a metal current collector (such as a nickel net) together for roll forming to obtain the air diffusion electrode.
Testing of steady-state current-voltage polarization curve: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. Under room temperature and normal pressure, a CHI660a electrochemical workstation of upper marine products is adopted, an air diffusion electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a nickel screen is used as a counter electrode, 6Mol/L KOH aqueous solution is used as electrolyte, and a three-electrode test system is used for carrying out steady-state current-voltage polarization curve test on the electrocatalytic activity of an electrocatalyst.
Compared with the background technology, the metal composite oxide electrocatalyst with the perovskite crystalline structure for the zinc-air battery and the preparation method thereof have the following advantages:
1. the obtained electrocatalyst has high electrocatalytic activity, good chemical stability and long service life, not only has high electrocatalytic activity for the reduction of oxygen, but also has high electrocatalytic activity for the precipitation of oxygen, and is a bifunctional electrocatalyst;
2. the preparation method can realize the uniform doping of the trace elements in the electrocatalyst product, and can obtain the product with uniform and consistent structure on the molecular level in a short time;
3. the chemical reaction in the reaction system is easy to carry out, the heat treatment temperature of the catalyst is lower, the heat treatment time is shorter, and the purity of the obtained product is higher and the particle size distribution is narrower;
4. the reaction process and the microstructure of the sol-gel are easy to control, side reactions are less, the conversion rate of the product is higher, and the quality and the production efficiency of the product are higher.
4. Description of the drawings
FIG. 1 is a graph comparing the steady state current-voltage polarization curves of air diffusion electrodes made with electrocatalysts of the present invention and the prior art. The symbols in FIG. 1 represent the following meanings:
a-steady state current-voltage polarization curve of air diffusion electrode using perovskite crystalline structure metal composite oxide obtained by the invention as electrocatalyst;
b-steady state current-voltage polarization curve of air diffusion electrode using electrolytic manganese dioxide as electrocatalyst;
c, taking spinel crystalline structure metal oxide as the steady state current-voltage polarization curve of the air diffusion electrode of the electrocatalyst;
fig. 2 is an X-ray diffraction (XRD) analysis pattern of the electrocatalyst obtained according to the present invention. The crystalline structure of the obtained electrocatalyst is proved to be perovskite crystalline structure by searching and checking a standard spectrogram.
5. Detailed description of the preferred embodiments
The present invention will be further described with reference to the following examples, but is not limited thereto.
Example 1
Preparation of the electrocatalyst: weighing La (NO) in a stoichiometric molar ratio La: mn = 1.0: 1.0 3 ) 3 ·6H 2 O and Mn (CH) 3 COO) 2 Adding deionized water to prepare saturated aqueous solution, and adding tartaric acid, glycol and metal ion according to the ratio of tartaric acid, glycol and metal ion total =1.5Tartaric acid and ethylene glycol were added to the above reaction system at a ratio of 3.5: 1.0, and the pH of the reaction system was adjusted to 1 with aqueous ammonia. Placing the reaction system in a constant-temperature water bath, dehydrating at 50 ℃ to obtain sol, continuously dehydrating to form wet gel,the wet gel was then dried by heating at 100 ℃ for 10 hours to give a honeycomb-like xerogel. Finally, the xerogel is thermally treated for 10 hours at 400 ℃ in the air atmosphere, and then is cooled to room temperature along with the furnace, so that the electrocatalyst with the perovskite crystalline structure is obtained.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring, coagulating, and rolling to obtain the catalyst film. The waterproof breathable film, the catalytic film and the current collector (nickel net) are overlapped together to be rolled and molded, so that the air diffusion electrode is obtained.
Testing of steady-state current-voltage polarization curve: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. Under room temperature and normal pressure, a CHI660a electrochemical workstation of upper marine products is adopted, an air diffusion electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a nickel screen is used as a counter electrode, 6Mol/L KOH aqueous solution is used as electrolyte, and a three-electrode test system is used for carrying out steady-state current-voltage polarization curve test on the electrocatalytic activity of an electrocatalyst. The test results showed that its current density at-0.6V (Hg/HgO as reference electrode) polarization potential was 190mA.cm -2 The current density at a polarization potential of 0.6V (Hg/HgO as a reference electrode) was 100mA.cm -2 。
Example 2
Preparation of the electrocatalyst: la (CH) was weighed in a stoichiometric molar ratio La: sr: co: fe = 0.8: 0.2: 0.6: 0.4 3 COO) 3 、 Sr(CH 3 COO) 2 、Co(NO 3 ) 3 And Fe (NO) 3 ) 3 Adding deionized water to prepare saturated aqueous solution, and adding malic acid and propanetriol in the reaction system according to the sum = 2.5: 4.5: 1.0 of malic acid, propanetriol and metal ionsAnd (3) adjusting the pH of the reaction system to 3 by using ammonia water. And (3) placing the reaction system in a constant-temperature water bath, dehydrating at 70 ℃ to obtain sol, continuously dehydrating to form wet gel, and heating and drying the wet gel at 150 ℃ for 5 hours to obtain the honeycomb-shaped xerogel. Finally, the xerogel is thermally treated for 5 hours at 650 ℃ in the air atmosphere, and then is cooled to room temperature along with the furnace, so that the electrocatalyst with the perovskite crystalline structure is obtained.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring to disperse, coagulating and rolling to obtain the catalyst film. The waterproof breathable film, the catalytic film and the current collector (nickel net) are overlapped together to be rolled and molded, so that the air diffusion electrode is obtained.
Testing of steady-state current-voltage polarization curve: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. Under room temperature and normal pressure, a three-electrode test system is used for carrying out steady-state current-voltage polarization curve test on the electrocatalytic activity of an electrocatalyst by adopting a CHI660a electrochemical workstation of upper marine products, taking an air diffusion electrode as a working electrode, taking an Hg/HgO electrode as a reference electrode, taking a nickel net as a counter electrode and taking 6Mol/L KOH aqueous solution as electrolyte. The test result shows that the current density of the electrode is 213mA cm at the polarization potential of-0.6V (Hg/HgO is a reference electrode) -2 And a current density at a polarization potential of 0.6V (Hg/HgO as a reference electrode) of 121mA.cm -2 。
Example 3
Preparation of the electrocatalyst: ce (NO) was weighed in a stoichiometric molar ratio Ce: ba: cu: mn = 0.9: 0.1: 0.2: 0.8 3 ) 3 ·6H 2 O、Ba(NO 3 ) 2 、Cu(NO 3 ) 2 And Mn (CH) 3 COO) 2 Adding deionized water to prepare saturated aqueous solution, adding citric acid and ethylene glycol into the reaction system according to the sum = 2.0: 3.5: 1.0 of citric acid, ethylene glycol and metal ions, and adjusting the pH of the reaction system to 4 by using ammonia water. And (3) placing the reaction system in a constant-temperature water bath, dehydrating at 80 ℃ to obtain sol, continuously dehydrating to form wet gel, and heating and drying the wet gel at 200 ℃ for 1 hour to obtain the honeycomb-shaped xerogel. Finally, the xerogel is thermally treated for 0.5 hour at 1000 ℃ in the air atmosphere, and then is cooled to room temperature along with the furnace, so that the electrocatalyst with the perovskite type crystal structure is obtained.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring, coagulating, and rolling to obtain the catalyst film. And (3) superposing the waterproof breathable film, the catalytic film and a current collector (nickel screen) together, and performing roll forming to obtain the air diffusion electrode.
Testing of steady-state current-voltage polarization curve: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. Under room temperature and normal pressure, a CHI660a electrochemical workstation of marine products is adopted, an air diffusion electrode is taken as a working electrode, an Hg/HgO electrode is taken as a reference electrode, a nickel screen is taken as a counter electrode, 6Mol/L KOH aqueous solution is taken as electrolyte, and a three-electrode test system is usedThe electrocatalytic activity of the electrocatalyst is tested for a steady-state current-voltage polarization curve. The test results show that the current density of the electrode under the polarization potential of-0.6V (Hg/HgO is a reference electrode) is 202mA -2 And the current density at 0.6V (Hg/HgO as reference electrode) polarization potential was 110mA.cm -2 。
Example 4
Preparation of the electrocatalyst: according to the chemical scaleWeighing Pr, sr, ni, co = 0.7: 0.3: 0.5 according to the molar ratio of Pr, sr, ni and Co 2 (C 2 O 4 ) 3 、 Sr(CH 3 COO) 2 、Ni(NO 3 ) 2 And Co (CH) 3 COO) 2 Adding deionized water to prepare saturated aqueous solution, adding ethylene diamine tetraacetic acid and ethylene glycol into the reaction system according to the sum = 1.5: 4.0: 1.0 of ethylene diamine tetraacetic acid, ethylene glycol and metal ions, and adjusting the pH of the reaction system to 6 by using ammonia water. And (3) placing the reaction system in a constant-temperature water bath, dehydrating at 75 ℃ to obtain sol, continuously dehydrating to form wet gel, and heating and drying the wet gel at 160 ℃ for 3 hours to obtain the honeycomb-shaped xerogel. Finally, the xerogel is thermally treated for 2 hours at 850 ℃ in the air atmosphere, and then is cooled to room temperature along with the furnace, so that the electrocatalyst with the perovskite type crystal structure is obtained.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring, coagulating, and rolling to obtain the catalyst film. The waterproof breathable film, the catalytic film and the current collector (nickel net) are overlapped together to be rolled and molded, so that the air diffusion electrode is obtained.
Testing of steady-state current-voltage polarization curves: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. Under room temperature and normal pressure, a three-electrode test system is used for carrying out steady-state current-voltage polarization curve test on the electrocatalytic activity of an electrocatalyst by adopting a CHI660a electrochemical workstation of upper marine products, taking an air diffusion electrode as a working electrode, taking an Hg/HgO electrode as a reference electrode, taking a nickel net as a counter electrode and taking 6Mol/L KOH aqueous solution as electrolyte. The test result shows that the current density of the electrode is 240mA.cm at the polarization potential of-0.6V (Hg/HgO is a reference electrode) -2 0.6V (Hg/HgO as reference electrode)The current density at polarization potential was 112mA.cm -2 。
Example 5
Preparation of the electrocatalyst: weighing La, ca, mn and Co in a stoichiometric molar ratio of 0.6: 0.4: 0.3: 0.7La(NO 3 ) 3 ·6H 2 O、Ca(NO 3 ) 2 、Mn(NO 3 ) 3 And Co (NO) 3 ) 2 Adding deionized water to prepare a saturated aqueous solution, adding citric acid and ethylene glycol into the reaction system according to the sum = 2.0: 4.0: 1.0 of citric acid, ethylene glycol and metal ions, and adjusting the pH of the reaction system to 2 by using ammonia water. And (3) putting the reaction system in a constant-temperature water bath, dehydrating at 85 ℃ to obtain sol, continuously dehydrating to form wet gel, and heating and drying the wet gel at 140 ℃ for 7 hours to obtain the honeycomb-shaped xerogel. Finally, the xerogel is thermally treated for 4 hours at 650 ℃ in air atmosphere, and then is cooled to room temperature along with the furnace, so that the electrocatalyst with the perovskite crystalline structure is obtained.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring to disperse, coagulating and rolling to obtain the catalyst film. And (3) superposing the waterproof breathable film, the catalytic film and a current collector (nickel screen) together, and performing roll forming to obtain the air diffusion electrode.
Testing of steady-state current-voltage polarization curves: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. Under room temperature and normal pressure, a CHI660a electrochemical workstation of upper marine products is adopted, an air diffusion electrode is taken as a working electrode, an Hg/HgO electrode is taken as a reference electrode, a nickel screen is taken as a counter electrode, 6Mol/L KOH aqueous solution is taken as electrolyte, and a three-electrode test system is used for electrocatalytic activity of an electrocatalystAnd (5) carrying out a steady-state current-voltage polarization curve test. The test result shows that the current density of the electrode is 250mA.cm at the polarization potential of-0.6V (Hg/HgO is a reference electrode) -2 And a current density of 135mA.cm at 0.6V (Hg/HgO as a reference electrode) polarization potential -2 。
Example 6
Preparation of the electrocatalyst: weighing Sr (NO) according to the stoichiometric molar ratio of Sr to Fe =1.0 to 1.0 3 ) 2 And Fe (NO) 3 ) 3 Adding deionized water to prepare saturated aqueous solution, adding tartaric acid and glycerol into the reaction system according to the total ratio of tartaric acid, glycerol and metal ions = 2.5: 3.5: 1.0, and adjusting the pH of the reaction system to 5 by using ammonia water. And (3) placing the reaction system in a constant-temperature water bath, dehydrating at 90 ℃ to obtain sol, continuously dehydrating to form wet gel, and heating and drying the wet gel at 140 ℃ for 7 hours to obtain the honeycomb-shaped xerogel. Finally, the xerogel is thermally treated for 7 hours at 550 ℃ in the air atmosphere, and then is cooled to room temperature along with the furnace, so that the electrocatalyst with the perovskite crystalline structure is obtained.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring to disperse, coagulating and rolling to obtain the catalyst film. And (3) superposing the waterproof breathable film, the catalytic film and a current collector (nickel screen) together, and performing roll forming to obtain the air diffusion electrode.
Testing of steady-state current-voltage polarization curves: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. Under room temperature and normal pressure, adopting a CHI660a electrochemical workstation of upper marine products, taking an air diffusion electrode as a working electrode, an Hg/HgO electrode as a reference electrode, a nickel screen as a counter electrode, and 6Mol/LKOH aqueous solution is used as electrolyte, and a three-electrode test system is used for carrying out steady-state current-voltage polarization curve test on the electrocatalytic activity of the electrocatalyst. The test result shows that the current density of the electrode is 200mA.cm at the polarization potential of-0.6V (Hg/HgO is a reference electrode) -2 The current density at 0.6V (Hg/HgO as reference electrode) polarization potential was 107mA -2 。
Example 7
Preparation of the electrocatalyst: weighing La (NO) in a stoichiometric molar ratio of La: ba: co: ni = 0.8: 0.2: 0.7: 0.3 3 ) 3 ·6H 2 O、 Ba(NO 3 ) 2 、CoC 2 O 4 And Ni (CH) 3 COO) 2 Adding deionized water to prepare a saturated aqueous solution, adding malic acid and glycerol into the reaction system according to the sum of malic acid, glycerol and metal ions = 2.0: 3.5: 1.0, and adjusting the pH of the reaction system to 3 by using ammonia water. And (3) placing the reaction system in a constant-temperature water bath, dehydrating at 65 ℃ to obtain sol, continuously dehydrating to form wet gel, and heating and drying the wet gel at 110 ℃ for 9 hours to obtain the honeycomb-shaped xerogel. Finally, the xerogel is thermally treated for 3 hours at 800 ℃ in the air atmosphere, and then is cooled to room temperature along with the furnace, so that the electrocatalyst with the perovskite crystalline structure is obtained.
Preparing an air diffusion electrode: uniformly mixing acetylene black and a pore-forming agent by using alcohol, adding polytetrafluoroethylene emulsion, continuously stirring to uniformly disperse the emulsion, and performing condensation and rolling to obtain a waterproof breathable film; mixing catalyst and active carbon with alcohol, adding PTFE emulsion, stirring to disperse, coagulating and rolling to obtain the catalyst film. The waterproof breathable film, the catalytic film and the current collector (nickel net) are overlapped together to be rolled and molded, so that the air diffusion electrode is obtained.
Testing of steady-state current-voltage polarization curves: the electrocatalytic activity of the electrocatalyst was tested by a steady-state current-voltage polarization curve. At room temperatureUnder the pressure, an electrochemical workstation of CHI660a of upper marine products is adopted, an air diffusion electrode is taken as a working electrode,the Hg/HgO electrode is a reference electrode, the nickel screen is a counter electrode, 6Mol/L KOH aqueous solution is electrolyte, and a three-electrode test system is used for carrying out steady-state current-voltage polarization curve test on the electrocatalytic activity of the electrocatalyst. The test result shows that the current density of the electrode is 220mA.cm at the polarization potential of-0.6V (Hg/HgO is a reference electrode) -2 And the current density at 0.6V (Hg/HgO as reference electrode) polarization potential was 118mA.cm -2 。
Claims (4)
1. An electrocatalyst for zinc-air battery with general formula A 1-x B x C 1-y D y O 3 Wherein A is a rare earth metal element; b is an alkaline earth metal element; c and D represent different or same transition metal elements; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and the crystalline structure of the electro-catalyst is a perovskite crystalline structure.
2. The zinc-air cell electrocatalyst according to claim 1, wherein the rare earth element a is lanthanum, cerium, or praseodymium; the alkaline earth metal element B is calcium, strontium, or barium; the transition metal element C is iron, cobalt, nickel, manganese or copper; the transition metal element D is iron, cobalt, nickel, manganese, or copper.
3. The method for preparing an electrocatalyst for a zinc-air battery according to claim 1, wherein the method for synthesizing a metal composite oxide electrocatalyst with a perovskite-type crystalline structure by a sol-gel method comprises the steps of:
(1) Weighing one or more of nitrate, acetate and oxalate of the metal elements according to the stoichiometric molar ratio A: B: C: D = 0-1.00: 1.00-0: 0-1.00: 1.00-0 of the perovskite crystalline structure metal composite oxide, and adding deionized water to prepare a saturated aqueous solution;
(2) Adding one or more of tartaric acid, citric acid, malic acid, and ethylenediamine tetraacetic acid, and polyalcohol ethylene glycol and/or glycerol into the reaction system, and adjusting pH of the reaction system to 1-6 with ammonia water; wherein the molar ratio of the organic acid to the total of the polyhydric alcohol and the metal ions is 1.5-2.5: 3.5-4.5: 1.0;
(3) Placing the reaction system in a constant-temperature water bath at 50-90 ℃, dehydrating to obtain sol, continuously dehydrating to form wet gel, and then heating and drying the wet gel at 100-200 ℃ for 1-10 hours to obtain honeycomb-shaped xerogel; finally, the xerogel is thermally treated for 0.5 to 10 hours at the temperature of 400 to 1000 ℃ in the air atmosphere, and then is cooled to the room temperature along with the furnace, so that the electrocatalyst with the perovskite crystalline structure is obtained.
4. The method of claim 3, wherein the rare earth element A is lanthanum, cerium, or praseodymium; the alkaline earth metal element B is calcium, strontium, or barium; the transition metal element C is iron, cobalt, nickel, manganese or copper; the transition metal element D is iron, cobalt, nickel, manganese, or copper.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100339160C (en) * | 2005-06-17 | 2007-09-26 | 中国科学院大连化学物理研究所 | Preparation method of perovskite type metal oxide catalyst |
| CN100386148C (en) * | 2006-05-18 | 2008-05-07 | 武汉大学 | Reduced catalyst of mono fluorin, and preparation method and usage |
| CN102569830A (en) * | 2011-12-19 | 2012-07-11 | 上海尧豫实业有限公司 | Metal air battery anode catalyst and preparation method thereof |
| CN107293760A (en) * | 2017-06-03 | 2017-10-24 | 上海博暄能源科技有限公司 | A kind of preparation method of metal-air battery perovskite type catalyst |
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| CN102569830A (en) * | 2011-12-19 | 2012-07-11 | 上海尧豫实业有限公司 | Metal air battery anode catalyst and preparation method thereof |
| CN102569830B (en) * | 2011-12-19 | 2016-12-07 | 上海尧豫实业有限公司 | Metal air battery anode catalyst and preparation method thereof |
| CN107293760B (en) * | 2017-06-03 | 2019-12-17 | 上海博暄能源科技有限公司 | Preparation method of perovskite type catalyst for metal-air battery |
| CN107293760A (en) * | 2017-06-03 | 2017-10-24 | 上海博暄能源科技有限公司 | A kind of preparation method of metal-air battery perovskite type catalyst |
| CN109560296B (en) * | 2017-09-27 | 2022-01-07 | 清远道动新材料科技有限公司 | Perovskite type catalyst, preparation method and application thereof, and zinc-air secondary battery |
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| CN108417407A (en) * | 2018-02-24 | 2018-08-17 | 云南大学 | A kind of electrode material for super capacitor of perovskite type manganese/cobalt/nickelate |
| CN109390598A (en) * | 2018-11-15 | 2019-02-26 | 河北工业大学 | A kind of preparation method and applications of difunctional perofskite type oxide oxygen electrode catalyst |
| CN109888315A (en) * | 2019-03-21 | 2019-06-14 | 深圳先进技术研究院 | A kind of processing method promoting B doping type perovskite catalyst chemical properties |
| CN112691657A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Sepiolite carrier, preparation method thereof, methane combustion catalyst and application thereof |
| CN112691657B (en) * | 2019-10-23 | 2023-01-24 | 中国石油化工股份有限公司 | Sepiolite carrier, preparation method thereof, methane combustion catalyst and application thereof |
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| CN114005999A (en) * | 2021-09-06 | 2022-02-01 | 中国地质大学(武汉)浙江研究院 | Bifunctional electrocatalyst and preparation method and application thereof |
| CN114005999B (en) * | 2021-09-06 | 2023-03-31 | 中国地质大学(武汉)浙江研究院 | Bifunctional electrocatalyst and preparation method and application thereof |
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