CN110142039B - Preparation method of catalyst and application of catalyst in metal-air battery - Google Patents

Preparation method of catalyst and application of catalyst in metal-air battery Download PDF

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CN110142039B
CN110142039B CN201910506500.5A CN201910506500A CN110142039B CN 110142039 B CN110142039 B CN 110142039B CN 201910506500 A CN201910506500 A CN 201910506500A CN 110142039 B CN110142039 B CN 110142039B
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oxygen reduction
reduction catalyst
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CN110142039A (en
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薛业建
颜杉杉
刘兆平
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Ningbo Institute of Material Technology and Engineering of CAS
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract

The invention provides a preparation method of a perovskite type composite oxygen reduction catalyst, and the scheme of the invention successfully prepares La by an intermittent stepwise improved solvothermal/hydrothermal synthesis method1‑ xMxMnO3‑CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0 nanocomposite oxygen reduction catalyst. This scheme is carried out by oxygen vacancy rich CeO2Material doping of element M with LaMnO3The oxygen reduction catalyst is used for surface oxygen vacancy modification, so that the intrinsic electrochemical catalytic performance of the composite material is greatly improved, and the composite material is applied to an aluminum-air battery. The composite catalyst material prepared by the method has small primary particles, uniform dispersion and higher specific surface area; the preparation process is simple and is beneficial to large-scale batch production.

Description

Preparation method of catalyst and application of catalyst in metal-air battery
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of a catalyst and application of the catalyst in a metal-air battery.
Background
Of the many oxygen reduction catalyst types, the perovskite-type oxygen reduction catalyst has long been recognized as one of the most potential replacements for noble Pt/C catalysts. The factors influencing the electrocatalytic performance of the perovskite type oxygen reduction catalyst mainly comprise a crystal structure, surface characteristics, an oxidation state, oxygen vacancy defects and the like. For LnMnO of equivalent specific surface3(Ln ═ La or Y) perovskite oxides, in the alkaline system, the oxygen reduction catalytic activity is La in that order>Pr>Nd>Sm>Gd>Y>Dy>Yb; the catalytic activity of the catalyst has a direct relationship with the ionic radius, LaMnO3The highest intrinsic oxygen reduction catalytic activity is shown. For LaMnO3Based on the perovskite-type oxide, the perovskite-type catalyst in which La is partially substituted with other elements can realize an energy band structure and Mn3+/Mn4+The valence is regulated and controlled, so that the oxygen reduction catalytic performance of the catalyst is improved; on the other hand, by improving the oxygen adsorption capacity of the catalyst, the oxygen reduction catalytic performance of the perovskite catalyst can be improved. As is well known, CeO2The oxygen storage material has excellent performance, and oxygen vacancies can be quickly formed and disappeared, so that the local oxygen vacancy concentration of the catalyst is effectively improved.
The existing preparation method 1: the oxide composite catalyst is physically mixed by multi-component ball milling or grinding. However, the method can only realize the physical mixing of a plurality of components under the macroscopic scale, can not form strong interaction among the components, and particularly can not effectively adjust the bonding energy of Mn-O-Ce.
The existing preparation method 2: the composite oxide material is prepared by a one-step hydrothermal method, a one-step solvothermal method, an impregnation method and a coprecipitation method. Generally, the material prepared by the one-step hydrothermal method/one-step solvothermal method is powder particles with irregular shapes, even contains a large amount of impurities of complex multi-element composite materials, and can influence the electrocatalytic activity of the catalyst; the oxide precursor prepared by the impregnation method/coprecipitation method needs further high-temperature calcination to obtain the target composite catalyst. The high-temperature calcination can cause the oxide catalyst to grow up and agglomerate seriously, and has lower specific surface area; thereby reducing the exposure of active sites and greatly reducing the catalytic performance of electrocatalysis. But also leads to poor phase formation of the crystal form, and even can only prepare simple oxide composite materials.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a preparation method of a perovskite type composite oxygen reduction catalyst and an application of the perovskite type composite oxygen reduction catalyst in a metal air battery.
The invention provides a preparation method of a perovskite type composite oxygen reduction catalyst, which comprises the following steps:
A) mixing a cerium source compound, an acid-base buffering agent, a surfactant and a solvent, and then carrying out solvothermal reaction under a closed condition to obtain a reaction solution;
B) adding a lanthanum source compound, a manganese source compound and a compound containing M element into the reaction solution to obtain a mixed solution, and performing hydrothermal reaction after adjusting the pH value of the mixed solution to obtain a catalyst precursor;
C) calcining the catalyst precursor to obtain the perovskite type composite oxygen reduction catalyst, wherein the chemical formula of the perovskite type composite oxygen reduction catalyst is La1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0。
Preferably, the cerium source compound is selected from cerium nitrate and/or cerium acetate;
the lanthanum source compound is selected from lanthanum nitrate and/or lanthanum acetate;
the compound containing M element is selected from one or more of strontium nitrate, strontium acetate, calcium nitrate and calcium acetate;
the manganese source compound is selected from manganese nitrate and/or manganese acetate;
the acid-base buffer is selected from urea, ammonium chloride or ammonium carbonate;
the surfactant is selected from tetrabutylammonium bromide;
the solvent is selected from ethylene glycol.
Preferably, the temperature of the solvothermal reaction is 80-250 ℃, and the time of the solvothermal reaction is 0.5-40 hours.
Preferably, the pH regulator for regulating the pH value of the mixed solution is selected from sodium hydroxide, potassium hydroxide or ammonia water, and the pH value is regulated to 6-14.
Preferably, the temperature of the hydrothermal reaction is 80-350 ℃, and the time of the hydrothermal reaction is 0.5-40 hours.
Preferably, the calcining temperature is 200-900 ℃, and the calcining time is 10-250 min.
The invention also provides the perovskite type composite oxygen reduction catalyst prepared by the preparation method, and the chemical formula of the perovskite type composite oxygen reduction catalyst is La1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0, the particle diameter of the perovskite type composite oxygen reduction catalyst is 30-500 nm, and the specific surface area is 29.9cm-2g-1Pore volume of 0.093cm3g-1。
The invention also provides an air cathode prepared from the perovskite type composite oxygen reduction catalyst prepared by the preparation method.
The invention also provides a metal-air battery, which comprises an air cathode, a metal anode and electrolyte, wherein the air cathode is the air cathode.
Compared with the prior art, the invention provides a preparation method of a perovskite type composite oxygen reduction catalyst, which is characterized by comprising the following steps: A) mixing a cerium source compound, an acid-base buffering agent, a surfactant and a solvent, and then carrying out solvothermal reaction under a closed condition to obtain a reaction solution; B) adding a lanthanum source compound, a manganese source compound and a compound containing M element into the reaction solution to obtain a mixed solution, and performing hydrothermal reaction after adjusting the pH value of the mixed solution to obtain a catalyst precursor; C) calcining the catalyst precursor to obtain the perovskite type composite oxygen reduction catalyst, wherein the chemical formula of the perovskite type composite oxygen reduction catalyst is La1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0. The scheme of the invention successfully prepares the La by an intermittent stepwise improved solvothermal/hydrothermal synthesis method1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0 nanocomposite oxygen reduction catalyst. This scheme is carried out by oxygen vacancy rich CeO2Material doping of element M with LaMnO3The oxygen reduction catalyst is used for surface oxygen vacancy modification, so that the intrinsic electrochemical catalytic performance of the composite material is greatly improved, and the composite material is preparedThe material is applied to aluminum air batteries. The composite catalyst material prepared by the method has small primary particles, uniform dispersion and higher specific surface area; the preparation process is simple and is beneficial to large-scale batch production.
Drawings
FIG. 1 is a schematic diagram of a process flow for preparing a perovskite-type composite oxygen reduction catalyst;
FIG. 2 is a TEM topography of the catalyst prepared in example 1;
FIG. 3 is a TEM topography of the catalyst prepared in example 1;
FIG. 4 is an adsorption-desorption curve of the catalyst prepared in example 1;
FIG. 5 is the XRD test results for the catalyst prepared in example 1;
FIG. 6 is an electrochemical polarization curve of the catalyst prepared in example 1;
FIG. 7 is a graph of the performance of an aluminum air cell prepared with the catalyst prepared in example 1;
FIG. 8 is a TEM topography of a catalyst prepared in a comparative example;
FIG. 9 is a XRD test result of the catalyst prepared in the comparative example;
FIG. 10 is an electrochemical polarization curve of a catalyst prepared in a comparative example;
fig. 11 is a graph showing the performance of an aluminum air cell prepared with the catalyst prepared in the comparative example.
Detailed Description
The invention provides a preparation method of a perovskite type composite oxygen reduction catalyst, which comprises the following steps:
A) mixing a cerium source compound, an acid-base buffering agent, a surfactant and a solvent, and then carrying out solvothermal reaction under a closed condition to obtain a reaction solution;
B) adding a lanthanum source compound, a manganese source compound and a compound containing M element into the reaction solution to obtain a mixed solution, and performing hydrothermal reaction after adjusting the pH value of the mixed solution to obtain a catalyst precursor;
C) calcining the catalyst precursor to obtain the perovskite type composite oxygen reduction catalystChemical formula is La1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0。
Firstly, mixing a cerium source compound, an acid-base buffering agent, a surfactant and a solvent, and then carrying out solvothermal reaction under a closed condition to obtain a reaction solution.
Wherein the cerium source compound is selected from cerium nitrate and/or cerium acetate; the acid-base buffer is selected from urea, ammonium chloride or ammonium carbonate, and is preferably urea; the surfactant is selected from tetrabutylammonium bromide; the solvent is selected from ethylene glycol.
In particular, according to CeO2In an amount of dissolving a cerium source compound in a solvent, wherein La is controlled1-xMxMnO3-CeO2CeO in2The solid content of (A) is in the range of 0.5-40%, preferably 2-20%, and more preferably 3-15%.
Then adding a surfactant into the solution, adding a certain amount of acid-base buffering agent, mixing and stirring to obtain a mixed solution.
Wherein the concentration range of the surfactant in the solution is 0.001 mmol/L-2 mmol/L, preferably 0.005 mmol/L-1 mmol/L, and more preferably 0.01 mmol/L-0.2 mmol/L; acid-base buffer and CeO2The molar ratio is (0.05-10): 1, preferably (0.1 to 1): 1, more preferably (0.2 to 0.8): 1.
and transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out solvothermal reaction at a certain temperature.
The temperature of the solvothermal reaction is as follows: 80-250 ℃, preferably 85-200 ℃, and further preferably 90-150 ℃; the solvothermal reaction time is 0.5-40 hours, preferably 1-30 hours, and more preferably 2-20 hours; after the reaction is finished, the reaction kettle is cooled to room temperature to obtain reaction liquid. In the present invention, room temperature is defined as 25. + -. 5 ℃.
And then, adding a lanthanum source compound, a manganese source compound and a compound containing M element into the reaction solution to obtain a mixed solution, adjusting the pH value of the mixed solution, and then carrying out hydrothermal reaction to obtain a catalyst precursor.
The lanthanum source compound is selected from lanthanum nitrate and/or lanthanum acetate; the compound containing M element is selected from one or more of strontium nitrate, strontium acetate, calcium nitrate and calcium acetate; the manganese source compound is selected from manganese nitrate and/or manganese acetate.
Specifically, La was added to the above reaction solution at room temperature1-xMxMnO3(0≤x<1.0, M is selected from Sr and/or Ca) stoichiometric ratio of lanthanum source compound, manganese source compound and compound containing M element, wherein the lanthanum source compound, the manganese source compound and the compound containing M element are added into the reaction liquid in the form of aqueous solution to form a mixed solvent of the step A) and deionized water.
The volume ratio range of the solvent to the water in the step A) is as follows: (10-0.1): 1, preferably (5-0.2): 1, more preferably (2 to 0.5): 1.
and (3) adjusting the pH value of the mixed solvent in the reaction kettle by adding a pH adjusting agent, wherein the pH adjusting agent is selected from sodium hydroxide, potassium hydroxide or ammonia water, and the pH value is adjusted to 6-14, preferably 7-12, and further preferably 8-10).
After the pH value is adjusted, carrying out hydrothermal reaction on the reaction kettle at a certain temperature, wherein the temperature of the hydrothermal reaction is 80-350 ℃, preferably 100-300 ℃, and further preferably 120-250 ℃; time range of the hydrothermal reaction: 0.5 to 40 hours, preferably 1 to 35 hours, and more preferably 2 to 30 hours. And after the reaction is finished, naturally cooling to room temperature to obtain a reaction product.
Finally, filtering the reaction product in the reaction kettle, repeatedly and alternately cleaning the reaction product with deionized water and ethanol for multiple times, and drying the reaction product in an oven at the temperature of 80-120 ℃ to obtain a catalyst precursor;
calcining the catalyst precursor at a certain temperature to obtain a composite catalyst material, wherein the calcining temperature is 200-900 ℃, preferably 300-800 ℃, and further preferably 400-700 ℃; the calcination time is 10-250 minutes, preferably 30-200 minutes, and more preferably 60-150 minutes.
In some embodiments of the present invention, the doping element M is strontium element, the preparation method of the perovskite-type composite oxygen reduction catalyst is shown in fig. 1, and fig. 1 is a schematic flow chart of the preparation process of the perovskite-type composite oxygen reduction catalyst.
Dissolving cerium nitrate in ethylene glycol, then adding tetrabutylammonium bromide and urea for mixing, and carrying out solvothermal reaction in a closed container;
then adding aqueous solution of lanthanum nitrate, manganese nitrate and strontium nitrate, adjusting the pH of the solution by using alkali liquor, and carrying out hydrothermal reaction to obtain reaction liquid;
and separating reaction products in the reaction liquid, washing, drying and calcining to obtain the perovskite type composite oxygen reduction catalyst.
The invention also provides a perovskite type composite oxygen reduction catalyst prepared by the preparation method according to any one of claims 1 to 6, and the chemical formula of the perovskite type composite oxygen reduction catalyst is La1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0, the particle diameter of the perovskite type composite oxygen reduction catalyst is 30-500 nm, and the specific surface area is 29.9cm-2g-1Pore volume of 0.093cm3g-1。
The invention also provides an air cathode prepared from the perovskite type composite oxygen reduction catalyst prepared by the preparation method.
The method for preparing the air cathode is not particularly limited, and the method known to those skilled in the art can be used.
In the present invention, it is preferred to prepare as follows:
adding a solvent into the perovskite type composite oxygen reduction catalyst and the conductive material under the condition of continuous stirring, and then adding polytetrafluoroethylene emulsion and polyvinyl alcohol aqueous solution to obtain air cathode catalyst slurry;
wherein the mass ratio of the perovskite type composite oxygen reduction catalyst to the conductive material is (0.1-9): 1, preferably (0.2-5): 1, more preferably (0.5 to 2): 1.
the solvent is selected from ethanol. The amount of the solvent added is such that the solid content of the perovskite type composite oxygen reduction catalyst and the conductive material is 1 wt% to 90 wt%, preferably 5 wt% to 70 wt%, and more preferably 10 wt% to 50 wt%.
60 wt% of the polytetrafluoroethylene emulsion (PTFE for short).
The mass ratio of the total mass of the perovskite type composite oxygen reduction catalyst and the conductive carbon material to the PTFE is (0.1-3): 1, preferably (0.2-2): 1, more preferably (0.5 to 1.5): 1.
the concentration of the polyvinyl alcohol aqueous solution is 10 wt%, and the polyvinyl alcohol aqueous solution can also be PVP or PVB water-soluble high polymer material aqueous solution.
And then, compounding the obtained air cathode catalyst slurry on a metal support to obtain an air cathode biscuit. Wherein, the loading range is as follows: 0.1mg/cm2～100mg/cm2Preferably 0.5mg/cm2～80mg/cm2Further preferably 1mg/cm2～60mg/cm2。
The compounding method is a coating method, an impregnation method or a filtering method.
The metal support is selected from a copper mesh, a nickel mesh, a stainless steel mesh, a copper foam or a nickel foam.
And then, roasting the air cathode biscuit at a certain temperature to obtain the air cathode. The sintering temperature is 200-500 ℃, preferably 220-450 ℃, and further preferably 250-400 ℃; the sintering time is 10-400 minutes, preferably 20-300 minutes, and more preferably 30-200 minutes.
The invention also provides a metal-air battery, which comprises an air cathode, a metal anode and electrolyte, wherein the air cathode is the air cathode.
The metal anode is selected from aluminum metal anodes and the electrolyte is preferably aqueous KOH.
La is prepared by an intermittent stepwise improved solvothermal/hydrothermal synthesis method1-xMxMnO3-CeO2Nano composite catalyst of CeO with oxygen vacancy rich surface2Material pair LaMnO3The perovskite oxygen reduction catalyst is used for surface oxygen vacancy modification, so that the electrocatalysis performance of the composite material is greatly improved, and the composite catalyst is applied to the cathode of an aluminum-air battery.
By adopting the scheme of the invention, the composite catalyst with two components uniformly dispersed can be obtained, the Mn-O-Ce bond energy of the surface active site of the composite catalyst is effectively regulated and controlled, the oxygen adsorption capacity and the oxygen adsorption capacity of the surface of the composite catalyst are greatly improved, and the electrocatalysis performance of the perovskite type composite oxygen reduction catalyst is essentially improved.
The composite catalyst material prepared by the method has small primary particles, uniform appearance and higher specific surface area; the preparation process is simple and is beneficial to large-scale batch production.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the perovskite-type composite oxygen reduction catalyst and its application in metal-air batteries, and the scope of the present invention is not limited by the following examples.
Example 1
First, according to CeO2The cerium nitrate is dissolved in glycol, and CeO is controlled2The solid content is 10%; adding a proper amount of tetrabutylammonium bromide surfactant into the solution, and controlling the concentration of the surfactant to be 0.1 mmol/L; adding a certain amount of urea, and controlling urea/CeO2The molar ratio is 0.4, and the mixture is fully stirred and uniformly mixed to prepare a mixed solution. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out solvothermal reaction for 6 hours at a certain temperature of 180 ℃; and (3) reducing the temperature of the reaction kettle to room temperature to obtain a first-step intermediate product.
Adding La into the first-step reaction kettle at room temperature0.7Sr0.3MnO3Controlling the water solution of lanthanum nitrate, strontium nitrate and manganese nitrate in stoichiometric ratio2/La0.7Sr0.3MnO3The mixture ratio is 2/3; forming a mixed solvent of glycol and deionized water, and controlling the ratio of glycol/water to be 1; and (3) adjusting the pH value of the mixed solvent to 9 by adding 0.1mol/L sodium hydroxide solution, carrying out solvothermal reaction for 6 hours at the temperature of 180 ℃ in the reaction kettle, and then naturally cooling to room temperature. Then, after the product in the reaction kettle is filtered, the product is repeatedly and alternately cleaned by deionized water and ethanolAfter 3 times, drying in an oven at 80 ℃ to obtain a composite catalyst precursor; calcining the precursor at the temperature of 600 ℃ for 120 minutes to obtain a composite catalyst material; the primary particle of the prepared composite catalyst material is about 200 +/-30 nm, and the secondary particle is about 3 +/-0.5 mu m; the specific surface area is 29.9m2Per g, pore volume 0.093cm3(ii) in terms of/g. The morphology, crystal form and electrochemical polarization curve of the prepared composite catalyst are shown in figures 2-6.
Taking the prepared composite catalyst powder and VXC-72 conductive carbon material, and controlling the ratio of the composite catalyst to the conductive carbon material to be 1; under the condition of continuous stirring, adding the mixture into ethanol, controlling the solid content to be 40%, and uniformly stirring; then adding a certain amount of polytetrafluoroethylene emulsion with the solid content of 60 wt%, controlling the total mass of the composite catalyst and the conductive carbon material/PTFE mass ratio to be 1, and continuously stirring uniformly; adding a prepared polyvinyl alcohol aqueous solution with the mass content of 10% into the slurry, controlling the mass percentage of polyvinyl alcohol to be 2%, continuously stirring and uniformly dispersing to obtain air cathode catalyst slurry; coating the slurry on a copper net support by a coating method to obtain an air cathode biscuit, and controlling the coating loading amount to be 50mg/cm2(ii) a And roasting the air cathode biscuit at the temperature of 300 ℃ for 120 minutes to obtain the finished air cathode.
And finally, assembling the air cathode sheet and the high-purity aluminum metal anode into a single cell, and testing the discharge performance in KOH with 4mol/L electrolyte. The highest power density of the tested aluminum-air battery is 261.6mW/cm2The specific test results are shown in fig. 7.
Example 2
First, according to CeO2The cerium nitrate is dissolved in glycol, and CeO is controlled2The solid content is 3%; adding a proper amount of tetrabutylammonium bromide surfactant into the solution, and controlling the concentration of the surfactant to be 0.01 mmol/L; adding a certain amount of urea, and controlling urea/CeO2The molar ratio is 0.2, and the mixture is fully stirred and uniformly mixed to prepare a mixed solution. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out solvothermal reaction for 2 hours at a certain temperature of 85 ℃; mixing the aboveThe reaction kettle is cooled to room temperature to obtain the intermediate product in the first step.
At room temperature, adding LaMnO into the first-step reaction kettle3Controlling CeO with stoichiometric ratio of lanthanum nitrate and manganese nitrate in water solution2/LaMnO3The mixture ratio is 0.1; forming a mixed solvent of glycol and deionized water, and controlling the ratio of glycol/water to be 2; and (3) adjusting the pH value of the mixed solvent to 8 by adding 0.1mol/L sodium hydroxide solution, carrying out solvothermal reaction for 2 hours at the temperature of 120 ℃ in the reaction kettle, and then naturally cooling to room temperature. Then, filtering the product in the reaction kettle, repeatedly and alternately cleaning the product for 3 times by using deionized water and ethanol, and drying the product in an oven at the temperature of 120 ℃ to obtain a composite catalyst precursor; and calcining the precursor at the temperature of 400 ℃ for 60 minutes to obtain the composite catalyst material. (ii) a The primary particle of the prepared composite catalyst material is about 180 +/-15 nm, and the secondary particle is about 2 +/-0.1 mu m; the specific surface area is 35.6m2Per g, pore volume 0.098cm3/g
Taking the prepared composite catalyst powder and VXC-72 conductive carbon material, and controlling the ratio of the composite catalyst to the conductive carbon material to be 0.5; under the condition of continuous stirring, adding the mixture into ethanol, controlling the solid content to be 10%, and uniformly stirring; then adding a certain amount of polytetrafluoroethylene emulsion with the solid content of 60 wt%, controlling the total mass of the composite catalyst and the conductive carbon material/PTFE mass ratio to be 0.5, and continuously and uniformly stirring; adding a prepared polyvinyl alcohol aqueous solution with the mass content of 10% into the slurry, controlling the mass percentage of polyvinyl alcohol to be 1%, continuously stirring and uniformly dispersing to obtain air cathode catalyst slurry; coating the slurry on a copper net support by a coating method to obtain an air cathode biscuit, and controlling the coating loading amount to be 5mg/cm2(ii) a And roasting the air cathode biscuit at the temperature of 250 ℃ for 30 minutes to obtain the finished air cathode.
And finally, assembling the air cathode sheet and the high-purity aluminum metal anode into a single cell, and testing the discharge performance in KOH with 4mol/L electrolyte. The highest power density of the tested aluminum-air battery is 220.5mW/cm2。
Example 3
First, according to CeO2The cerium nitrate is dissolved in glycol, and CeO is controlled2The solid content is 15%; adding a proper amount of tetrabutylammonium bromide surfactant into the solution, and controlling the concentration of the surfactant to be 0.2 mmol/L; adding a certain amount of urea, and controlling urea/CeO2The molar ratio is 0.8, and the mixture is fully stirred and uniformly mixed to prepare a mixed solution. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out solvothermal reaction for 20 hours at a certain temperature of 200 ℃; and (3) reducing the temperature of the reaction kettle to room temperature to obtain a first-step intermediate product.
Adding La into the first-step reaction kettle at room temperature0.3Sr0.7MnO3Controlling the water solution of lanthanum nitrate, strontium nitrate and manganese nitrate in stoichiometric ratio2/La0.3Sr0.7MnO3The mixture ratio is 2; forming a mixed solvent of glycol and deionized water, and controlling the ratio of glycol/water to be 2; and (3) adjusting the pH value of the mixed solvent to 10 by adding 0.1mol/L sodium hydroxide solution, carrying out solvothermal reaction on the reaction kettle at the temperature of 250 ℃ for 30 hours, and then naturally cooling to room temperature. Then, filtering the product in the reaction kettle, repeatedly and alternately cleaning the product for 3 times by using deionized water and ethanol, and drying the product in an oven at the temperature of 120 ℃ to obtain a composite catalyst precursor; calcining the precursor at 700 ℃ for 150 minutes to obtain a composite catalyst material; the primary particle of the prepared composite catalyst material is about 300 +/-30 nm, and the secondary particle is about 4 +/-0.5 mu m; the specific surface area is 22.5m2Per g, pore volume 0.055cm3/g。
Taking the prepared composite catalyst powder and VXC-72 conductive carbon material, and controlling the ratio of the composite catalyst to the conductive carbon material to be 2; adding the mixture into ethanol under the condition of continuous stirring, controlling the solid content to be 50%, and uniformly stirring; then adding a certain amount of polytetrafluoroethylene emulsion with the solid content of 60 wt%, controlling the total mass of the composite catalyst and the conductive carbon material/PTFE mass ratio to be 1.5, and continuously and uniformly stirring; then adding the prepared polyvinyl alcohol aqueous solution with the mass content of 10 wt% into the slurry, controlling the mass percent of the polyvinyl alcohol to be 5%,continuously stirring and uniformly dispersing to obtain air cathode catalyst slurry; coating the slurry on a copper net support by a coating method to obtain an air cathode biscuit, and controlling the coating loading amount to be 60mg/cm2(ii) a And roasting the air cathode biscuit at the temperature of 400 ℃ for 200 minutes to obtain the finished air cathode.
And finally, assembling the air cathode sheet and the high-purity aluminum metal anode into a single cell, and testing the discharge performance in KOH with 4mol/L electrolyte. The tested aluminum-air battery has the highest power density of 245.3mW/cm2。
Example 4
First, according to CeO2The cerium nitrate is dissolved in glycol, and CeO is controlled2The solid content is 12 percent; adding a proper amount of tetrabutylammonium bromide surfactant into the solution, and controlling the concentration of the surfactant to be 0.15 mmol/L; adding a certain amount of urea, and controlling urea/CeO2The molar ratio is 0.5, and the mixture is fully stirred and uniformly mixed to prepare a mixed solution. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out solvothermal reaction for 4 hours at a certain temperature of 200 ℃; and (3) reducing the temperature of the reaction kettle to room temperature to obtain a first-step intermediate product.
Adding La into the first-step reaction kettle at room temperature0.5Sr0.5MnO3Controlling the water solution of lanthanum nitrate, strontium nitrate and manganese nitrate in stoichiometric ratio2/La0.5Sr0.5MnO3The mixture ratio is 1; forming a mixed solvent of glycol and deionized water, and controlling the ratio of glycol/water to be 0.8; and adjusting the pH value of the mixed solvent to 9 by adding 0.1mol/L sodium hydroxide solution, carrying out solvothermal reaction for 16 hours at 190 ℃, and then naturally cooling to room temperature. Then, filtering the product in the reaction kettle, repeatedly and alternately cleaning the product for 3 times by using deionized water and ethanol, and drying the product in an oven at 110 ℃ to obtain a composite catalyst precursor; calcining the precursor at 650 ℃ for 150 minutes to obtain a composite catalyst material, wherein the primary particles of the prepared composite catalyst material are about 250 +/-20 nm, and the secondary particles are about 3 +/-0.2 mu m; the specific surface area is 26.8m2Per g, poreThe volume is 0.073cm3/g。
Taking the prepared composite catalyst powder and VXC-72 conductive carbon material, and controlling the ratio of the composite catalyst to the conductive carbon material to be 1.5; under the condition of continuous stirring, adding the mixture into ethanol, controlling the solid content to be 45%, and uniformly stirring; then adding a certain amount of polytetrafluoroethylene emulsion with the solid content of 60 wt%, controlling the total mass of the composite catalyst and the conductive carbon material/PTFE mass ratio to be 1.5, and continuously and uniformly stirring; adding a prepared polyvinyl alcohol aqueous solution with the mass content of 10% into the slurry, controlling the mass percentage of polyvinyl alcohol to be 2.5%, continuously stirring and uniformly dispersing to obtain air cathode catalyst slurry; coating the slurry on a copper net support by a coating method to obtain an air cathode biscuit, and controlling the coating loading amount to be 75mg/cm2(ii) a And roasting the air cathode biscuit at the temperature of 280 ℃ for 100 minutes to obtain the finished air cathode.
And finally, assembling the air cathode sheet and the high-purity aluminum metal anode into a single cell, and testing the discharge performance in KOH with 4mol/L electrolyte. The tested aluminum-air battery has the highest power density of 241.8mW/cm2。
Example 5
First, according to CeO2The cerium nitrate is dissolved in glycol, and CeO is controlled2The solid content is 8 percent; adding a proper amount of tetrabutylammonium bromide surfactant into the solution, and controlling the concentration of the surfactant to be 0.2 mmol/L; adding a certain amount of urea, and controlling urea/CeO2The molar ratio is 0.5, and the mixture is fully stirred and uniformly mixed to prepare a mixed solution. Transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out solvothermal reaction for 5 hours at a certain temperature of 150 ℃; and (3) reducing the temperature of the reaction kettle to room temperature to obtain a first-step intermediate product.
Adding La into the first-step reaction kettle at room temperature0.6Sr0.4MnO3Controlling the water solution of lanthanum nitrate, strontium nitrate and manganese nitrate in stoichiometric ratio2/La0.6Sr0.4MnO3The mixture ratio is 0.5; and a mixed solvent of ethylene glycol and deionized water is formed,controlling the ratio of ethylene glycol to water to be 2; and adjusting the pH value of the mixed solvent to 10 by adding 0.1mol/L sodium hydroxide solution, carrying out solvothermal reaction for 5 hours at the temperature of 220 ℃, and then naturally cooling to room temperature. Then, filtering the product in the reaction kettle, repeatedly and alternately cleaning the product for 3 times by using deionized water and ethanol, and drying the product in an oven at 110 ℃ to obtain a composite catalyst precursor; calcining the precursor at 680 ℃ for 100 minutes to obtain a composite catalyst material, wherein the primary particles of the prepared composite catalyst material are about 280 +/-30 nm, and the secondary particles are about 3 +/-0.2 mu m; the specific surface area is 24.3m2Per g, pore volume 0.068cm3/g。
Taking the prepared composite catalyst powder and VXC-72 conductive carbon material, and controlling the ratio of the composite catalyst to the conductive carbon material to be 1.5; under the condition of continuous stirring, adding the mixture into ethanol, controlling the solid content to be 35%, and uniformly stirring; then adding a certain amount of polytetrafluoroethylene emulsion with the solid content of 60 wt%, controlling the total mass of the composite catalyst and the conductive carbon material/PTFE mass ratio to be 2, and continuously and uniformly stirring; adding a prepared polyvinyl alcohol aqueous solution with the mass content of 10% into the slurry, controlling the mass percentage of polyvinyl alcohol to be 2.5%, continuously stirring and uniformly dispersing to obtain air cathode catalyst slurry; coating the slurry on a copper net support by a coating method to obtain an air cathode biscuit, and controlling the coating loading amount to be 55mg/cm2(ii) a And roasting the air cathode biscuit at the temperature of 280 ℃ for 150 minutes to obtain the finished air cathode.
And finally, assembling the air cathode sheet and the high-purity aluminum metal anode into a single cell, and testing the discharge performance in KOH with 4mol/L electrolyte. The highest power density of the tested aluminum-air battery is 233.4mW/cm2。
Comparative example
First, according to CeO2/La0.7Sr0.3MnO3Amount of (CeO)2/La0.7Sr0.3MnO32/3) dissolving cerium nitrate, lanthanum nitrate, strontium nitrate and manganese nitrate in deionized water; then adding appropriate amount of tetrabutylammonium bromide (T for short) into the solutionBAB) surfactant, wherein the concentration of the surfactant is controlled to be 0.1 mmol/L; adding a certain amount of urea, and controlling urea/CeO2The molar ratio is 0.4, and the mixture is fully stirred and uniformly mixed to prepare a mixed solution. Adjusting the pH value of the mixed solvent to 9 by adding 0.1mol/L sodium hydroxide solution; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining; the reaction kettle is subjected to hydrothermal reaction for 6 hours at 180 ℃, and then is naturally cooled to room temperature. Then, filtering the product in the reaction kettle, repeatedly and alternately cleaning the product for 3 times by using deionized water and ethanol, and drying the product in an oven at the temperature of 80 ℃ to obtain a composite catalyst precursor; and calcining the precursor at the temperature of 600 ℃ for 120 minutes to obtain the composite catalyst material. The morphology, crystal form and electrochemical polarization curve of the prepared composite catalyst are shown in figures 8-10. The prepared composite catalyst material has non-uniform particle size of 5-500 nm; the secondary particles are seriously agglomerated, about 6 +/-3 mu m; the specific surface area is 15m2Per g, pore volume 0.055cm3/g
Taking the prepared composite catalyst powder and VXC-72 conductive carbon material, and controlling the ratio of the composite catalyst to the conductive carbon material to be 1; under the condition of continuous stirring, adding the mixture into ethanol, controlling the solid content to be 40 wt%, and uniformly stirring; then adding a certain amount of polytetrafluoroethylene emulsion with the solid content of 60 Wt%, controlling the total mass of the composite catalyst and the conductive carbon material/PTFE mass ratio to be 1, and continuously and uniformly stirring; adding a prepared polyvinyl alcohol aqueous solution with the mass content of 10% into the slurry, controlling the mass percentage of polyvinyl alcohol to be 2%, continuously stirring and uniformly dispersing to obtain air cathode catalyst slurry; coating the slurry on a copper net support by a coating method to obtain an air cathode biscuit, and controlling the coating loading amount to be 80mg/cm2(ii) a And roasting the air cathode biscuit at the temperature of 200 ℃ for 120 minutes to obtain the finished air cathode.
And finally, assembling the air cathode sheet and the high-purity aluminum metal anode into a single cell, and testing the discharge performance in KOH with 4mol/L electrolyte. The highest power density of the tested aluminum-air battery is 198.6mW/cm2The specific test results are shown in fig. 11.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A preparation method of a perovskite type composite oxygen reduction catalyst is characterized by comprising the following steps:
A) mixing a cerium source compound, an acid-base buffering agent, a surfactant and a solvent, and then carrying out solvothermal reaction under a closed condition to obtain a reaction solution;
B) adding a lanthanum source compound, a manganese source compound and a compound containing M element into the reaction solution to obtain a mixed solution, and performing hydrothermal reaction after adjusting the pH value of the mixed solution to obtain a catalyst precursor;
C) calcining the catalyst precursor to obtain the perovskite type composite oxygen reduction catalyst, wherein the chemical formula of the perovskite type composite oxygen reduction catalyst is La1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0。
2. The method according to claim 1, wherein the cerium source compound is selected from cerium nitrate and/or cerium acetate;
the lanthanum source compound is selected from lanthanum nitrate and/or lanthanum acetate;
the compound containing M element is selected from one or more of strontium nitrate, strontium acetate, calcium nitrate and calcium acetate;
the manganese source compound is selected from manganese nitrate and/or manganese acetate;
the acid-base buffer is selected from urea, ammonium chloride or ammonium carbonate;
the surfactant is selected from tetrabutylammonium bromide;
the solvent is selected from ethylene glycol.
3. The method according to claim 1, wherein the temperature of the solvothermal reaction is 80 to 250 ℃ and the time of the solvothermal reaction is 0.5 to 40 hours.
4. The method according to claim 1, wherein the pH adjuster for adjusting the pH of the mixed solution is selected from sodium hydroxide, potassium hydroxide, and ammonia water, and the pH is adjusted to 6 to 14.
5. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 80 to 350 ℃ for 0.5 to 40 hours.
6. The method according to claim 1, wherein the calcination temperature is 200 to 900 ℃ and the calcination time is 10 to 250 min.
7. The perovskite type composite oxygen reduction catalyst prepared by the preparation method according to any one of claims 1 to 6, wherein the chemical formula of the perovskite type composite oxygen reduction catalyst is La1-xMxMnO3-CeO2M is selected from Sr and/or Ca, 0 ≦ x<1.0, the particle diameter of the perovskite type composite oxygen reduction catalyst is 30-500 nm, and the specific surface area is 29.9cm- 2g-1Pore volume of 0.093cm3g-1。
8. An air cathode, characterized in that it is prepared from the perovskite-type composite oxygen reduction catalyst prepared by the preparation method according to any one of claims 1 to 6.
9. A metal-air battery comprising an air cathode, a metal anode, and an electrolyte, wherein the air cathode is the air cathode of claim 8.
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