CN112421064A - A2Mn2-XWXO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof - Google Patents

A2Mn2-XWXO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof Download PDF

Info

Publication number
CN112421064A
CN112421064A CN202011395541.0A CN202011395541A CN112421064A CN 112421064 A CN112421064 A CN 112421064A CN 202011395541 A CN202011395541 A CN 202011395541A CN 112421064 A CN112421064 A CN 112421064A
Authority
CN
China
Prior art keywords
perovskite oxide
catalytic material
nitrogen
composite catalytic
doped carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011395541.0A
Other languages
Chinese (zh)
Other versions
CN112421064B (en
Inventor
李凤姣
王文伟
张哲鸣
李瑞宇
崔彦辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Automotive Research Institute of Beijing University of Technology
Original Assignee
Shenzhen Automotive Research Institute of Beijing University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Automotive Research Institute of Beijing University of Technology filed Critical Shenzhen Automotive Research Institute of Beijing University of Technology
Priority to CN202011395541.0A priority Critical patent/CN112421064B/en
Publication of CN112421064A publication Critical patent/CN112421064A/en
Application granted granted Critical
Publication of CN112421064B publication Critical patent/CN112421064B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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

Abstract

The present application provides a2Mn2‑xWxO6Perovskite oxide and nitrogen-doped carbon composite catalytic material, and preparation method and application thereof, wherein A in the composite catalytic material2Mn2‑xWxO6Perovskite oxide, A is selected from one or more atoms of Ca, Sr and Ba, x is mole fraction, and 0 < x ≦ 1. The composite catalytic material, the hydrophobic breathable layer and the current collector are prepared into a battery cathode, and the battery cathode can be applied to a metal air battery to improve the output power of the battery.

Description

A2Mn2-xWxO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a battery A2Mn2-xWxO6A perovskite oxide and nitrogen-doped carbon composite catalytic material, a preparation method and application thereof.
Background
The reaction efficiency of the cathode oxygen reduction reaction of the metal-air battery is a key factor influencing the overall output power of the metal-air battery. Perovskite oxides are of great interest as a class of metal-air battery cathode catalytic materials with high intrinsic activity, low cost and excellent oxygen reduction reaction performance. However, the perovskite oxide composite material has the disadvantages of low specific surface area and poor electrical conductivity, and if most of the perovskite oxide contacts carbon at high temperature, the perovskite oxide structure is easily decomposed due to carbothermic reduction reaction, so that most of the perovskite cannot stably exist after in-situ compounding with the carbon at high temperature, and the generated secondary structure is unfavorable for the catalytic activity and stability of oxygen reduction reaction. In the prior art, when the perovskite oxide is directly used for preparing the cathode catalytic material of the metal battery, the conductivity and the activity of the perovskite oxide can not achieve the ideal effect; in addition, when the perovskite oxide in the prior art is prepared into an electrode or a battery, carbon black needs to be physically added during testing, and the operation steps are complicated.
Disclosure of Invention
The invention provides a2Mn2-xWxO6The composite catalytic material of perovskite oxide and nitrogen-doped carbon, and the preparation method and the application thereof are used for improving the performance of the metal-air battery.
In a first aspect, the present application provides a composition based on A2Mn2-xWxO6The composite catalytic material of perovskite oxide and nitrogen-doped carbon consists of A2Mn2-xWxO6Perovskite oxide, carbon black and nitrogen source; wherein, A is2Mn2-xWxO6In the perovskite oxide, A comprises at least one of Ca, Sr and Ba, x is a mole fraction, and 0 < x ≦ 1. The present application describes based on A2Mn2-xWxO6A composite catalytic material of perovskite oxide and nitrogen-doped carbon, which is not easily decomposed at high temperature in the presence of a large amount of carbon and can retain A2Mn2-xWxO6The perovskite oxide has a stable structure, has the advantages of good activity, strong conductivity and good dispersibility, can effectively improve the reaction efficiency of the cathode oxygen reduction reaction of the metal-air battery, can be applied to the metal-air battery, and improves the output power and other performances of the battery. Furthermore, A2Mn2-xWxO6The composite catalytic material of perovskite oxide and nitrogen-doped carbon does not need to be additionally added with conductive materials such as carbon black and the like during oxygen reduction reaction or battery performance test, and the steps are simpler and more convenient.
In one embodiment, the carbon black is in combination with A2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-20: 1, preferably 1: 1-5: 1. In the above examples, the carbon black is selected from one or more of the types Vulcan XC-72, BP 2000, Ketjenblack EC 300J and Ketjenblack EC 600J, Super Li.
In one embodiment, the nitrogen source is the same as the A2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-200: 1, preferably 1: 1-20: 1. In the above examples, the nitrogen source comprises urea, glucosamine hydrochloride, melamine, dicyandiamide, g-C3N4At least one of polyaniline, polypyrrole, and polyacrylonitrile. The nitrogen source is adopted to dope the carbon black in the application because the doped nitrogen atoms can effectively change the surface electronic property of the carbon material and increase the defect sites of the carbon material, thereby improving the electrocatalytic property.
In a second aspect, the present application provides a metal-air battery cathode comprising the composite catalytic material of the first aspect, further comprising a hydrophobic gas-permeable layer and a current collector. The electrode reaction of the air electrode takes place on the gas-liquid-solid three-phase interface, namely, oxygen continuously enters the three-phase interface through the hydrophobic air-permeable layer to react, and the hydrophobic air-permeable layer can be diffused by oxygen to complete the electrochemical reaction. The current collector is a structure that collects current, and in the present application, the current collector may be Al foil or Cu foil or nickel foam, etc.
In a third aspect, the present application provides a metal-air cell comprising the metal-air cell cathode of the second aspect. The lithium air battery cathode can be used as a cathode of a lithium air battery, a zinc air battery, an aluminum air battery or a magnesium air battery.
In a fourth aspect, the present application provides a composition based on A as defined in the first aspect2Mn2-xWxO6The preparation method of the perovskite oxide and nitrogen-doped carbon composite catalytic material comprises the following steps:
(1) preparation A2Mn2-xWxO6Perovskite oxide: a is metal ions and comprises at least one of Ca, Sr and Ba, x is a mole fraction, and x is more than 0 and less than or equal to 1; dissolving nitrate or acetate of A, manganese acetate tetrahydrate and ammonium metatungstate in deionized water according to a stoichiometric ratio to prepare a metal salt solution; adding citric acid monohydrate, stirring and heating at 60-100 ℃ until gel is formed; drying the obtained gel at 80-140 ℃ for 4-24 hours, then heating to 200-300 ℃ and preserving the heat for 6-12 hours to obtain a catalytic material precursor; calcining the precursor of the catalytic material at the temperature of 800-1000 ℃ for 8-24 hours to obtain the impure phase A2Mn2-xWxO6Calcining the perovskite oxide in a high-purity mixed gas of hydrogen/nitrogen or high-purity hydrogen for 8-24 hours at the temperature of 1000-1100 ℃ to obtain pure-phase A2Mn2-xWxO6A perovskite oxide; the purpose of calcination in a muffle furnace is to obtain A in an impure phase2Mn2-xWxO6Perovskite oxides, the purpose of further calcination in a tube furnaceIn order to obtain phase-pure A2Mn2-xWxO6A perovskite oxide;
(2) preparation A2Mn2-xWxO6The perovskite oxide and nitrogen-doped carbon composite catalytic material comprises the following components in percentage by weight: carbon black, nitrogen source and the above A2Mn2-xWxO6Adding perovskite oxide into solvent, stirring and heating at 50-100 ℃ until the solvent is completely volatilized to obtain an intermediate mixture, fully and uniformly grinding, calcining at 600-1100 ℃ for 5-24 hours in argon or nitrogen to obtain the A2Mn2-xWxO6A composite catalytic material of perovskite oxide and nitrogen-doped carbon.
The method adopts a one-pot method to calcine the mixture of the perovskite oxide, the carbon black and the nitrogen source, the conventional calcining temperature is 600 ℃ or above, and for general perovskite oxides, the perovskite oxides are easy to decompose due to carbothermic reduction reaction under the conditions of high temperature and carbon existence, so that the perovskite oxides can not keep stability after being calcined under the high temperature condition of carbon existence. In the application, firstly, the A (metal ions including at least one of Ca, Sr and Ba) is prepared from three raw materials of nitrate or acetate of A, manganese acetate tetrahydrate and ammonium metatungstate, wherein the A can maintain a stable structure under the condition of high temperature and in the presence of carbon2Mn2-xWxO6Mixing perovskite oxide with carbon black and nitrogen source, and calcining at high temperature in argon or nitrogen atmosphere to obtain A2Mn2-xWxO6The perovskite oxide and nitrogen-doped carbon composite catalytic material can keep good stability and conductivity after high-temperature calcination in the prepared composite catalytic material.
In the preparation method, the stoichiometric ratio of the nitrate or acetate of the A, the manganese acetate tetrahydrate and the ammonium metatungstate is 2: (2-x): x/12. For example, when x takes 1, the nitrate or acetate salt of a: manganese acetate tetrahydrate: the mol ratio of ammonium metatungstate is 2: 1: 1/12, respectively; when x is 0.5, the nitrate or acetate salt of a: manganese acetate tetrahydrate: the mol ratio of ammonium metatungstate is 2: 1.5: 0.5/12.
In one embodiment, in the step (2), the solvent includes any one of ethanol, acetone or deionized water; the nitrogen source comprises urea, glucosamine hydrochloride, melamine, dicyandiamide and g-C3N4At least one of polyaniline, polypyrrole, and polyacrylonitrile; the carbon black is selected from one or more of Vulcan XC-72, BP 2000, Ketjenblack EC 300J, Ketjenblack EC 600J and Super Li.
In one embodiment, the nitrogen source is the same as the A2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-200: 1, preferably 1: 1-20: 1; said carbon black and said A2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-20: 1, preferably 1: 1-5: 1.
Has the advantages that: the catalyst is prepared by adding A with excellent catalytic performance and stability2Mn2-xWxO6Calcining perovskite oxide with carbon black and nitrogen source to form A2Mn2-xWxO6The composite catalytic material of perovskite oxide and nitrogen-doped carbon not only can maintain A2Mn2-xWxO6The perovskite oxide has a stable structure and has good conductivity and dispersibility, and the in-situ doped nitrogen atoms can effectively change the surface electronic property of the carbon material and increase the defect sites of the carbon material, so that the reaction efficiency of the cathode of the metal-air battery and the overall performance of the battery can be effectively improved.
Drawings
FIG. 1 shows Ca in example 12Mn1.2W0.8O6Cathode and Ca2Mn1.2W0.8O6-a graph of the half-wave potential versus the negative electrode of the N-C composite catalytic material;
FIG. 2 shows Ca prepared in example 12Mn1.2W0.8O6Zinc-air battery and Ca2Mn1.2W0.8O6-power density comparison graph of N-C composite catalytic material zinc air cell;
FIG. 3 shows Ba in example 21.6Sr0.4MnWO6Cathode electrode and Ba1.6Sr0.4MnWO6-a graph of the half-wave potential versus the negative electrode of the N-C composite catalytic material;
FIG. 4 shows Ba prepared in example 21.6Sr0.4MnWO6Aluminum air cell and Ba1.6Sr0.4MnWO6-power density comparison plot of N-C composite catalytic material aluminum air cell;
FIG. 5 shows Sr in example 32MnWO6Cathode electrode and Sr2MnWO6-a graph of the half-wave potential versus the negative electrode of the N-C composite catalytic material;
FIG. 6 is Sr prepared in example 32MnWO6Magnesium air battery and Sr2MnWO6-power density comparison graph of N-C composite catalytic material magnesium air battery.
Detailed Description
This application will A2Mn2-xWxO6After the perovskite oxide and the carbon black are mixed, nitrogen is doped in situ, the composite catalytic material is prepared in one step, the carbon black is not required to be added when a later-stage assembled battery is tested, the preparation process is optimized, the preparation steps are saved, and good conductivity can be still kept at high temperature; meanwhile, when the composite carbon black is used and nitrogen source doping is carried out, A2Mn2-xWxO6The perovskite oxide can still maintain the stable structure during high-temperature preparation, so that the perovskite oxide has good dispersibility and conductivity, and the A is further improved2Mn2-xWxO6The characteristic activity of the perovskite oxide itself.
Example 1
1.1 preparation of Ca2Mn1.2W0.8O6Perovskite oxide:
dissolving calcium nitrate, manganese acetate tetrahydrate and ammonium metatungstate in stoichiometric ratio in deionized water, and adding citric acid monohydrate into the above metal salt solution, wherein the citric acid monohydrate and metal ions (including calcium ions and manganese ions)And tungsten ions) is 1.5: 1, then the solution is continuously stirred and heated in a constant-temperature water bath at 80 ℃ until gel is formed, the obtained gel is dried for 12 hours in a blast drying oven at 140 ℃, and then the temperature is raised to 240 ℃ and kept for 10 hours, thus obtaining the precursor of the catalytic material. Calcining the precursor of the catalytic material in a muffle furnace at 1000 ℃ for 8 hours, then transferring the precursor to a tubular furnace, calcining the precursor in a high-purity hydrogen/nitrogen mixed gas at 1050 ℃ for 10 hours to obtain Ca2Mn1.2W0.8O6A perovskite oxide.
1.2 preparation of Ca2Mn1.2W0.8O6The composite catalytic material of perovskite oxide and nitrogen (polypyrrole) doped carbon (carbon black) comprises the following components:
7.5 g of polypyrrole, 2.0 g of carbon black Vulcan XC-72 and 0.5 g of Ca as described in step 1.12Mn1.2W0.8O6Respectively adding perovskite oxide into 50 mL of ethanol, and continuously stirring and heating in a constant-temperature water bath at 75 ℃ until the solvent is completely volatilized completely to obtain Ca2Mn1.2W0.8O6The mixture of perovskite oxide, carbon black and polypyrrole is fully and uniformly ground, then the mixture is put into a tube furnace and is calcined for 10 hours at 1100 ℃ in argon atmosphere to obtain the Ca2Mn1.2W0.8O6Composite catalytic material of perovskite oxide and nitrogen-doped carbon, marked as Ca2Mn1.2W0.8O6-N-C。
1.3 comparative Ca2Mn1.2W0.8O6Cathode and Ca2Mn1.2W0.8O6-performance of the cathode electrode of N-C composite catalytic material:
adding Ca in step 1.12Mn1.2W0.8O6Preparing into an electrode, testing the performance of oxygen reduction reaction in alkaline solution at the rotating speed of 1600 rpm, and adding carbon black during testing. The preparation process of the electrode comprises the following steps: 2.5 mg of Ca2Mn1.2W0.8O6And 7.5 mg of carbon black Vulcan XC-72 to 1 ml of a fraction consisting of ethanol and 5% NafionIn the dispersion, the volume ratio of ethanol to 5% Nafion is 4:1, ultrasonic dispersion is carried out for more than half an hour, then 10 microliter of dispersed catalyst ink is taken out and dripped on a glassy carbon electrode, and Ca is measured2Mn1.2W0.8O6The half-wave potential of (2) was 0.72V (relative to the reversible hydrogen electrode), as shown in fig. 1.
Adding Ca in step 1.22Mn1.2W0.8O6the-N-C composite catalytic material is prepared into an electrode, the oxygen reduction reaction performance is tested in an alkaline solution at the rotating speed of 1600 rpm, and carbon black is not required to be added during testing. The preparation process of the electrode comprises the following steps: adding 10.0mg of Ca2Mn1.2W0.8O6the-N-C composite catalytic material is directly added into 1 ml of dispersion liquid consisting of ethanol and 5 percent Nafion, the volume ratio of the ethanol to the 5 percent Nafion is 4:1, ultrasonic dispersion is carried out for more than half an hour, then 10 microliter of dispersed catalyst ink is taken out and dripped on a glassy carbon electrode, and Ca is measured2Mn1.2W0.8O6The half-wave potential of the-N-C composite catalytic material is 0.81V (relative to a reversible hydrogen electrode), as shown in FIG. 1. Ca2Mn1.2W0.8O6Half-wave potential ratio Ca of-N-C composite catalytic material2Mn1.2W0.8O6Positive 90 mV (vs. reversible hydrogen electrode) indicates Ca2Mn1.2W0.8O6The oxygen reduction performance of the-N-C composite catalytic material is improved.
1.4 Metal-air Battery Performance:
the Ca prepared in step 1.12Mn1.2W0.8O6A catalyst paste consisting of perovskite oxide and carbon black Vulcan XC-72, a foamed nickel current collector and hydrophobic breathable carbon paper are assembled into an air cathode of the zinc-air battery, a polished zinc sheet with the thickness of 0.5 cm is used as an anode, and the maximum power density of the zinc-air battery is measured to be 99 mW cm-2As shown in fig. 2.
The Ca prepared in step 1.22Mn1.2W0.8O6Catalyst paste consisting of-N-C composite catalytic material (carbon black is not additionally added in the catalyst paste) and foamed nickel current collectorThe hydrophobic air-permeable carbon paper is assembled into an air cathode of the zinc-air battery, a polished zinc sheet with the thickness of 0.5 cm is used as an anode, and the measured maximum power density of the zinc-air battery is 120 mW cm-2As shown in fig. 2. Namely, the carbon black is added and the nitrogen source is doped during the preparation, so that the conductivity of the composite catalytic material can be effectively improved and the Ca is kept2Mn1.2W0.8O6The perovskite oxide has a stable structure, and carbon black is not required to be added during testing, so that the operation is simpler and more convenient.
Example 2
2.1 preparation of Ba1.6Sr0.4MnWO6Perovskite oxide:
dissolving barium nitrate, strontium nitrate, manganese acetate tetrahydrate and ammonium metatungstate in deionized water according to a stoichiometric ratio, adding citric acid monohydrate into the metal salt solution, wherein the molar ratio of the citric acid monohydrate to metal ions (including barium ions, strontium ions, manganese ions and tungsten ions) is 2: 1, continuously stirring and heating the solution in a constant-temperature water bath at 100 ℃ until gel is formed, drying the obtained gel in a forced air drying oven at 90 ℃ for 24 hours, and heating to 300 ℃ for heat preservation for 6 hours to obtain the catalytic material precursor. Calcining the precursor of the catalytic material in a muffle furnace at 800 ℃ for 12 hours, then transferring the precursor to a tubular furnace, calcining the precursor in high-purity hydrogen at 1100 ℃ for 15 hours to obtain Ba1.6Sr0.4MnWO6A perovskite oxide.
2.2 preparation of Ba1.6Sr0.4MnWO6The perovskite oxide and nitrogen (polyacrylonitrile) doped carbon (carbon black) composite catalytic material comprises the following components in percentage by weight:
4.8 g polyacrylonitrile, 3.6 g carbon black Ketjenblack EC 300J and 0.8 g Ba as described in step 2.11.6Sr0.4MnWO6Respectively adding perovskite oxide into 60 mL of deionized water, and continuously stirring and heating in a constant-temperature water bath at 80 ℃ until the solvent is completely volatilized completely to obtain Ba1.6Sr0.4MnWO6The mixture of perovskite oxide, carbon black and polyacrylonitrile is fully and uniformly ground and then put into a tube furnace, and nitrogen is addedCalcining at 900 ℃ for 12 hours in atmosphere to obtain the Ba1.6Sr0.4MnWO6Composite catalytic material of perovskite oxide and nitrogen-doped carbon, marked as Ba1.6Sr0.4MnWO6-N-C。
2.3 comparison of Ba1.6Sr0.4MnWO6Cathode electrode and Ba1.6Sr0.4MnWO6-performance of the cathode electrode of N-C composite catalytic material:
reacting Ba prepared in step 2.11.6Sr0.4MnWO6And (3) preparing an electrode, testing the oxygen reduction reaction performance in an alkaline solution at the rotating speed of 1600 rpm, and adding carbon black during testing. The preparation process of the electrode comprises the following steps: 5.0 mg of Ba1.6Sr0.4MnWO6And 5.0 mg of carbon black Ketjenblack EC 300J were added to 1 ml of a dispersion consisting of ethanol and 5% Nafion in a volume ratio of ethanol to 5% Nafion of 4:1, ultrasonically dispersed for more than half an hour, 10. mu.l of dispersed catalyst ink was taken out therefrom and dropped on a glassy carbon electrode, and Ba was detected1.6Sr0.4MnWO6The half-wave potential of (2) was 0.73V (relative to the reversible hydrogen electrode), as shown in fig. 3.
Mixing Ba in step 2.21.6Sr0.4MnWO6the-N-C composite catalytic material is prepared into an electrode, the oxygen reduction reaction performance is tested in an alkaline solution at the rotating speed of 1600 rpm, and carbon black is not required to be added during testing. The preparation process of the electrode comprises the following steps: 10.0mg of Ba1.6Sr0.4MnWO6the-N-C composite catalytic material is directly added into 1 ml of dispersion liquid consisting of ethanol and 5 percent Nafion, the volume ratio of the ethanol to the 5 percent Nafion is 4:1, ultrasonic dispersion is carried out for more than half an hour, then 10 microliter of dispersed catalyst ink is taken out and dripped on a glassy carbon electrode, and Ba is detected1.6Sr0.4MnWO6The half-wave potential of the-N-C composite catalytic material is 0.84V (relative to a reversible hydrogen electrode), as shown in FIG. 3. Ba1.6Sr0.4MnWO6Half-wave potential ratio Ba of-N-C composite catalytic material1.6Sr0.4MnWO6Positive 110 mV (relative to a reversible hydrogen electrode), with Ba being similarly stated1.6Sr0.4MnWO6The oxygen reduction performance of the-N-C composite catalytic material is improved.
2.4 Metal-air Battery Performance:
reacting Ba prepared in step 2.11.6Sr0.4MnWO6The catalyst paste consisting of perovskite oxide and carbon black Ketjenblack EC 300J, a foamed nickel current collector and hydrophobic breathable carbon paper are assembled into an aluminum-air battery air cathode, an aluminum sheet is used as an anode, and the maximum power density of the aluminum-air battery is 185 mW cm-2As shown in fig. 4.
Reacting Ba prepared in step 2.21.6Sr0.4MnWO6Assembling a catalyst paste (carbon black is not additionally added) consisting of the-N-C composite catalytic material, a foamed nickel current collector and hydrophobic breathable carbon paper to form an air cathode of the aluminum-air battery, taking an aluminum sheet as an anode, and measuring the maximum power density of the aluminum-air battery to be 225 mW cm-2As shown in fig. 4. Description of Ba1.6Sr0.4MnWO6The performance of the metal-air battery made of the-N-C composite catalytic material is improved.
Example 3
3.1 preparation of Sr2MnWO6Perovskite oxide:
dissolving strontium acetate, manganese acetate tetrahydrate and ammonium metatungstate in deionized water according to a stoichiometric ratio, adding citric acid monohydrate into the metal salt solution, wherein the molar ratio of the citric acid monohydrate to metal ions (including strontium ions, manganese ions and tungsten ions) is 1:1, continuously stirring and heating the solution in a constant-temperature water bath at 80 ℃ until gel is formed, drying the obtained gel in an air-blowing drying oven at 100 ℃ for 12 hours, and heating to 250 ℃ for 6 hours to obtain a catalytic material precursor. Calcining the precursor of the catalytic material in a muffle furnace at 900 ℃ for 12 hours, then transferring the precursor to a tubular furnace, calcining the precursor in a high-purity hydrogen/nitrogen mixed gas at 1000 ℃ for 24 hours to obtain Sr2MnWO6A perovskite oxide.
3.2 preparation of Sr2MnWO6The perovskite oxide and nitrogen (urea and polypyrrole) doped carbon (carbon black) composite catalytic material comprises the following components:
6.4 g of urea, 1.1 g of polypyrrole, 2.2 g of carbon black Super Li and 0.6 g of Sr described in step 2.12MnWO6Respectively adding perovskite oxide into 70 mL of acetone solvent, and continuously stirring and heating in a constant-temperature water bath at 70 ℃ until the solvent is completely volatilized completely to obtain Sr2MnWO6The mixture of perovskite oxide, carbon black, urea and polypyrrole is fully and uniformly ground, then the mixture is put into a tube furnace and calcined for 18 hours at 850 ℃ in nitrogen atmosphere, and the Sr is obtained2MnWO6Composite catalytic material of perovskite oxide and nitrogen-doped carbon, marked as Sr2MnWO6-N-C。
3.3 comparison of Sr2MnWO6Cathode electrode and Sr2MnWO6-performance of the cathode electrode of N-C composite catalytic material:
sr prepared in step 3.12MnWO6And (3) preparing an electrode, testing the oxygen reduction reaction performance in an alkaline solution at the rotating speed of 1600 rpm, and adding carbon black during testing. The preparation process of the electrode comprises the following steps: 2.0 mg of Sr2MnWO6And 8.0 mg of carbon black Super Li were added to 1 ml of a dispersion composed of ethanol and 5% Nafion in a volume ratio of 4:1, ultrasonically dispersed for over half an hour, 10. mu.l of dispersed catalyst ink was taken out therefrom and dropped on a glassy carbon electrode, and Sr was measured2MnWO6The half-wave potential of (2) was 0.72V (relative to the reversible hydrogen electrode), as shown in fig. 5.
Sr in step 3.22MnWO6the-N-C composite catalytic material is prepared into an electrode, the oxygen reduction reaction performance is tested in an alkaline solution at the rotating speed of 1600 rpm, and carbon black is not required to be added during testing. The preparation process of the electrode comprises the following steps: 10.0mg of Sr2MnWO6the-N-C composite catalytic material is directly added into 1 ml of dispersion liquid consisting of ethanol and 5 percent Nafion, the volume ratio of the ethanol to the 5 percent Nafion is 4:1, the mixture is dispersed by ultrasonic for more than half an hour, then 10 microliter of dispersed catalyst ink is taken out and dripped on a glassy carbon electrode, and the Sr is measured2MnWO6The half-wave potential of the-N-C composite catalytic material is 0.85V (relative to a reversible hydrogen electrode)) As shown in fig. 5. Sr2MnWO6Half-wave potential ratio Sr of-N-C composite catalytic material2MnWO6Positive 130 mV (relative to a reversible hydrogen electrode), with Sr being likewise stated2MnWO6The oxygen reduction performance of the-N-C composite catalytic material is improved.
3.4 Metal-air Battery Performance:
sr prepared in step 3.12MnWO6A catalyst paste consisting of perovskite oxide and carbon black Super Li, a foamed nickel current collector and hydrophobic breathable carbon paper are assembled into the magnesium-air battery air cathode, a magnesium sheet is used as an anode, and the maximum power density of the magnesium-air battery is 97 mW cm-2As shown in fig. 6.
Sr prepared in step 3.22MnWO6Assembling a catalyst paste (carbon black is not additionally added) consisting of the-N-C composite catalytic material, a foamed nickel current collector and hydrophobic breathable carbon paper to form an air cathode of the magnesium-air battery, taking a magnesium sheet as an anode, and measuring the maximum power density of the magnesium-air battery to be 110 mW cm-2As shown in fig. 6. Also explain Sr2MnWO6The performance of the metal-air battery made of the-N-C composite catalytic material is improved.
In summary, A is used in this application2Mn2-xWxO6Perovskite oxide and nitrogen-doped carbon are used for preparing the cathode material for the metal-air battery. The perovskite oxide composite material can still maintain the stable structure of the perovskite oxide in high-purity mixed gas or high-purity hydrogen under the severe conditions that the calcination temperature is 1000-1100 ℃, and in addition, the perovskite oxide composite material can not be decomposed under the conditions of high temperature and the simultaneous existence of carbon black and a nitrogen source, thereby being beneficial to forming A2Mn2-xWxO6The composite catalytic material of perovskite oxide and nitrogen-doped carbon black finally improves the oxygen reduction activity and stability of the metal-air battery cathode and the overall performance of the battery.
The above description is only a few specific examples of the present invention, but the present invention is not limited to the above detailed methods. Any modification of the present invention by equivalent substitution or addition of auxiliary components within the technical scope of the present invention will be covered by the protection scope of the present invention.

Claims (10)

1. Based on A2Mn2-xWxO6The composite catalytic material of perovskite oxide and nitrogen-doped carbon is characterized in that the composite catalytic material is prepared from A2Mn2-xWxO6Perovskite oxide, carbon black and nitrogen source; wherein, A is2Mn2-xWxO6In the perovskite oxide, A comprises at least one of Ca, Sr and Ba, x is a mole fraction, and 0 < x ≦ 1.
2. The compound of claim 1 based on A2Mn2-xWxO6A composite catalytic material of perovskite oxide and nitrogen-doped carbon, characterized in that the carbon black and the A are2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-20: 1, preferably 1: 1-5: 1; the nitrogen source and the A2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-200: 1, preferably 1: 1-20: 1.
3. The compound of claim 1 based on A2Mn2-xWxO6The composite catalytic material of perovskite oxide and nitrogen-doped carbon is characterized in that the nitrogen source comprises urea, glucosamine hydrochloride, melamine, dicyandiamide and g-C3N4At least one of polyaniline, polypyrrole, and polyacrylonitrile.
4. A metal-air battery cathode comprising the composite catalytic material of any of claims 1-3, further comprising a hydrophobic gas permeable layer and a current collector.
5. A metal-air cell comprising the metal-air cell cathode of claim 4.
6. A is as claimed in any one of claims 1 to 3, based on2Mn2-xWxO6The preparation method of the perovskite oxide and nitrogen-doped carbon composite catalytic material is characterized by comprising the following steps:
(1) preparation A2Mn2-xWxO6Perovskite oxide: a is at least one of Ca, Sr and Ba, x is a mole fraction, and x is more than 0 and less than or equal to 1; dissolving nitrate or acetate of A, manganese acetate tetrahydrate and ammonium metatungstate in deionized water according to a stoichiometric ratio to prepare a metal salt solution; adding citric acid monohydrate, stirring and heating at 60-100 ℃ until gel is formed; drying the obtained gel at 80-140 ℃ for 4-24 hours, then heating to 200-300 ℃ and preserving the heat for 6-12 hours to obtain a catalytic material precursor; calcining the precursor of the catalytic material at the temperature of 800-1000 ℃ for 8-24 hours to obtain the impure phase A2Mn2-xWxO6Calcining the perovskite oxide in a high-purity mixed gas of hydrogen/nitrogen or high-purity hydrogen for 8-24 hours at the temperature of 1000-1100 ℃ to obtain pure-phase A2Mn2-xWxO6A perovskite oxide;
(2) preparation A2Mn2-xWxO6The perovskite oxide and nitrogen-doped carbon composite catalytic material comprises the following components in percentage by weight: carbon black, nitrogen source and the above A2Mn2-xWxO6Adding perovskite oxide into solvent, stirring and heating at 50-100 ℃ until the solvent is completely volatilized to obtain an intermediate mixture, fully and uniformly grinding, calcining at 600-1100 ℃ for 5-24 hours in argon or nitrogen to obtain the A2Mn2-xWxO6A composite catalytic material of perovskite oxide and nitrogen-doped carbon.
7. The compound of claim 6 based on A2Mn2-xWxO6The preparation method of the perovskite oxide and nitrogen-doped carbon composite catalytic material is characterized in that in the step (2), the solution is adoptedThe agent comprises any one of ethanol, acetone or deionized water.
8. The compound of claim 6 based on A2Mn2-xWxO6The preparation method of the perovskite oxide and nitrogen-doped carbon composite catalytic material is characterized in that in the step (2), the nitrogen source comprises urea, glucosamine hydrochloride, melamine, dicyandiamide and g-C3N4At least one of polyaniline, polypyrrole, and polyacrylonitrile.
9. The compound of claim 6 based on A2Mn2-xWxO6The preparation method of the composite catalytic material of perovskite oxide and nitrogen-doped carbon is characterized in that the nitrogen source and the A are2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-200: 1, preferably 1: 1-20: 1.
10. The compound of claim 6 based on A2Mn2-xWxO6Preparation method of perovskite oxide and nitrogen-doped carbon composite catalytic material, carbon black and A2Mn2-xWxO6The mass ratio of the perovskite oxide is 1: 1-20: 1, preferably 1: 1-5: 1.
CN202011395541.0A 2020-12-03 2020-12-03 A2Mn2-xWxO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof Active CN112421064B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011395541.0A CN112421064B (en) 2020-12-03 2020-12-03 A2Mn2-xWxO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011395541.0A CN112421064B (en) 2020-12-03 2020-12-03 A2Mn2-xWxO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112421064A true CN112421064A (en) 2021-02-26
CN112421064B CN112421064B (en) 2022-07-12

Family

ID=74829997

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011395541.0A Active CN112421064B (en) 2020-12-03 2020-12-03 A2Mn2-xWxO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112421064B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114700104A (en) * 2022-05-06 2022-07-05 济南大学 Preparation method of carbon-doped porous microsphere lead-free double perovskite composite photocatalyst with graphite-phase carbon nitride as template

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005179168A (en) * 2003-03-28 2005-07-07 Dowa Mining Co Ltd Perovskite type compound oxide and method for manufacturing the same
US20150065333A1 (en) * 2013-09-02 2015-03-05 Agency For Science, Technology And Research Bifunctional catalysts for oxygen reduction and evolution reactions and rechargeable metal air batteries using the same
CN107195914A (en) * 2017-05-25 2017-09-22 大连理工大学 It is a kind of to load N doping carbon-supported catalysts and preparation method thereof without crystal formation Mn oxide
CN109119648A (en) * 2018-08-24 2019-01-01 广东工业大学 A kind of LaCoO3-δ/ CNTs dual-function composite catalyst and its preparation method and application
CN111834639A (en) * 2020-07-29 2020-10-27 郑州大学 Composite catalyst for cathode of metal-air battery and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005179168A (en) * 2003-03-28 2005-07-07 Dowa Mining Co Ltd Perovskite type compound oxide and method for manufacturing the same
US20150065333A1 (en) * 2013-09-02 2015-03-05 Agency For Science, Technology And Research Bifunctional catalysts for oxygen reduction and evolution reactions and rechargeable metal air batteries using the same
CN107195914A (en) * 2017-05-25 2017-09-22 大连理工大学 It is a kind of to load N doping carbon-supported catalysts and preparation method thereof without crystal formation Mn oxide
CN109119648A (en) * 2018-08-24 2019-01-01 广东工业大学 A kind of LaCoO3-δ/ CNTs dual-function composite catalyst and its preparation method and application
CN111834639A (en) * 2020-07-29 2020-10-27 郑州大学 Composite catalyst for cathode of metal-air battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KUN ZHENG等: ""Evaluation of W-containing Sr1−xBaxFe0.75W0.25O3–δ (x=0, 0.5, 1) anode materials for solid oxide fuel cells"", 《SOLID STATE IONICS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114700104A (en) * 2022-05-06 2022-07-05 济南大学 Preparation method of carbon-doped porous microsphere lead-free double perovskite composite photocatalyst with graphite-phase carbon nitride as template
CN114700104B (en) * 2022-05-06 2023-12-19 济南大学 Preparation method of carbon-doped porous microsphere lead-free double perovskite composite photocatalyst taking graphite phase carbon nitride as template

Also Published As

Publication number Publication date
CN112421064B (en) 2022-07-12

Similar Documents

Publication Publication Date Title
Wang et al. Rechargeable Li–O 2 batteries with a covalently coupled MnCo 2 O 4–graphene hybrid as an oxygen cathode catalyst
CN106654194B (en) A kind of SiO of element dopingxAnode material and its preparation method and application
EP3333944B1 (en) Cathode active material for lithium secondary battery and preparation method therefor
Zhao et al. Strontium-doped perovskite oxide La1-xSrxMnO3 (x= 0, 0.2, 0.6) as a highly efficient electrocatalyst for nonaqueous Li-O2 batteries
Oh et al. The bifunctional electrocatalytic activity of perovskite La 0.6 Sr 0.4 CoO 3− δ for oxygen reduction and evolution reactions
US20120115048A1 (en) Positive electrode for lithium air battery, method of preparing the positive electrode, and lithium air battery including the positive electrode
US9236641B2 (en) Air battery catalyst and air battery using the same
Jung et al. Manganese oxide/carbon composite nanofibers: electrospinning preparation and application as a bi-functional cathode for rechargeable lithium–oxygen batteries
CN108565478B (en) Amino carbon nanotube loaded nickel cobaltate composite electrocatalytic material and preparation and application thereof
JP2004265806A (en) Lithium metal composite oxide particle, manufacturing method thereof, electrode structure containing the composite oxide, manufacturing method of the electrode structure and lithium secondary battery having the electrode structure
CN112103518B (en) Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material
CN108428870B (en) Large-scale preparation method and application of two-dimensional carbon sheet aerogel material compounded by metal and metal derivatives thereof
KR101484503B1 (en) Cathode Catalyst for Lithium-Air Battery, Method of Manufacturing the Same, and Lithium-Air Battery Comprising the Same
Gong et al. Fabrication of perovskite-based porous nanotubes as efficient bifunctional catalyst and application in hybrid lithium–oxygen batteries
Lim et al. Electrochemical and catalytic properties of V2O5/Al2O3 in rechargeable Li–O2 batteries
CN112421064B (en) A2Mn2-xWxO6Perovskite oxide and nitrogen-doped carbon composite catalytic material and preparation method and application thereof
CN110112385B (en) Method for improving stability and rate performance of ternary cathode material
CN113571719B (en) Biomass carbon material derived transition metal-based catalyst, preparation method and application thereof, and solid zinc-air battery
CN113555550A (en) General formula AB2O5Application of compound as lithium-sulfur battery positive electrode reaction catalyst
CN111740117A (en) Preparation method and application of electrocatalytic oxygen reduction catalytic material N-PC @ CBC
US10249882B2 (en) Positive electrode for lithium air battery, method of preparing same and lithium air battery including same
Sasidharachari et al. Facile synthesis and evaluation of MnCo 2 O 4.5 nanoparticles as a bifunctional catalyst for zinc-air battery
CN110148763A (en) A kind of Fe doping Mn with hollow nanometer frame structure3O4The preparation method and application of carbon-nitrogen material
KR20190057530A (en) Positive electrode active material for lithium secondary battery and method for preparing the same
CN114784304A (en) Bimetallic atom doped porous carbon material catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant