CN113087022A - Preparation method and application of lanthanum manganate with three-dimensional ordered porous structure - Google Patents
Preparation method and application of lanthanum manganate with three-dimensional ordered porous structure Download PDFInfo
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- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000008025 crystallization Effects 0.000 claims abstract description 14
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 13
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910002328 LaMnO3 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention provides a preparation method and application of lanthanum manganate with a three-dimensional ordered porous structure. The preparation method comprises the following steps: step 1, mixing lanthanum nitrate and manganese nitrate according to a molar ratio of 1: 1, uniformly mixing, then adding citric acid and dissolving in deionized water and absolute ethyl alcohol to prepare a solution; step 2, adding a methyl methacrylate monomer and an azobisisobutyronitrile initiator into the solution obtained in the step 1 to form a mixed solution; step 3, heating the mixed solution obtained in the step 2 in a water bath to 70-90 ℃, and stirring and polymerizing for 2-4 hours; step 4, transferring the obtained polymer to a crystallization kettle for crystallization for 10-13 h at the temperature of 100-120 ℃; and 5, calcining the sample obtained in the step 4 in a muffle furnace at 600-800 ℃ for 3-5 h to obtain the lanthanum manganate with the three-dimensional ordered porous structure. The preparation process of the lanthanum manganate with the three-dimensional ordered porous structure is simple, the production resources are rich, and the morphology and the pore size of the product particles are controllable.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method and application of lanthanum manganate with a three-dimensional ordered porous structure.
Background
The metal-air battery has the advantages of high specific energy power, small internal resistance, stable discharge voltage, no toxicity or pollution, long service life, simple operation process, low price and the like; in addition, the system also has the characteristics of abundant resources and reusability, and can be applied to plug-in hybrid electric vehicles, electric vehicles and smart power grids. The aluminum-air battery has the highest energy density, light weight and environmental protection, and is one of the most promising power batteries for electric vehicles.
The perovskite type oxide has good oxidation reduction capability, oxygen storage and release capability and sintering resistance capability, and is widely applied to the aspects of catalysts and catalyst carriers. The perovskite oxide prepared by the researched soft template has the defect of poor thermal stability, and the nano porous structure is difficult to control accurately. At present, three-dimensional ordered macroporous lanthanum manganate with mesoporous pore walls can be prepared by a double-template method and used as an aluminum air battery catalyst. Polymethyl methacrylate (PMMA) microspheres are used as a hard template, L-lysine or triblock copolymer P123 is used as a soft template, polyethylene glycol 400 is used as an additive,methanol and water are used as solvents, a mixed solution containing the soft template agent, the additive, the solvent and soluble metal salt is soaked in a PMMA hard template, and a two-step roasting method (roasting in nitrogen atmosphere and then in air atmosphere) is adopted to prepare a three-dimensional ordered macroporous structural perovskite type oxide LaMnO with a mesoporous pore wall3. The raw materials are cheap and easy to obtain, the preparation method is simple, and the catalytic performance is good. Single-phase perovskite type oxide LaMnO prepared by using same3Has the characteristics of porous structure and higher specific surface area, and has good application prospect in the aspects of superconducting materials, photonic crystals, catalysts, separation, electrodes and the like.
However, these methods are complicated in preparation process, and further improvement is expected.
Disclosure of Invention
The invention provides a preparation method of lanthanum manganate with a three-dimensional ordered porous structure, which comprises the following steps:
step 3, heating the mixed solution obtained in the step 2 in a water bath to 70-90 ℃, and stirring and polymerizing for 2-4 hours;
and 5, calcining the sample obtained in the step 4 in a muffle furnace at 600-800 ℃ for 3-5 h to obtain the lanthanum manganate with the three-dimensional ordered porous structure.
In the preparation method of the lanthanum manganate with the three-dimensional ordered porous structure, the lanthanum nitrate, the manganese nitrate, the citric acid, the deionized water, the ethanol, the MMA and the azobisisobutyronitrile are respectively 5mmol, 10mmol, 5ml, 15ml, 2.41g and 5 ml.
In the preparation method of the lanthanum manganate with the three-dimensional ordered porous structure, the lanthanum nitrate and the manganese nitrate in the step 1 are La (NO)3)3·6H2O and Mn (NO)3)2。
The invention also provides application of the lanthanum manganate with the three-dimensional ordered porous structure prepared by the preparation method, the lanthanum manganate with the three-dimensional ordered porous structure and acetylene black are mixed according to the mass ratio of 6:4 to be used as an air electrode catalyst layer, a working electrode with the length of 4cm and the width of 3cm is pressed, an aluminum plate is used as a negative electrode, 6mol/L KOH solution is adopted as electrolyte, and an aluminum-air battery is formed in an organic glass frame.
The preparation process of the lanthanum manganate with the three-dimensional ordered porous structure is simple, the production resources are rich, and the morphology and the pore size of the product particles are controllable. In addition, the method for preparing the lanthanum manganate with the three-dimensional ordered porous structure is simple and easy to operate, and is convenient for large-scale production, and the produced lanthanum manganate with the three-dimensional ordered porous structure can expand the selection of aluminum air electrode catalysts and has a guiding function for developing new metal-air batteries.
Drawings
FIG. 1 is an XRD (X-ray diffraction) diagram of lanthanum manganate with a three-dimensional ordered porous structure prepared in example 2 of the invention;
FIG. 2 is a scanning electron microscope image of lanthanum manganate with a three-dimensional ordered porous structure prepared in example 2 of the present invention;
FIG. 3 is a cyclic voltammetry graph of lanthanum manganate with a three-dimensional ordered porous structure prepared in example 2 of the present invention;
FIG. 4 is a linear scanning curve diagram of lanthanum manganate with a three-dimensional ordered porous structure prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of lanthanum manganate with a three-dimensional ordered porous structure as an aluminum air electrode catalyst material. The preparation process of the lanthanum manganate with the three-dimensional ordered porous structure is simple, the production resources are rich, and the morphology and the pore size of the product particles are controllable.
The preparation method of the aluminum air electrode catalyst material lanthanum manganate with the three-dimensional ordered porous structure comprises the following specific steps:
step 3, heating the mixed solution obtained in the step 2 in a water bath to 70-90 ℃, and stirring and polymerizing for 2-4 hours;
and 5, calcining the sample obtained in the step 4 in a muffle furnace at 600-800 ℃ for 3-5 h to remove the PMMA template and obtain a lanthanum manganate product with a three-dimensional ordered porous structure.
In the step 1, the lanthanum nitrate, the manganese nitrate, the citric acid, the deionized water, the ethanol, the MMA and the azobisisobutyronitrile are respectively 5mmol, 10mmol, 5ml, 15ml, 2.41g and 5 ml.
In the step 1, the lanthanum nitrate and the manganese nitrate are La (NO)3)3·6H2O and Mn (NO)3)2。
The method for preparing the lanthanum manganate with the three-dimensional ordered porous structure is simple and easy to operate, is convenient for large-scale production, can expand the selection of aluminum air electrode catalysts, and has a guiding function for developing new metal-air batteries.
Example 1
The preparation method of the air electrode catalyst material lanthanum manganate with a three-dimensional ordered porous structure comprises the following specific steps:
step 3, heating the mixed solution in the step 2 to 70 ℃ in a water bath, and stirring and polymerizing for 2 hours;
and 5, calcining the sample obtained in the step 4 in a muffle furnace at 600 ℃ for 3h to remove the PMMA template and obtain a lanthanum manganate product with a three-dimensional ordered porous structure.
Example 2
The preparation method of the air electrode catalyst material lanthanum manganate with a three-dimensional ordered porous structure comprises the following specific steps:
step 3, heating the mixed solution in the step 2 in a water bath to 80 ℃, and stirring and polymerizing for 3 hours;
and 5, calcining the sample obtained in the step 4 in a muffle furnace at 700 ℃ for 4h to remove the PMMA template and obtain a lanthanum manganate product with a three-dimensional ordered porous structure. The prepared LaMnO with three-dimensional ordered porous structure3The XRD pattern and the scanning electron micrograph are shown in FIG. 1 and FIG. 2, respectively. As can be seen from FIG. 1, characteristic diffraction peaks appear near 23 °, 33 °, 41 °, 48 °, 59 °, 68 °, 78 °, corresponding to perovskite LaMnO3The positions of the theoretical diffraction peaks coincide. As can be seen from FIG. 2, LaMnO was prepared3Has three-dimensional ordered porous structure.
Polishing the glassy carbon electrode to a mirror surface by using alumina powder, then ultrasonically washing the mirror surface by using distilled water and alcohol, and preparing the LaMnO with the three-dimensional ordered porous structure3Adding into alcohol and deionized water solution, using 0.1ml 5 wt% Nafion as adhesive, ultrasonic mixing uniformly, dripping on glassy carbon electrode, drying electrode, and using. The electrochemical workstation of Switzerland PGSTAT302N type is adopted to carry out cyclic voltammetry test and linear scanning test, and the test adopts a three-electrode test system: the counter electrode adopts a platinum electrode, the reference electrode adopts a saturated calomel electrode, and the working electrode adopts a load IIILaMnO with dimensional ordered porous structure3The electrolyte of the glassy carbon electrode is 0.1mol/L KOH solution. The scanning potential window of the cyclic voltammetry test is-0.8V-0.2V, and the scanning speed is 50mV s-1. The linear scanning test has a scanning range of-1V to 0.2V and a scanning speed of 50 mV.s-1The rotation speed is 1600 rpm. LaMnO with three-dimensional ordered porous structure prepared by the embodiment3The cyclic voltammogram is shown in FIG. 3, and it can be seen from FIG. 3 that the reduction peak appears between-0.2V and-0.4V, and the maximum peak current density is much greater than that of the coprecipitation method (coprecipitation method LaMnO)3Preparation: adding La (NO)3)2·6H2O and Mn (NO)3)2In a molar ratio of 1: dissolving 1 by using distilled water, dropwise adding 6mol/LNaOH solution to form a precipitate until the pH value reaches 10, finishing dropwise adding NaOH, stirring until the precipitate is completely separated out, filtering the mixed solution, washing the precipitate by using distilled water and absolute ethyl alcohol to be neutral, drying in an oven, and roasting at 700 ℃ in a muffle furnace for 3 hours to obtain a lanthanum manganate sample. ) The prepared lanthanum manganate. Illustrating the three-dimensional ordered porous structure LaMnO3Has better oxygen reduction performance. LaMnO with three-dimensional ordered porous structure prepared by the embodiment3The linear scan plot is shown in FIG. 4, and from FIG. 4 it can be seen that the limiting current density has far exceeded that of the coprecipitated lanthanum manganate process, which further confirms the three-dimensional ordered porous structure LaMnO3Has more excellent electrocatalytic activity.
Example 3
The preparation method of the air electrode catalyst material lanthanum manganate with a three-dimensional ordered porous structure comprises the following specific steps:
step 3, heating the mixed solution in the step 2 in a water bath to 90 ℃, and stirring and polymerizing for 4 hours;
and 5, calcining the sample obtained in the step 4 in a muffle furnace at 800 ℃ for 5h to remove the PMMA template and obtain a lanthanum manganate product with a three-dimensional ordered porous structure.
Those skilled in the art will appreciate that the above embodiments are merely exemplary embodiments and that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the application.
Claims (4)
1. A preparation method of lanthanum manganate with a three-dimensional ordered porous structure is characterized by comprising the following steps:
step 1, mixing lanthanum nitrate and manganese nitrate according to a molar ratio of 1: 1, uniformly mixing, then adding citric acid and dissolving in deionized water and absolute ethyl alcohol to prepare a solution;
step 2, adding a methyl methacrylate monomer and an azobisisobutyronitrile initiator into the solution obtained in the step 1 to form a mixed solution;
step 3, heating the mixed solution obtained in the step 2 in a water bath to 70-90 ℃, and stirring and polymerizing for 2-4 hours;
step 4, transferring the obtained polymer to a crystallization kettle for crystallization for 10-13 h at the temperature of 100-120 ℃;
and 5, calcining the sample obtained in the step 4 in a muffle furnace at 600-800 ℃ for 3-5 h to obtain the lanthanum manganate with the three-dimensional ordered porous structure.
2. The method for preparing lanthanum manganate with three-dimensional ordered porous structure as claimed in claim 1, wherein the concentration of lanthanum nitrate, manganese nitrate, citric acid, deionized water, ethanol, methyl methacrylate and azobisisobutyronitrile is 5mmol, 10mmol, 5ml, 15ml, 2.41g, 5ml respectively.
3. The method for preparing lanthanum manganate with three-dimensional ordered porous structure as claimed in claim 1, wherein lanthanum nitrate and manganese nitrate in step 1 are La (NO)3)3·6H2O and Mn (NO)3)2。
4. The application of the lanthanum manganate with the three-dimensional ordered porous structure prepared by the preparation method according to any one of claims 1 to 3 is characterized in that the lanthanum manganate with the three-dimensional ordered porous structure and acetylene black are mixed according to the mass ratio of 6:4 to serve as an air electrode catalyst layer, a working electrode with the length of 4cm and the width of 3cm is pressed, an aluminum plate serves as a negative electrode, 6mol/L KOH solution is adopted as electrolyte, and an aluminum-air battery is formed in an organic glass frame.
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