CN111725528A - Manganese dioxide composite porous graphene cathode catalyst and preparation method and application thereof - Google Patents
Manganese dioxide composite porous graphene cathode catalyst and preparation method and application thereof Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 154
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/33—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention discloses a manganese dioxide composite porous graphene cathode catalyst, a preparation method and application thereof, relating to the technical field of lithium air batteries and comprising a substrate and a composite material compounded with the substrate; the matrix comprises porous reduced graphene oxide, and the composite material comprises manganese dioxide; the mass ratio of the manganese dioxide to the porous reduced graphene oxide is 10: 1-1: 10. The catalyst is prepared by the following steps: A. preparing porous reduced graphene oxide; B. uniformly mixing a manganese dioxide precursor in a solution for reducing graphene oxide, and heating for oxidation and reduction; C. filtering and drying to obtain the catalyst. The manganese dioxide composite porous graphene material prepared by the invention has a unique pore structure, high-efficiency dual-function ORR and OER activities which are synergistically combined, and has very high discharge specific capacity and good cycle capacity.
Description
Technical Field
The invention relates to the technical field of lithium-air batteries, in particular to a manganese dioxide composite porous graphene cathode catalyst and a preparation method and application thereof.
Background
Fossil fuels are currently the most important energy source of human society, and with the increasing prosperity of human society and the rapid development of scientific technology, the traditional fossil fuels cannot meet the human demand for energy. The development of advanced energy conversion and storage devices such as lithium ion batteries, fuel cells and lithium air batteries is imminent. The lithium-air battery has the characteristics of high specific capacity, environmental protection and the like, and is an excellent choice. The graphene has a unique single-layer carbon atom two-dimensional honeycomb crystal structure, is excellent in conductivity and high in theoretical specific surface area, and can be used for improving the electrochemical performance of materials and improving the specific capacity of the lithium-air battery. Metal oxides, such as cobalt oxide, manganese oxide, iron oxide, copper oxide, vanadium oxide, and the like, have a high theoretical specific capacity, which makes their wide application in lithium air batteries possible. Manganese dioxide has the advantages of two-way catalytic performance of ORR and OER, low cost, environmental friendliness, high natural abundance and the like, and becomes a research hotspot in the field. However, the dioxide electrode fails to exhibit the expected performance due to its easy agglomeration, low specific surface area and inherent low conductivity.
Recently, researches on metal oxide/graphene composite electrodes are reported successively, and a chinese patent with publication number CN105719852A provides a preparation method of a three-dimensional nano-porous graphene/manganese dioxide composite electrode material, which comprises the following steps: taking the atomic ratio of Cu to Mn as 1:1 to 1: 3, performing dealloying treatment on the alloy foil between the two parts to prepare a nano porous metal foil with a hierarchical nano porous structure, wherein the nano porous metal foil changes along with dealloying time and dealloying corrosive liquid concentration; calcining the nano porous metal foil at the temperature of 700-1000 ℃ in the atmosphere of acetylene, argon and hydrogen, and cooling the sample to room temperature in the atmosphere of argon; immersing the nano porous metal in corrosive liquid to remove the nano porous metal, and then cleaning to obtain a self-supporting three-dimensional nano porous graphene film; and uniformly depositing manganese dioxide on the surface of the three-dimensional nano porous graphene by using a multi-step current method to prepare the three-dimensional nano porous graphene/manganese dioxide composite electrode material. However, the synthesis method is complex, the formed crystal form is unstable, the pore size is different, and the product performance is not optimal.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a manganese dioxide composite porous graphene cathode catalyst, a preparation method and application thereof, and also provides application of the cathode catalyst in a lithium air battery. The catalyst has extremely high dual catalytic activity, excellent electrochemical stability, higher specific capacity in the application of the lithium air battery, and excellent cycle performance of the battery.
The purpose of the invention is realized by the following technical scheme: a manganese dioxide composite porous graphene cathode catalyst comprises a substrate and a composite material compounded with the substrate; the matrix comprises porous reduced graphene oxide, and the composite material comprises manganese dioxide; the mass ratio of the manganese dioxide to the porous reduced graphene oxide is 10: 1-1: 10.
PreferablySaid metal oxide comprises manganese dioxide, said manganese dioxide comprising α -MnO2、β-MnO2、γ-MnO2、-MnO2、λ-MnO2Preferably α -MnO2or-MnO2。
A method for preparing the manganese dioxide composite porous graphene cathode catalyst according to claim 1 or 2, comprising the steps of:
A. preparing porous reduced graphene oxide: mixing graphene oxide powder with a solvent to obtain a dispersion liquid a; adding a template b into the dispersion liquid a to obtain a dispersion liquid c; carrying out solvothermal reaction, then filtering, washing and drying to obtain solid powder d, and carrying out heat treatment on the solid powder d to obtain the porous reduced graphene oxide e;
B. uniformly mixing a manganese dioxide precursor which completely generates manganese dioxide according to a stoichiometric coefficient with a porous reduced graphene oxide e dispersion liquid, and carrying out a solvothermal reaction in an isopropanol solution to obtain manganese dioxide composite porous reduced graphene oxide f;
C. and (3) alternately pumping, filtering and cleaning the manganese dioxide composite porous reduced graphene oxide f by using water and ethanol, and drying in vacuum to obtain the manganese dioxide composite porous graphene cathode catalyst.
Preferably, the porous reduced graphene oxide comprises 1-10 layers of graphene oxide.
Preferably, the solvent in step a comprises one or more of ultrapure water, deionized water, absolute ethanol, isopropanol, N-dimethylformamide and dimethyl sulfoxide;
the template comprises one or more of silicon dioxide, zinc oxide, magnesium oxide, polystyrene spheres and polymethyl methacrylate spheres, and the size of the template is 50 nm-500 nm;
the concentration of the graphene oxide powder in the dispersion liquid is 0.1-5 mg/mL; the mass ratio of the graphene oxide powder to the template is 1: 1-1: 10.
Preferably, the temperature of the solvothermal reaction in the step A is 60-180 ℃ and the time is 0.5-24 h; the temperature of the heat treatment of the solid powder d is 300-600 ℃, and the time is 0.5-3 h.
Preferably, in step B, the manganese dioxide precursor includes one or more of simple substance, acid or salt of manganese dioxide or organic substance thereof; mixing a manganese dioxide precursor and reduced porous graphene oxide, and reacting in an isopropanol solution at the temperature of 60-100 ℃ for 0.5-2 h; the source simple substance, organic substance, acid or salt of manganese dioxide represents a manganese source substance of manganese dioxide in the manganese dioxide composite porous graphene.
Preferably, the acid or salt of manganese dioxide comprises one or more of potassium permanganate, manganese chloride, manganese sulfate, manganese carbonate, manganese nitrate, manganese stearate, manganese acid phosphate.
Preferably, the filtration and cleaning in the step C is one or more of centrifugation, suction filtration and normal pressure filtration; the vacuum temperature is 80-120 ℃ and the time is 6-12 h.
Use of the manganese dioxide composite porous graphene cathode catalyst according to claim 1 or 2 as a battery cathode oxygen reduction catalyst for a lithium air battery.
The metal oxide composite graphene has good electronic conductivity, and among a plurality of metal oxide composite graphene, manganese dioxide composite graphene is popular due to low cost and wider working voltage in aqueous solution, so that the manganese dioxide composite graphene becomes a current research hotspot. By adopting an optimized chemical method, stacking among graphene sheet layers in the reduction process is avoided, the specific surface area of a product is increased, the high-efficiency dual-function ORR and OER activity of the composite material is coordinated, and the composite material has high specific discharge capacity and good cycle capacity.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method is simple, and the size of the porous graphene and the morphology of the composite material can be well controlled by adjusting the concentration of the graphene oxide, the size of the template and the addition amount of the manganese dioxide precursor; according to the invention, through an optimized chemical method, stacking among graphene sheet layers in the reduction process is avoided by using a hard template, and the specific surface area is increased;
(2) the invention can adjust the oxygen reduction activity of the catalyst by adjusting the composite amount of manganese dioxide;
(3) the porous graphene material prepared by the method has high porosity and large specific surface area, and is beneficial to reducing the mass transfer resistance of oxygen and electrolyte in the lithium air battery;
(4) the manganese dioxide composite porous graphene material prepared by the invention has a unique pore structure, high-efficiency dual-function ORR and OER activity, very high discharge specific capacity and good cycle capacity;
(5) the template method for preparing the three-dimensional nano structure is a hydrothermal method with simple synthesis method and simple hollow shape formed by evaporation of a spherical template and consistent gap size, and the method is easy to form α -MnO with structural advantage and good electrochemical performance2A crystalline form;
(6) manganese dioxide composite porous graphene is widely researched in the fields of photocatalysis and capacitors, and almost no attention is paid to the field of lithium-air batteries; the porous graphene structure synthesized by the template method is an original structural method, and the problem caused by accumulation of byproducts in mass transfer, electron transfer and circulation processes of the lithium-air battery can be solved by related application of the structural design of the composite manganese dioxide on the porous graphene structure.
Description of the drawings:
fig. 1 is a Transmission Electron Microscope (TEM) photograph of the composite porous graphene catalyst cathode prepared in example 1 of the present invention.
Detailed Description
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values are to be considered as specifically disclosed herein, the invention is described in detail below with reference to specific examples:
example 1
A preparation method of a manganese dioxide composite porous graphene cathode catalyst comprises the following steps:
A. preparing porous reduced graphene oxide: adding 0.5g of graphene oxide powder into 100mL of deionized water, and stirring and ultrasonically treating the mixture until the graphene oxide is completely dispersed to obtain a dispersion liquid a;
weighing 1.0g of polystyrene spheres (with the size of 100nm) of the template b, ultrasonically dispersing the template b in 30mL of deionized water to obtain a dispersion g, slowly adding 100mg of hydrazine hydrate (the mass fraction is 80%) into the dispersion g under the condition of stirring, and adding 28% ammonia water to adjust the pH value to 12. Next, the mixture was heated to 95 ℃ in an oil bath and subjected to vigorous magnetic stirring. After 2 hours after the reaction, the mixture was precipitated by adding a trace amount of HCl (18% wt%) to give a solid powder d, washed several times with water, filtered, washed and dried to give a solid powder d.
And (3) treating the solid powder d for 2 hours under the protection of argon at 500 ℃ to obtain the solid powder porous reduced graphene oxide e.
B. 0.1g of the treated porous graphene oxide was uniformly suspended in 100mL of isopropanol in a three-necked flask, and 0.0867g of MnCl was added2·4H2And O. When the slurry was heated to about 83 ℃, 0.0726g of KMnO dissolved in 5mL of deionized water was quickly added4And injected therein. Reflux for 30 min.
C. Reduction of manganese dioxide composite to graphene oxide f (MnO)2/rGO) nanocomposite precipitate was filtered and washed with deionized water and ethanol. The scanning electron microscope picture of the manganese dioxide composite porous graphene catalyst electrode obtained by vacuum drying at 120 ℃ for 9h is shown in figure 1.
Fig. 1 is a Transmission Electron Microscope (TEM) photograph of the composite porous graphene catalyst cathode prepared in example 1 of the present invention, which shows that the pore size distribution is from 100nm to 5 μm, the distribution is relatively uniform, and the porosity is high, which is beneficial to the mass transfer of oxygen and electrolyte; wherein FIG. 1A is the surface topography at the 200nm scale (high power) of the material; FIG. 1B is a surface topography at 0.5um (low power) magnification of the material
Example 2
A preparation method of a manganese dioxide composite porous graphene cathode catalyst comprises the following steps:
A. preparing porous reduced graphene oxide: adding 0.01g of graphene oxide powder into 100mL of deionized water, and stirring and ultrasonically treating the mixture until the graphene oxide is completely dispersed to obtain a dispersion liquid B;
0.1g of polymethyl methacrylate spheres (200 nm in size) is weighed and ultrasonically dispersed in 30mL of deionized water to obtain a dispersion liquid F, then 100mg of hydrazine hydrate (80 mass percent) is slowly added into the dispersion liquid F under the condition of stirring, and then 28 percent of ammonia water is added to adjust the pH value to 12. Next, the mixture was heated to 180 ℃ in an oil bath and subjected to vigorous magnetic stirring. After 3 hours after the reaction, the mixture was precipitated by adding a trace amount of HCl (18% wt%) to give solid powder D, which was washed several times with water.
And (3) treating the solid powder D for 3 hours under the protection of argon at 300 ℃ to obtain the solid powder porous reduced graphene oxide F.
B. 0.1g of treated MWCNT was suspended in 100mL of isopropanol in a three-necked flask and different stoichiometries of MnCl were added2·4H2And O. When the slurry was heated to about 60 ℃, KMnO dissolved in 5mL of deionized water was quickly removed4And injected therein. Reflux for 120 min.
C. Reduction of manganese dioxide composite to graphene oxide (MnO)2/rGO) nanocomposite precipitate was filtered and washed with deionized water and ethanol. The scanning electron microscope picture of the manganese dioxide composite porous graphene catalyst electrode obtained by vacuum drying for 6 hours at 120 ℃ is the same as that of the embodiment 1.
Example 3
A preparation method of a manganese dioxide composite porous graphene cathode catalyst comprises the following steps:
A. adding 0.3g of graphene oxide powder into 100mL of absolute ethyl alcohol, and stirring and ultrasonically treating until the graphene oxide is completely dispersed to obtain a dispersion liquid B;
0.3g of silicon dioxide (350 nm in size) is weighed and ultrasonically dispersed in 30mL of deionized water to obtain a dispersion liquid F, then 100mg of hydrazine hydrate (80 mass percent) is slowly added into the dispersion liquid F under the condition of stirring, and 28 percent of ammonia water is added to adjust the pH value to 12. Next, the mixture was heated to 160 ℃ in an oil bath and subjected to vigorous magnetic stirring. After 24 hours after the reaction, the mixture was precipitated by adding a trace amount of HCl (18% wt%) to give a solid powder D, which was washed several times with water.
And (3) treating the solid powder D for 0.5h under the protection of argon at 600 ℃ to obtain the solid powder porous reduced graphene oxide F.
B. 0.1g of treated MWCNT was suspended in 100mL of isopropanol in a three-necked flask and different stoichiometries of MnCl were added2·4H2And O. KMnO dissolved in 5mL deionized water is rapidly dissolved when the slurry is heated to about 100 deg.C4And injected therein. Reflux for 30 min.
C. Reduction of manganese dioxide composite to graphene oxide (MnO)2/rGO) nanocomposite precipitate was filtered and washed with deionized water and ethanol. The scanning electron microscope picture of the manganese dioxide composite porous graphene catalyst electrode obtained by vacuum drying for 6 hours at the temperature of 80 ℃ is the same as that of the embodiment 1.
Example 4
A preparation method of a manganese dioxide composite porous graphene cathode catalyst comprises the following steps:
A. adding 0.5g of graphene oxide powder into 100mL of deionized water, and stirring and ultrasonically treating the mixture until the graphene oxide is completely dispersed to obtain a dispersion liquid B;
1.0g of polystyrene nanosphere (450 nm in size) is weighed and ultrasonically dispersed in 30mL of deionized water to obtain a dispersion liquid F, then 100mg of hydrazine hydrate (the mass fraction is 80%) is slowly added into the dispersion liquid F under the condition of stirring, and 28% of ammonia water is added to adjust the pH value to 12. Next, the mixture was heated to 170 ℃ in an oil bath and subjected to vigorous magnetic stirring. After 12 hours after the reaction, the mixture was precipitated by adding a trace amount of HCl (18% wt%) to give solid powder D, which was washed several times with water.
And (3) treating the solid powder D for 2 hours under the protection of argon at 500 ℃ to obtain the solid powder porous reduced graphene oxide F.
B. 0.1g of treated MWCNT was suspended in 100mL of isopropanol in a three-necked flask and different stoichiometries of MnCl were added2·4H2And O. When the slurry was heated to about 90 ℃, KMnO dissolved in 5mL deionized water was rapidly dissolved4And injected therein. Reflux for 60 minutes.
C. Reduction of manganese dioxide composite to graphene oxide (MnO)2/rGO) nanocomposite precipitate was filtered and washed with deionized water and ethanol. The scanning electron microscope picture of the manganese dioxide composite porous graphene catalyst electrode obtained by vacuum drying for 9 hours at 100 ℃ is the same as that of the embodiment 1.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. The manganese dioxide composite porous graphene cathode catalyst is characterized by comprising a matrix and a composite material compounded with the matrix; the matrix comprises porous reduced graphene oxide, and the composite material comprises manganese dioxide; the mass ratio of the manganese dioxide to the porous reduced graphene oxide is 10: 1-1: 10.
2. The manganese dioxide composite porous graphene cathode catalyst of claim 1, wherein the manganese dioxide comprises α -MnO2、β-MnO2、γ-MnO2、-MnO2、λ-MnO2One or more of (a).
3. The preparation method of the manganese dioxide composite porous graphene cathode catalyst according to claim 1 or 2, characterized by comprising the following steps:
A. preparing porous reduced graphene oxide: mixing graphene oxide powder with a solvent to obtain a dispersion liquid a; adding a template b into the dispersion liquid a to obtain a dispersion liquid c; carrying out solvothermal reaction, then filtering, washing and drying to obtain solid powder d, and carrying out heat treatment on the solid powder d to obtain the porous reduced graphene oxide e;
B. uniformly mixing a manganese dioxide precursor which completely generates manganese dioxide according to a stoichiometric coefficient with a porous reduced graphene oxide e dispersion liquid, and carrying out a solvothermal reaction in an isopropanol solution to obtain manganese dioxide composite porous reduced graphene oxide f;
C. and (3) alternately pumping, filtering and cleaning the manganese dioxide composite porous reduced graphene oxide f by using water and ethanol, and drying in vacuum to obtain the manganese dioxide composite porous graphene cathode catalyst.
4. The preparation method of the manganese dioxide composite porous graphene cathode catalyst according to claim 3, wherein the porous reduced graphene oxide comprises 1-10 layers of graphene oxide.
5. The preparation method of the manganese dioxide composite porous graphene cathode catalyst according to claim 3, wherein the solvent in the step A comprises one or more of ultrapure water, deionized water, absolute ethyl alcohol, isopropyl alcohol, N-dimethylformamide and dimethyl sulfoxide;
the template comprises one or more of silicon dioxide, zinc oxide, magnesium oxide, polystyrene spheres and polymethyl methacrylate spheres, and the size of the template is 50 nm-500 nm;
the concentration of the graphene oxide powder in the dispersion liquid is 0.1-5 mg/mL; the mass ratio of the graphene oxide powder to the template is 1: 1-1: 10.
6. The preparation method of the manganese dioxide composite porous graphene cathode catalyst according to claim 3, wherein the temperature of the solvothermal reaction in the step A is 60-180 ℃ and the time is 0.5-24 h; the temperature of the heat treatment of the solid powder d is 300-600 ℃, and the time is 0.5-3 h.
7. The preparation method of the manganese dioxide composite porous graphene cathode catalyst according to claim 3, wherein in the step B, the manganese dioxide precursor comprises one or more of manganese dioxide source simple substance, acid or salt or organic matter thereof; the manganese dioxide precursor and the reduced porous graphene oxide are mixed and then react in an isopropanol solution at the temperature of 60-100 ℃ for 0.5-2 h.
8. The method for preparing the manganese dioxide composite porous graphene cathode catalyst according to claim 7, wherein the acid or salt of manganese dioxide comprises one or more of potassium permanganate, manganese chloride, manganese sulfate, manganese carbonate, manganese nitrate, manganese stearate, and manganese acid phosphate.
9. The preparation method of the manganese dioxide composite porous graphene cathode catalyst according to claim 3, wherein the filtration and cleaning in the step C is one or more of centrifugation, suction filtration or normal pressure filtration; the vacuum temperature is 80-120 ℃ and the time is 6-12 h.
10. Use of the manganese dioxide composite porous graphene cathode catalyst according to claim 1 or 2 as a battery cathode oxygen reduction catalyst for a lithium air battery.
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