CN110048130B - Manganese dioxide/carbon black composite material and preparation method and application thereof - Google Patents

Manganese dioxide/carbon black composite material and preparation method and application thereof Download PDF

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CN110048130B
CN110048130B CN201910280868.4A CN201910280868A CN110048130B CN 110048130 B CN110048130 B CN 110048130B CN 201910280868 A CN201910280868 A CN 201910280868A CN 110048130 B CN110048130 B CN 110048130B
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carbon black
manganese dioxide
composite material
black composite
manganese
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CN110048130A (en
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施志聪
李冠洲
黄宗雄
姚伟聪
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Guangdong University of Technology
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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
    • H01M4/88—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
    • 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
    • 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
    • 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 invention relates to the technical field of functional materials, in particular to a manganese dioxide/carbon black composite material and a preparation method and application thereof. The invention discloses a manganese dioxide/carbon black composite material, which comprises carbon black and manganese dioxide loaded on the surface of the carbon black; the manganese dioxide/carbon black composite material is a hierarchical pore structure simultaneously comprising mesopores and macropores; the manganese dioxide in the manganese dioxide/carbon black composite material is in a round cake shape, and the particle size of the carbon black is 25 nm-150 nm. The composite material has quasi-four-electron transfer oxygen reduction reaction, good oxygen reduction performance, excellent stability and low price, and can be applied to zinc-air batteries. In the application of the zinc-air battery, the zinc-air battery has good rate capability and can provide high specific capacity, and the problem that the existing oxygen reduction catalyst is expensive or poor in catalytic performance is solved.

Description

Manganese dioxide/carbon black composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of functional materials, in particular to a manganese dioxide/carbon black composite material and a preparation method and application thereof.
Background
Nowadays, whether it is a fuel cell (such as a hydrogen-air fuel cell) or a metal-air cell (such as a zinc-air cell or a lithium-air cell), the cathode oxygen reduction reaction has the problems of slow kinetics (the rate is only one thousandth of that of the anode reaction) and high reaction overpotential, and the problems limit the industrialization development of the fuel cell and the metal-air cell. Therefore, it is generally necessary to introduce an oxygen reduction reaction catalyst in a fuel cell or a metal air cell.
Commonly used oxygen reduction catalysts are noble metals such as platinum, rhodium, and the like. Platinum is considered to be one of the most active single-component electrocatalysts, however, the practical application thereof is limited by the disadvantages of small reserves, high cost, poor stability and easy methanol poisoning. And the transition metal oxides with lower cost, such as cobaltosic oxide, ferroferric oxide, cuprous oxide and the like, have poor conductivity and low catalytic performance.
Disclosure of Invention
The invention provides a manganese dioxide/carbon black composite material and a preparation method and application thereof, and solves the problems of high price or poor catalytic performance of the existing oxygen reduction catalyst.
The specific technical scheme is as follows:
the invention provides a manganese dioxide/carbon black composite material, which comprises carbon black and manganese dioxide loaded on the surface of the carbon black;
the manganese dioxide/carbon black composite material is of a hierarchical pore structure simultaneously comprising mesopores and macropores;
the manganese dioxide in the manganese dioxide/carbon black composite material is in a round cake shape, and the particle size of the carbon black is 25 nm-150 nm, and more preferably 50 nm.
In the invention, the manganese dioxide/carbon black composite material is in a round cake shape. Compared with powder, the round cake-shaped structure is not easy to agglomerate.
Preferably, the mesopores have a pore size of 2nm to 40nm, more preferably 2.5nm, 3.8nm and 32.0nm, and the macropores have a pore size of 50nm to 60nm, more preferably 50.3 nm.
The invention also provides a preparation method of the manganese dioxide/carbon black composite material, which comprises the following steps:
step 1: carrying out oxidation treatment on carbon black to obtain first carbon black;
step 2: and sequentially adding deionized water, a manganese salt solution and a reducing agent into the first carbon black, and then reacting to obtain the manganese dioxide/carbon black composite material.
In step 1 of the invention, the carbon black is oxidized, thereby increasing the carbon black and MnO2The binding site therebetween and the active site of the oxygen reduction reaction of the carbon black itself.
In the invention, the carbon black is preferably one or more of acetylene black (ACEF), conductive carbon black (Super P Li) and Ketjen black (EC-300J), and more preferably conductive carbon black, acetylene black or Ketjen black;
the reducing agent is preferably one or more of manganese sulfate, sodium sulfite and hydrazine, and is more preferably hydrazine;
the manganese salt is preferably one or more of potassium permanganate, sodium permanganate and ammonium permanganate, more preferably potassium permanganate.
In the invention, deionized water is added into the first carbon black in the step 2 to obtain a first carbon black dispersion liquid, wherein the concentration of the first carbon black in the dispersion liquid is 0.2 g/L-20 g/L;
in the step 2, the reaction is a constant-temperature water bath reaction and ultrasonic treatment is carried out at the same time; the temperature of the constant-temperature water bath reaction is 50-100 ℃, the more preferable temperature is 80 ℃, the reaction time is 1-150 h, the more preferable time is 3-4 h, the ultrasonic power is 100-2000W, the more preferable time is 330W, and the ultrasonic time is 0.5-12 h, the more preferable time is 3-4 h; after the reaction is finished, obtaining a solid-liquid mixture;
after obtaining the solid-liquid mixture and before obtaining the manganese dioxide/carbon black composite material, the method further comprises the following steps: carrying out suction filtration, washing and drying; wherein, the times of suction filtration and washing are both 3-5 times, and the washing liquid is deionized water; the drying temperature is 60-150 ℃, and the drying time is 3-15 h.
Preferably, the oxidation treatment comprises the steps of:
step a: mixing the carbon black with concentrated acid to obtain a dispersion liquid of the carbon black;
step b: adding a strong oxidant into the dispersion liquid of the carbon black to carry out oxidation reaction.
In the invention, the concentrated acid is preferably one or more of concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid and concentrated phosphoric acid;
the strong oxidant is preferably one or more of potassium permanganate, potassium perchlorate and potassium dichromate, and more preferably potassium permanganate.
In the invention, the temperature of the oxidation reaction is 50-100 ℃, more preferably 80 ℃, and the time of the oxidation reaction is 1-150 h, more preferably 2-5 h; carrying out oxidation reaction in a water bath kettle while stirring;
after the oxidation reaction, before obtaining the first carbon black, further comprising: adding a hydrogen peroxide solution and ice blocks to terminate the reaction to obtain a yellow solid-liquid mixture, and then carrying out suction filtration, washing and drying to obtain first carbon black; wherein the times of suction filtration and washing are 6-12 times, the drying temperature is 60-130 ℃, and the drying time is 3-15 h.
Preferably, the concentration of the carbon black in the dispersion of the carbon black is 5g/L to 10g/L, more preferably 5g/L to 8 g/L.
Preferably, the mass ratio of the carbon black to the strong oxidant is 10: 1-1: 20, and more preferably 8: 1-1: 8.
Preferably, the mass ratio of the first carbon black to the manganese salt in the manganese salt solution is 10: 1-1: 10, and more preferably 8: 1-1: 8.
Preferably, the mass ratio of the first carbon black to the reducing agent is 1:10 to 55:1, more preferably 1:10 to 40: 1.
Preferably, the concentration of the manganese salt in the manganese salt solution is 10 g/L-100 g/L, and more preferably 10 g/L-80 g/L.
Preferably, the volume ratio of the mass of the first carbon black to the deionized water is 0.2 g/L-20 g/L, and more preferably 1 g/L-20 g/L.
The invention also provides the application of the manganese dioxide/carbon black composite material in a zinc-air battery.
According to the technical scheme, the invention has the following advantages:
the invention provides a manganese dioxide/carbon black composite material, which has quasi-four-electron transfer oxygen reduction reaction, good oxygen reduction performance, excellent stability and low price.
The preparation method is simple to operate, and the manganese dioxide/carbon black composite material can be obtained only by two steps of carbon black oxidation and manganese salt reduction. In addition, the preparation method has the advantages of easily available raw materials, abundant reserves and low price, and is beneficial to the realization of industrial production.
In addition, the manganese dioxide/carbon black composite material prepared by the preparation method is used in a zinc-air battery, so that the zinc-air battery has good rate capability and high specific capacity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is an XRD spectrum of manganese dioxide/carbon black composite as provided in example 1 of the present invention;
FIG. 2 is an SEM photograph of (a) the carbon black after oxidation treatment in example 1 of the present invention, and (b) to (d) are SEM photographs of manganese dioxide/carbon black composites provided in example 1 of the present invention;
FIG. 3 is a thermogravimetric plot of a manganese dioxide/carbon black composite provided in example 1 of the present invention;
fig. 4 is an adsorption/desorption curve of manganese dioxide/carbon black composite material provided in example 1 of the present invention, wherein the internal figure is a pore size distribution curve of a circular cake-shaped manganese dioxide/carbon black composite material of the present invention;
FIG. 5 is an LSV curve for oxygen reduction of manganese dioxide/carbon black composite and Pt/C (20%) provided in example 1 of the present invention;
FIG. 6 shows manganese dioxide/carbon black composite and Pt/C (20%) at 0.1mol L according to example 1 of the present invention- 1A graph showing the current on the disk and ring electrodes in KOH solution and a graph showing the reaction electron transfer number and peroxide yield for both materials;
FIG. 7 is a graph showing a long term constant current discharge curve of a Zn-air battery using a manganese dioxide/carbon black composite as a cathode catalyst according to example 1 of the present invention;
fig. 8 is a graph showing the rate discharge curve of a Zn-air battery using manganese dioxide/carbon black composite as a cathode catalyst provided in example 1 of the present invention.
Detailed Description
The embodiment of the invention provides a manganese dioxide/carbon black composite material and a preparation method and application thereof, which are used for solving the problems of high price or poor catalytic performance of the existing oxygen reduction catalyst.
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
200mL of concentrated sulfuric acid and 1.5g of Super P Li were mixed in a 500mL round-bottom flask by magnetic stirring to obtain an acidic dispersion solution having a concentration of 7.5 g/L. Subsequently, 1.5g of potassium permanganate was slowly added to the dispersion, and stirred for 30min to obtain a purplish red mixture.
The mixture of the purple red is placed in a water bath at the temperature of 80 ℃ and stirred for 2.5h at constant temperature, then 20mL of hydrogen peroxide and 300g of ice blocks are slowly added into the mixture, and the mixture is uniformly mixed to obtain a yellow dispersion solution. And performing vacuum filtration and deionized water washing, circulating for 6 times, and performing forced air drying at 100 ℃ for 12 hours to obtain the oxidized Super P Li.
Adding deionized water into the oxidized Super P Li to obtain a Super P Li dispersion solution, adding 400mL of the oxidized Super P Li dispersion solution with the concentration of 1mg/mL and 4mL of a potassium permanganate solution with the concentration of 60mg/mL into a 500mL glass bottle, uniformly mixing, dropwise adding 8.0mL of hydrazine, covering the glass bottle with a cover, and placing the glass bottle into an ultrasonic reactor to perform water bath reaction at the temperature of 80 ℃ while performing ultrasonic treatment for 3 hours (the ultrasonic power is 300W).
And finally, repeatedly filtering the mixture obtained by the reaction, washing the mixture for 3 times by using deionized water, and carrying out forced air drying at 100 ℃ for 12 hours to obtain the manganese dioxide/carbon black composite material.
Example 2
100mL of concentrated sulfuric acid, 100mL of concentrated nitric acid, and 1.5g of acetylene black were mixed in a 500mL round-bottom flask by magnetic stirring to obtain an acidic dispersion solution having a concentration of 7.5 g/L. Subsequently, 1.5g of potassium permanganate was slowly added to the dispersion, and stirred for 30min to obtain a reddish-purple mixture.
The purple mixture is placed in a water bath at the temperature of 80 ℃ and stirred for 2 hours at constant temperature, then 30mL of hydrogen peroxide and 300g of ice blocks are slowly added into the mixture, and the mixture is uniformly mixed to obtain a yellow dispersion solution. And carrying out vacuum filtration and deionized water washing, circulating for 6 times, and carrying out forced air drying at 100 ℃ for 12 hours to obtain the acetylene black subjected to oxidation treatment.
Adding deionized water into the oxidized acetylene black to obtain acetylene black dispersion, adding 400mL of the oxidized acetylene black dispersion with the concentration of 2mg/mL and 4mL of potassium permanganate solution with the concentration of 80mg/mL into a 500mL glass bottle, uniformly mixing, then dropwise adding 10.0mL of hydrazine, covering the glass bottle with a cover, placing the glass bottle into an ultrasonic reactor, and carrying out water bath reaction at the temperature of 80 ℃ while carrying out ultrasonic treatment for 4 hours (the ultrasonic power is 330W).
And finally, repeatedly filtering the mixture obtained by the reaction, washing the mixture for 3 times by using deionized water, and carrying out forced air drying at 100 ℃ for 12 hours to obtain the round cake-shaped manganese dioxide/carbon black composite material.
Example 3
100mL of concentrated sulfuric acid, 100mL of concentrated phosphoric acid, and 1.5g of Ketjen black were mixed in a 500mL round-bottomed flask by magnetic stirring to obtain an acidic dispersion solution having a concentration of 7.5 g/L. Subsequently, 1.5g of potassium permanganate was slowly added to the dispersion, and stirred for 30min to obtain a purplish red mixture.
The purple mixture is placed in a water bath at the temperature of 80 ℃ and stirred for 5 hours at constant temperature, then 30mL of hydrogen peroxide and 300g of ice blocks are slowly added into the mixture, and the mixture is uniformly mixed to obtain a yellow dispersion solution. And (3) carrying out vacuum filtration and deionized water washing, circulating for 6 times, and carrying out forced air drying at 100 ℃ for 12 hours to obtain the oxidized Ketjen black.
Adding deionized water into the oxidized Keqin to obtain Keqin dispersion liquid, adding 400mL of the oxidized Keqin black dispersion liquid with the concentration of 2mg/mL and 4mL of the potassium permanganate solution with the concentration of 80mg/mL into a 500mL glass bottle, uniformly mixing, then dropwise adding 10.0mL of hydrazine, covering the glass bottle with a cover, placing the glass bottle in an ultrasonic reactor, carrying out water bath reaction at the temperature of 80 ℃, and carrying out ultrasonic treatment for 3.5 hours (the ultrasonic power is 330W).
And finally, repeatedly filtering the mixture obtained by the reaction, washing the mixture for 3 times by using deionized water, and carrying out forced air drying at 100 ℃ for 12 hours to obtain the round cake-shaped manganese dioxide/carbon black composite material.
Example 4
The crystal structure of the manganese dioxide/carbon black composite material obtained in example 1 was tested by an X-ray powder diffractometer (Rigaku UItima type III, Japan). The manganese dioxide/carbon black composite sample provided in example 1 had a scan angle of 10 ° to 70 ° and a scan speed of 4 °/min.
As shown in FIG. 1, example 1 two of the present inventionManganese oxide/carbon Black composites having MnO2Typical X-ray characteristic diffraction peaks of the compound, and the peaks of steamed bread in the vicinity of 25 degrees and 43.3 degrees are X-ray diffraction peaks of the carbon black material.
Example 5
The manganese dioxide/carbon black composite provided in example 1 was analyzed for its micro-morphology, structure, etc. before and after it was analyzed by a Hitachi-Su8010 Scanning Electron Microscope (SEM).
As shown in FIG. 2(a), the carbon black material after oxidation treatment has spherical particles, and the size of the carbon sphere particles is about 100 nm.
As can be seen from FIGS. 2(a) to (d), MnO was present on the surface of carbon black in the final manganese dioxide/carbon black composite2Particles, MnO2The particles are round cakes, the particle diameter of the carbon black is obviously reduced, the carbon spheres with the particle diameter of 100nm after oxidation treatment are changed into the carbon spheres with the particle diameter of 50nm finally, the specific surface area of the carbon black is increased, and the carbon black and MnO are added2The contact area of (2) is also increased, which is beneficial to the smooth proceeding of the catalytic reaction.
Example 6
Thermogravimetric analysis of the manganese dioxide/carbon black composite provided in example 1 was performed using a TA instruments SDT 2960 differential-thermogravimetric analyzer.
As shown in FIG. 3, MnO2The loading in the manganese dioxide/carbon black composite of example 1 was 17.02% with a rapid mass loss between 240 ℃ and 515 ℃ as shown, resulting from the carbon black of the manganese dioxide/carbon black composite of example 1 being combusted in air.
Example 7
The manganese dioxide/carbon black composite of example 1 was subjected to specific surface and pore size tests using a specific surface and pore size analyzer (3H-2000PS1) from Behcard instruments, Inc., Beijing.
As shown in fig. 4, the adsorption/desorption curves of the manganese dioxide/carbon black composite material of example 1 are in accordance with H3 type curve, which indicates that the pores in the tested material are in the form of plate-like/particle-formed slit-shaped pores, and are consistent with the SEM image of fig. 2. As can be seen from the internal drawing in FIG. 4, the manganese dioxide/carbon black composite material of example 1 has a specific surface area of 66.9169m2g-1Hole, holeThe diameters of the mesoporous carbon material are mainly 2.5nm, 3.8nm and 32.0nm, and the diameters of the macroporous carbon material are 50.3nm, and the macroporous structure is increased due to the appearance of a cake-shaped structure, so that the composite material has a hierarchical pore structure.
Example 8
The manganese dioxide/carbon black composite catalyst and the Pt/C catalyst provided in example 1 were subjected to electrocatalytic performance characterization using a rotary ring electrode device (RRDE 3A) of ALS corporation of japan and an electrochemical workstation of chenhua CHI 750e type.
As shown in FIG. 5, a glassy carbon disk was used as the working electrode, a catalyst layer was coated thereon, an Ag/AgCl electrode was used as the reference electrode, and a Pt wire electrode was used as the counter electrode. Wherein the half-wave potential of Pt/C is 0.81V vs. RHE, and the limiting current density is 4.25mA cm-2The half-wave potential of the manganese dioxide/carbon black composite material is 0.75V vs. RHE, and the limiting current density is 4.00mA cm-2The manganese dioxide/carbon black composite provided in example 1 has oxygen reduction catalytic performance relatively close to that of Pt/C.
Example 9
The disc electrode current and the ring electrode current of the manganese dioxide/carbon black composite material under a double potentiostat are provided by a rotating ring electrode device (RRDE 3A) test example 1, and the corresponding electron transfer number and the yield of hydrogen peroxide in the reaction can be calculated according to the ring current and the disc current data.
The scanning potential range is 0.1 to-0.7V (vs. Ag/AgCl), and the scanning speed is 2mV s-10.1mol L of electrolyte-1KOH, rotational speed 1600 rpm.
As can be seen from FIG. 6, the electron transfer number n of Pt/C was about 3.92 in the potential range of-0.7 to-0.15V, and the yield of hydrogen peroxide was 4.1%, and example 1 provided that the electron transfer number n of manganese dioxide/carbon black composite was about 3.67 in the potential range of-0.7 to-0.15V, and the yield of hydrogen peroxide was 16.3%, indicating that the catalytic performance of the composite was good.
Example 10
This example is to examine the long-term constant-current discharge performance and rate capability of the Zn-air battery using the manganese dioxide/carbon black composite provided in example 1 as a cathode catalyst.
As shown in fig. 7, in order to use the sample of the present invention as a long-term constant current discharge curve, it can be seen from fig. 7 that the Zn-air battery using the manganese dioxide/carbon black composite as a cathode catalyst provided in example 1 did not observe a significant voltage drop during long-term discharge until the voltage dropped rapidly after the Zn anode was completely consumed.
As shown in FIG. 7, when normalized to the mass of zinc flakes consumed, the Zn-air cell using the manganese dioxide/carbon black composite as the cathode catalyst provided in example 1 was operated at 10mA cm-2Specific capacity at time of 674.8mAh g-1At 20mA cm-2When the concentration is 641.7mAh g-1。
As shown in fig. 8, the manganese dioxide/carbon black composite provided in example 1 is used as a typical constant current discharge curve for zinc-air cell cathode catalysts at different current densities. At a catalyst loading of 1.0mg cm-2Under the condition of (1), the Zn-air battery taking the sample as the catalyst has excellent rate performance.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. A manganese dioxide/carbon black composite, characterized in that the manganese dioxide/carbon black composite comprises carbon black and manganese dioxide loaded on the surface of the carbon black;
the manganese dioxide/carbon black composite material is of a hierarchical pore structure simultaneously comprising mesopores and macropores;
the manganese dioxide in the manganese dioxide/carbon black composite material is in a round cake shape, and the particle size of the carbon black is 25 nm-150 nm;
the preparation method of the manganese dioxide/carbon black composite material comprises the following steps:
step 1: carrying out oxidation treatment on carbon black to obtain first carbon black;
step 2: sequentially adding deionized water, a manganese salt solution and a reducing agent into the first carbon black, and then reacting to obtain a manganese dioxide/carbon black composite material;
the aperture of the mesopores is 2 nm-40 nm, and the aperture of the macropores is 50 nm-60 nm.
2. The manganese dioxide/carbon black composite according to claim 1, characterized in that said oxidation treatment comprises the following steps:
step a: mixing the carbon black with concentrated acid to obtain a dispersion liquid of the carbon black;
step b: adding a strong oxidant into the dispersion liquid of the carbon black to carry out oxidation reaction.
3. The manganese dioxide/carbon black composite material according to claim 2, wherein the concentration of the carbon black in the dispersion of the carbon black is 5 to 10 g/L.
4. The manganese dioxide/carbon black composite material according to claim 2, wherein the mass ratio of the carbon black to the strong oxidant is 10:1 to 1: 20.
5. The manganese dioxide/carbon black composite material according to claim 1, wherein the mass ratio of the first carbon black to the manganese salt in the manganese salt solution is 10:1 to 1: 10.
6. The manganese dioxide/carbon black composite material according to claim 1, wherein the mass ratio of the first carbon black to the reducing agent is 1:10 to 55: 1.
7. The manganese dioxide/carbon black composite according to claim 1, wherein the concentration of manganese salt in the manganese salt solution is 10 to 100 g/L.
8. Use of the manganese dioxide/carbon black composite of claim 1 in a zinc air cell.
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