CN110048130A - A kind of manganese dioxide/carbon black composite material and its preparation method and application - Google Patents
A kind of manganese dioxide/carbon black composite material and its preparation method and application Download PDFInfo
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- CN110048130A CN110048130A CN201910280868.4A CN201910280868A CN110048130A CN 110048130 A CN110048130 A CN 110048130A CN 201910280868 A CN201910280868 A CN 201910280868A CN 110048130 A CN110048130 A CN 110048130A
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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
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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
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- 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 invention relates to technical field of function materials more particularly to a kind of manganese dioxide/carbon black composite material and the preparation method and application thereof.The invention discloses a kind of manganese dioxide/carbon black composite material, manganese dioxide/carbon black composite material includes carbon black and the manganese dioxide for being supported on carbon blacksurface；Manganese dioxide/carbon black composite material is while including mesoporous and macropore hierarchical porous structure；Manganese dioxide is in round pie in manganese dioxide/carbon black composite material, and the partial size of carbon black is 25nm~150nm.The composite material has the oxygen reduction reaction of quasi- four electronics transfers, and hydrogen reduction is functional, excellent in stability, cheap, and can apply to zinc-air battery.In the application of zinc-air battery, so that zinc-air battery has good high rate performance and can provide high specific capacity, solve the problems, such as that existing oxygen reduction catalyst is expensive or catalytic performance is poor.
Description
Technical field
The present invention relates to technical field of function materials more particularly to a kind of manganese dioxide/carbon black composite material and its preparations
Method and application.
Background technique
Now, either (such as zinc-air is electric for fuel cell (such as hydrogen-air fuel cell) or metal-air battery
Pond, lithium-air battery), there are dynamics for Cathodic oxygen reduction slowly (one thousandth that rate only has anode reaction), reaction
The higher problem of overpotential, these problems limit the industrialized development of fuel cell, metal-air battery.Therefore, in fuel
It usually requires to introduce oxygen reduction reaction catalyst in battery or metal-air battery.
Common oxygen reduction catalyst has noble metal such as platinum, rhodium etc..Platinum is considered as the highest one pack system electro-catalysis of activity
One of agent, however, the disadvantages of reserves are few, at high cost, stability is poor and easy methanol poisoning limits its practical application.And cost
The electric conductivity such as lower transition metal oxide such as cobaltosic oxide, ferroso-ferric oxide, cuprous oxide are bad, and catalytic performance is not
It is high.
Summary of the invention
The present invention provides a kind of manganese dioxide/carbon black composite materials and the preparation method and application thereof, solve existing
The problem that oxygen reduction catalyst is expensive or catalytic performance is poor.
Its specific technical solution is as follows:
The present invention provides a kind of manganese dioxide/carbon black composite material, the manganese dioxide/carbon black composite material includes charcoal
Manganese dioxide that is black and being supported on the carbon blacksurface；
Manganese dioxide/the carbon black composite material is while including mesoporous and macropore hierarchical porous structure；
Manganese dioxide described in the manganese dioxide/carbon black composite material is in round pie, and the partial size of the carbon black is 25nm
~150nm, more preferably 50nm.
In the present invention, manganese dioxide/carbon black composite material is round pie.Relative to powdered, round pie structure is not easy to send out
Raw agglomeration.
Preferably, the mesoporous aperture is 2nm~40nm, more preferably 2.5nm, 3.8nm and 32.0nm, described big
The aperture in hole is 50nm~60nm, more preferably 50.3nm.
The present invention also provides the preparation methods of above-mentioned manganese dioxide/carbon black composite material, comprising the following steps:
Step 1: carbon black being subjected to oxidation processes, obtains the first carbon black；
Step 2: being reacted, obtained after sequentially adding deionized water, manganese salt solution and reducing agent in the first carbon black of Xiang Suoshu
To manganese dioxide/carbon black composite material.
In step 1 of the present invention, carbon black is subjected to oxidation processes, to increase carbon black and MnO2Between binding site and charcoal
It is black itself oxygen reduction reaction active site.
In the present invention, carbon black is preferably acetylene carbon black (ACEF), conductive black (Super P Li) and Ketjen black (EC-
One or more of 300J), more preferably conductive black, acetylene carbon black or Ketjen black；
Reducing agent is preferably one of manganese sulfate, sodium sulfite and hydrazine or a variety of, more preferably hydrazine；
Manganese salt is preferably one of potassium permanganate, sodium permanganate and ammonium permanganate or a variety of, more preferably potassium permanganate.
In the present invention, deionized water is added in first carbon black in step 2, obtains the dispersion liquid of the first carbon black, wherein the first charcoal
The black concentration in the dispersion liquid is 0.2g/L~20g/L；
In step 2, the reaction is that water bath with thermostatic control reacts while carrying out ultrasound；Water bath with thermostatic control reaction temperature be 50~
100 DEG C, more preferably 80 DEG C, reaction time are 1h~150h, and more preferably 3~4h, ultrasonic power is 100~2000W, more excellent
It is selected as 330W, ultrasonic time is 0.5h~12h, more preferably 3~4h；It is described after reaction, obtain being solidliquid mixture；
After obtaining solidliquid mixture, it is described obtain manganese dioxide/carbon black composite material before, further includes: filter, washing
And drying；Wherein, it filters and washing times is 3~5 times, cleaning solution is deionized water；The temperature of the drying is 60~150
DEG C, the time of the drying is 3~15h.
Preferably, the oxidation processes the following steps are included:
Step a: the carbon black is mixed with concentrated acid, obtains the dispersion liquid of the carbon black；
Strong oxidizer is added in the dispersion liquid of b: Xiang Suoshu carbon black of step and carries out oxidation reaction.
In the present invention, concentrated acid is preferably the one or more of the concentrated sulfuric acid, concentrated hydrochloric acid, concentrated nitric acid and concentrated phosphoric acid；
Strong oxidizer is preferably one or more of potassium permanganate, potassium hyperchlorate and potassium bichromate, more preferably Gao Meng
Sour potassium.
In the present invention, the temperature of the oxidation reaction is 50~100 DEG C, more preferably 80 DEG C, the oxidation reaction when
Between be 1h~150h, more preferably 2~5h；Oxidation reaction carries out in water-bath, is reacted while stirring；
After the oxidation reaction, before obtaining the first carbon black, further includes: be added hydrogenperoxide steam generator and ice cube terminate it is anti-
It answers, obtains yellow solidliquid mixture, then filtered, washed and dried, obtain the first carbon black；Wherein, it filters and washs
Number is 6~12 times, and dry temperature is 60~130 DEG C, and the dry time is 3~15h.
Preferably, the concentration of carbon black described in the dispersion liquid of the carbon black be 5g/L~10g/L, more preferably 5g/L~
8g/L。
Preferably, the mass ratio of the carbon black and the strong oxidizer is 10:1~1:20, more preferably 8:1~1:8.
Preferably, first carbon black and the mass ratio of manganese salt in the manganese salt solution are 10:1~1:10, more preferably
8:1~1:8.
Preferably, the mass ratio of first carbon black and the reducing agent is 1:10~55:1, more preferably 1:10~
40:1。
Preferably, the concentration of manganese salt is 10g/L~100g/L, more preferably 10 g/L~80g/L in the manganese salt solution.
Preferably, the volume ratio of the quality Yu the deionized water of first carbon black is the g/L of 0.2g/L~20, more excellent
It is selected as 1g/L~20g/L.
The present invention also provides application of the above-mentioned manganese dioxide/carbon black composite material in zinc-air battery.
As can be seen from the above technical solutions, the invention has the following advantages that
The present invention provides a kind of manganese dioxide/carbon black composite material, which has the oxygen of quasi- four electronics transfers
Reduction reaction, hydrogen reduction is functional, excellent in stability, cheap.
Preparation method of the present invention is easy to operate, and only needing carbon black oxidation and manganese salt to restore two steps can be obtained titanium dioxide
Manganese/carbon black composite material.In addition, the preparation method raw material are easy to get, rich reserves, cheap, conducive to industrialized production
It realizes.
In addition, manganese dioxide/carbon black composite material made from the preparation method is in zinc-air battery, so that zinc air is electric
Pond has good high rate performance and high specific capacity.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is manganese dioxide/carbon black composite material XRD spectra that the embodiment of the present invention 1 provides；
(a) is the carbon black SEM figure in the embodiment of the present invention 1 after oxidation processes in Fig. 2, and (b)~(d) is the embodiment of the present invention
1 manganese dioxide/carbon black composite material SEM the figure provided；
Fig. 3 is manganese dioxide/carbon black composite material thermogravimetric curve that the embodiment of the present invention 1 provides；
Fig. 4 is manganese dioxide/carbon black composite material absorption/desorption curve that the embodiment of the present invention 1 provides, wherein internal
Attached drawing is the pore size distribution curve of round pie manganese dioxide/carbon black composite material of the present invention；
Fig. 5 is the hydrogen reduction LSV of manganese dioxide/carbon black composite material and Pt/C (20%) that the embodiment of the present invention 1 provides
Curve；
Fig. 6 is manganese dioxide/carbon black composite material that the embodiment of the present invention 1 provides and Pt/C (20%) in 0.1mol L- 1The reaction electron transfer number and peroxide of electric current display figure and two kinds of materials in KOH solution on disc electrode and ring electrode
Yield figure；
Fig. 7 is Zn- air of the manganese dioxide/carbon black composite material that provides of the embodiment of the present invention 1 as cathod catalyst
The long-time constant current discharge curve of battery；
Fig. 8 is Zn- air of the manganese dioxide/carbon black composite material that provides of the embodiment of the present invention 1 as cathod catalyst
The rate discharge curves of battery.
Specific embodiment
The embodiment of the invention provides a kind of manganese dioxide/carbon black composite materials and the preparation method and application thereof, for solving
The problem that certainly existing oxygen reduction catalyst is expensive or catalytic performance is bad.
It in order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below will be to of the invention real
The technical solution applied in example is clearly and completely described, it is clear that the embodiments described below are only present invention a part
Embodiment, and not all embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of all other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The 200mL concentrated sulfuric acid and 1.5g Super P Li are mixed in 500mL round-bottomed flask by magnetic agitation, obtained
Concentration is the acidic dispersion solution of 7.5g/L.Then to 1.5g potassium permanganate is slowly added into dispersion liquid, stirring 30min is obtained
The mixture of aubergine.
The mixture of above-mentioned aubergine is placed on constant temperature in 80 DEG C of water-baths and stirs 2.5h, and is slowly added in backward mixture
Enter the hydrogen peroxide of 20mL and the ice cube of 300g, obtains the dispersion solution of yellow after mixing.Pass through vacuum filtration, deionization
Water washing recycles 6 times, and 100 DEG C of forced air drying 12h obtain the Super P Li of oxidation processes.
Deionized water is added to the Super P Li of oxidation processes, obtains Super P Li dispersion liquid, toward the glass of 500mL
In glass bottle be added 400mL 1mg/mL oxidation processes after Super P Li dispersion liquid and 4mL 60mg/mL liquor potassic permanganate,
The hydrazine of 8.0mL is added dropwise again after mixing, vial is placed in ultrasonic reactor in 80 DEG C of water-baths after closeing the lid
Ultrasonic 3h (ultrasonic power 300W).
The mixture that finally reaction is obtained is washed 3 times by suction filtration repeatedly, deionized water, and 100 DEG C of forced air drying 12h are obtained
To manganese dioxide/carbon black composite material.
Embodiment 2
The 100mL concentrated sulfuric acid, 100mL concentrated nitric acid and 1.5g acetylene black are mixed in 500mL round-bottomed flask by magnetic agitation
In, obtain the acidic dispersion solution that concentration is 7.5g/L.Then to 1.5g potassium permanganate is slowly added into dispersion liquid, stir
30min obtains the mixture of aubergine.
The mixture of above-mentioned aubergine is placed on constant temperature in 80 DEG C of water-baths and stirs 2h, and is slowly added in backward mixture
The hydrogen peroxide of 30mL and the ice cube of 300g obtain the dispersion solution of yellow after mixing.Pass through vacuum filtration, deionized water
Washing recycles 6 times, and 100 DEG C of forced air drying 12h obtain the acetylene black of oxidation processes.
Deionized water is added to the acetylene black of oxidation processes, obtains acetylene black dispersion liquid, is added into the vial of 500mL
The liquor potassic permanganate of acetylene black dispersion liquid and 4mL 80mg/mL, drips again after mixing after 400mL 2mg/mL oxidation processes
Vial is placed in ultrasonic reactor ultrasound 4h (the ultrasonic function in 80 DEG C of water-baths after closeing the lid by the hydrazine for adding 10.0mL
Rate is 330W).
The mixture that finally reaction is obtained is washed 3 times by suction filtration repeatedly, deionized water, and 100 DEG C of forced air drying 12h are obtained
To round pie manganese dioxide/carbon black composite material.
Embodiment 3
The 100mL concentrated sulfuric acid, 100mL concentrated phosphoric acid and 1.5g Ketjen black are mixed in 500mL round-bottomed flask by magnetic agitation
In, obtain the acidic dispersion solution that concentration is 7.5g/L.Then to 1.5g potassium permanganate is slowly added into dispersion liquid, stir
30min obtains the mixture of aubergine.
The mixture of above-mentioned aubergine is placed on constant temperature in 80 DEG C of water-baths and stirs 5h, and is slowly added in backward mixture
The hydrogen peroxide of 30mL and the ice cube of 300g obtain the dispersion solution of yellow after mixing.Pass through vacuum filtration, deionized water
Washing recycles 6 times, and 100 DEG C of forced air drying 12h obtain the Ketjen black of oxidation processes.
Deionized water is added to section's qin of oxidation processes, obtains section's qin dispersion liquid, is added into the vial of 500mL
The liquor potassic permanganate of Ketjen black dispersion liquid and 4mL 80mg/mL, drips again after mixing after 400mL 2mg/mL oxidation processes
Vial is placed in ultrasonic reactor the ultrasound 3.5h (ultrasound in 80 DEG C of water-baths after closeing the lid by the hydrazine for adding 10.0mL
Power is 330W).
The mixture that finally reaction is obtained is washed 3 times by suction filtration repeatedly, deionized water, and 100 DEG C of forced air drying 12h are obtained
To round pie manganese dioxide/carbon black composite material.
Embodiment 4
Using titanium dioxide made from x-ray powder diffraction instrument (III type of Rigaku Rigaku UItima) testing example 1
Manganese/carbon black composite material crystal structure.Manganese dioxide/carbon black composite material Sample Scan angle that embodiment 1 provides is 10 °
~70 °, scanning speed is 4 °/min.
As shown in Figure 1,1 manganese dioxide of the embodiment of the present invention/carbon black composite material has MnO2The typical X-ray of compound
Characteristic diffraction peak, the steamed bun peak near 25 ° and 43.3 ° are the X-ray diffraction peaks of carbon black materials.
Embodiment 5
It is multiple that manganese dioxide/carbon black is provided to embodiment 1 using Hitachi-Su8010 type scanning electron microscope (SEM)
The front and back of condensation material carries out microscopic appearance, structure etc. and is analyzed.
As shown in Fig. 2 (a), the carbon black materials after oxidation processes are in spherical particle, and carbon ball particle size is in 100nm or so.
By Fig. 2 (a)~(d) it is found that there are MnO for carbon blacksurface in final manganese dioxide/carbon black composite material2Particle,
MnO2Particle is round pie, and particle size carbon black therein obviously becomes smaller, and the carbon ball of 100nm becomes final after oxidation processes
The carbon ball of 50nm, so that the specific surface area of carbon black increases, carbon black and MnO2Contact area also will increase, be conducive to catalysis reaction
Go on smoothly.
Embodiment 6
It is multiple that manganese dioxide/carbon black is provided to embodiment 1 using 2960 differentials of TA instrument companies of U.S. SDT-thermogravimetric analyzer
Condensation material carries out thermogravimetric analysis.
As shown in figure 3, MnO2Carrying capacity in 1 manganese dioxide of embodiment/carbon black composite material is 17.02%, in figure
Quality immediate loss between 240 DEG C~515 DEG C is fired in air by 1 manganese dioxide of embodiment/carbon black composite material carbon black
Caused by burning.
Embodiment 7
Using the specific surface and Porosimetry (3H-2000PS1) of Beijing Bei Shide Instrument Ltd. to embodiment 1 two
Manganese oxide/carbon black composite material carries out specific surface and opening size test.
As shown in figure 4,1 manganese dioxide of embodiment/carbon black composite material absorption/desorption curve meets H3 type curve, it should
Class curve, which shows to measure and monitor the growth of standing timber, expects that Hole is the slit-shaped apertures that sheet/particle is formed, and matches with the SEM figure of Fig. 2.By in Fig. 4
Internal attached drawing is it is found that the specific surface area in 1 manganese dioxide of embodiment/carbon black composite material is 66.9169m2g-1, aperture is mainly
Mesoporous and 50.3nm the macropore of 2.5nm, 3.8nm, 32.0nm, due to there is round pie structure, macroporous structure also increases therewith
It is more, to make the composite material that hierarchical porous structure be presented.
Embodiment 8
Using rotating ring electrode device (RRDE 3A) He Chenhua CHI 750e type electrochemical operation of Japanese ALS company
It stands and electrocatalysis characteristic characterization is carried out to the manganese dioxide/carbon black composite material catalyst and Pt/C catalyst of the offer of embodiment 1.
As shown in figure 5, using glass carbon disk as working electrode, catalyst layer laid on is made using Ag/AgCl electrode
For reference electrode, it is used as using Pt electrodes to electrode.Wherein, the half wave potential of Pt/C is 0.81V vs.RHE, carrying current
Density is 4.25mA cm-2, manganese dioxide/carbon black composite material half wave potential is 0.75V vs.RHE, and limiting current density is
4.00mA cm-2, manganese dioxide/carbon black composite material hydrogen reduction catalytic performance relatively Pt/C that embodiment 1 provides.
Embodiment 9
Manganese dioxide/carbon black composite material is provided double by rotating ring electrode device (RRDE 3A) testing example 1
Disc electrode electric current and ring electrode electric current under potentiostat, can be calculated corresponding electronics according to circular current and disk current data
Shift the yield of hydrogen peroxide in number and reaction.
Scanning potential range is 0.1 to -0.7V (vs.Ag/AgCl), and scanning speed is 2mV s-1, electrolyte 0.1mol
L-1KOH, rotation speed 1600rpm.
It will be appreciated from fig. 6 that Pt/C electron transfer number is about 3.92 in -0.7 to -0.15V potential range, peroxidating
The yield of hydrogen is 4.1%, and embodiment 1 provides manganese dioxide/carbon black composite material electron transfer number -0.7 to -0.15V
It is about 3.67 in potential range, the yield of hydrogen peroxide is 16.3%, illustrates that the composite material catalytic performance is good.
Embodiment 10
The present embodiment is that manganese dioxide/carbon black composite material that detection embodiment 1 provides is empty as the Zn- of cathod catalyst
Long-time constant current discharge performance and high rate performance when pneumoelectric pond.
As shown in fig. 7, for use sample of the present invention as long-time constant current discharge curve, from Fig. 7 as can be seen that
Manganese dioxide/carbon black composite material that embodiment 1 provides does not have in long-term electric discharge as the Zn- air cell of cathod catalyst
Apparent voltage decline is observed, until Zn anode is totally consumed rear voltage decline rapidly.
As shown in figure Fig. 7, when normalizing to consumed zinc metal sheet quality, manganese dioxide/carbon black that embodiment 1 provides is compound
Material as cathod catalyst Zn- air cell in 10mA cm-2When specific capacity be 674.8mAh g-1, in 20mA cm-2
When be 641.7mAh g-1。
As shown in figure 8, manganese dioxide/carbon black composite material that embodiment 1 provides is as zinc-air battery cathod catalyst
Typical constant current discharge curve under different current densities.It is 1.0mg cm in catalyst loading-2Under conditions of, the present invention
Sample is that the Zn- air cell of catalyst has excellent high rate performance.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of manganese dioxide/carbon black composite material, which is characterized in that the manganese dioxide/carbon black composite material includes carbon black
With the manganese dioxide for being supported on the carbon blacksurface；
Manganese dioxide/the carbon black composite material is while including mesoporous and macropore hierarchical porous structure；
Manganese dioxide described in the manganese dioxide/carbon black composite material is in round pie, the partial size of the carbon black be 25nm~
150nm。
2. manganese dioxide/carbon black composite material according to claim 1, which is characterized in that the mesoporous aperture is 2nm
~40nm, the aperture of the macropore are 50nm~60nm.
3. the preparation method of manganese dioxide/carbon black composite material of any of claims 1 or 2, which is characterized in that including following step
It is rapid:
Step 1: carbon black being subjected to oxidation processes, obtains the first carbon black；
Step 2: being reacted after sequentially adding deionized water, manganese salt solution and reducing agent in the first carbon black of Xiang Suoshu, obtain two
Manganese oxide/carbon black composite material.
4. preparation method according to claim 3, which is characterized in that the oxidation processes the following steps are included:
Step a: the carbon black is mixed with concentrated acid, obtains the dispersion liquid of the carbon black；
Strong oxidizer is added in the dispersion liquid of b: Xiang Suoshu carbon black of step and carries out oxidation reaction.
5. the preparation method according to claim 4, which is characterized in that the concentration of carbon black described in the dispersion liquid of the carbon black
For 5g/L~10g/L.
6. the preparation method according to claim 4, which is characterized in that the mass ratio of the carbon black and the strong oxidizer is
10:1~1:20.
7. preparation method according to claim 3, which is characterized in that manganese salt in first carbon black and the manganese salt solution
Mass ratio be 10:1~1:10.
8. preparation method according to claim 3, which is characterized in that the mass ratio of first carbon black and the reducing agent
For 1:10~55:1.
9. preparation method according to claim 3, which is characterized in that the concentration of manganese salt is 10g/L in the manganese salt solution
~100g/L.
10. application of the manganese dioxide/carbon black composite material of any of claims 1 or 2 in zinc-air battery.
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| CN112670526A (en) * | 2020-12-23 | 2021-04-16 | 广东海洋大学 | Preparation method and application of amorphous manganese dioxide modified shrimp shell carbon base frame |
| CN113150579A (en) * | 2021-03-24 | 2021-07-23 | 茂名环星新材料股份有限公司 | Method for removing impurities in carbon black and application thereof |
| CN113193178A (en) * | 2020-12-07 | 2021-07-30 | 北京服装学院 | Preparation method of manganese dioxide nanosheet coated carbon fiber for supplying power to intelligent clothes |
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| CN108550871A (en) * | 2018-05-11 | 2018-09-18 | 广东工业大学 | A kind of manganese dioxide/carbon black composite material and its preparation method and application |
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| CN113193178A (en) * | 2020-12-07 | 2021-07-30 | 北京服装学院 | Preparation method of manganese dioxide nanosheet coated carbon fiber for supplying power to intelligent clothes |
| CN112670526A (en) * | 2020-12-23 | 2021-04-16 | 广东海洋大学 | Preparation method and application of amorphous manganese dioxide modified shrimp shell carbon base frame |
| CN112670526B (en) * | 2020-12-23 | 2022-03-04 | 广东海洋大学 | Preparation method and application of amorphous manganese dioxide modified shrimp shell carbon base frame |
| CN113150579A (en) * | 2021-03-24 | 2021-07-23 | 茂名环星新材料股份有限公司 | Method for removing impurities in carbon black and application thereof |
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