CN102275903B - The preparation method of a kind of Graphene and manganese dioxide nano-composite material - Google Patents

The preparation method of a kind of Graphene and manganese dioxide nano-composite material Download PDF

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CN102275903B
CN102275903B CN201110135866.XA CN201110135866A CN102275903B CN 102275903 B CN102275903 B CN 102275903B CN 201110135866 A CN201110135866 A CN 201110135866A CN 102275903 B CN102275903 B CN 102275903B
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graphene
manganese dioxide
composite
dioxide nano
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CN102275903A (en
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秦宗益
郭娜
王凌凤
蔡雅萌
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东华大学
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Abstract

The present invention relates to the preparation method of a kind of Graphene and manganese dioxide nano-composite material, comprise: graphite, saltpetre, dense sulphur are uniformly mixed by (1), add potassium permanganate, in 30 ~ 40 DEG C of reaction 20 ~ 40min, at room temperature add deionized water, then add hydrogen peroxide after reacting 15 ~ 30min and obtain graphite oxide; (2) above-mentioned graphite oxide is scattered in water, adds hydrazine hydrate, after 95 DEG C of reaction 1 ~ 24h, obtained Graphene; (3) by above-mentioned Graphene ultrasonic disperse in saturated potassium permanganate solution, add acid, in 60 ~ 80 DEG C reaction 1 ~ 5h, obtain Graphene and manganese dioxide nano-composite material.The present invention reacts and is simply easy to control, easy to operate, technique is simple; Obtain matrix material and have broad application prospects, can be used for catalyzer, biological sensing material, the electrode materials of lithium ion battery and electrode material for super capacitor etc.

Description

The preparation method of a kind of Graphene and manganese dioxide nano-composite material
Technical field
The invention belongs to the preparation field of manganese dioxide nano-composite material, particularly the preparation method of a kind of Graphene and manganese dioxide nano-composite material.
Background technology
The diversity of manganese bioxide material due to its structure and the physics-chem characteristic of uniqueness thereof, cheap, environmental friendliness in addition, as a kind of important electrode materials, be widely used in (CN 1758468A in the chemical power sources such as drying battery, alkaline Mn cell, Zn-Mg battery, magnesium manganese cell, lithium-manganese cell; CN 1594212; CN 95103067.1; CN 200510014876.2; CN200810027780.3; CN 200810027780.3), as a kind of Multifunctional fine inorganic functional material, be applicable as molecular sieve, advanced catalysts material etc.As a kind of both sexes transition metal oxide, have a wide range of applications in industrial production and environmental improvement, as organic pollutant absorption degradation, process mercurous, the heavy metal wastewater thereby aspect such as cadmium, lead, chromium and metalloid arsenic and also have stronger application prospect (CN 1935355A).Particularly nano level Manganse Dioxide has a lot of unique performance, key state as special microtexture and larger specific surface area, surface is different from granule interior with electronic state, surface atom coordination is incomplete, surfactivity position is caused to increase, along with the reduction of particle diameter, smooth surface degree is deteriorated, define rough atomic steps, add the contact surface of chemical reaction.Particularly it has good chemical property, superior ion/electron conductivity and relative high current potential and makes it have very important application (CN 200410020888.1 in electrochemical field; CN 200510014876.2; CN200910049408.7; CN 201010123751.4; CN 201010039644.3).The method preparing nano-manganese dioxide has varied, mainly contain hydrothermal synthesis method, Low Temperature Solid-Phase synthesis method, organic-water two phase reaction method, coprecipitation method, reflux cooling, agglutinating nature yeast, microemulsion method and thermal decomposition method etc., especially Manganse Dioxide thin slice has the nanostructure of high-specific surface area is the important goal (CN 02157737.4 that synthetic work is pursued; CN200810200287.7; CN 200910139589.2; CN200910019398.2; CN 200910304513.0).But the product that most methods obtains be pattern different powders or particulate, size distribution is wide, and agglomeration is more serious.Nano-manganese dioxide deposit with use procedure in can there is serious agglomeration, make its cannot give play to monodisperse status exist property and advantage.When being used as electrode materials, also also exist and be used alone Manganse Dioxide and there is the shortcomings such as the poor and utilization ratio of electron conduction is not high, therefore usually make nano-manganese dioxide and have to be combined with each other compared with the carbon-based material of bigger serface, can further improve its activity and stability, and the synergistic effect (CN 200410041356.6 both playing; CN 200610068772.4; CN 200710156155.4; CN 200910071880.0; CN200910071963.X).
The bidimensional cycle honeycomb lattice structure that Graphene is made up of carbon six-ring, have excellent electroconductibility, thermal conductivity and mechanical property etc. are a kind of desirable carrier (CN 101800302A; CN 101877405A; US 20100081057); The Graphene that Chen Weixiang etc. are prepared by hydrothermal method/Ru nano composite material has higher ratio capacitance as electrode material for super capacitor, and when the content of Ru is 48.9%, the ratio capacitance of matrix material reaches 583F/g (CN 101714463A).Graphene also has good electrochemical stability, large specific surface area and wide electrochemical window, its distinctive laminate structure is conducive to electrolytic solution and spreads rapidly therein, realize the high-power discharge and recharge of electronic component instantaneous time, these features become a kind of potential lithium ion battery electrode material and electrode material for super capacitor (US 20100081057A1; CN 101849302A; CN 1017494874A).He Yushi etc. prepare silicon/carbon/graphite in lithium ion batteries alkene nanometer sheet-cobaltous hydroxide composite negative pole material by hydrothermal method, when the electric current of 200mA/g carries out discharge and recharge, the reversible specific capacity of matrix material can be stabilized in more than 900mAh/g (CN 101867046A).Graphene/amorphous the manganese dioxide composite material that utilized microwave irradiation to prepare such as nearest Yan, as the electrode materials superior performance of the ultracapacitor of high-speed sweep, ratio capacitance when 2mV/s is up to 310F/g, and the ratio capacitance when 500mV/s is still up to 228F/g (Carbon 2010; 48:3825 ~ 3833).Wu etc. prepare Graphene/manganese dioxide nanowire matrix material, and are assembled into the electrochemical capacitor of excellent performance as positive electrode material, at 7.0Wh kg -1time power density up to 5000Wkg -1, after 1000 circulations, ratio capacitance decays to 21% (ACS NANO 2010; 4:5835 ~ 5842).As can be seen here, nano-manganese dioxide and Graphene compound combine both excellent properties, and produce significant synergistic effect.We adopt carbon nanotube successfully the load of flap manganese dioxide nanocrystal to be got on as carrier, this material has the CV curve of obvious rectangular characteristic when being used as electrode of super capacitor, and has higher ratio capacitance value and good stable electrochemical property (CN 201010256458.5).Have not yet to see bibliographical information flap or bar-shaped manganese dioxide nanocrystal loaded on Graphene.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of Graphene and manganese dioxide nano-composite material, and the method reaction is simply easy to control, and easy to operate, technique is simple, is convenient to industrialization; Obtain matrix material and have broad application prospects, can be used for catalyzer, biological sensing material, the electrode materials of lithium ion battery and electrode material for super capacitor etc.
The preparation method of a kind of Graphene of the present invention and manganese dioxide nano-composite material, comprising:
(1) graphite, saltpetre, the vitriol oil are uniformly mixed in ice-water bath, adding with the mass ratio of graphite is the potassium permanganate of 1 ~ 5: 1, in 30 ~ 40 DEG C of reaction 20 ~ 40min, at room temperature adding with the volume mass ratio of graphite is the deionized water of 100 ~ 200ml: 1g, adding with the volume mass ratio of graphite after reacting 15 ~ 30min is again the hydrogen peroxide of 10 ~ 30ml: 1g, by extremely neutral through suction filtration, washing for the product obtained, obtained graphite oxide; Wherein, the vitriol oil is 20 ~ 40ml: 1g with the volume mass ratio of graphite, and the mass volume ratio of saltpetre and the vitriol oil is 20 ~ 50g: 1L;
(2) be scattered in by above-mentioned graphite oxide in water and obtain graphite oxide dispersion, adding with the volume mass ratio of graphite oxide is the hydrazine hydrate of 1 ~ 3ml: 1g, after 95 DEG C of reaction 1 ~ 24h, by product washing to neutral, obtains Graphene;
(3) by above-mentioned Graphene in mass ratio 10 ~ 30: 1 ultrasonic disperse in saturated potassium permanganate solution graphene dispersing solution, adding with the mol ratio of potassium permanganate is the acid of 2 ~ 5: 1, in 60 ~ 80 DEG C of ultrasonic wave added reaction 1 ~ 5h, by the product that obtains through suction filtration, washing until neutrality, vacuum-drying, obtains Graphene and manganese dioxide nano-composite material.
Vitriol oil mass percent in described step (1) is 98%.
Interpolation potassium permanganate mode in described step (1) for progressively to add in 20 ~ 50min.
In graphite oxide dispersion in described step (2), graphite oxide mass percent is 1 ~ 3%.
The solid content of the graphene dispersing solution in described step (3) is 2 ~ 5g/L.
Acid in described step (3) is concentrated hydrochloric acid or the vitriol oil.
Ultrasonic power in described step (3) is 150 ~ 1000W.
Graphene in described step (3) and manganese dioxide nano-composite material are flap or bar-shaped.
Vacuum-drying temperature in described step (3) is 80 ~ 120 DEG C, and the time is 12 ~ 24h.
By changing the ratio of Graphene and potassium permanganate, Manganse Dioxide and the graphene nanocomposite material of Manganse Dioxide different loads amount can be obtained.
beneficial effect
(1) preparation method of the present invention is simple and easy to operate, and the chemical species of needs is few and with low cost, and reaction is simply easy to control, and environmentally safe does not need expensive equipment, is suitable for suitability for industrialized production;
(2) flap or bar-shaped manganese dioxide nanocrystal have larger specific surface area, increase the conversion zone of active substance; The introducing of Graphene can serve as efficient carrier, improves the service efficiency of Manganse Dioxide and prevents from reuniting; When as electrode materials, greatly can reduce the internal resistance of electrode, electronics be shifted in the material smooth and easy, improve the performance of matrix material greatly;
(3) Graphene prepared of the present invention and manganese dioxide nano-composite material, this material has good application prospect in fields such as chemical industry catalysis, environmental improvement, bio-sensing and energy energy storage.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope figure that flap manganese dioxide nanocrystal loads on Graphene;
Fig. 2 is the field emission scanning electron microscope figure that bar-shaped manganese dioxide nanocrystal loads on Graphene;
Fig. 3 is the X-ray diffractogram of Graphene and manganese dioxide nano-composite material;
Fig. 4 is that Graphene and flap manganese dioxide nanocrystal combined electrode are at 1M Li 2sO 4the volt-ampere curve figure of the rectangular characteristic in solution, under the scanning speed of 1mV/s.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
First 1g graphite, 0.75g SODIUMNITRATE and 23ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 3g potassium permanganate; Then in the water-bath of 35 DEG C, 40min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 10ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.1ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 1h, add the saturated solution of 2.724g potassium permanganate, drip 3.1g hydrochloric acid, ultrasonic wave added reaction 3h at 70 DEG C; Products therefrom until neutral, at 80 DEG C of vacuum-drying 24h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is flap (see Fig. 1), and its crystalline structure is α type Manganse Dioxide (see Fig. 3), and its charge capacity is 50.8wt.%.
Embodiment 2
First 1g graphite, 0.75g SODIUMNITRATE and 23ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 3g potassium permanganate; Then in the water-bath of 35 DEG C, 20min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 10ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.2ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 2h, add the saturated solution of 1.816g potassium permanganate, drip 2.06g hydrochloric acid, ultrasonic wave added reaction 2h at 70 DEG C; Products therefrom until neutral, at 80 DEG C of vacuum-drying 24h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is flap, and its crystalline structure is α type Manganse Dioxide, and its charge capacity is 48.7wt.%.
Embodiment 3
First 1g graphite, 0.75g SODIUMNITRATE and 23ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 3g potassium permanganate; Then in the water-bath of 35 DEG C, 40min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 10ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.3ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 3h, add the saturated solution of 1.008g potassium permanganate, drip 1g hydrochloric acid, ultrasonic wave added reaction 4h at 70 DEG C; Products therefrom until neutral, at 80 DEG C of vacuum-drying 24h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is bar-shaped (see Fig. 2), and its crystalline structure is α type Manganse Dioxide, and its charge capacity is 42.9wt.%.
Embodiment 4
First 1g graphite, 0.9g SODIUMNITRATE and 27ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 4g potassium permanganate; Then in the water-bath of 35 DEG C, 40min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 10ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.1ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 1h, add the saturated solution of 2.724g potassium permanganate, drip 3.1g hydrochloric acid, ultrasonic wave added reaction 2h at 70 DEG C; Products therefrom until neutral, at 80 DEG C of vacuum-drying 24h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is flap, and its crystalline structure is α type Manganse Dioxide, and its charge capacity is 47.3wt.%.Take 0.5g matrix material, after fully levigate in ball mill, add acetylene black and 8% ptfe emulsion of 10%, be evenly coated in after being modulated into pasty state in nickel foam, first 80 DEG C of oven dry, then make electrode under 10MPa pressure; Be to electrode with Pt electrode, Ag/AgCl is reference electrode, 1M Li 2sO 4the aqueous solution is electrolytic solution, composition three-electrode system.This combined electrode, under 1mV/s scanning speed, shows the volt-ampere curve figure (see Fig. 4) of rectangular characteristic.The ratio capacitance value recorded under the scanning speed of 1mV/s is about 440F/g; Circulate after 1000 times under the scanning speed of 5mV/s, the decay of ratio capacitance value is no more than 10%.
Embodiment 5
First 1g graphite, 0.9g SODIUMNITRATE and 27ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 4g potassium permanganate; Then in the water-bath of 35 DEG C, 30min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 15ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.2ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 1h, add the saturated solution of 1.816g potassium permanganate, drip 2.06g hydrochloric acid, ultrasonic wave added reaction 5h at 70 DEG C; Products therefrom until neutral, at 120 DEG C of vacuum-drying 12h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is bar-shaped, and its crystalline structure is α type Manganse Dioxide, and its charge capacity is 45.5wt.%.Take 0.1g matrix material, measure the H of 10mL 30% 2o 2, join in the methylene blue dye solution of 100mL 10mg/L concentration successively, under constant speed stirs, carry out catalysis degeneration experiment, after 60min, the degradation rate of methylene blue is 63.5%.
Embodiment 6
First 1g graphite, 1g SODIUMNITRATE and 30ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 5g potassium permanganate; Then in the water-bath of 35 DEG C, 40min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 18ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.3ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 1h, add the saturated solution of 1.008g potassium permanganate, drip 1g hydrochloric acid, ultrasonic wave added reaction 3h at 70 DEG C; Products therefrom until neutral, at 80 DEG C of vacuum-drying 24h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is bar-shaped, and its crystalline structure is α type Manganse Dioxide, and its charge capacity is 40.7wt.%.Take 5g matrix material and 60mg oxygenant dioxide peroxide, be placed in the 100ml waste water containing staining agent naphthol green, the COD in waste water crfor 1481mg/L, after the catalyzed oxidation of 30min, record the COD in waste water crclearance reaches 71%, and percent of decolourization is 97%, and still remains good catalytic activity after recycling 9 times, COD crclearance still can reach 68%.
Embodiment 7
First 1g graphite, 1g SODIUMNITRATE and 30ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 5g potassium permanganate; Then in the water-bath of 35 DEG C, 40min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 18ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.1ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 3h, add the saturated solution of 2.724g potassium permanganate, drip 3.1g hydrochloric acid, ultrasonic wave added reaction 3h at 70 DEG C; Products therefrom until neutral, at 80 DEG C of vacuum-drying 24h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is flap, and its crystalline structure is α type Manganse Dioxide, and its charge capacity is 49.3wt.%.Take 0.5g matrix material, after fully levigate in ball mill, add acetylene black and 8% ptfe emulsion of 10%, be evenly coated in after being modulated into pasty state on Copper Foil as lithium ion battery negative material, under the current density of 100mAh/g, the reversible specific capacity obtained by charge-discharge test is 400mAh/g, and after 100 circulations, reversible specific capacity is 310mAh/g.
Embodiment 8
First 1g graphite, 1g SODIUMNITRATE and 40ml 98wt.% sulfuric acid are fully uniformly mixed in ice-water bath, in 0.5h, progressively add 5g potassium permanganate; Then in the water-bath of 35 DEG C, 40min is reacted; At room temperature add the deionized water and stirring 15min of 46ml again, finally add 140ml deionized water and 30ml hydrogen peroxide; Products therefrom until neutral, obtains graphite oxide through repeatedly filtering, washing.Be distributed in 50ml water by 0.1g graphite oxide, add the hydrazine hydrate of 0.2ml, reflux 1h in 95 DEG C of water-baths, and products therefrom until neutral, obtains Graphene through repeatedly filtering, washing.Again 0.1g Graphene is added in 50ml deionized water; After ultrasonic disperse 1h, add the saturated solution of 1.816g potassium permanganate, drip 2.06g hydrochloric acid, ultrasonic wave added reaction 4h at 70 DEG C; Products therefrom until neutral, at 80 DEG C of vacuum-drying 24h, obtains Graphene and manganese dioxide nano-composite material through repeatedly filtering, washing.Manganese dioxide nanocrystal prepared under this condition is bar-shaped, and its crystalline structure is α type Manganse Dioxide, and its charge capacity is 44.3wt.%.Take 0.5g matrix material and add 50ml 44mg/m 3formaldehyde solution in, sealing 12h after, the clearance recording formaldehyde is 87.2%.

Claims (8)

1. a preparation method for Graphene and manganese dioxide nano-composite material, comprising:
(1) graphite, saltpetre, the vitriol oil are uniformly mixed in ice-water bath, adding with the mass ratio of graphite is the potassium permanganate of 1 ~ 5:1, in 30 ~ 40 DEG C of reaction 20 ~ 40min, at room temperature add with the volume mass of graphite than the deionized water being 100 ~ 200ml:1g, add after reacting 15 ~ 30min again with the volume mass of graphite than the hydrogen peroxide being 10 ~ 30ml:1g, by extremely neutral through suction filtration, washing for the product obtained, obtained graphite oxide; Wherein, the vitriol oil is 20 ~ 40ml:1g with the volume mass ratio of graphite, and the mass volume ratio of saltpetre and the vitriol oil is 20 ~ 50g:1L;
(2) above-mentioned graphite oxide is scattered in water and obtains graphite oxide dispersion, add with the volume mass of graphite oxide than the hydrazine hydrate being 1 ~ 3ml:lg, in 95 DEG C of water-baths after back flow reaction 1 ~ 24h, by product washing to neutral, obtained Graphene;
(3) by above-mentioned Graphene in mass ratio 10 ~ 30:1 ultrasonic disperse in saturated potassium permanganate solution graphene dispersing solution, adding with the mol ratio of potassium permanganate is the acid of 2 ~ 5:1, in 60 ~ 80 DEG C of ultrasonic wave added reaction 1 ~ 5h, by the product that obtains through suction filtration, washing until neutrality, vacuum-drying, obtains Graphene and manganese dioxide nano-composite material; In Graphene and manganese dioxide nano-composite material, manganese dioxide nanocrystal is flap or bar-shaped.
2. the preparation method of a kind of Graphene according to claim 1 and manganese dioxide nano-composite material, is characterized in that: the vitriol oil mass percent in described step (1) is 98%.
3. the preparation method of a kind of Graphene according to claim 1 and manganese dioxide nano-composite material, is characterized in that: the interpolation potassium permanganate mode in described step (1) for progressively to add in 20 ~ 50min.
4. the preparation method of a kind of Graphene according to claim 1 and manganese dioxide nano-composite material, is characterized in that: in the graphite oxide dispersion in described step (2), graphite oxide mass percent is 1 ~ 3%.
5. the preparation method of a kind of Graphene according to claim 1 and manganese dioxide nano-composite material, is characterized in that: the solid content of the graphene dispersing solution in described step (3) is 2 ~ 5g/L.
6. the preparation method of a kind of Graphene according to claim 1 and manganese dioxide nano-composite material, is characterized in that: the acid in described step (3) is concentrated hydrochloric acid or the vitriol oil.
7. the preparation method of a kind of Graphene according to claim 1 and manganese dioxide nano-composite material, is characterized in that: the ultrasonic power in described step (3) is 150 ~ 1000W.
8. the preparation method of a kind of Graphene according to claim 1 and manganese dioxide nano-composite material, is characterized in that: the vacuum-drying temperature in described step (3) is 80 ~ 120 DEG C, and the time is 12 ~ 24h.
CN201110135866.XA 2011-05-24 2011-05-24 The preparation method of a kind of Graphene and manganese dioxide nano-composite material CN102275903B (en)

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