CN102275903A - Preparation method of graphene and manganese dioxide composite material - Google Patents

Preparation method of graphene and manganese dioxide composite material Download PDF

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CN102275903A
CN102275903A CN201110135866XA CN201110135866A CN102275903A CN 102275903 A CN102275903 A CN 102275903A CN 201110135866X A CN201110135866X A CN 201110135866XA CN 201110135866 A CN201110135866 A CN 201110135866A CN 102275903 A CN102275903 A CN 102275903A
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graphene
manganese dioxide
composite
dioxide nano
graphite
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CN102275903B (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 invention relates to a preparation method of a graphene and manganese dioxide composite material. The preparation method comprises the following steps of: (1) stirring and uniformly mixing graphite, potassium nitrate and concentrated sulfuric acid, adding potassium permanganate, reacting for 20-40 min at a temperature of 30-40 DEG C, adding deionized water at the room temperature, reacting for 15-30min again, and then adding hydrogen peroxide to prepare graphite oxide; (2) dispersing the graphite oxide in water, adding hydrazine hydrate, and reacting for 1-24h at the temperature of 95 DEG C to obtain the graphene; and (3) ultrasonically dispersing the grasphene in a saturated potassium permanganate solution, adding acid, and reacting for 1-5 h at the temperature of 60-80 DEG C to obtain the graphene and manganese dioxide composite material. The preparation method has the advantages of simple reaction, easiness in control, convenience in operation and simple process; and the obtained composite material has a wide application prospect and can be applied to a catalytic agent, a biosensing material, an electrode material of a lithium ion battery, an electrode material of a super capacitor and the like.

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, the preparation method of particularly a kind of Graphene and manganese dioxide nano-composite material.
Background technology
Manganese bioxide material is because its diversity structure and unique physics-chem characteristic thereof, cheap in addition, environmental friendliness, 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 multi-functional meticulous inorganic functional material, be applicable as molecular sieve, advanced catalysts material etc.As a kind of both sexes transition metal oxide, in industrial production and environmental improvement, have a wide range of applications, as the absorption degradation of organic pollutant, handle heavy metal wastewater thereby aspects such as mercurous, cadmium, lead, chromium and metalloid arsenic stronger application prospect (CN 1935355A) is also arranged.Particularly nano level Manganse Dioxide has a lot of particular performances, key attitude as special microtexture and bigger specific surface area, surface is different with granule interior with electronic state, the surface atom coordination is incomplete, cause the surfactivity position to increase, along with reducing of particle diameter, smooth surface degree variation, form rough atomic steps, increased the contact surface of chemical reaction.Particularly its have good electrochemical, superior ion/electron conductivity make it very important application be arranged with relative high current potential in electrochemical field (CN 200410020888.1; CN 200510014876.2; CN200910049408.7; CN 201010123751.4; CN 201010039644.3).The method for preparing nano-manganese dioxide has varied, mainly contain hydrothermal synthesis method, low temperature solid-phase synthesis, organic-water two phase reaction method, coprecipitation method, reflux cooling, gel-sol method, microemulsion method and thermal decomposition method etc., especially to have the nanostructure of high-specific surface area be that (CN 02157737.4 for the important goal pursued of synthetic work to the Manganse Dioxide thin slice; CN200810200287.7; CN 200910139589.2; CN200910019398.2; CN 200910304513.0).But the product that most methods obtains different powder or the particulates that be pattern, size distribution is wide, and agglomeration is more serious.Nano-manganese dioxide deposit with use in can have serious agglomeration, make it can't give play to property and the advantage that exists with monodisperse status.As electrode materials the time, also exist independent use Manganse Dioxide and have the relatively poor and not high shortcoming of utilization ratio of electron conduction, nano-manganese dioxide and the carbon-based material that has than bigger serface are combined with each other, can further improve the active and stable of its, and (CN 200410041356.6 to bring into play both synergistic effect; CN 200610068772.4; CN 200710156155.4; CN 200910071880.0; CN200910071963.X).
The cellular lattice structure of bidimensional cycle that Graphene is made up of the carbon six-ring has excellent electroconductibility, and thermal conductivity and mechanical property etc. are a kind of ideal carrier (CN 101800302A; CN 101877405A; US 20100081057); The Graphene of usefulness Hydrothermal Preparation such as Chen Weixiang/Ru nano composite material has higher ratio electric capacity as electrode material for super capacitor, and when the content of Ru was 48.9%, the ratio electric capacity of matrix material reached 583F/g (CN 101714463A).Graphene also has good electrochemical stability, big specific surface area and wide electrochemical window, its distinctive laminate structure help electrolytic solution within it portion spread rapidly, realize high-power the discharging and recharging of electronic component instantaneous time, these characteristics make it 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. go out silicon/carbon/graphite in lithium ion batteries alkene nanometer sheet-cobaltous hydroxide composite negative pole material by Hydrothermal Preparation, and when the electric current of 200mA/g discharged and recharged, the reversible specific capacity of matrix material can be stabilized in 900mAh/g above (CN 101867046A).Nearest Yan etc. utilizes microwave irradiation to prepare Graphene/amorphous manganese dioxide composite material, electrode materials superior performance as the ultracapacitor of high-speed sweep, ratio electric capacity when 2mV/s is up to 310F/g, and still (Carbon 2010 up to 228F/g for the ratio electric capacity when 500mV/s; 48:3825~3833).Wu etc. prepare Graphene/manganese dioxide nano line matrix material, and are assembled into the electrochemical capacitor of excellent performance as positive electrode material, at 7.0Wh kg -1The time power density up to 5000Wkg -1, be 21% (ACS NANO 2010 than capacitance fade through 1000 circulation backs; 4:5835~5842).This shows, the compound excellent properties that combines both of nano-manganese dioxide and Graphene, 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 specific capacitance and good electrochemical stability (CN 201010256458.5).Have not yet to see flap or bar-shaped manganese dioxide nanocrystal are loaded to bibliographical information on the Graphene.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of Graphene and manganese dioxide nano-composite material, and the reaction of this method simply is easy to control, and is easy to operate, technology is simple, is convenient to industrialization; The matrix material that obtains has broad application prospects, and 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 comprises:
(1) graphite, saltpetre, the vitriol oil are mixed in ice-water bath, the mass ratio of adding and graphite is 1~5: 1 potassium permanganate, in 30~40 ℃ of reaction 20~40min, the volume mass ratio that at room temperature adds with graphite is the deionized water of 100~200ml: 1g, reacting the volume mass ratio that adds behind 15~30min with graphite again is the hydrogen peroxide of 10~30ml: 1g, the product that obtains is extremely neutral through suction filtration, washing, make graphite oxide; Wherein, the vitriol oil is 20~40ml: 1g with the volume mass ratio of graphite, and the mass volume ratio of the saltpetre and the vitriol oil is 20~50g: 1L;
(2) above-mentioned graphite oxide is scattered in the water the graphite oxide dispersion liquid, the volume mass ratio that adds with graphite oxide is the hydrazine hydrate of 1~3ml: 1g, behind 95 ℃ of reaction 1~24h, the product washing to neutral, is made Graphene;
(3) above-mentioned Graphene is pressed mass ratio 10~30: 1 ultra-sonic dispersion gets the Graphene dispersion liquid in saturated potassium permanganate solution, the mol ratio of adding and potassium permanganate is 2~5: 1 acid, in 60~80 ℃ of ultrasonic assisted reaction 1~5h, with the product that obtains through suction filtration, washing until neutrality, vacuum-drying promptly gets Graphene and manganese dioxide nano-composite material.
Vitriol oil mass percent in the described step (1) is 98%.
Interpolation potassium permanganate mode in the described step (1) is progressively to add in 20~50min.
The graphite oxide mass percent is 1~3% in the graphite oxide dispersion liquid in the described step (2).
The solid content of the Graphene dispersion liquid in the described step (3) is 2~5g/L.
Acid in the described step (3) is the concentrated hydrochloric acid or the vitriol oil.
Ultrasonic power in the described step (3) is 150~1000W.
Graphene and manganese dioxide nano-composite material in the described step (3) are flap or bar-shaped.
Vacuum-drying temperature in the described step (3) is 80~120 ℃, and the time is 12~24h.
By changing the ratio of Graphene and potassium permanganate, can obtain the Manganse Dioxide and the graphene nano matrix material of Manganse Dioxide different loads amount.
Beneficial effect
(1) preparation method of the present invention is simple and easy to operate, and the pharmaceutical chemicals kind that needs is few and with low cost, and reaction simply is 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 bigger specific surface area, increase the conversion zone of active substance; The introducing of Graphene can be served as carrier efficiently, improves the service efficiency of Manganse Dioxide and prevents and reunite; As electrode materials the time, can reduce the internal resistance of electrode greatly, it is smooth and easy to make that electronics shifts in material, has improved performance of composites greatly;
(3) Graphene and the manganese dioxide nano-composite material of the present invention's preparation, this material has good prospects for application in fields such as chemical industry catalysis, environmental improvement, bio-sensing and energy energy storage.
Description of drawings
Fig. 1 loads to field emission scanning electron microscope figure on the Graphene for the flap manganese dioxide nanocrystal;
Fig. 2 is that bar-shaped manganese dioxide nanocrystal loads to the field emission scanning electron microscope figure on the 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 the solution, under the scanning speed of 1mV/s.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Earlier 1g graphite, 0.75g SODIUMNITRATE and 23ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 3g potassium permanganate; In 35 ℃ water-bath, react 40min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 10ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.1ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 1h, add the saturated solution of 2.724g potassium permanganate, drip 3.1g hydrochloric acid, ultrasonic assisted reaction 3h under 70 ℃; Products therefrom at 80 ℃ of vacuum-drying 24h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Prepared manganese dioxide nanocrystal is the flap (see figure 1) under this condition, and its crystalline structure is a α type Manganse Dioxide (see figure 3), and its charge capacity is 50.8wt.%.
Embodiment 2
Earlier 1g graphite, 0.75g SODIUMNITRATE and 23ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 3g potassium permanganate; In 35 ℃ water-bath, react 20min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 10ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.2ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 2h, add the saturated solution of 1.816g potassium permanganate, drip 2.06g hydrochloric acid, ultrasonic assisted reaction 2h under 70 ℃; Products therefrom at 80 ℃ of vacuum-drying 24h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Manganese dioxide nanocrystal prepared under this condition is flap, and its crystalline structure is a α type Manganse Dioxide, and its charge capacity is 48.7wt.%.
Embodiment 3
Earlier 1g graphite, 0.75g SODIUMNITRATE and 23ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 3g potassium permanganate; In 35 ℃ water-bath, react 40min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 10ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.3ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 3h, add the saturated solution of 1.008g potassium permanganate, drip 1g hydrochloric acid, ultrasonic assisted reaction 4h under 70 ℃; Products therefrom at 80 ℃ of vacuum-drying 24h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Prepared manganese dioxide nanocrystal is bar-shaped (see figure 2) under this condition, and its crystalline structure is a α type Manganse Dioxide, and its charge capacity is 42.9wt.%.
Embodiment 4
Earlier 1g graphite, 0.9g SODIUMNITRATE and 27ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 4g potassium permanganate; In 35 ℃ water-bath, react 40min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 10ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.1ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 1h, add the saturated solution of 2.724g potassium permanganate, drip 3.1g hydrochloric acid, ultrasonic assisted reaction 2h under 70 ℃; Products therefrom at 80 ℃ of vacuum-drying 24h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Manganese dioxide nanocrystal prepared under this condition is flap, and its crystalline structure is a α type Manganse Dioxide, and its charge capacity is 47.3wt.%.Take by weighing the 0.5g matrix material, in ball mill fully levigate after, add 10% acetylene black and 8% ptfe emulsion, be evenly coated on the nickel foam after being modulated into pasty state, earlier 80 ℃ of oven dry, under 10MPa pressure, make electrode again; With the Pt electrode is counter electrode, and Ag/AgCl is a reference electrode, 1M Li 2SO 4The aqueous solution is electrolytic solution, forms three-electrode system.This combined electrode shows the volt-ampere curve figure (see figure 4) of rectangular characteristic under the 1mV/s scanning speed.The ratio capacitance that records under the scanning speed of 1mV/s is about 440F/g; After circulation under the scanning speed of 5mV/s 1000 times, be no more than 10% than the decay of capacitance.
Embodiment 5
Earlier 1g graphite, 0.9g SODIUMNITRATE and 27ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 4g potassium permanganate; In 35 ℃ water-bath, react 30min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 15ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.2ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 1h, add the saturated solution of 1.816g potassium permanganate, drip 2.06g hydrochloric acid, ultrasonic assisted reaction 5h under 70 ℃; Products therefrom at 120 ℃ of vacuum-drying 12h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Prepared manganese dioxide nanocrystal is bar-shaped under this condition, and its crystalline structure is a α type Manganse Dioxide, and its charge capacity is 45.5wt.%.Take by weighing the 0.1g matrix material, measure the H of 10mL 30% 2O 2, join successively in the methylene blue dye solution of 100mL 10mg/L concentration, under stirring, constant speed carries out the catalyzed degradation experiment, and behind 60min, the degradation rate of methylene blue is 63.5%.
Embodiment 6
Earlier 1g graphite, 1g SODIUMNITRATE and 30ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 5g potassium permanganate; In 35 ℃ water-bath, react 40min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 18ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.3ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 1h, add the saturated solution of 1.008g potassium permanganate, drip 1g hydrochloric acid, ultrasonic assisted reaction 3h under 70 ℃; Products therefrom at 80 ℃ of vacuum-drying 24h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Prepared manganese dioxide nanocrystal is bar-shaped under this condition, and its crystalline structure is a α type Manganse Dioxide, and its charge capacity is 40.7wt.%.Take by weighing 5g matrix material and 60mg oxygenant dioxide peroxide, place the 100ml waste water that contains the staining agent naphthol green, the COD in the waste water CrBe 1481mg/L, behind the catalyzed oxidation of 30min, record the COD in the waste water CrClearance reaches 71%, and percent of decolourization is 97%, and recycles and still keeping good catalytic activity, COD after 9 times CrClearance still can reach 68%.
Embodiment 7
Earlier 1g graphite, 1g SODIUMNITRATE and 30ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 5g potassium permanganate; In 35 ℃ water-bath, react 40min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 18ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.1ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 3h, add the saturated solution of 2.724g potassium permanganate, drip 3.1g hydrochloric acid, ultrasonic assisted reaction 3h under 70 ℃; Products therefrom at 80 ℃ of vacuum-drying 24h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Manganese dioxide nanocrystal prepared under this condition is flap, and its crystalline structure is a α type Manganse Dioxide, and its charge capacity is 49.3wt.%.Take by weighing the 0.5g matrix material, in ball mill fully levigate after, the acetylene black and 8% ptfe emulsion of adding 10%, be evenly coated on the Copper Foil as lithium ion battery negative material after being modulated into pasty state, under the current density of 100mAh/g, the reversible specific capacity that obtains by charge-discharge test is 400mAh/g, and 100 times circulation back reversible specific capacity is 310mAh/g.
Embodiment 8
Earlier 1g graphite, 1g SODIUMNITRATE and 40ml 98wt.% sulfuric acid are fully mixed in ice-water bath, in 0.5h, progressively add 5g potassium permanganate; In 35 ℃ water-bath, react 40min then; The deionized water and stirring 15min that at room temperature adds 46ml again adds 140ml deionized water and 30ml hydrogen peroxide at last; Products therefrom obtains graphite oxide through filtering repeatedly, wash until neutrality.The 0.1g graphite oxide is distributed in the 50ml water, adds the hydrazine hydrate of 0.2ml, the 1h that in 95 ℃ of water-baths, refluxes, products therefrom obtains Graphene through filtering repeatedly, wash until neutrality.Again the 0.1g Graphene is added in the 50ml deionized water; Behind the ultra-sonic dispersion 1h, add the saturated solution of 1.816g potassium permanganate, drip 2.06g hydrochloric acid, ultrasonic assisted reaction 4h under 70 ℃; Products therefrom at 80 ℃ of vacuum-drying 24h, promptly gets Graphene and manganese dioxide nano-composite material through filtering repeatedly, wash until neutrality.Prepared manganese dioxide nanocrystal is bar-shaped under this condition, and its crystalline structure is a α type Manganse Dioxide, and its charge capacity is 44.3wt.%.Take by weighing the 0.5g matrix material and add 50ml 44mg/m 3Formaldehyde solution in, the sealing 12h after, the clearance that records formaldehyde is 87.2%.

Claims (9)

1. the preparation method of Graphene and manganese dioxide nano-composite material comprises:
(1) graphite, saltpetre, the vitriol oil are mixed in ice-water bath, the mass ratio of adding and graphite is 1~5: 1 potassium permanganate, in 30~40 ℃ of reaction 20~40min, the volume mass ratio that at room temperature adds with graphite is the deionized water of 100~200ml: 1g, reacting the volume mass ratio that adds behind 15~30min with graphite again is the hydrogen peroxide of 10~30ml: 1g, the product that obtains is extremely neutral through suction filtration, washing, make graphite oxide; Wherein, the vitriol oil is 20~40ml: 1g with the volume mass ratio of graphite, and the mass volume ratio of the saltpetre and the vitriol oil is 20~50g: 1L;
(2) above-mentioned graphite oxide is scattered in the water the graphite oxide dispersion liquid, the volume mass ratio that adds with graphite oxide is the hydrazine hydrate of 1~3ml: 1g, behind 95 ℃ of reaction 1~24h, the product washing to neutral, is made Graphene;
(3) above-mentioned Graphene is pressed mass ratio 10~30: 1 ultra-sonic dispersion gets the Graphene dispersion liquid in saturated potassium permanganate solution, the mol ratio of adding and potassium permanganate is 2~5: 1 acid, in 60~80 ℃ of ultrasonic assisted reaction 1~5h, with the product that obtains through suction filtration, washing until neutrality, vacuum-drying promptly gets Graphene and manganese dioxide nano-composite material.
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 the 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 the described step (1) is for progressively adding 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: the graphite oxide mass percent is 1~3% in the graphite oxide dispersion liquid in the described step (2).
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 dispersion liquid in the 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 the described step (3) is the 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 the 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: Graphene and manganese dioxide nano-composite material in the described step (3) are flap or bar-shaped.
9. 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 the described step (3) is 80~120 ℃, and the time is 12~24h.
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