CN103950923B - A kind of novel method preparing high-quality Graphene - Google Patents
A kind of novel method preparing high-quality Graphene Download PDFInfo
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Abstract
The present invention relates to Graphene production field, particularly a kind of novel method preparing high-quality Graphene.The environment that it utilizes enclosed high pressure constant temperature to stir, allows nitration mixture (vitriol oil and strong phosphoric acid) and potassium permanganate even inflation graphite oxide raw material, then purify, ultrasonic, thermal reduction process obtains high-quality graphene powder.Compared with the Graphene that traditional chemical stripping legal system is standby, schedule of operation of the present invention is simple, consuming time few, with low cost, can obtain textural defect few, and conductivity is excellent, the graphene powder of few layer (less than 10 layers) high-quality.Meanwhile, this preparation method's reaction conditions gentleness is controlled, and energy consumption is low, cheaper starting materials, easily realizes scale operation.Its graphene powder prepared has fine application prospect in fields such as lithium ion battery, ultracapacitor, solar cells.
Description
(1) technical field
The present invention relates to Graphene production field, particularly a kind of novel method preparing high-quality Graphene.
(2) background technology
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the individual layer flat film that honeycomb lattice arrangement is formed, and only has the two-dimensional material of a carbon atom thickness, is the elementary cell building other dimension carbonaceous material (as zero dimension soccerballene, one dimension carbon nanotube and three-dimensional graphite).Graphene has excellent physical and chemical performance, and such as, under normal temperature, the electronic mobility of Graphene is more than 15000 cm
2/ Vs, than CNT (carbon nano-tube) or silicon wafer height; Its intensity reaches 130GPa, is more than 100 times of steel; Its thermal conductivity can reach 5300 W/mK, higher than carbon nanotube and diamond; Its resistivity only about 10
-6Ω cm, than copper or silver lower; The diamond of its hardness ratio Mohs' hardness 10 grades is also high; The theoretical value of the specific surface area of single-layer graphene reaches 2630 m
2/ g.At present, the potential application of Graphene widely, mainly be used in transparent conductive film, the field such as nano electron device (transistor, the interconnected memory semiconductor of transistor circuit), conductive ink, solar cell, lithium cell, ultracapacitor, sensor and biological medicine.
High-quality Graphene thin layer how is produced in the real challenge of current Graphene research, large-scale application can be carried out, mainly contain two aspects: one is the high-quality graphene preparing individual layer, large size, electric property excellence, for field of microelectronic devices, realize the preparation in macroscopic quantity of Graphene on the other hand.At present, the preparation method of Graphene mainly comprises micromechanics partition method, chemistry redox method, metallic surface chemical Vapor deposition process (CVD), silicon carbide epitaxial growth method and cutting carbon nanotubes method etc.Chemistry redox method is known as the method likely realizing scale operation at present.One of its typical chemistry redox method is exactly Hummers method, graphite is carried out temperature control intercalation oxide treatment, obtains graphite oxide, then carries out stripping to it and obtain graphene oxide, eventually passes reduction treatment and obtains Graphene.But this method also comes with some shortcomings, the stability as temperature control intercalation oxide treatment is difficult to control completely, and production cost is more high.Therefore, a kind ofly can to operate in a large number, easily in the urgent need to developing, low cost and the eco-friendly novel method preparing high-quality graphene.
(3) summary of the invention
The present invention in order to make up the defect of prior art, provide a kind of novelty, easily, fast, low cost, can the novel method of preparation high-quality Graphene of the few layer (less than 10 layers) of high-quality of scale operation.
The present invention is achieved through the following technical solutions:
Prepare a novel method for high-quality Graphene, it is characterized in that, carry out as follows:
1) oxide treatment: 1g natural graphite and magnetic agitation limit, 40 ~ 100ml nitration mixture limit are mixed in reactor, slowly add 3 ~ 8g potassium permanganate in temperature again lower than when 20 DEG C; Afterwards reactor is sealed, react 1 ~ 4 hour under 60 ~ 90 DEG C of temperature constant magnetic stirrings, take out and be cooled to room temperature; Then be diluted to 400mL solution, add 2 ~ 6mL hydrogen peroxide and obtain glassy yellow graphite oxide solution;
2) purification & isolation: adopt differential centrifugation mode, carry out pickling graphite oxide solution 2 ~ 4 times with the sulphuric acid soln that massfraction is 4.5 ~ 5.5%, by deionized water centrifuge washing graphite oxide solution 5 ~ 6 times, remove sulfate ion, pH is 6 ~ 7, obtains graphite oxide viscous fluid;
3) ultrasonic drying: mix with the organic solvent of 1 ~ 3 volume with the graphite oxide viscous fluid of 1 volume, put into ultrasonator, ultrasonic power 100 ~ 600W, sonic oscillation 1 ~ 2 hour, lyophilize obtains graphene oxide;
4) thermal reduction process: dried graphene oxide is put into tube furnace, first under air conditions, heated up with the temperature rise rate of 8 ~ 12 DEG C/min, 290 ~ 310 DEG C of insulations 2 ~ 5 minutes; Afterwards, under nitrogen protection, 1000 ~ 1050 DEG C of insulations 1 minute ~ 3 hours, be cooled to room temperature; Grind again, and use organic solvent ultrasonic disperse, dry to obtain graphene powder at 50 ~ 60 DEG C;
Described nitration mixture consists of: the volume ratio of the vitriol oil and strong phosphoric acid is 7:3 ~ 9:1;
Described organic solvent is one or more mixtures mixed with arbitrary proportion in alcohols, ketone and aldehydes.
In step 2) in, the rotating speed of pickling is 800 ~ 5000 revs/min, and the rotating speed of washing is 8000 ~ 12000 revs/min.
In step 4), the temperature rise rate under air conditions was 10 DEG C/min, 300 DEG C of insulations 3 minutes.
The invention has the beneficial effects as follows:
1, in the present invention, graphite oxidation process abandons the heating and oxidation Controlling Technology of complicated graphite intercalation compound, directly by graphite raw material airtight temperature constant magnetic stirring in reactor, simple to operate;
2, the oxidation expansion process in the present invention is liquid-phase chemical reaction, airtightly in reactor completes, and the degrees of expansion of graphite is high, and homogeneity is good, can ensure high yield and the homogeneity of subsequent products;
3, in the present invention, phosphoric acid has the effect of assisted oxidation and protection graphene film Rotating fields, farthest can retain the structure of Graphene and electricity and mechanical property.4, whole reaction process is very little on the impact of environment, and only containing a small amount of acid and manganic compound ion in waste liquid, processing cost is low.
4, the Graphene that prepared by the present invention is the few layer graphene powder of high-quality, and the sheet number of plies is 2 ~ 7 layers, lamella size more than 1 μm, and specific surface area is 390 ~ 560 m
2/ g, specific conductivity is 1700 ~ 7450 S/m;
5, to prepare the temperature of reaction of high-quality graphene powder low in the present invention, and schedule of operation is simple, expends time in short, is able to batch production, has the rosy prospect of heavy industrialization application.
(4) accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern (XRD) of graphene oxide (embodiment one, embodiment two and embodiment eight) prepared by the present invention;
Fig. 2 is the x-ray diffraction pattern (XRD) of Graphene (embodiment one, embodiment two and embodiment eight) prepared by the present invention;
Fig. 3 is the X-Ray Photoelectron spectrogram (XPS) of embodiment one graphene oxide C 1s peak position; Its C/O=2.06;
Fig. 4 is the X-Ray Photoelectron spectrogram (XPS) of embodiment one Graphene C 1s peak position; Its C/O=74.76;
Fig. 5 is the X-Ray Photoelectron spectrogram (XPS) of embodiment eight Graphene C 1s peak position; Its C/O=9.56;
Fig. 6 is atomic power (AFM) figure (a) and elevation carrection figure (b) of embodiment one graphene oxide; The thickness of its single-layer graphene oxide is 1.059 nm, lamella size about 1 μm;
Fig. 7 is atomic power (AFM) figure (a) and elevation carrection figure (b) of embodiment eight graphene oxide; The thickness of its single-layer graphene oxide is 1.080 nm, lamella size about 2 μm;
Fig. 8 is the transmission electron microscope picture (TEM) of embodiment one Graphene;
Fig. 9 is the transmission electron microscope picture (TEM) of embodiment eight Graphene.
(5) embodiment
Be below specific embodiments of the invention (organic solvent in following embodiment is one or more mixtures mixed with arbitrary proportion in alcohols, ketone and aldehydes):
Embodiment one:
1) oxide treatment: 1g natural graphite and the 40ml nitration mixture that is made up of the 28ml vitriol oil and 12ml strong phosphoric acid being mixed in stirs in reactor and by magnetic agitation (also can will be added in reactor by the vitriol oil and strong phosphoric acid respectively, lower same), in temperature lower than slowly adding 3g potassium permanganate when 20 DEG C again; Cover tightly reactor afterwards and make it sealing, put into the inherent 60 DEG C of constant temperature of thermostat container, react 4 hours under magnetic stirring, now produce high pressure in reactor, reactor is taken out and is cooled to room temperature; Then reaction solution is transferred in beaker and is diluted to 400mL solution, add 2mL hydrogen peroxide and obtain glassy yellow graphite oxide solution;
2) purification & isolation: under the condition of 800 revs/min is the sulphuric acid soln centrifuge washing graphite oxide solution 3 times of 4.5% with massfraction; Get upper liquid, wash centrifugal 5 ~ 6 times with the Water Under of 8000 revs/min, make sulfate radical-free ion in solution, pH is 6 ~ 7, obtains graphite oxide viscous fluid.
3) ultrasonic drying: mix with the organic solvent of 1 volume with the graphite oxide viscous fluid of 1 volume, put into ultrasonator, ultrasonic power 100W, sonic oscillation 1 hour, lyophilize obtains graphene oxide;
4) thermal reduction process: dried graphene oxide is put into tube furnace, first under air conditions, heated up with the temperature rise rate of 8 DEG C/min, 290 DEG C of insulations 2 minutes; Afterwards, under nitrogen protection, 1000 DEG C of insulations 1 minute, then be cooled to room temperature; Grind again, and use organic solvent ultrasonic disperse, dry to obtain graphene powder at 50 DEG C;
In the present embodiment gained graphene powder, the number of plies of Graphene is 3-7 layer, good crystallinity, and carbon-to-oxygen ratio is 74.76, specific surface area about 390.8 m
2/ g, specific conductivity about 3402 S/m.
Embodiment two:
1) oxide treatment: 1g natural graphite and the 60ml nitration mixture that is made up of the 48ml vitriol oil and 12ml strong phosphoric acid to be mixed in reactor and to stir by magnetic agitation, slowly adding 5g potassium permanganate in temperature again lower than when 20 DEG C; Cover tightly reactor afterwards and make it sealing, put into the inherent 75 DEG C of constant temperature of thermostat container, react 2.5 hours under magnetic stirring, now produce high pressure in reactor, reactor is taken out and is cooled to room temperature; Then reaction solution is transferred in beaker and is diluted to 400mL solution, add 4mL hydrogen peroxide and obtain glassy yellow graphite oxide solution;
2) purification & isolation: under the condition of 3000 revs/min is the sulphuric acid soln centrifuge washing graphite oxide solution 2 times of 5% with massfraction; Get upper liquid, wash centrifugal 5 ~ 6 times with the Water Under of 10000 revs/min, make sulfate radical-free ion in solution, pH is 6 ~ 7, obtains graphite oxide viscous fluid.
3) ultrasonic drying: mix with the organic solvent of 2 volumes with the graphite oxide viscous fluid of 1 volume, put into ultrasonator, ultrasonic power 400W, sonic oscillation 1.5 hours, lyophilize obtains graphene oxide;
4) thermal reduction process: dried graphene oxide is put into tube furnace, first under air conditions, heated up with the temperature rise rate of 10 DEG C/min, 300 DEG C of insulations 3 minutes; Afterwards, under nitrogen protection, 1020 DEG C of insulations 1 hour, then be cooled to room temperature; Grind again, and use organic solvent ultrasonic disperse, dry to obtain graphene powder at 55 DEG C;
In the present embodiment gained graphene powder, the number of plies of graphene film is 3 ~ 7 layers, good crystallinity, specific surface area about 440.9 m
2/ g, specific conductivity about 5631 S/m.
Embodiment three:
1) oxide treatment: 1g natural graphite and the 100ml nitration mixture that is made up of the 90ml vitriol oil and 10ml strong phosphoric acid to be mixed in reactor and to stir by magnetic agitation, slowly adding 3g potassium permanganate in temperature again lower than when 20 DEG C; Cover tightly reactor afterwards and make it sealing, put into the inherent 90 DEG C of constant temperature of thermostat container, react 1 hour under magnetic stirring, now produce high pressure in reactor, reactor is taken out and is cooled to room temperature; Then reaction solution is transferred in beaker and is diluted to 400mL solution, add 6mL hydrogen peroxide and obtain glassy yellow graphite oxide solution;
2) purification & isolation: under the condition of 5000 revs/min is the sulphuric acid soln centrifuge washing graphite oxide solution 4 times of 5% with massfraction; Get upper liquid, wash centrifugal 5 ~ 6 times with the Water Under of 12000 revs/min, make sulfate radical-free ion in solution, pH is 6 ~ 7, obtains graphite oxide viscous fluid.
3) ultrasonic drying: mix with the organic solvent of 3 volumes with the graphite oxide viscous fluid of 1 volume, put into ultrasonator, ultrasonic power 600W, sonic oscillation 2 hours, lyophilize obtains graphene oxide;
4) thermal reduction process: dried graphene oxide is put into tube furnace, first under air conditions, heated up with the temperature rise rate of 12 DEG C/min, 310 DEG C of insulations 5 minutes; Afterwards, under nitrogen protection, 1050 DEG C of insulations 3 hours, then be cooled to room temperature; Grind again, and use organic solvent ultrasonic disperse, dry to obtain graphene powder at 60 DEG C;
In the present embodiment gained graphene powder, the number of plies of Graphene is 2 ~ 4 layers, good crystallinity, specific surface area about 480.0 m
2/ g, specific conductivity about 4210 S/m.
Embodiment four:
1) oxide treatment: 1g natural graphite and the 60ml nitration mixture that is made up of the 54ml vitriol oil and 6ml strong phosphoric acid to be mixed in reactor and to stir by magnetic agitation, slowly adding 3g potassium permanganate in temperature again lower than when 20 DEG C; Cover tightly reactor afterwards and make it sealing, put into the inherent 80 DEG C of constant temperature of thermostat container, react 2 hours under magnetic stirring, now produce high pressure in reactor, reactor is taken out and is cooled to room temperature; Then reaction solution is transferred in beaker and is diluted to 400mL solution, add 3mL hydrogen peroxide and obtain glassy yellow graphite oxide solution;
2) purification & isolation: under the condition of 4000 revs/min is the sulphuric acid soln centrifuge washing graphite oxide solution 4 times of 5% with massfraction; Get upper liquid, wash centrifugal 5 ~ 6 times with the Water Under of 12000 revs/min, make sulfate radical-free ion in solution, pH is 6 ~ 7, obtains graphite oxide viscous fluid.
3) ultrasonic drying: mix with the organic solvent of 2 volumes with the graphite oxide viscous fluid of 1 volume, put into ultrasonator, ultrasonic power 500W, sonic oscillation 2 hours, lyophilize obtains graphene oxide;
4) thermal reduction process: dried graphene oxide is put into tube furnace, first under air conditions, heated up with the temperature rise rate of 10 DEG C/min, 300 DEG C of insulations 3 minutes; Afterwards, under nitrogen protection, 1050 DEG C of insulations 2 hours, then be cooled to room temperature; Grind again, and use organic solvent ultrasonic disperse, dry to obtain graphene powder at 60 DEG C;
In the present embodiment gained graphene powder, the number of plies of graphene film is 4 ~ 7 layers, good crystallinity, specific surface area about 561.6 m
2/ g, specific conductivity about 7450 S/m.
Embodiment five:
1) oxide treatment: 1g natural graphite and the 40ml nitration mixture that is made up of the 32ml vitriol oil and 8ml strong phosphoric acid to be mixed in reactor and to stir by magnetic agitation, slowly adding 8g potassium permanganate in temperature again lower than when 20 DEG C; Cover tightly reactor afterwards and make it sealing, put into the inherent 75 DEG C of constant temperature of thermostat container, react 3 hours under magnetic stirring, now produce high pressure in reactor, reactor is taken out and is cooled to room temperature; Then reaction solution is transferred in beaker and is diluted to 400mL solution, add 5mL hydrogen peroxide and obtain glassy yellow graphite oxide solution;
2) purification & isolation: under the condition of 4200 revs/min is the sulphuric acid soln centrifuge washing graphite oxide solution 3 times of 5% with massfraction; Get upper liquid, wash centrifugal 5 ~ 6 times with the Water Under of 11000 revs/min, make sulfate radical-free ion in solution, pH is 6 ~ 7, obtains graphite oxide viscous fluid.
3) ultrasonic drying: mix with the organic solvent of 2 volumes with the graphite oxide viscous fluid of 1 volume, put into ultrasonator, ultrasonic power 500W, sonic oscillation 3 hours, lyophilize obtains graphene oxide;
4) thermal reduction process: dried graphene oxide is put into tube furnace, first under air conditions, heated up with the temperature rise rate of 10 DEG C/min, 300 DEG C of insulations 3 minutes; Afterwards, under nitrogen protection, 1050 DEG C of insulations 3 hours, then be cooled to room temperature; Grind again, and use organic solvent ultrasonic disperse, dry to obtain graphene powder at 60 DEG C;
In the present embodiment gained graphene powder, the number of plies of Graphene is 2 ~ 4 layers, good crystallinity, specific surface area about 419.2 m
2/ g, specific conductivity about 1715 S/m.
Embodiment six:
Nitration mixture is 60ml, and be made up of the 42ml vitriol oil and 18ml strong phosphoric acid, other are with embodiment two.
In the present embodiment gained graphene powder, the number of plies of Graphene is 3 ~ 5 layers, good crystallinity, and C/O ratio is 9.56, specific surface area about 545.5 m
2/ g, specific conductivity about 4813 S/m.
Embodiment seven:
Nitration mixture is 40ml, and be made up of the 36ml vitriol oil and 4ml strong phosphoric acid, other are with embodiment one.
In the present embodiment gained graphene powder, the number of plies of Graphene is 3 ~ 5 layers, good crystallinity, specific surface area about 541.2 m
2/ g, specific conductivity about 4548 S/m.
Embodiment eight:
Nitration mixture is 100ml, and be made up of the 80ml vitriol oil and 20ml strong phosphoric acid, other are with embodiment three.
In the present embodiment gained graphene powder, the number of plies of Graphene is 3 ~ 7 layers, good crystallinity, specific surface area about 391.5 m
2/ g, specific conductivity about 3723 S/m.
Embodiment nine:
Nitration mixture is 100ml, and be made up of the 70ml vitriol oil and 30ml strong phosphoric acid, other are with embodiment three.
In the present embodiment gained graphene powder, the number of plies of Graphene is 3 ~ 7 layers, good crystallinity, specific surface area about 399 m
2/ g, specific conductivity about 3750 S/m.
Except technical characteristic described in specification sheets, all the other technical characteristics are those skilled in the art's known technology.
Claims (3)
1. prepare a novel method for high-quality Graphene, it is characterized in that, carry out as follows:
1) oxide treatment: 1g natural graphite and magnetic agitation limit, 40 ~ 100ml nitration mixture limit are mixed in reactor, slowly add 3 ~ 8g potassium permanganate in temperature again lower than when 20 DEG C; Afterwards reactor is sealed, react 1 ~ 4 hour under 60 ~ 90 DEG C of temperature constant magnetic stirrings, take out and be cooled to room temperature; Then be diluted to 400mL solution, add 2 ~ 6mL hydrogen peroxide and obtain glassy yellow graphite oxide solution;
2) purification & isolation: adopt differential centrifugation mode, carry out pickling graphite oxide solution 2 ~ 4 times with the sulphuric acid soln that massfraction is 4.5 ~ 5.5%, by deionized water centrifuge washing graphite oxide solution 5 ~ 6 times, remove sulfate ion, pH is 6 ~ 7, obtains graphite oxide viscous fluid;
3) ultrasonic drying: mix with the organic solvent of 1 ~ 3 volume with the graphite oxide viscous fluid of 1 volume, put into ultrasonator, ultrasonic power 100 ~ 600W, sonic oscillation 1 ~ 2 hour, lyophilize obtains graphene oxide;
4) thermal reduction process: dried graphene oxide is put into tube furnace, first under air conditions, heated up with the temperature rise rate of 8 ~ 12 DEG C/min, 290 ~ 310 DEG C of insulations 2 ~ 5 minutes; Afterwards, under nitrogen protection, 1000 ~ 1050 DEG C of insulations 1 minute ~ 3 hours, be cooled to room temperature; Grind again, and use organic solvent ultrasonic disperse, dry to obtain graphene powder at 50 ~ 60 DEG C;
Described nitration mixture consists of: the volume ratio of the vitriol oil and strong phosphoric acid is 7:3 ~ 9:1;
Described organic solvent is one or more mixtures mixed with arbitrary proportion in alcohols, ketone and aldehydes.
2. the novel method of preparation high-quality Graphene according to claim 1, is characterized in that, in step 2) in, the rotating speed of pickling is 800 ~ 5000 revs/min, and the rotating speed of washing is 8000 ~ 12000 revs/min.
3. the novel method of preparation high-quality Graphene according to claim 1 and 2, is characterized in that, in step 4), the temperature rise rate under air conditions is 10 DEG C/min, 300 DEG C of insulations 3 minutes.
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