CN103950923A - New method for preparing high-quality graphene - Google Patents
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Abstract
The invention relates to the field of graphene production, and in particular relates to a new method for preparing high-quality graphene. The method comprises the following steps: in a sealed high-pressure and constant-temperature stirring environment, enabling mixed acid (concentrated sulfuric acid and concentrated phosphoric acid) and potassium permanganate to uniformly expand a graphite oxide raw material, and then performing purification, ultrasound treatment and thermal reduction treatment to obtain high-quality graphene powder. Compared with graphene prepared by using a conventional chemical stripping method, the new method disclosed by the invention is simple in operation procedure, less in time consumption and low in cost, and can be used for obtaining the high-quality graphene powder with less structural defects, excellent electrical conductivity and fewer layers (less than 10 layers). Meanwhile, the preparation method is mild and controllable in reaction condition, low in energy consumption, cheap in raw material and easy in implementation of large-scale production. The prepared graphene powder has bright application prospects in the fields of lithium ion batteries, super-capacitors, solar batteries and the like.
Description
(1) technical field
The present invention relates to Graphene production field, particularly a kind of novel method of preparing high-quality Graphene.
(2) background technology
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital forms hexangle type and is the individual layer flat film that honeycomb lattice arrangement forms, and only has the two-dimensional material of a carbon atom thickness, is the elementary cell that builds other dimension carbonaceous material (as zero dimension soccerballene, one dimension carbon nanotube and three-dimensional graphite).Graphene has excellent physical and chemical performance, and for example, under normal temperature, the electronic mobility of Graphene surpasses 15000 cm
2/ Vs, ratio nano carbon pipe 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 approximately 10
-6Ω cm is lower than copper or silver; The diamond that its hardness ratio Mohs' hardness is 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 is very extensive, mainly be used in transparent conductive film, the fields such as nano electron device (transistor, the interconnected internal memory semi-conductor of transistor circuit), conductive ink, solar cell, lithium cell, ultracapacitor, sensor and biological medicine.
The real challenge of current Graphene research is how to produce high-quality Graphene thin layer, can carry out large-scale application, mainly contain two aspects: the one, prepare the high-quality graphene of individual layer, large size, electric property excellence, for field of microelectronic devices, realize on the other hand the preparation in macroscopic quantity of Graphene.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 to be known as at present the method that likely realizes scale operation.One of its typical chemistry redox method is exactly Hummers method, and graphite is carried out to temperature control intercalation oxide treatment, obtains graphite oxide, then it is peeled off and obtains graphene oxide, finally by crossing reduction processing, obtains Graphene.But this method also comes with some shortcomings, as the stability of temperature control intercalation oxide treatment is difficult to control completely, production cost is more high.Therefore, in the urgent need to develop a kind of can be in a large number, easily operation, the low-cost and eco-friendly novel method of preparing high-quality graphene.
(3) summary of the invention
The present invention is in order to make up the defect of prior art, provide a kind of novelty, easily, fast, cheaply, the novel method of the preparation high-quality Graphene of the few layer of high-quality (10 layers following) that can scale operation.
The present invention is achieved through the following technical solutions:
A novel method of preparing high-quality Graphene, is characterized in that, carries out as follows:
1) oxide treatment: 1g natural graphite and magnetic agitation limit, 40～100ml nitration mixture limit are mixed in reactor, slowly add again 3～8g potassium permanganate in temperature lower than 20 ℃ in the situation that; By reactor sealing, under 60～90 ℃ of temperature constant magnetic stirrings, react 1～4 hour afterwards, take out and be cooled to room temperature; Then be diluted to 400mL solution, add 2～6mL hydrogen peroxide to obtain glassy yellow graphite oxide solution;
2) purification is separated: adopt differential centrifugation mode, the sulphuric acid soln that is 4.5～5.5% with massfraction carries out pickling graphite oxide solution 2～4 times, uses deionized water centrifuge washing graphite oxide solution 5～6 times, removes sulfate ion, pH is 6～7, obtains graphite oxide viscous fluid;
3) ultrasonic dry: with the graphite oxide viscous fluid of 1 volume, mix with the organic solvent of 1～3 volume, put into ultrasonator, ultrasonic power is 100～600W approximately, sonic oscillation 1～2 hour, lyophilize obtains graphene oxide;
4) thermal reduction is processed: dried graphene oxide is put into tube furnace, first, under air conditions, with the temperature rise rates of 8～12 ℃/min, heat up, 290～310 ℃ of insulations 2～5 minutes; Afterwards, under nitrogen protection, 1000～1050 ℃ of insulations 1 minute～3 hours, be cooled to room temperature; Grind again, and with the ultrasonic dispersion of organic solvent, at 50～60 ℃, dry to obtain graphene powder;
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 that mix with arbitrary proportion in alcohols, ketone and aldehydes.
In step 2) in, the rotating speed of pickling is 800～5000 revs/min, the rotating speed of washing is 8000～12000 revs/min.
In step 4), temperature rise rate was 10 ℃/min, 300 ℃ of insulations 3 minutes.
The invention has the beneficial effects as follows:
1, in the present invention, graphite oxidation process has been abandoned the intensification oxidation control technique 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, airtight completing in reactor, and the degrees of expansion of graphite is high, and homogeneity is good, can guarantee high yield and the homogeneity of subsequent products;
3, in the present invention, phosphoric acid has the effect of assisted oxidation and protection graphene sheet layer structure, can farthest retain structure and electricity and the mechanical property of Graphene.4, whole reaction process is very little on the impact of environment, only contains a small amount of acid and manganic compound ion in waste liquid, and 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, and more than lamella size 1 μ m, 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, can mass production, there is the rosy prospect of heavy industrialization application.
(4) accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern (XRD) of the graphene oxide (embodiment one, embodiment two and embodiment eight) prepared of the present invention;
Fig. 2 is the x-ray diffraction pattern (XRD) of the Graphene (embodiment one, embodiment two and embodiment eight) prepared of the present invention;
Fig. 3 is the sub-spectrogram of X-ray photoelectric (XPS) of embodiment one graphene oxide C 1s peak position; Its C/O=2.06;
Fig. 4 is the sub-spectrogram of X-ray photoelectric (XPS) of embodiment one Graphene C 1s peak position; Its C/O=74.76;
Fig. 5 is the sub-spectrogram of X-ray photoelectric (XPS) of embodiment eight Graphene C 1s peak positions; Its C/O=9.56;
Fig. 6 is atomic power (AFM) figure (a) and the height survey sheet (b) of embodiment one graphene oxide; The thickness of its mono-layer graphite oxide alkene is 1.059 nm, lamella size approximately 1 μ m;
Fig. 7 is atomic power (AFM) figure (a) and the height survey sheet (b) of embodiment eight graphene oxides; The thickness of its mono-layer graphite oxide alkene is 1.080 nm, lamella size approximately 2 μ m;
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 Graphenes.
(5) embodiment
Be below specific embodiments of the invention (organic solvent in following embodiment is one or more mixtures that mix with arbitrary proportion in alcohols, ketone and aldehydes):
Embodiment mono-:
1) oxide treatment: 1g natural graphite and the 40ml nitration mixture that is comprised of the 28ml vitriol oil and 12ml strong phosphoric acid are mixed in reactor and by magnetic agitation and stir and (also can will respectively the vitriol oil and strong phosphoric acid be added in reactor, lower with), in temperature, slowly add again 3g potassium permanganate lower than 20 ℃ in the situation that; Cover tightly afterwards reactor and make it sealing, put into the inherent 60 ℃ of constant temperature of thermostat container, under magnetic agitation, react 4 hours, now in reactor, produce high pressure, 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 to obtain glassy yellow graphite oxide solution;
2) purification is separated: under the condition of 800 revs/min, and the sulphuric acid soln centrifuge washing graphite oxide solution that is 4.5% with massfraction 3 times; Get upper strata liquid, with the Water Under of 8000 revs/min, wash centrifugal 5～6 times, make sulfate radical-free ion in solution, pH is 6～7, obtains graphite oxide viscous fluid.
3) ultrasonic dry: with the graphite oxide viscous fluid of 1 volume, mix with the organic solvent of 1 volume, put into ultrasonator, the about 100W of ultrasonic power, sonic oscillation 1 hour, lyophilize obtains graphene oxide;
4) thermal reduction is processed: dried graphene oxide is put into tube furnace, first, under air conditions, with the temperature rise rates of 8 ℃/min, heat up, 290 ℃ of insulations 2 minutes; Afterwards, under nitrogen protection, 1000 ℃ of insulations 1 minute, then be cooled to room temperature; Grind again, and with the ultrasonic dispersion of organic solvent, at 50 ℃, dry to obtain graphene powder;
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 approximately 390.8 m
2/ g, specific conductivity approximately 3402 S/m.
Embodiment bis-:
1) oxide treatment: 1g natural graphite and the 60ml nitration mixture that is comprised of the 48ml vitriol oil and 12ml strong phosphoric acid are mixed in reactor and by magnetic agitation and are stirred, slowly add again 5g potassium permanganate in temperature lower than 20 ℃ in the situation that; Cover tightly afterwards reactor and make it sealing, put into the inherent 75 ℃ of constant temperature of thermostat container, under magnetic agitation, react 2.5 hours, now in reactor, produce high pressure, 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 to obtain glassy yellow graphite oxide solution;
2) purification is separated: under the condition of 3000 revs/min, and the sulphuric acid soln centrifuge washing graphite oxide solution that is 5% with massfraction 2 times; Get upper strata liquid, with the Water Under of 10000 revs/min, wash centrifugal 5～6 times, make sulfate radical-free ion in solution, pH is 6～7, obtains graphite oxide viscous fluid.
3) ultrasonic dry: with the graphite oxide viscous fluid of 1 volume, mix with the organic solvent of 2 volumes, put into ultrasonator, the about 400W of ultrasonic power, sonic oscillation 1.5 hours, lyophilize obtains graphene oxide;
4) thermal reduction is processed: dried graphene oxide is put into tube furnace, first, under air conditions, with the temperature rise rates of 10 ℃/min, heat up, 300 ℃ of insulations 3 minutes; Afterwards, under nitrogen protection, 1020 ℃ of insulations 1 hour, then be cooled to room temperature; Grind again, and with the ultrasonic dispersion of organic solvent, at 55 ℃, dry to obtain graphene powder;
In the present embodiment gained graphene powder, the number of plies of graphene film is 3～7 layers, good crystallinity, specific surface area approximately 440.9 m
2/ g, specific conductivity approximately 5631 S/m.
Embodiment tri-:
1) oxide treatment: 1g natural graphite and the 100ml nitration mixture that is comprised of the 90ml vitriol oil and 10ml strong phosphoric acid are mixed in reactor and by magnetic agitation and are stirred, slowly add again 3g potassium permanganate in temperature lower than 20 ℃ in the situation that; Cover tightly afterwards reactor and make it sealing, put into the inherent 90 ℃ of constant temperature of thermostat container, under magnetic agitation, react 1 hour, now in reactor, produce high pressure, 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 to obtain glassy yellow graphite oxide solution;
2) purification is separated: under the condition of 5000 revs/min, and the sulphuric acid soln centrifuge washing graphite oxide solution that is 5% with massfraction 4 times; Get upper strata liquid, with the Water Under of 12000 revs/min, wash centrifugal 5～6 times, make sulfate radical-free ion in solution, pH is 6～7, obtains graphite oxide viscous fluid.
3) ultrasonic dry: with the graphite oxide viscous fluid of 1 volume, mix with the organic solvent of 3 volumes, put into ultrasonator, the about 600W of ultrasonic power, sonic oscillation 2 hours, lyophilize obtains graphene oxide;
4) thermal reduction is processed: dried graphene oxide is put into tube furnace, first, under air conditions, with the temperature rise rates of 12 ℃/min, heat up, 310 ℃ of insulations 5 minutes; Afterwards, under nitrogen protection, 1050 ℃ of insulations 3 hours, then be cooled to room temperature; Grind again, and with the ultrasonic dispersion of organic solvent, at 60 ℃, dry to obtain graphene powder;
In the present embodiment gained graphene powder, the number of plies of Graphene is 2～4 layers, good crystallinity, specific surface area approximately 480.0 m
2/ g, specific conductivity approximately 4210 S/m.
Embodiment tetra-:
1) oxide treatment: 1g natural graphite and the 60ml nitration mixture that is comprised of the 54ml vitriol oil and 6ml strong phosphoric acid are mixed in reactor and by magnetic agitation and are stirred, slowly add again 3g potassium permanganate in temperature lower than 20 ℃ in the situation that; Cover tightly afterwards reactor and make it sealing, put into the inherent 80 ℃ of constant temperature of thermostat container, under magnetic agitation, react 2 hours, now in reactor, produce high pressure, 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 to obtain glassy yellow graphite oxide solution;
2) purification is separated: under the condition of 4000 revs/min, and the sulphuric acid soln centrifuge washing graphite oxide solution that is 5% with massfraction 4 times; Get upper strata liquid, with the Water Under of 12000 revs/min, wash centrifugal 5～6 times, make sulfate radical-free ion in solution, pH is 6～7, obtains graphite oxide viscous fluid.
3) ultrasonic dry: with the graphite oxide viscous fluid of 1 volume, mix with the organic solvent of 2 volumes, put into ultrasonator, the about 500W of ultrasonic power, sonic oscillation 2 hours, lyophilize obtains graphene oxide;
4) thermal reduction is processed: dried graphene oxide is put into tube furnace, first, under air conditions, with the temperature rise rates of 10 ℃/min, heat up, 300 ℃ of insulations 3 minutes; Afterwards, under nitrogen protection, 1050 ℃ of insulations 2 hours, then be cooled to room temperature; Grind again, and with the ultrasonic dispersion of organic solvent, at 60 ℃, dry to obtain graphene powder;
In the present embodiment gained graphene powder, the number of plies of graphene film is 4～7 layers, good crystallinity, specific surface area approximately 561.6 m
2/ g, specific conductivity approximately 7450 S/m.
Embodiment five:
1) oxide treatment: 1g natural graphite and the 40ml nitration mixture that is comprised of the 32ml vitriol oil and 8ml strong phosphoric acid are mixed in reactor and by magnetic agitation and are stirred, slowly add again 8g potassium permanganate in temperature lower than 20 ℃ in the situation that; Cover tightly afterwards reactor and make it sealing, put into the inherent 75 ℃ of constant temperature of thermostat container, under magnetic agitation, react 3 hours, now in reactor, produce high pressure, 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 to obtain glassy yellow graphite oxide solution;
2) purification is separated: under the condition of 4200 revs/min, and the sulphuric acid soln centrifuge washing graphite oxide solution that is 5% with massfraction 3 times; Get upper strata liquid, with the Water Under of 11000 revs/min, wash centrifugal 5～6 times, make sulfate radical-free ion in solution, pH is 6～7, obtains graphite oxide viscous fluid.
3) ultrasonic dry: with the graphite oxide viscous fluid of 1 volume, mix with the organic solvent of 2 volumes, put into ultrasonator, the about 500W of ultrasonic power, sonic oscillation 3 hours, lyophilize obtains graphene oxide;
4) thermal reduction is processed: dried graphene oxide is put into tube furnace, first, under air conditions, with the temperature rise rates of 10 ℃/min, heat up, 300 ℃ of insulations 3 minutes; Afterwards, under nitrogen protection, 1050 ℃ of insulations 3 hours, then be cooled to room temperature; Grind again, and with the ultrasonic dispersion of organic solvent, at 60 ℃, dry to obtain graphene powder;
In the present embodiment gained graphene powder, the number of plies of Graphene is 2～4 layers, good crystallinity, specific surface area approximately 419.2 m
2/ g, specific conductivity approximately 1715 S/m.
Embodiment six:
Nitration mixture is 60ml, the 42ml vitriol oil and 18ml strong phosphoric acid, consists of, and other are with embodiment bis-.
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 approximately 545.5 m
2/ g, specific conductivity approximately 4813 S/m.
Embodiment seven:
Nitration mixture is 40ml, the 36ml vitriol oil and 4ml strong phosphoric acid, consists of, and other are with embodiment mono-.
In the present embodiment gained graphene powder, the number of plies of Graphene is 3～5 layers, good crystallinity, specific surface area approximately 541.2 m
2/ g, specific conductivity approximately 4548 S/m.
Embodiment eight:
Nitration mixture is 100ml, the 80ml vitriol oil and 20ml strong phosphoric acid, consists of, and other are with embodiment tri-.
In the present embodiment gained graphene powder, the number of plies of Graphene is 3～7 layers, good crystallinity, specific surface area approximately 391.5 m
2/ g, specific conductivity approximately 3723 S/m.
Embodiment nine:
Nitration mixture is 100ml, the 70ml vitriol oil and 30ml strong phosphoric acid, consists of, and other are with embodiment tri-.
In the present embodiment gained graphene powder, the number of plies of Graphene is 3～7 layers, good crystallinity, specific surface area approximately 399 m
2/ g, specific conductivity approximately 3750 S/m.
Except technical characterictic described in specification sheets, all the other technical characterictics are those skilled in the art's known technology.
Claims (3)
1. a novel method of preparing high-quality Graphene, is characterized in that, carries out as follows:
1) oxide treatment: 1g natural graphite and magnetic agitation limit, 40～100ml nitration mixture limit are mixed in reactor, slowly add again 3～8g potassium permanganate in temperature lower than 20 ℃ in the situation that; By reactor sealing, under 60～90 ℃ of temperature constant magnetic stirrings, react 1～4 hour afterwards, take out and be cooled to room temperature; Then be diluted to 400mL solution, add 2～6mL hydrogen peroxide to obtain glassy yellow graphite oxide solution;
2) purification is separated: adopt differential centrifugation mode, the sulphuric acid soln that is 4.5～5.5% with massfraction carries out pickling graphite oxide solution 2～4 times, uses deionized water centrifuge washing graphite oxide solution 5～6 times, removes sulfate ion, pH is 6～7, obtains graphite oxide viscous fluid;
3) ultrasonic dry: with the graphite oxide viscous fluid of 1 volume, mix with the organic solvent of 1～3 volume, put into ultrasonator, ultrasonic power is 100～600W approximately, sonic oscillation 1～2 hour, lyophilize obtains graphene oxide;
4) thermal reduction is processed: dried graphene oxide is put into tube furnace, first, under air conditions, with the temperature rise rates of 8～12 ℃/min, heat up, 290～310 ℃ of insulations 2～5 minutes; Afterwards, under nitrogen protection, 1000～1050 ℃ of insulations 1 minute～3 hours, be cooled to room temperature; Grind again, and with the ultrasonic dispersion of organic solvent, at 50～60 ℃, dry to obtain graphene powder;
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 that mix 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, 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), temperature rise rate is 10 ℃/min, 300 ℃ of insulations 3 minutes.
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|---|---|---|---|---|
| CN104140098A (en) * | 2014-08-22 | 2014-11-12 | 东莞市长安东阳光铝业研发有限公司 | Application of micro-expanded graphite material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN102530928A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Method for preparing graphene composite material loading amorphous carbon |
| CN102616772A (en) * | 2012-04-06 | 2012-08-01 | 泰州巨纳新能源有限公司 | Method for preparing waste recovered graphite powder into graphene |
| CN103420363A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Preparation method and application of graphene paper |
-
2014
- 2014-05-07 CN CN201410189973.4A patent/CN103950923B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530928A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Method for preparing graphene composite material loading amorphous carbon |
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN102616772A (en) * | 2012-04-06 | 2012-08-01 | 泰州巨纳新能源有限公司 | Method for preparing waste recovered graphite powder into graphene |
| CN103420363A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Preparation method and application of graphene paper |
Cited By (23)
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|---|---|---|---|---|
| CN104150471A (en) * | 2014-07-31 | 2014-11-19 | 山东玉皇新能源科技有限公司 | Method for reducing graphene oxide |
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| CN104140098A (en) * | 2014-08-22 | 2014-11-12 | 东莞市长安东阳光铝业研发有限公司 | Application of micro-expanded graphite material |
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