CN102167312B - Preparation method of graphene integrating processes of stripping, separating and reducing - Google Patents
Preparation method of graphene integrating processes of stripping, separating and reducing Download PDFInfo
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- CN102167312B CN102167312B CN2011101032701A CN201110103270A CN102167312B CN 102167312 B CN102167312 B CN 102167312B CN 2011101032701 A CN2011101032701 A CN 2011101032701A CN 201110103270 A CN201110103270 A CN 201110103270A CN 102167312 B CN102167312 B CN 102167312B
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Abstract
The invention belongs to the technical field of a nano-material, and in particular relates to a preparation method of graphene integrating with processes of stripping, separating and reducing. The method comprises the steps of stripping, separating and reducing graphite oxide through an electric field by a stripping power source, a separating power source and a reducing power source in sequence to integrate with the three processes such as the stripping, the separating, the reducing and the like, so that the preparation efficiency and the quality of the grapheme are improved, the preparation cost is reduced, and the method is suitable for the batch production.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of integral preparation method of Graphene.
Background technology
Performances such as the mechanics of the many excellences of Graphene, electricity, calorifics make it have broad application prospects in fields such as matrix material, micro-nano devices.Link to each other with the σ key between the carbon atom in the Graphene two dimensional surface, given mechanical properties such as its high Young's modulus, intensity.The Young's modulus of Graphene can reach 1.01 TPa.Single-layer graphene can be used as the sample loading film of transmission electron microscope, has observed the image of Wasserstoffatoms, and excellent mechanical property makes Graphene also be with a wide range of applications in the nano-machine devices field.Current carrier in the Graphene has the characteristic feature of two-dimentional dirac fermion, and the current-carrying proton rest mass is zero, has irregular quantum hall effect, and its carrier mobility is up to 200,000 cm2V
-1s
-1High carrier mobility has given Graphene superpower conductive capability; Make electronics not receive scattering,, be expected to raw material as the graphene-based field-effect transistor of preparation for the transistor of making extremely speed conversion provides condition in the interior motion of sub-micro distance; Have potential using value and wide application prospect at nano electron device, be expected to become the substitute of silicon.The detector of Graphene preparation is expected to realize the detection of individual molecule or atom in addition.With the Graphene is the electrode for capacitors of feedstock production, has highly than electric capacity (117F/g) and energy density (31.9 Wh/kg), is superior to individual layer and multi-layer nano carbon pipe.Heat conductivility under the Graphene room temperature is superior to carbon nanotube (3000～3500 Wm
-1K
-1), the thermal conductivity peak is 5300 Wm
-1K
-1Fabulous heat conductivility makes Graphene be expected to as the cooling integrated material of ultra-large nanometer.
The preparation of Graphene is to carry out Graphene research and the prerequisite of using, and obtains the Graphene that the number of plies is consistent, textural defect is few, is the basis of Graphene performance and applied research thereof; In enormous quantities, cheap preparation method is the assurance that Graphene can practical application in industry, the Graphene of preparation property and structure also is to guarantee that Graphene is applied in the basis of different field.At present graphene preparation method comprises that micromechanics peels off method, epitaxial growth method and chemical method.
Peel off in the method in micromechanical forces; Introduce certain defective (as etch highly about 5 μ m chain-wales) on the surface of pyrolytic graphite with certain means (like oxygen plasma); Then itself and another kind of material (like silicon-dioxide) are rubbed; Can produce some tiny wafers, just contain the Graphene of individual layer in these little wafers, just can find the Graphene of individual layer by opticmicroscope and AFM.Peel off legal system at micromechanics and be equipped with in the graphene film process, found the graphite flake layer that the number of plies is different, pattern differs greatly.This method at first prepares the Graphene that the tiny wafer of numerous graphite is then sought individual layer therein, and not only screening process wastes time and energy, and the number of plies of gained graphene film, pattern have randomness, is difficult to control.Micromechanics is peeled off legal system, and to be equipped with the Graphene quality better, generally is called pure Graphene (Pristine graphene).But the production efficiency that micromechanical forces is peeled off method is low, is difficult to scale operation.Graphene by this method preparation is mainly used in fundamental research at present.
Epitaxial growth method can be divided into two types again.A kind of is chemical Vapor deposition process, and basic ideas are: hydrocarbon polymer decomposes down at high temperature (1000 ℃), is deposited on nickel or the transition metal substrate, forms graphene film.Second method is pyrolysis 4H-SiC or 6H-SiC crystal; Utilize the hydrogen lithographic technique to handle 4H-SiC or 6H-SiC crystal prototype; Make it reach the planeness of atomic level; Then in high vacuum, be heated to 1000 ℃ to remove the oxide compound on surface, 1400 ℃ of insulation for some time, obtain graphene film at last.Although the number of plies major influence factors of graphene film is a Heating temperature, lateral dimension can be achieved through the pattern of control carborundum crystals, and the number of plies of products therefrom still is difficult to control.Phase coherence and elastic scattering distance that the Graphene of this method preparation has very high structural integrity, long distance can reach micron order, can be used for making the electron device of nanoscale.But, cause its cost higher owing to need the environment of high temperature high vacuum in its preparation process.Chemical method is introduced some chemical substance or chemical group in graphite layers, to reduce the graphite layers Van der Waals force, is convenient to graphite is peeled off the Graphene lamella.Different according to the mode of peeling off, chemical method is divided into three kinds substantially: method, ultrasonic method, the ultrasonic method of peeling off of Rapid Thermal expansion peeled off are peeled off in the Rapid Thermal expansion.
Summary of the invention
The object of the present invention is to provide the method for preparing Graphene that a kind of efficient is high, cost is low, be suitable for mass production.
The present invention prepares from chemical method and peels off, separates the Graphene process and three processes such as reduction are started with; Utilize electric field that graphite oxide is peeled off, separated and reduces; And realize peeling off, separating and three processes such as reduction integrated, improve Graphene preparation efficiency and quality, reduce cost.
Device used in the present invention is as shown in Figure 1.This device comprises and separates with direct supply 1, reduces with direct supply 2, peels off with AC power 3, first reducing electrode 4, first separate mesh electrode 5, electrochemical vessel 6, first stripping electrode 8, second stripping electrode 9, second reducing electrode 10 and second separate mesh electrode 11 etc.Wherein electrochemical vessel 6 adopts glass to make, and highly is 100～1000 millimeters, and length is 100～2000 millimeters, and width is 50～1000 millimeters, and thickness of glass is 5～20 millimeters.Hold electrochemical solution 7 in the electrochemical vessel 6; But separating use direct supply 1 is voltage controller power source, and range of regulation is 5～100 volts.But it is voltage controller power source that direct supply 2 is used in reduction, and range of regulation is 1～50 volt, uses AC power 3 to be pressure regulation and variable-frequency power sources but peel off, and range of regulation is 10～100 volts, and frequency is regulated between 0～7kHz.It is right that 2 separate mesh electrodes, 2 stripping electrodes and 2 reducing electrodes are corresponding positive and negative electrode, all adopts copper plate electrode, and each electrode height is 150～1200 millimeters, and width is 50～1000 millimeters, and thickness is 1～5 millimeter.
The concrete steps of the inventive method are following:
(1) at first graphite oxide is dissolved in the deionized water, the preparation graphite oxide solution, the particle diameter of graphite oxide is 20～140 μ m, the concentration of graphene oxide solution is 0.5 ~ 10 mg/ml.
(2) get an amount of above-mentioned graphite oxide colloidal sol, add electrochemical vessel.
(3) startup is peeled off and is used AC power, graphite oxide is carried out electric field peel off, and peels off voltage and between 10～150 volts, regulates, and frequency is regulated between 0～7kHz, and temperature is controlled at 20～80 degrees centigrade, and splitting time was regulated between 10～120 minutes.
(4) start separation and use direct supply, graphite oxide is separated, separation voltage is regulated between 5～100 volts, and temperature is controlled at 20～80 degrees centigrade, and disengaging time was regulated between 2～10 minutes.
(5) start reduction and use direct supply, graphite oxide is carried out electrochemical reduction, recovery voltage is regulated between 1～50 volt, and temperature is controlled at 20～80 degrees centigrade, and the recovery time was regulated between 5～60 minutes.
(6) from electrochemical vessel, pipette through peeling off, separate and process such as reduction and the Graphene solution for preparing with transfer pipet.
Compare with other graphene preparation method, the present invention has following advantage:
(1) preparation efficiency is than higher;
(2) pollution-free;
(3) device is simple, and is with low cost;
(4) amplify easily, realize the scale preparation of Graphene.
Description of drawings
Fig. 1 integrates and peels off, separates and the Graphene preparation facilities synoptic diagram of process such as reduction.
The AFM picture of the Graphene of Fig. 2 embodiment 1 preparation.
The AFM picture of the Graphene of Fig. 3 embodiment 2 preparations.
The AFM picture of the Graphene of Fig. 4 embodiment 3 preparations.
Embodiment
The graphite oxide of choosing particle diameter and be 25 microns is dissolved in the deionized water, preparation graphite oxide solution 2000ml, and the concentration of graphene oxide solution is 1 mg/ml.Measure the graphite oxide colloidal sol that 1500ml prepares, add in the electrochemical vessel.Start and peel off power supply, graphite oxide is carried out electric field peel off, peel off voltage and be made as 50 volts, frequency is made as 2kHz, and temperature is controlled at 30 degrees centigrade.After peeling off 50 minutes, start separate power supplies, graphite oxide is separated, separation voltage is made as 60 volts, 30 degrees centigrade of temperature controls.Separate after 5 minutes, start reduction power supply, graphite oxide is carried out electrochemical reduction, recovery voltage is made as 20 volts, and temperature is controlled at 30 degrees centigrade.After 30 minutes recovery times, from electrochemical vessel, pipette through peeling off, separate and process such as reduction and the Graphene solution for preparing with transfer pipet.Carry out atomic force microscope observation on the sheet mica with dropping in behind 10 times of the Graphene solution dilutions, observations is as shown in Figure 2.Graphene thickness is single-layer graphene about 1.22 nanometers.
The graphite oxide of choosing particle diameter and be 50 microns is dissolved in the deionized water, preparation graphite oxide solution 2000ml, and the concentration of graphene oxide solution is 2 mg/ml.Measure the graphite oxide colloidal sol that 1500ml prepares, add in the electrochemical vessel.Start and peel off power supply, graphite oxide is carried out electric field peel off, peel off voltage and be made as 75 volts, frequency is made as 1kHz, and temperature is controlled at 30 degrees centigrade.After peeling off 70 minutes, start separate power supplies, graphite oxide is separated, separation voltage is made as 60 volts, 30 degrees centigrade of temperature controls.Separate after 5 minutes, start reduction power supply, graphite oxide is carried out electrochemical reduction, recovery voltage is made as 20 volts, and temperature is controlled at 30 degrees centigrade.After 30 minutes recovery times, from electrochemical vessel, pipette through peeling off, separate and process such as reduction and the Graphene solution for preparing with transfer pipet.Carry out atomic force microscope observation on the sheet mica with dropping in behind 10 times of the Graphene solution dilutions, observations is as shown in Figure 3.Graphene thickness is single-layer graphene about 1.03 nanometers.
Embodiment 3
The graphite oxide of choosing particle diameter and be 100 microns is dissolved in the deionized water, preparation graphite oxide solution 2000ml, and the concentration of graphene oxide solution is 1 mg/ml.Measure the graphite oxide colloidal sol that 1500ml prepares, add in the electrochemical vessel.Start and peel off power supply, graphite oxide is carried out electric field peel off, peel off voltage and be made as 100 volts, frequency is made as 5kHz, and temperature is controlled at 30 degrees centigrade.After peeling off 100 minutes, start separate power supplies, graphite oxide is separated, separation voltage is made as 70 volts, 30 degrees centigrade of temperature controls.Separate after 8 minutes, start reduction power supply, graphite oxide is carried out electrochemical reduction, recovery voltage is made as 30 volts, and temperature is controlled at 30 degrees centigrade.After 50 minutes recovery times, from electrochemical vessel, pipette through peeling off, separate and process such as reduction and the Graphene solution for preparing with transfer pipet.Carry out atomic force microscope observation on the sheet mica with dropping in behind 10 times of the Graphene solution dilutions, observations is as shown in Figure 3.Graphene thickness is single-layer graphene about 1.31 nanometers.
Claims (1)
1. incorporate graphene preparation method is characterized in that concrete steps are:
(1) at first graphite oxide is dissolved in the deionized water, the preparation graphite oxide solution, the particle diameter of graphite oxide is 20～140 μ m, the concentration of graphite oxide solution is 0.5 ~ 10 mg/ml;
(2) get an amount of above-mentioned graphite oxide solution, add in the electrochemical vessel;
(3) startup is peeled off and is used AC power, graphite oxide is carried out electric field peel off, and it is 10～150 volts that voltage is peeled off in control, and frequency is 0～7kHz, and controlled temperature is at 20～80 degrees centigrade, and splitting time is 10～120 minutes;
(4) start separation and use direct supply, graphite oxide is separated, the control separation voltage is 5～100 volts, and temperature is at 20～80 degrees centigrade, and disengaging time is 2～10 minutes;
(5) start reduction and use direct supply, graphite oxide is carried out electrochemical reduction, the control recovery voltage is 1～50 volt, and temperature is 20～80 degrees centigrade, and the recovery time is 5～60 minutes;
(6) with transfer pipet from electrochemical vessel, pipette through peeling off, separation and reduction process and the Graphene solution for preparing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW201326036A (en) * | 2011-12-27 | 2013-07-01 | Ind Tech Res Inst | Methods of forming graphene |
| CN103204493B (en) * | 2012-01-12 | 2015-09-30 | 中国科学院微电子研究所 | The preparation method of graphene wafer |
| CN103253654A (en) * | 2012-02-20 | 2013-08-21 | 海洋王照明科技股份有限公司 | Method for preparing graphene by peeling intercalated graphite through electric field |
| CN102583356B (en) * | 2012-03-20 | 2015-01-21 | 无锡格菲电子薄膜科技有限公司 | Method for transferring and washing graphene film |
| CN102645421B (en) * | 2012-04-21 | 2013-11-27 | 吉林大学 | Method of in-situ assembly, electrochemical reduction and representation of graphene oxide |
| CN103794370A (en) * | 2012-10-29 | 2014-05-14 | 海洋王照明科技股份有限公司 | Graphene/ionic liquid composite material and preparation method thereof, combined electrode and preparation method thereof and electrochemical capacitor |
| CN102963887B (en) * | 2012-11-30 | 2015-01-14 | 同济大学 | Electrochemistry stripping and reducing integrated graphene preparation method |
| CN103971946A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Preparation method for graphene-ionic liquid composite materials and preparation method for supercapacitor |
| CN104008895A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene-ionic liquid composite electrode and preparation method thereof, and electrochemical capacitor |
| CN105845552A (en) * | 2016-03-14 | 2016-08-10 | 山东大学 | Photoelectrochemical etching method for removing SiC substrate epitaxial graphene buffer layer |
| CN110272040B (en) * | 2018-03-15 | 2022-11-11 | 中国人民解放军军事科学院防化研究院 | Preparation method of high-purity graphene oxide |
| CN111312892B (en) * | 2019-11-29 | 2022-02-22 | 大连理工大学 | Magnetic sensor with ultrahigh three-dimensional magnetic field detection sensitivity and manufacturing method thereof |
| CN112607729A (en) * | 2020-12-23 | 2021-04-06 | 中钢集团南京新材料研究院有限公司 | Device for stripping graphene by using alternating electric field and using method thereof |
| CN113249740B (en) * | 2021-06-21 | 2022-10-04 | 广西师范大学 | Method for preparing graphene by electrochemical continuous and synchronous stripping and reduction |
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| CN101591014B (en) * | 2009-06-30 | 2010-12-29 | 湖北大学 | Method for realizing large-scale preparation of monolayer oxidized graphene |
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