CN101830458A - Preparation method of high purity and high concentration graphene suspension - Google Patents
Preparation method of high purity and high concentration graphene suspension Download PDFInfo
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- CN101830458A CN101830458A CN 201010164567 CN201010164567A CN101830458A CN 101830458 A CN101830458 A CN 101830458A CN 201010164567 CN201010164567 CN 201010164567 CN 201010164567 A CN201010164567 A CN 201010164567A CN 101830458 A CN101830458 A CN 101830458A
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Abstract
The invention relates to a preparation method of a high purity and high concentration graphene suspension, which comprises the following steps of: reacting natural crystalline flake graphite with a strong oxidizer to obtain graphite oxide; spreading the graphite oxide into a dispersing agent, and obtaining a graphene oxide suspension by ultrasonic dispersion; mixing the graphene oxide suspension with hydrazine hydrate under the protection of nitrogen and reacting at constant temperature under ultrasonic radiation to prepare stable graphene suspension. Compared with the traditional method for preparing the graphene suspension, the method introduces ultrasonic in the reduction process of the graphite oxide. The invention has the following advantages that the prepared graphene suspension has high concentration (higher than 1 mg.mL<-1>), high purity (without influence of surface active agents and other impurities), high dispersionstability (time for stable dispersion is more than 60 days) and the like; the graphene prepared by the method has high electrical conductivity (high than 700 S.m<-1>), less number of layers, is simple and easy to implement, and is very suitable for large scale production in industy.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to the preparation method of a kind of high purity, high concentration graphene suspension.
Background technology
In recent years, ultrasonic wave has been widely used in preparing nano material, and it can produce intensive cavitation and vibration effect when passing liquid medium, thereby for chemical reaction provides unique reacting environment, has developed into a kind of pervasive preparation method of nano material.The high temperature that cavitation effect of ultrasonic waves produced and reduced the specific surface free energy of tiny crystal grains at a large amount of micro-bubbles that solid surface produced has suppressed nucleus and has assembled and grow up; Strong shock wave that ultrasonic cavitation produces and microjet are sheared particulate and crushing effect has reduced Van der Waals force between molecule effectively, thereby effectively stop the reunion of molecule; Ultrasonic wave can form the fluidic turbulence again in liquid, help the dispersion of molecule and stablizing of suspension.
Graphene (Graphene) is since 2004 wait to be found by professor Geim of Univ Manchester UK, caused the extensive concern of scientific circles with its particular structure and excellent performance, predictedly will cause revolutionary variation (Novoselov K.S.et al.Science in a lot of fields, 2004,306 (5296), 666-669).Graphene has special cellular two-dirnentional structure as a kind of new allotropic substance in the carbon, is made up of the monolayer carbon atom, therefore has excellent electricity, mechanics and thermal property.Graphene has high electronic mobility (2 * 10
5Cm
2(Vs)
-1), higher 100 times than the electronic mobility of silicon semiconductor, higher 20 times than the electronic mobility of gallium arsenide, can extensively be used in electron device and the nanometer circuit.Graphene is real superficiality solid, and the theoretical specific surface area of single-layer graphene is up to 2600m
2G
-1, be the ideal energy storage material.Graphene has excellent mechanical property, and its ideal tensile strength is up to 110-130GPa; And having the thermal conductivity of superelevation, the thermal conductivity that is obtained by contactless measuring technology is 3080-5150W (mK)
-1, can be widely used in the matrix material, and the raising performance of composites (Rao C.N.R.et al Angewandte Chemie-International Edition, 2009,48,7752-7778).
Graphene is restricted its processing and application because intensive π-π interaction between layer and the layer is very easily reunited.The excellent properties of Graphene and its single layer structure are closely bound up, and reuniting causes piling up of Graphene lamella to make the excellent properties of Graphene be difficult to show.Preparation method of graphene is a lot, and for example chemical vapour deposition, solvent are peeled off with micromechanics and peeled off etc., and all there is the shortcoming of workability difference in the Graphene of these methods preparations.Graphene is difficult for hydrophilic and oleophilic by a large amount of pure carbon atomic buildings; Graphene has high-specific surface area, and the Van der Waals force between layer and the layer makes it that irreversible reunion very easily take place; The difficult wetting property of Graphene makes it be difficult to be scattered in and be prepared into stable graphene suspension in water or the organic solvent.These limited Graphene in spin coating, drip be coated with, the application of spraying, liquid-liquid self-assembly and prepare composite, therefore, the high concentration graphene suspension of preparing stable dispersion then is an effective way of expanding the Graphene Application Areas.
Oxidation-reduction method is one of important method of preparation Graphene, yet make graphene oxide in the process that Graphene transforms by reductive agent, often is accompanied by the reunion of Graphene, is difficult to obtain the high concentration graphene suspension of stable dispersion.In early days, in reduction process, add tensio-active agent, polymkeric substance or other modifier and can access stable graphene suspension, but the impurity that these methods are introduced has reduced the purity of Graphene, causes the reduction of Graphene specific conductivity, thermal conductivity variation, has limited the application of Graphene.Afterwards, the scholar utilized ammoniacal liquor to regulate pH in the chemical reduction process, also can obtain stable graphene suspension by electrostatic interaction, but be only applicable to low concentration (0.5mgmL
-1), excessive concentration will reunite (Li, D.et al.Nature Nanotechnology, 2008,3 (2), 101-105); The graphene suspension that utilizes microwave and high temperature (150 ℃) environment to prepare in N,N-dimethylacetamide also has the low (0.56mgmL of concentration
-1), the low (200Sm of specific conductivity
-1) shortcoming.Existent method is difficult to prepare the Graphene of high conductivity and the suspension of high-concentration stable thereof at present.Therefore, expand the Application Areas of Graphene, the preparation method who seeks a kind of simple stable high concentration graphene suspension seems particularly urgent.
Summary of the invention
The objective of the invention is to the limitation that still exists in the preparation of present graphene suspension, the preparation method of a kind of high purity, high concentration graphene suspension is provided.The present invention by ultrasonic wave effect prepared the Graphene of high conductivity and the high concentration graphene suspension of stable dispersion thereof, and reduced temperature of reaction, shortened the reaction times, make production technique be easy to industrialization.
For achieving the above object, the technical solution used in the present invention is:
1) preparation of graphite oxide:
After getting 2-50g natural flake graphite and 25-600mL strong acid solution and mixing, the oxygenant that adds 3-75g again reacts 0.5-4h in-2 ℃ to 4 ℃ water-baths after, again in 20-40 ℃ of reaction 0.5-24h, and then the distilled water that adds 50-1150mL reacts 0.5-12h at 60-100 ℃, stop oxidizing reaction with the 0.1-3L distilled water diluting again, filtration also is washed with distilled water to neutrality, and vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid joined be configured to 1.0-2.0mgmL in the dispersion agent
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 0.5-12h under the ultrasonic wave effect, obtain uniform and stable graphene oxide suspension;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 40-80 ℃ and adds reductive agent; be to react 10-180min under the ultrasonic wave radiation of 20-100kHz in frequency; obtain uniform and stable high concentration graphene suspension, wherein the mass ratio of graphene oxide suspension and reductive agent is 10: 5-9.
It is that 90-98% sulfuric acid, concentration are 60-67% nitric acid or both mixing acid that strong acid solution of the present invention adopts concentration;
Oxygenant is one or more in SODIUMNITRATE, potassium permanganate, potassium perchlorate, Potcrate, the Vanadium Pentoxide in FLAKES, if adopt potassium permanganate need add the remaining potassium permanganate of hydrogen peroxide reduction;
Dispersion agent is water, ethanol, n-formyl sarcolysine base pyrrolidone, N, one or more in dinethylformamide, the cyclopentanone;
Reductive agent is one or more in hydrazine, dimethylhydrazine, quadrol, Ursol D, sodium borohydride, the Resorcinol.
The present invention adopts the ultrasonic wave radiation, its effect not only makes unstripped graphite oxide peel off into the graphene oxide of individual layer or few layer, and the self-assembly that has significantly suppressed the graphene film interlayer with pile up, these can be owing to the cavatition in the ultrasonic wave radiation effect.Strong shock wave that cavatition produced and microjet have weakened the Van der Waals force between graphene layer and the layer, have suppressed the reunion of graphene film interlayer, for the graphene suspension for preparing high-concentration stable provides condition.Cavitation bubble crumble and fall high pressure and the partial high temperature of moment of being produced have quickened the reduction reaction of graphene oxide, have improved production efficiency.
Description of drawings
Fig. 1 for the high concentration graphene suspension of the present invention preparation place after 60 days photo.
Fig. 2 prepares graphene oxide (a) and Graphene (b) transmission electron microscope (TEM) photo for the present invention.
Fig. 3 is that graphite (a) and the present invention prepare graphite oxide (b) and Graphene (c) Raman (Raman) spectrogram.
Fig. 4 is the graphite oxide (b) and Graphene (c) fourier-transform infrared (FTIR) spectrogram of graphite (a) and the present invention's preparation.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1:
1) preparation of graphite oxide:
Getting 2g natural flake graphite and 25mL concentration is after 98% sulfuric acid mixes, add again 1g SODIUMNITRATE and 2g potassium permanganate reacts 4h in-2 ℃ of water-baths after, again in 40 ℃ of reaction 0.5h, and then the distilled water that adds 50mL reacts 12h at 60 ℃, stop adding the remaining potassium permanganate of hydrogen peroxide reduction again after the oxidizing reaction with the 0.1L distilled water diluting again, filtration also is washed with distilled water to neutrality, and vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid is added to the water is configured to 1.0mgmL
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 2h under the ultrasonic wave effect, obtain uniform and stable graphene oxide and (see a) suspension of Fig. 2;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 60 ℃ and adds hydrazine; be to react 10-180min under the ultrasonic wave radiation of 20-100kHz in frequency; obtain uniform and stable high concentration graphene (seeing Fig. 2 b) suspension, wherein the mass ratio of graphene oxide suspension and hydrazine is 10: 5.
Embodiment 2:
1) preparation of graphite oxide:
Getting 50g natural flake graphite and 400mL concentration is that 90% sulfuric acid, 200ml concentration are after 67% nitric acid mixes, SODIUMNITRATE, 30g potassium perchlorate and the 35g Potcrate that adds 10g again reacts 3h in-1 ℃ of water-bath after, again in 20 ℃ of reaction 24h, and then the distilled water that adds 1150mL reacts 5h at 80 ℃, stop oxidizing reaction with the 3L distilled water diluting again, filtration also is washed with distilled water to neutrality, and vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid joined be configured to 1.1mgmL in the ethanol
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 3h under the ultrasonic wave effect, obtain uniform and stable graphene oxide suspension;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 40 ℃ and adds under the ultrasonic wave radiation that dimethylhydrazines are 20-100kHz in frequency and react 10-180min; obtain uniform and stable high concentration graphene (seeing Fig. 2 b) suspension, wherein the mass ratio of graphene oxide suspension and reductive agent is 10: 9.
Embodiment 3:
1) preparation of graphite oxide:
Getting 15g natural flake graphite and 100mL concentration is after 93% sulfuric acid mixes, the potassium perchlorate that adds 20g again, after in 2 ℃ of water-baths, reacting 1h, again in 30 ℃ of reaction 12h, and then the distilled water that adds 200mL reacts 0.5h at 100 ℃, stop oxidizing reaction with the 0.5L distilled water diluting again, filter and be washed with distilled water to neutrality, vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid joined in the n-formyl sarcolysine base pyrrolidone be configured to 2.0mgmL
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 5h under the ultrasonic wave effect, obtain uniform and stable graphene oxide suspension;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 70 ℃ and adds quadrol; be to react 10-180min under the ultrasonic wave radiation of 20-100kHz in frequency; obtain uniform and stable high concentration graphene suspension, wherein the mass ratio of graphene oxide suspension and reductive agent is 10: 8.
Embodiment 4:
1) preparation of graphite oxide:
Getting 30g natural flake graphite and 400mL concentration is after 60% nitric acid mixes, the Vanadium Pentoxide in FLAKES that adds 40g again reacts 0.5h in 4 ℃ of water-baths after, again in 25 ℃ of reaction 20h, and then the distilled water that adds 60mL reacts 7h at 70 ℃, stop oxidizing reaction with the 1.5L distilled water diluting again, filtration also is washed with distilled water to neutrality, and vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid is joined N, be configured to 1.2mgmL in the dinethylformamide
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 10h under the ultrasonic wave effect, obtain uniform and stable graphene oxide suspension;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 70 ℃ and adds under the ultrasonic wave radiation that Ursol D are 20-100kHz in frequency and react 10-180min; obtain uniform and stable high concentration graphene suspension, wherein the mass ratio of graphene oxide suspension and reductive agent is 10: 7.
Embodiment 5:
1) preparation of graphite oxide:
After getting 40g natural flake graphite and 500mL concentration and be 63% nitric acid and mixing, the Vanadium Pentoxide in FLAKES that adds 60g again reacts 2h in 0 ℃ of water-bath after, again in 35 ℃ of reaction 6h, and then the distilled water that adds 800mL reacts 2h at 90 ℃, stop oxidizing reaction with the 2L distilled water diluting again, filtration also is washed with distilled water to neutrality, and vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid joined be configured to 1.5mgmL in the cyclopentanone
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 12h under the ultrasonic wave effect, obtain uniform and stable graphene oxide suspension;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 50 ℃ and adds Resorcinol, hydrazine; be to react 10-180min under the ultrasonic wave radiation of 20-100kHz in frequency; obtain uniform and stable high concentration graphene (seeing Fig. 2 b) suspension, wherein the mass ratio of graphene oxide suspension and reductive agent is 10: 2: 4.
Embodiment 6:
1) preparation of graphite oxide:
After getting 20g natural flake graphite and 300mL concentration and be 95% sulfuric acid and mixing, the SODIUMNITRATE that adds 50g is again reacted 1.5h in 1 ℃ of water-bath after, again in 32 ℃ of reaction 10h, and then the distilled water that adds 400mL reacts 10h at 85 ℃, stop oxidizing reaction with the 1L distilled water diluting again, filtration also is washed with distilled water to neutrality, and vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid is joined water and N, be configured to 1.8mgmL in the dinethylformamide
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 0.5h under the ultrasonic wave effect, obtain uniform and stable graphene oxide suspension;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 80 ℃ and adds Ursol D and sodium borohydride; be to react 10-180min under the ultrasonic wave radiation of 20-100kHz in frequency; obtain uniform and stable high concentration graphene (seeing Fig. 2 b) suspension, wherein the mass ratio of graphene oxide suspension and reductive agent is 10: 4: 4.5.
Outstanding feature of the present invention is:
(1) provides a kind of high conductivity (＞700Sm
-1) Graphene and high density (＞1mgmL thereof
-1) preparation method of suspension;
(2) high concentration graphene suspension of preparation stability better can be stablized and place more than the 60d;
(3) ultrasonic wave can be peeled off the reunion of unstripped Graphene and inhibition Graphene, and therefore the Graphene number of plies of preparation is less, and quality is higher;
(4) in the reduction process of graphene oxide, introduce ultrasonic wave, accelerated the speed of reduction reaction greatly, improved production efficiency;
(5) preparation method's desired reaction temperature of the present invention is low, and safety is easy to operate, technological process is simple and easy to do, be convenient to amplify production, low operation cost;
The graphene suspension of the high-concentration stable of the present invention's preparation has improved the workability of Graphene significantly, make it can be widely used in spin coating, drip and to be coated with, to spray, liquid-liquid self-assembly and prepare composite, the device that helps Graphene can be used for constructing electron devices such as nano level computer chip, electrode of solar battery, electrode of super capacitor, transmitter, field-effect transistor.Adopt the graphene suspension of the present invention's preparation to improve consistency and the dispersiveness of Graphene in matrix material, improved the mechanical property and the barrier property of matrix material.The present invention has extremely important actual application value.
The present invention adopts and introduce hyperacoustic method in the reduction process of graphene oxide, after the graphene suspension of preparing leaves standstill 60 days, still presents the phenomenon (Fig. 1) of stable homogeneous.The photo (Fig. 2) of transmission electron microscope (TEM) shows that the graphene oxide of the present invention's preparation and Graphene have flat and thin laminated structure, and tangible agglomeration does not take place the Graphene of preparation, and ultrasonic wave has played important effect.Raman (Raman) spectrum proof graphite has destroyed orderly crystalline structure in the process of graphite oxide, under ultrasonic wave through behind the hydrazine hydrate reduction, the part defective (Fig. 3) of having recovered the crystalline structure of Graphene partial order and having repaired Graphene.Fourier infrared conversion spectrum (FT-IR) is graphite oxide more thorough by hydrazine hydrate reduction under ultrasonic wave as can be seen, almost sloughed all oxy radicals, near the structure (Fig. 4) of graphite.
Claims (5)
1. the preparation method of the graphene suspension of a high purity, high density is characterized in that:
1) preparation of graphite oxide:
After getting 2-50g natural flake graphite and 25-600mL strong acid solution and mixing, the oxygenant that adds 3-75g again reacts 0.5-4h in-2 ℃ to 4 ℃ water-baths after, again in 20-40 ℃ of reaction 0.5-24h, and then the distilled water that adds 50-1150mL reacts 0.5-12h at 60-100 ℃, stop oxidizing reaction with the 0.1-3L distilled water diluting again, filtration also is washed with distilled water to neutrality, and vacuum-drying obtains oxidation graphite solid;
2) preparation of graphene oxide suspension:
Oxidation graphite solid joined be configured to 1.0-2.0mgmL in the dispersion agent
-1Graphite oxide suspension, this graphite oxide suspension is disperseed 0.5-12h under the ultrasonic wave effect, obtain uniform and stable graphene oxide suspension;
3) preparation of graphene suspension:
With graphene oxide suspension under nitrogen protection; control reaction temperature is 40-80 ℃ and adds reductive agent; be to react 10-180min under the ultrasonic wave radiation of 20-100kHz in frequency; obtain uniform and stable high concentration graphene suspension, wherein the mass ratio of graphene oxide suspension and reductive agent is 10: 5-9.
2. the preparation method of the graphene suspension of high purity according to claim 1, high density is characterized in that: it is that 90-98% sulfuric acid, concentration are 60-67% nitric acid or both mixing acid that described strong acid solution adopts concentration.
3. the preparation method of the graphene suspension of high purity according to claim 1, high density, it is characterized in that: described oxygenant is one or more in SODIUMNITRATE, potassium permanganate, potassium perchlorate, Potcrate, the Vanadium Pentoxide in FLAKES, if adopt potassium permanganate need add the remaining potassium permanganate of hydrogen peroxide reduction.
4. the preparation method of the graphene suspension of high purity according to claim 1, high density is characterized in that: described dispersion agent is water, ethanol, n-formyl sarcolysine base pyrrolidone, N, one or more in dinethylformamide, the cyclopentanone.
5. the preparation method of the graphene suspension of high purity according to claim 1, high density is characterized in that: described reductive agent is one or more in hydrazine, dimethylhydrazine, quadrol, Ursol D, sodium borohydride, the Resorcinol.
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