CN103407998A - Preparation method of high concentration and small flake diameter graphene dispersion - Google Patents
Preparation method of high concentration and small flake diameter graphene dispersion Download PDFInfo
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Abstract
Belonging to the technical field of nanometer new materials, the invention relates to a preparation method of a high concentration graphene dispersion. The method includes the steps of: firstly taking graphite powder as a raw material, oxidizing the graphite powder by a Hummers method to obtain graphite oxide, then reducing the obtained graphite oxide to obtain reduced graphite oxide, then mixing the reduced graphite oxide with a solvent, putting the mixture into a ball milling tank to perform ball milling so as to obtain a reduced graphene oxide dispersion, then drying the dispersion, dispersing the product in water and various polar solvents, and preparing the graphene dispersion according to a required concentration. The method provided in the invention has a simple process, is economical and environment friendly, and the prepared graphene dispersion can maintain high concentration stable dispersion.
Description
Technical field
What the present invention relates to is the nanometer new material technology field, specifically the preparation method of a kind of high density small pieces footpath graphene dispersing solution.
Background technology
Graphene be 2004 by the physicist An Deliehaimu of Univ Manchester UK and Constantine Nuo Woxiaoluofu from isolated a kind of by the accurate bi-dimensional cellular shape crystalline network novel material formed of piling up of monolayer carbon atom graphite, it has the performance of a lot of excellences, for example high electronic mobility 2 * 10
5m
2/ (Vs), the heat conductivility 5000W/ (mK) of superelevation, the specific surface area 2630m of super large
2/ g (calculated value) etc., therefore be subject to the generally favor from physics and Material Field investigator always, the studied battery that is applied to, electrical condenser, field-effect transistor, sensor, electromechanical resonator, polymer nanocomposites, electrochemical appliance, and emerging, the traditional field such as light emitting devices.
In recent years, the preparation high dispersive, high density, Graphene hydrophilic or oleophylic and conduction excellence have huge application demand.The main problem that current investigators run into is exactly, due to nano effect, between the lamella of Graphene and lamella, easily form the van der waals forces effect, this causes Graphene to be difficult under high density, in long-time stable existence liquid, the practical application of Graphene basis material is by greatly limited.Investigators disperse constantly to explore aspect problem at Graphene, and probing direction mainly is divided into two large classes, the direct dispersion of a class research Graphene, and another large class is the dispersion of carrying out again after the Graphene initial oxidation is processed in research.These two large class methods all cut both ways.The method that Graphene directly disperses, to the conjugation result that Graphene is complete, destroy less, the excellent properties that can keep Graphene, but owing to lacking good Interface adhesive strength, be difficult to the graphene dispersing solution of accomplishing that high-concentration stable disperses, such as people (Khan U such as Umar Khan, O'Neill A, Lotya M, et al.High ?Concentration Solvent Exfoliation of Graphene[J] .Small, 2010, 6 (7): 864-871.) studied a kind of method for preparing the high concentration graphene dispersion liquid, prepared dispersion liquid concentration can reach 1.2mg/ml, individual layer content can reach 4%.This method depends in N-methyl-2 pyrrolidone long-time lower powered ultrasonic, and ultrasonic time reaches 460h most.But the mean sizes that analysis and observation obtains lamella is still more than 1um, ultrasonicly for a long time be unfavorable for industrialized application.Mustafa Lotya(Lotya M, King P J, Khan U, et al.High-concentration, surfactant-stabilized graphene dispersions[J] .ACS nano, 2010,4 (6): 3155-3162.) utilize the tensio-active agent Sodium cholic acid, the long-time ultrasonic dispersed graphite alkene of peeling off of low power in water, gained graphene dispersing solution concentration can reach 0.3mg/ml, the concentration of the graphene dispersing solution that this method obtains still is difficult to meet application demand, and the interpolation of tensio-active agent has affected the graphene conductive performance.
And the method for Graphene initial oxidation redispersion is had to a large advantage, after oxidation, a lot of oxygen containing polar groups are contained on the surface of Graphene, the existence of these polar groups can make graphene sheet layer and solvent produce stronger interaction force, is dispersed in solvent with high density.This method drawback can produce more defect exactly, affects the heat-conductivity conducting performance of Graphene excellence.Folke Johannes for example
experimental group (
F J, Fabritius M, M ü lhaupt R.Emulsifier ?Free Graphene Dispersions with High Graphene Content for Printed Electronics and Freestanding Graphene Films[J] .Advanced Functional Materials, 2012, 22 (6): 1136-1144.) under the condition of not using any tensio-active agent, through peroxidation, high temperature reduction, the process of high pressure homogenizer, can access the redox graphene dispersion liquid of concentration up to 15mg/ml, and dispersion liquid can prepare and conducts electricity the film of flexible.But film prepared by its dispersion liquid is subject to the impact of defect, do not show the due excellent electric property of Graphene.
Summary of the invention
The purpose of this invention is to provide the preparation method of a kind of high density small pieces footpath graphene dispersing solution, the dispersion liquid made by this method can either reach high density, meets application demand, can guarantee again the satisfactory electrical conductivity of Graphene.
To achieve these goals, the present invention adopts following technical scheme:
The preparation method of a kind of high density small pieces footpath graphene dispersing solution, realize as follows:
1) at first Graphite Powder 99 is obtained to graphite oxide by the Hummers method by its oxidation;
2) then by this graphite oxide reduction, obtain reduction-oxidation graphite;
3) the above-mentioned reduction-oxidation graphite of preparing and solvent are obtained to the reduction-oxidation graphite suspension that concentration is 0.01-10mg/ml together, this reduction-oxidation graphite suspension is packed in the ball grinder of ball mill and carried out ball milling, by ball milling, the reduction-oxidation graphite flake layer is peeled off to fragmentation; Wherein, drum's speed of rotation is controlled at 30-500 rev/min, and Ball-milling Time is 2～300 hours;
4), after ball milling finishes, namely obtain the redox graphene dispersion liquid of stable dispersion; This redox graphene dispersion liquid is centrifugal, and 100～15000 rev/mins of centrifugal rotational speeds, to remove unstripped thicker graphene film fully, and then obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um;
5) by 4) the abundant washing and drying of redox graphene dispersion liquid that step obtains, products therefrom is scattered in common polar solvent according to concentration requirement, namely obtains high density small pieces footpath graphene dispersing solution.
The raw material of above-mentioned Graphite Powder 99 is one or more the mixture in natural graphite, expansible black lead, expanded graphite, high orientation graphite and thermo-cracking graphite.
The method of graphite oxide reduction is to Microwave reduction method or the high temperature reduction method of mechanism for take thermal reduction, and wherein, the temperature of reaction of described high temperature reduction method is 150～400 ° of C.
Above-mentioned solvent is METHYLPYRROLIDONE.
Above-mentioned solvent is one or more mixed solvents that are made into the ratio of 1～99:1 in METHYLPYRROLIDONE and water, methane amide, dimethyl sulfoxide (DMSO), acetonitrile, DMF, hexamethylphosphoramide, methyl alcohol, ethanol, acetic acid, Virahol, pyridine, Tetramethyl Ethylene Diamine, acetone, triethylamine, propyl carbinol, dioxane, tetrahydrofuran (THF), methyl-formiate, Tributylamine, methylethylketone, ethyl acetate, trioctylamine, methylcarbonate, isopropyl ether, trieline, phenyl ether, methylene dichloride, chloroform, ethylene dichloride.
The type of ball mill comprises various star formula ball mills, agitating ball mill, tank abrading-ball grinding machine and horizontal ball mill.
The abrading-ball that ball mill adopts is zirconium oxide balls, steel ball, agate abrading-ball, aluminum oxide abrading-ball or silicon nitride abrading-ball.
Described common polar solvent is one or more the mixture in water, METHYLPYRROLIDONE, methane amide, dimethyl sulfoxide (DMSO), acetonitrile, DMF, hexamethylphosphoramide, methyl alcohol, ethanol, acetic acid, Virahol, pyridine, Tetramethyl Ethylene Diamine, acetone, triethylamine, propyl carbinol, dioxane, tetrahydrofuran (THF), methyl-formiate, Tributylamine, methylethylketone, ethyl acetate, trioctylamine, methylcarbonate, ether, isopropyl ether, n-butyl ether, trieline, phenyl ether, methylene dichloride, chloroform, ethylene dichloride.
After adopting such scheme, compared with prior art, the present invention has the following advantages:
1) to prepare graphene dispersing solution technique simple for the inventive method, and equipment is simple, and cost is low, is applicable to scale operation.
2) by the inventive method, can access the graphene dispersing solution that high-concentration stable disperses.We have prepared the dispersion liquid that concentration is 10mg/ml at present, meet application demand fully.The stability aspect, the obvious reunion of nothing, demixing phenomenon in 1 year;
3) graphene dispersing solution for preparing of the present invention, peeled off into the structure of the Graphite Powder 99 of three-dimensional order most of sheet footpath at the individual layer of 100～1000nm or be less than the graphene film of 5 layers.Product conductivity excellence.
The accompanying drawing explanation
Fig. 1 is preparation flow figure of the present invention;
Fig. 2 is the transmission electron micrograph of high density small pieces footpath graphene dispersing solution.
Embodiment
The preparation method of high density small pieces of the present invention footpath graphene dispersing solution, its preparation flow as shown in Figure 1.By the high density small pieces footpath graphene dispersing solution that the inventive method prepares, its transmission electron micrograph as shown in Figure 2.
Embodiment 1:
The 2.0g natural graphite powder is obtained to graphite oxide by the Hummers method by its oxidation; The graphite oxide made is dried at the temperature of 45 ° of C, the 0.3g graphite oxide of getting after oven dry is put into microwave reactor reaction 20 seconds, obtains reduction-oxidation graphite.Take 0.075g reduction-oxidation graphite, itself and 30ml METHYLPYRROLIDONE are mixed, obtain the reduction-oxidation graphite suspension.Get the zirconium white pearl of zirconium content more than 97%, the reduction-oxidation graphite suspension is packed in the ball grinder of star formula ball mill and carried out ball milling, drum's speed of rotation is controlled at the speed of 320 rev/mins, and the reduction-oxidation graphite flake layer is peeled off to fragmentation, and Ball-milling Time is set to 5 hours.After ball milling finishes, namely obtain the reduced graphene dispersion liquid of the stable dispersion of black.For obtaining the less Graphene in sheet footpath, we are further centrifugal by the redox graphene dispersion liquid, and 6000 rev/mins of centrifugal rotational speeds, set of time are 15 minutes, to remove unstripped thicker graphene film fully, obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um.The abundant washing and drying products therefrom of the dispersion liquid more than obtained, can be scattered in water, and can be according to the required 5.0mg/ml dispersion liquid that is configured to of concentration.
Embodiment 2:
2.0g expansible black lead powder is obtained to graphite oxide by the Hummers method by its oxidation; 45 ° of C of the graphite oxide that makes are dried, get the 0.3g graphite oxide and put into the retort furnace 30 minutes that is warming up to 150 ° of C, obtain reduction-oxidation graphite, repeatedly prepare the reduction-oxidation graphite of q.s.Take 10g reduction-oxidation graphite, itself and 1000ml are mixed with the mixed solvent that the volume ratio of 9:1 mixes by METHYLPYRROLIDONE and water, obtain the reduction-oxidation graphite suspension.Get the steel ball pearl, the reduction-oxidation graphite suspension is packed in the ball grinder of agitating ball mill and carried out ball milling, drum's speed of rotation is controlled at the speed of 350 rev/mins, and the reduction-oxidation graphite flake layer is peeled off to fragmentation, and Ball-milling Time is set to 300 hours.After ball milling finishes, namely obtain the reduced graphene dispersion liquid of the stable dispersion of black.For obtaining the less Graphene in sheet footpath, we are further centrifugal by the redox graphene dispersion liquid, and 2000 rev/mins of centrifugal rotational speeds, set of time are 30 minutes, to remove unstripped thicker graphene film fully, obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um.The abundant washing and drying products therefrom of the dispersion liquid more than obtained, can be scattered in METHYLPYRROLIDONE, and can be according to the required 10.0mg/ml dispersion liquid that is configured to of concentration.
Embodiment 3:
2.0g expansible black lead powder is obtained to graphite oxide by the Hummers method by its oxidation; 45 ° of C of the graphite oxide that makes are dried, get the 0.3g graphite oxide and put into the retort furnace 30 minutes that is warming up to 300 ° of C, obtain reduction-oxidation graphite, repeatedly prepare the reduction-oxidation graphite of q.s.Take 5g reduction-oxidation graphite, itself and 1000ml are mixed with the mixed solvent that the volume ratio of 9:1 mixes by METHYLPYRROLIDONE and ethanol, obtain the reduction-oxidation graphite suspension.Get the agate ball pearl, will in reduction-oxidation graphite suspension tank filling abrading-ball grinding machine, carry out ball milling, drum's speed of rotation is controlled at the speed of 250 rev/mins the reduction-oxidation graphite flake layer is peeled off to fragmentation, and Ball-milling Time is set to 24 hours.After ball milling finishes, namely obtain the reduced graphene dispersion liquid of the stable dispersion of black.For obtaining the less Graphene in sheet footpath, we are further centrifugal by the redox graphene dispersion liquid, and 3000 rev/mins of centrifugal rotational speeds, set of time are 15 minutes, to remove unstripped thicker graphene film fully, obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um.The abundant washing and drying products therefrom of the dispersion liquid more than obtained, can be scattered in DMF, and can be according to the required 10.0mg/ml dispersion liquid that is configured to of concentration.
Embodiment 4:
The 2.0g expanded graphite is obtained to graphite oxide by the Hummers method by its oxidation; 45 ° of C of the graphite oxide that makes are dried, get the 0.3g graphite oxide and put into the retort furnace 30 minutes that is warming up to 400 ° of C, obtain reduction-oxidation graphite, repeatedly prepare the reduction-oxidation graphite of q.s.Take 3.75kg reduction-oxidation graphite, itself and 500L are mixed to the reduction-oxidation graphite suspension obtained by METHYLPYRROLIDONE and acetone with the mixed solvent that the volume ratio of 9:1 mixes.Get the aluminum oxide pearl, the reduction-oxidation graphite suspension is packed in horizontal ball mill and carried out ball milling, drum's speed of rotation is controlled at the speed of 35 rev/mins, and the reduction-oxidation graphite flake layer is peeled off to fragmentation, and Ball-milling Time is set to 72 hours.After ball milling finishes, namely obtain the reduced graphene dispersion liquid of the stable dispersion of black.For obtaining the less Graphene in sheet footpath, we are further centrifugal by the redox graphene dispersion liquid, and 4000 rev/mins of centrifugal rotational speeds, set of time are 15 minutes, to remove unstripped thicker graphene film fully, obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um.The abundant washing and drying products therefrom of the dispersion liquid more than obtained, can be scattered in tetrahydrofuran (THF), and can be according to the required 1.0mg/ml dispersion liquid that is configured to of concentration.
Embodiment 5:
The high orientation of 2.0g graphite is obtained to graphite oxide by the Hummers method by its oxidation; The 45 ° of C of graphite oxide that make are dried, get the 0.3g graphite oxide and put into microwave reactor reaction 20 seconds, obtain reduction-oxidation graphite.Take 0.3mg reduction-oxidation graphite, itself and 30ml are mixed with the mixed solvent that the volume ratio of 9:1 mixes by METHYLPYRROLIDONE and chloroform, obtain the reduction-oxidation graphite suspension.Get the silicon nitride abrading-ball, the reduction-oxidation graphite suspension is packed in the ball grinder of star formula ball mill and carried out ball milling, drum's speed of rotation is controlled at the speed of 350 rev/mins, and the reduction-oxidation graphite flake layer is peeled off to fragmentation, and Ball-milling Time is set to 96 hours.After ball milling finishes, namely obtain the reduced graphene dispersion liquid of the stable dispersion of black.For obtaining the less Graphene in sheet footpath, we are further centrifugal by the redox graphene dispersion liquid, and 5000 rev/mins of centrifugal rotational speeds, set of time are 15 minutes, to remove unstripped thicker graphene film fully, obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um.The abundant washing and drying products therefrom of the dispersion liquid more than obtained, can be scattered in methylene dichloride, and can be according to the required 1.0mg/ml dispersion liquid that is configured to of concentration.
Embodiment 6:
2.0g thermo-cracking graphite is obtained to graphite oxide by the Hummers method by its oxidation; 45 ° of C of the graphite oxide that makes are dried, get the 0.3g graphite oxide and put into the retort furnace 30 minutes that is warming up to 200 ° of C, obtain reduction-oxidation graphite, repeatedly prepare the reduction-oxidation graphite of q.s.Take 1g reduction-oxidation graphite, itself and 1000ml are mixed with the mixed solvent that the volume ratio of 9:1 mixes by METHYLPYRROLIDONE and propyl carbinol, obtain the reduction-oxidation graphite suspension.Get the steel ball pearl, the reduction-oxidation graphite suspension is packed in the ball grinder of agitating ball mill and carried out ball milling, drum's speed of rotation is controlled at the speed of 210 rev/mins the reduction-oxidation graphite flake layer is peeled off to fragmentation, and Ball-milling Time is set to 120 hours.After ball milling finishes, namely obtain the reduced graphene dispersion liquid of the stable dispersion of black.For obtaining the less Graphene in sheet footpath, we are further centrifugal by the redox graphene dispersion liquid, and 7000 rev/mins of centrifugal rotational speeds, set of time are 15 minutes, to remove unstripped thicker graphene film fully, obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um.The abundant washing and drying products therefrom of the dispersion liquid more than obtained, can be scattered in methyl alcohol, and can be according to the required 1.0mg/ml dispersion liquid that is configured to of concentration.
Embodiment 7:
The high orientation of 2.0g graphite is obtained to graphite oxide by the Hummers method by its oxidation; 45 ° of C of the graphite oxide that makes are dried, get the 0.3g graphite oxide and put into the retort furnace 30 minutes that is warming up to 240 ° of C, obtain reduction-oxidation graphite, repeatedly prepare the reduction-oxidation graphite of q.s.Take 10g reduction-oxidation graphite, itself and 1000ml are mixed with the mixed solvent that the volume ratio of 9:1 mixes by METHYLPYRROLIDONE and DMF, obtain the reduction-oxidation graphite suspension.Get the agate ball pearl, will in reduction-oxidation graphite suspension tank filling abrading-ball grinding machine, carry out ball milling, drum's speed of rotation is controlled at the speed of 150 rev/mins, and the reduction-oxidation graphite flake layer is peeled off to fragmentation, and Ball-milling Time is set to 200 hours.After ball milling finishes, namely obtain the reduced graphene dispersion liquid of the stable dispersion of black.For obtaining the less Graphene in sheet footpath, we are further centrifugal by the redox graphene dispersion liquid, and 15000 rev/mins of centrifugal rotational speeds, set of time are 15 minutes, to remove unstripped thicker graphene film fully, obtain the redox graphene dispersion liquid that the sheet footpath is less than 1um.The abundant washing and drying products therefrom of the dispersion liquid more than obtained, can be scattered in methyl-formiate, and can be according to the required 1.0mg/ml dispersion liquid that is configured to of concentration.
Claims (8)
1. the preparation method of high density small pieces footpath graphene dispersing solution, is characterized in that, realizes as follows:
1) at first Graphite Powder 99 is obtained to graphite oxide by the Hummers method by its oxidation;
2) then by this graphite oxide reduction, obtain reduction-oxidation graphite;
3) the above-mentioned reduction-oxidation graphite of preparing and solvent are obtained to the reduction-oxidation graphite suspension that concentration is 0.01-10mg/ml together, this reduction-oxidation graphite suspension is packed in the ball grinder of ball mill and carried out ball milling, by ball milling, the reduction-oxidation graphite flake layer is peeled off to fragmentation; Wherein, drum's speed of rotation is controlled at 30-500 rev/min, and Ball-milling Time is 2～300 hours;
4), after ball milling finishes, namely obtain the redox graphene dispersion liquid of stable dispersion; This redox graphene dispersion liquid is centrifugal, and 100～15000 rev/mins of centrifugal rotational speeds, to remove unstripped thicker graphene film fully, and then obtain the redox graphene dispersion liquid that particle diameter is less than 1um;
5) by 4) the abundant washing and drying of redox graphene dispersion liquid that step obtains, products therefrom is scattered in common polar solvent according to concentration requirement, namely obtains high density small pieces footpath graphene dispersing solution.
2. the preparation method of high density small pieces according to claim 1 footpath graphene dispersing solution is characterized in that: the raw material of above-mentioned Graphite Powder 99 is one or more the mixture in natural graphite, expansible black lead, expanded graphite, high orientation graphite and thermo-cracking graphite.
3. the preparation method of high density small pieces according to claim 1 footpath graphene dispersing solution, it is characterized in that: by the method for graphite oxide reduction for take Microwave reduction method or the high temperature reduction method of thermal reduction as mechanism, wherein, the temperature of reaction of described high temperature reduction method is 150～400 ° of C.
4. the preparation method of high density small pieces according to claim 1 footpath graphene dispersing solution, it is characterized in that: above-mentioned solvent is METHYLPYRROLIDONE.
5. the preparation method of high density small pieces according to claim 1 footpath graphene dispersing solution, it is characterized in that: above-mentioned solvent is by METHYLPYRROLIDONE and water, methane amide, dimethyl sulfoxide (DMSO), acetonitrile, N, dinethylformamide, hexamethylphosphoramide, methyl alcohol, ethanol, acetic acid, Virahol, pyridine, Tetramethyl Ethylene Diamine, acetone, triethylamine, propyl carbinol, dioxane, tetrahydrofuran (THF), methyl-formiate, Tributylamine, methylethylketone, ethyl acetate, trioctylamine, methylcarbonate, isopropyl ether, trieline, phenyl ether, methylene dichloride, chloroform, the mixed solvent that one or more in ethylene dichloride are made into the ratio of 1～99:1.
6. the preparation method of high density small pieces according to claim 1 footpath graphene dispersing solution, it is characterized in that: the type of ball mill comprises various star formula ball mills, agitating ball mill, tank abrading-ball grinding machine and horizontal ball mill.
7. the preparation method of high density small pieces according to claim 1 footpath graphene dispersing solution, it is characterized in that: the abrading-ball that ball mill adopts is zirconium oxide balls, steel ball, agate abrading-ball, aluminum oxide abrading-ball or silicon nitride abrading-ball.
8. the preparation method of high density small pieces according to claim 1 footpath graphene dispersing solution, it is characterized in that: described common polar solvent is water, METHYLPYRROLIDONE, methane amide, dimethyl sulfoxide (DMSO), acetonitrile, N, dinethylformamide, hexamethylphosphoramide, methyl alcohol, ethanol, acetic acid, Virahol, pyridine, Tetramethyl Ethylene Diamine, acetone, triethylamine, propyl carbinol, dioxane, tetrahydrofuran (THF), methyl-formiate, Tributylamine, methylethylketone, ethyl acetate, trioctylamine, methylcarbonate, ether, isopropyl ether, n-butyl ether, trieline, phenyl ether, methylene dichloride, chloroform, the mixture of one or more in ethylene dichloride.
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