CN107879332B - Method for preparing graphene by stripping graphite by time-space synchronous ultrasonic ball milling method - Google Patents
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Abstract
The invention discloses a method for preparing graphene by stripping graphite by a time-space synchronous ultrasonic ball milling method, which comprises the following steps: adding a graphite raw material and a stripping reagent into ultrasonic ball milling equipment, carrying out ball milling for 2-96 h in an ultrasonic environment, and separating, washing and drying the mixture to obtain graphene powder. The method adopts a time-space synchronous ultrasonic method and a ball milling method to strip graphite, and the two methods have synergistic effect to lead graphite interlayer in-situ expansion to be simultaneously subjected to ball milling strong shearing force. The method has the advantages of high efficiency and high yield, and is suitable for preparing the graphene in batches.
Description
Technical Field
The invention relates to a preparation method of graphene, in particular to a method for preparing graphene by stripping graphite by a time-space synchronous ultrasonic ball milling method.
Background
Graphene is a two-dimensional material consisting of a single layer of carbon atoms. Since the discovery of graphene, due to its peculiar properties, it is receiving attention from researchers, and has been developing a wide application prospect in the fields of new energy, new materials, etc.
At present, the preparation method of graphene in batches is mainly divided into a chemical oxidation-reduction method, a physical stripping method and a chemical vapor deposition method. The chemical oxidation-reduction method has the advantage of easy mass preparation, but also has the defect of generating a large amount of waste acid and heavy metal pollution. Although the chemical vapor deposition method can prepare graphene films and a small amount of powder in batches, the method needs harsh conditions such as high temperature and the like, and the prepared graphene is mostly in a film form and is not beneficial to being used as a filler additive. In contrast, the physical stripping method has the potential for large-scale preparation of graphene. The physical stripping method mainly utilizes mechanical external force to overcome Van der Waals force between graphite layers, so that the graphite layers are stripped from top to bottom to form the graphene nanosheets.
The ultrasonic stripping method is to utilize the cavitation of ultrasonic waves to weaken and overcome the van der Waals attraction between graphene layers, and specifically to strip and disperse graphene by strong impact and pressure fluctuation generated by the growth and the rupture of micro-nano foams caused by the ultrasonic waves. N-methylpyrrolidone was the earlier solvent for ultrasonic exfoliation of graphene, which resulted in 0.01mg/mL graphene dispersion (Adv Funct Mater,2009,19, 3680). Ortho-dichlorobenzene was also used as a reagent for ultrasonic exfoliation of graphene, and a dispersion of 0.03mg/mL was obtained (Nano Lett,2009,9, 3460). The method for preparing graphene by stripping graphite by the ultrasonic method is simple and feasible, but the graphene obtained by the method has low dispersion concentration which is generally less than 0.01mg/mL, and the generated stripping force is weak and the stripping efficiency is low.
The common ball milling method is also one of the methods for preparing graphene, and the method utilizes the strong shearing force generated by mutual impact and rolling of ball milling media to strip graphite. The Chinese patent CN103570005A mixes graphite with sodium sulfate and the like, then ball-milling is carried out for 8-12 hours at a high speed, and then purifying is carried out to obtain graphene powder. In patent CN105883773A, graphite is mixed with sodium benzenesulfonate, cyclopentadiene, a sand grinding agent and the like, ball-milled at 2000rpm for 4-48 hours, and then separated and purified to obtain graphene powder. The ball milling method is convenient for equipment maintenance and operation, and can prepare a large amount of graphene, but the method has long preparation time and low graphene yield.
In summary, the graphene prepared by the current mechanical stripping method has the defects of low yield and low preparation efficiency, and a method for simultaneously acting on graphite in the same time and space by using an ultrasonic mode and a ball milling mode for graphene stripping does not exist in the prior art.
Disclosure of Invention
The invention aims to provide a high-efficiency method for preparing graphene by stripping graphite by a time-space synchronous ultrasonic ball milling method.
In order to achieve the purpose, the method for preparing the graphene by stripping the graphite by the time-space synchronous ultrasonic ball milling method, provided by the invention, comprises the following steps: adding a graphite raw material and a stripping reagent into ultrasonic ball milling equipment, carrying out ball milling in an ultrasonic environment, wherein the ball milling time is preferably 2-96 h, and separating and drying the mixture to obtain graphene powder.
Optionally, the stripping agent is an organic solvent comprising N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, isopropanol, acetone, ethanol, cyclohexanone, chloroform, a fluorine-containing aromatic hydrocarbon, octafluorotoluene, hexafluorobenzene, pentafluorobenzonitrile, pentafluoropyrimidine, trichloromethane, cyclopentanone, dimethyl sulfoxide, tetrahydrofuran, γ -butyrolactone, N-dodecylpyrrolidone, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone.
Optionally, the stripping agent is a surfactant-water system configured by a surfactant and water, and the surfactant comprises: sodium cholate, sodium deoxycholate, taurine sodium cholate, 3- [ (3-cholamidopropyl) dimethylamino ] disulfonic acid inner salt, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, didodecyldimethylammonium bromide, dodecyl maltose, polyvinylpyrrolidone, sodium polystyrene sulfonate, polyoxyethylene stearate, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, sorbitan monooleate polyoxyethylene ether, polyethylene glycol octyl phenyl ether and cellulose nanocrystal.
Optionally, the stripping agent is a conjugated structure molecule solvent, and the conjugated structure molecule comprises: 1-aminopyrene, 1-pyrenemethylamine hydrochloride, pyrene, benzylamine, 7,8, 8-tetracyano-p-benzoquinodimethane, 9-anthracenecarboxylic acid, 1-pyrenebutanol, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenesulfonic acid hydrate, 1-pyrenesodium sulfonate, 6, 8-dihydroxy-1, 3-pyrene sulfonate, 8-hydroxypyrene 1,3, 6-trisulfonic acid sodium salt, 1,3,6, 8-pyrenetetrasulfonic acid sodium salt, N-dimethyl diazapyrene chloride salt and coronenetetracarboxylic acid potassium salt.
Optionally, the stripping agent is an ionic liquid, the cation of the ionic liquid comprises one or more of an imidazole cation, a pyridine cation, a quaternary ammonium salt cation, and a quaternary phosphonium salt cation, and the anion of the ionic liquid comprises one or more of a tetrafluoroborate anion, a hexafluorophosphate anion, a chloride ion, and a bromide ion.
Optionally, the stripping agent is an ionic liquid-filler shear thickening system configured from an ionic liquid and a filler; wherein the cation of the ionic liquid comprises one or more of an imidazole cation, a pyridine cation, a quaternary ammonium salt cation, and a quaternary phosphonium salt cation, and the anion of the ionic liquid comprises one or more of a tetrafluoroborate anion, a hexafluorophosphate anion, a chloride ion, and a bromide ion; the filler comprises one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, nickel oxide, copper oxide, beryllium oxide, carbon spheres, polymer microspheres and carbon nanotubes, and the size of the filler is 1 nm-100 mu m. The shear thickening system is characterized in that the viscosity of the system shows 2-3 orders of magnitude increase along with the increase of the shear rate. According to the scheme, by utilizing the shear thickening characteristic of a shear thickening system, the viscosity is greatly increased at a certain shear rate, and graphene can be stripped from a graphite raw material; and when the high shear rate is removed, the viscosity of the mixed liquid is greatly reduced, and the mixed liquid is in a fluid state, so that the separation and collection of graphene are facilitated.
Optionally, the graphite starting material comprises one or more of natural graphite, synthetic graphite, expanded graphite, graphite fluoride and graphite oxide.
Preferably, the ultrasonic power of the ultrasonic ball milling equipment is 0.2-1000 kW, and the rotating speed is 100-750 rpm.
The invention has the beneficial effects that: the method utilizes the synergistic stripping action of the ultrasonic and the ball milling in the same time and space to strip the graphite, namely the material is subjected to the synergistic action of the strong shearing of the ball milling while being subjected to the ultrasonic cavitation of the ultrasonic wave, so that the graphite interlayer is subjected to the strong shearing force of the ball milling while being expanded in situ, and the graphene can be prepared in batches more easily. The synergistic effect is generated by the synergistic effect of ultrasonic cavitation between graphite layers and the strong shearing effect of ball milling in the same time and space. The method has the advantages of unique process, mild conditions and controllable cost, and is suitable for preparing the graphene in batches.
Drawings
Fig. 1 to 3 are transmission electron microscope photographs of the graphene prepared in examples 1,3 and 5, respectively.
Detailed Description
The method for preparing the graphene by stripping the graphite by the time-space synchronous ultrasonic ball milling method comprises the following steps: adding a graphite raw material and a stripping reagent into ultrasonic ball milling equipment, and carrying out ball milling for 2-96 h in an ultrasonic environment, wherein the ultrasonic power of the ultrasonic ball milling equipment is 0.2-1000 kW, and the rotating speed is 100-750 rpm. And separating, washing and drying the mixture to obtain graphene powder. The stripping agent may be used in several types of reagents:
1) conventional organic stripping solvents including N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, isopropanol, acetone, ethanol, cyclohexanone, chloroform, fluorine-containing aromatic hydrocarbons, octafluorotoluene, hexafluorobenzene, pentafluorobenzonitrile, pentafluoropyrimidine, trichloromethane, cyclopentanone, dimethyl sulfoxide, tetrahydrofuran, γ -butyrolactone, N-dodecylpyrrolidone, N-vinylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone;
2) a surfactant-water system formulated from a surfactant and water, the surfactant comprising: sodium cholate, sodium deoxycholate, sodium taurocholate, 3- [ (3-cholamidopropyl) dimethylamino ] disulfonate, sodium dodecylbenzenesulfonate, didodecyldimethylammonium bromide, dodecylmaltose, polyvinylpyrrolidone, sodium polystyrene sulfonate, polyoxyethylene stearate, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, sorbitan monooleate polyoxyethylene ether, polyethylene glycol octylphenyl ether, and cellulose nanocrystal;
3) a conjugated structure molecule solvent, the conjugated structure molecule comprising: 1-aminopyrene, 1-pyrenemethylamine hydrochloride, pyrene, benzylamine, 7,8, 8-tetracyano-p-benzoquinodimethane, 9-anthracenecarboxylic acid, 1-pyrenebutanol, 1-pyrenecarboxylic acid, 1-pyrenebutyric acid, 1-pyrenesulfonic acid hydrate, 1-pyrenesodium sulfonate, 6, 8-dihydroxy-1, 3-pyrene sulfonate, 8-hydroxypyrene 1,3, 6-trisulfonic acid sodium salt, 1,3,6, 8-pyrenetetrasulfonic acid sodium salt, N-dimethyl diazapyrene chloride salt and coronenetetracarboxylic acid potassium salt.
4) An ionic liquid consisting of a cation and an anion, wherein the cation comprises an imidazole cation, a pyridine cation, a quaternary ammonium salt cation or a quaternary phosphonium salt cation, and the anion comprises a tetrafluoroborate anion, a hexafluorophosphate anion, a chloride ion or a bromide ion;
5) the ionic liquid-filler shear thickening system is prepared from the ionic liquid and a filler, wherein the filler comprises one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, nickel oxide, copper oxide, beryllium oxide, carbon spheres, polymer microspheres and carbon nanotubes, and the size of the filler is 1 nm-100 mu m.
The present invention will be described in further detail with reference to specific examples.
Example 1
Putting 5g of graphite and 50ml of N-methyl pyrrolidone into an ultrasonic ball mill, controlling the ultrasonic power at 1.5kW, carrying out ball milling at the rotating speed of 500rpm, carrying out ultrasonic ball milling for 2 hours, and separating, washing and drying the product to obtain graphene powder.
Example 2
Putting 5g of graphite and 150mL of N, N-dimethylformamide into an ultrasonic ball mill, controlling the ultrasonic power at 5kW, controlling the ball milling rotation speed at 500rpm, and carrying out ultrasonic ball milling for 1h, and then separating, washing and drying the product to obtain graphene powder.
Example 3
Putting 5g of graphite and 50mL of 1-butyl-3-methylimidazolium hexafluorophosphate into an ultrasonic ball mill, controlling the ultrasonic power at 2.5kW, controlling the ball milling rotation speed at 500rpm, and performing ultrasonic ball milling for 3 hours, and separating, washing and drying the product to obtain graphene powder.
Example 4
Putting 5g of graphite, 5g of polyethylene oxide-propylene oxide-ethylene oxide (P123) aqueous solution and 150mL of water into an ultrasonic ball mill, controlling the ultrasonic power at 5kW, carrying out ball milling at the rotating speed of 500rpm, carrying out ultrasonic ball milling for 1h, and separating, washing and drying the product to obtain graphene powder.
Example 5
Putting 5g of graphite, 5g of sodium dodecyl benzene sulfonate and 150mL of water into an ultrasonic ball mill, controlling the ultrasonic power at 5kW, carrying out ball milling at the rotating speed of 500rpm, carrying out ultrasonic ball milling for 1h, and separating, washing and drying the product to obtain graphene powder.
Example 6
The ionic liquid-silica shear thickening system adopted in the embodiment specifically comprises: taking 15g of nano silicon dioxide, adding the nano silicon dioxide into 50mL of 1-hydroxyethyl-3-methylimidazole tetrafluoroborate, performing ultrasonic dispersion for 1h, adding 5g of graphite, controlling the ultrasonic power at 5kW, performing ball milling at the rotating speed of 500rpm, performing ultrasonic ball milling for 1h, and separating, washing and drying the product to obtain graphene powder.
Comparative example 1
5g of graphite and 50mL of N-methylpyrrolidone are firstly put into a common ultrasonic machine for 1.5kW, are subjected to ultrasonic treatment for 2 hours, are then put into a ball mill for ball milling for 2 hours at the rotating speed of 500rpm, and are separated, washed and dried to obtain graphene powder.
Comparative example 2
And (3) transferring 5g of graphite and 50mL of N-methyl pyrrolidone into a ball mill for ball milling for 2h at the rotating speed of 500rpm, and separating, washing and drying the product to obtain graphene powder.
Comparative example 3
And (3) transferring 5g of graphite and 50mL of N-methyl pyrrolidone into a ball mill for ball milling for 2h at the rotating speed of 500rpm, putting the graphite and the N-methyl pyrrolidone into a common ultrasonic machine for 1.5kW, and performing ultrasonic treatment on a product for 2 hours to obtain graphene powder through separation, washing and drying.
Analysis of results
The concentrations of the dispersions (before separation) and the yields of graphene prepared in the examples and the comparative examples were measured and compared with the concentrations of the dispersions disclosed in the literature, and the results are shown in table 1.
Table 1 graphene yield and dispersion concentration in each example, comparative example and literature
As shown in the above table, the graphene prepared in each example has a graphene dispersion concentration of 2.5-8.9 mg/mL, and the yield of graphene is lower than five layers, that is, the mass percentage of graphene in all graphene is 65-78% lower than five layers (including 5 layers). In the comparison example, the concentration of the graphene dispersion liquid is 0.11-0.16 mg/mL, and the yield of the graphene is 9-18% when the graphene is lower than five layers; the graphene dispersion described in the reference has a concentration of 0.01 to 0.7 mg/mL. The comparison shows that the concentration of the graphene dispersion liquid and the yield of the graphene which is lower than five layers are far higher than those of the comparison example and the reference document, and the graphene dispersion liquid is suitable for preparing a large amount of high-concentration and high-stability dispersed graphene.
The transmission electron micrographs of the graphene products prepared in example 1, example 3 and example 5 are shown in fig. 1, fig. 2 and fig. 3, respectively. As can be seen from the photographs: the transmission electron microscope photographs of the graphene products prepared in example 1, example 3 and example 5 are all semitransparent, complete in structure and few in layer number.
Claims (7)
1. A method for preparing graphene by stripping graphite by a time-space synchronous ultrasonic ball milling method is characterized by comprising the following steps: the method comprises the following steps: adding a graphite raw material and a stripping reagent into an ultrasonic ball milling device, carrying out ball milling in an ultrasonic environment, and utilizing the synergistic stripping effect of the ultrasonic and the ball milling in the same time and space to ensure that the graphite interlayer is subjected to strong shearing force of the ball milling while in-situ expanding so as to strip graphene, and separating and drying the stripped mixture to obtain graphene powder; the ultrasonic power of the ultrasonic ball milling equipment is 0.2-100 kW, the rotating speed is 100-750 rpm, and the ball milling time in the ultrasonic environment is 2-96 hours.
2. The method for preparing graphene by stripping graphite by the spatiotemporal synchronous ultrasonic ball milling method according to claim 1, which is characterized in that: the stripping reagent is an organic solvent, and the organic solvent comprises any one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, isopropanol, acetone, ethanol, cyclohexanone, chloroform, fluorine-containing aromatic hydrocarbon, octafluorotoluene, hexafluorobenzene, pentafluorobenzonitrile, pentafluoropyrimidine, trichloromethane, cyclopentanone, dimethyl sulfoxide, tetrahydrofuran, gamma-butyrolactone, N-dodecyl pyrrolidone, N-vinyl pyrrolidone or 1, 3-dimethyl-2-imidazolidinone.
3. The method for preparing graphene by stripping graphite by the spatiotemporal synchronous ultrasonic ball milling method according to claim 1, which is characterized in that: the stripping reagent is a surfactant-water system prepared from a surfactant and water, and the surfactant comprises: sodium cholate, sodium deoxycholate, sodium taurocholate, 3- [ (3-cholamidopropyl) dimethylamino ] disulfonate, sodium dodecylbenzenesulfonate, didodecyldimethylammonium bromide, dodecylmaltose, polyvinylpyrrolidone, sodium polystyrenesulfonate, polyoxyethylene stearate, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, sorbitan monooleate polyoxyethylene ether, polyethylene glycol octylphenyl ether, or cellulose nanocrystal.
4. The method for preparing graphene by stripping graphite by the space-time synchronous ultrasonic ball milling method according to claim 1, which is characterized in that: the stripping reagent is a conjugated structure molecule solvent, and the conjugated structure molecule comprises: any one of 1-aminopyrene, 1-pyrenemethylamine hydrochloride, pyrene, benzylamine, 7,8, 8-tetracyano-p-phenylenediamine dimethane, 9-anthracenecarboxylic acid, 1-pyrenebutanol, 1-pyrenecarboxylic acid, 1-pyrenebutanoic acid, 1-pyrenesulfonic acid hydrate, 1-pyrene sodium sulfonate, 6, 8-dihydroxy-1, 3-pyrene sulfonate, 8-hydroxypyrene 1,3, 6-trisulfonic acid sodium salt, 1,3,6, 8-pyrenetetrasulfonic acid sodium salt or N, N-dimethyl diazapyrene chloride salt.
5. The method for preparing graphene by stripping graphite by the spatiotemporal synchronous ultrasonic ball milling method according to claim 1, which is characterized in that: the stripping agent is an ionic liquid, the cation of the ionic liquid comprises one or more of imidazole cation, pyridine cation, quaternary ammonium salt cation or quaternary phosphonium salt cation, and the anion of the ionic liquid comprises one or more of tetrafluoroborate anion, hexafluorophosphate anion, chloride ion or bromide ion.
6. The method for preparing graphene by stripping graphite by the spatiotemporal synchronous ultrasonic ball milling method according to claim 1, which is characterized in that: the stripping agent is an ionic liquid-filler shear thickening system prepared from ionic liquid-filler; wherein the cation of the ionic liquid comprises one or more of an imidazole cation, a pyridine cation, a quaternary ammonium salt cation, or a quaternary phosphonium salt cation, and the anion of the ionic liquid comprises one or more of a tetrafluoroborate anion, a hexafluorophosphate anion, a chloride ion, or a bromide ion; the filler comprises one or more of silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, nickel oxide, copper oxide, beryllium oxide, carbon spheres, polymer microspheres or carbon nanotubes, and the size of the filler is 1 nm-100 mu m.
7. The method for preparing graphene by stripping graphite by the space-time synchronous ultrasonic ball milling method according to any one of claims 1-5, characterized by comprising the following steps: the graphite raw material comprises one or more of natural graphite, synthetic graphite, expanded graphite, graphite fluoride or graphite oxide.
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