CN110745812A - Method for preparing graphene or graphite film ultra-quickly - Google Patents
Method for preparing graphene or graphite film ultra-quickly Download PDFInfo
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Abstract
The invention relates to the field of preparation of graphene and a graphite film, in particular to an ultrafast preparation method of graphene or a graphite film, which is suitable for efficient preparation of graphene and the graphite film. According to the method, the high-temperature matrix is rapidly cooled (quenched) in the liquid carbon source, and the graphene or graphite film grows on the surface of the matrix by utilizing the cracking of the liquid carbon source in the quenching process. The preparation method disclosed by the invention is simple in preparation process, high in efficiency, low in cost and good in controllability, can be used for preparing films, powder and complex macrostructures of graphene and graphite in batches and composite materials of the films and a matrix, and lays a foundation for the application of the graphene and the graphite films in the fields of electronic devices, photoelectric devices, electrochemical energy storage, anticorrosion and wear-resistant coatings, high-strength and high-conductivity composite materials, transparent conductive films, electromagnetic shielding, heat management and thermoelectricity.
Description
The technical field is as follows:
the invention relates to the field of preparation of graphene and a graphite film, in particular to an ultrafast preparation method of graphene or a graphite film, which is suitable for efficient preparation of graphene and the graphite film.
Background art:
in 2004, scientists at manchester university in the united kingdom obtained graphite sheets, namely graphene, with a single atomic layer and a few atomic layer thick from highly oriented pyrolytic graphite for the first time by mechanical exfoliation. Due to the special two-dimensional structure, the ultrahigh specific surface area, and the excellent physical and chemical properties such as electrical, thermal, mechanical, optical and chemical stability, the material has important application prospects in the aspects of electronic devices, optoelectronic devices, sensing devices, electrochemical energy storage, composite materials, thermal management and the like. The graphite film is a graphite sheet with the thickness ranging from nanometer to micrometer, has the performances of high electric conductivity, high heat conductivity, higher extreme ultraviolet light transmittance and the like, and has important application in the aspects of electromagnetic shielding, heat management, energy storage, extreme ultraviolet lithography and the like.
Efficient preparation of graphene and graphite films is the key to determining their applications. The main preparation methods of graphene at present include a micro-mechanical stripping method, a chemical stripping method and a chemical vapor deposition method. The high-quality graphene is obtained by stripping highly ordered graphite materials such as highly oriented pyrolytic graphite by a micro-mechanical stripping method, but the preparation efficiency is extremely low, and the large-area graphene is difficult to obtain. The chemical stripping method takes graphite powder as a raw material, and weakens the interaction between layers by a chemical method to obtain the graphene. The method can realize large-scale production and has low cost, but the obtained graphene has small size and can inevitably introduce defects in the chemical stripping process, so that high-quality graphene is difficult to obtain. The chemical vapor deposition method adopts a metal matrix, and graphene is assembled and grown on the surface of carbon atoms generated by decomposing carbon sources such as methane at high temperature, so that the obtained graphene has high quality, can realize large-area preparation, has good controllability, but has longer production period and high preparation cost, and is difficult to obtain the graphene with small grain size. The graphite film is mainly prepared by a method of high-temperature pressure treatment of a polymer film at present, and recently, the graphene oxide or graphene film is also reported to be prepared by high-temperature pressure treatment. However, these methods require a long-time high-temperature treatment at-3000 ℃, have a long preparation period (mostly over 1 hour), have high requirements on production equipment, and have high production cost. The graphite film can be obtained by adopting a chemical vapor deposition method and changing experimental conditions, and the method has the problem of long preparation period although the preparation temperature is lower.
The invention content is as follows:
the invention aims to provide a method for preparing graphene or a graphite film at an ultra-fast speed, solves the problems of complex process, long production period, high cost and the like of the existing preparation method, and lays a foundation for researching intrinsic physical properties of the graphene and the graphite film and realizing scale application of the graphene and the graphite film.
The technical scheme of the invention is as follows:
a method for preparing graphene or graphite film ultra-fast is characterized in that a high-temperature matrix is adopted, the graphene or graphite film is rapidly cooled in a liquid carbon source through quenching under the protection of gas, and the graphene or graphite film grows on the surface of the matrix by utilizing the cracking of the liquid carbon source in the quenching process.
According to the method for preparing the graphene or graphite film ultrafast, the matrix is one or more than two of metal, carbide, nitride and oxide, and the shape of the matrix is any shape of foil, porous foam or powder; wherein: the metal is one or more than two of copper, platinum, nickel, cobalt, gold, ruthenium, palladium, molybdenum, tungsten, aluminum, copper-nickel alloy and molybdenum-nickel alloy; the carbide is one or more than two of silicon carbide, tungsten carbide and molybdenum carbide; the nitride is one or more than two of silicon nitride, tungsten nitride and molybdenum nitride; the oxide is one or more of silicon oxide, aluminum oxide, magnesium oxide, copper oxide and nickel oxide.
In the method for ultrafast preparation of graphene or graphite film, the liquid carbon source is a liquid carbon-containing compound, including but not limited to one or more of methanol, ethanol, isopropanol, acetone, benzene, toluene, cyclohexane, acetaldehyde, diethyl ether, acetic acid, ethyl acetate and carbon disulfide; alternatively, the liquid carbon source is a carbon-containing compound which is dissolved in a solvent or is in a molten state and is solid at room temperature, and includes, but is not limited to, paraffin or a high molecular polymer, and the high molecular polymer is one or more of polymethyl methacrylate, polycarbonate, polystyrene, polyethylene and polypropylene.
According to the method for preparing the graphene or the graphite film ultra-fast, the initial temperature of a high-temperature matrix is between the decomposition temperature of a liquid carbon source and the melting point of the matrix, and the temperature of the liquid carbon source is between the solidification temperature of the liquid carbon source and the vaporization temperature of the liquid carbon source.
According to the method for preparing the graphene or the graphite film ultrafast, the protective gas is nitrogen or inert gas or mixed gas of the nitrogen and the inert gas in the preparation process.
The method for preparing the graphene or graphite film at the ultra-fast speed realizes the control of the thickness, the grain size and the crystallinity of the graphene or graphite film by changing the components, the thickness and the initial temperature of the matrix and the type and the temperature of the liquid carbon source.
The method for preparing the graphene or graphite film ultra-fast adopts the quenching method to grow the graphene or graphite film on the surface of the matrix, and adopts the etching method or the electrochemical gas bubbling method to separate the graphene or graphite film from the surface of the matrix or use the graphene or graphite film together with the matrix.
The design principle of the invention is as follows:
according to the invention, the growth matrix is heated to a certain temperature and then placed in the liquid carbon source, the liquid carbon source can be rapidly decomposed to generate a large amount of carbon atoms after contacting the high-temperature matrix, so that a graphene or graphite film is formed on the surface of the substrate, and meanwhile, the temperature of the liquid carbon source can be rapidly reduced along with the heat transfer of the matrix to the liquid carbon source, namely quenching. When the temperature of the substrate is reduced to a certain degree, the energy is not enough to be continuously provided to decompose the liquid carbon source, and the growth of the graphene or the graphite film is stopped. The growth of the graphene or the graphite film occurs in the substrate cooling process, and the cooling rate of the matrix in the liquid carbon source is very high, so the growth rate is very high.
The invention has the advantages and beneficial effects that:
1. the invention provides a brand-new ultra-fast preparation method of graphene and a graphite film, the growth of the graphene and the graphite film can be completed within several seconds, and the method has the advantages of simple process, high efficiency, low requirement on equipment, convenience in operation, low cost, easiness in performance regulation and control and batch preparation.
2. The method can be used for preparing the graphene and complex macroscopic structures such as films, powder and foams of the graphite, and the number of layers and the size of crystal grains of the graphene and the graphite can be regulated and controlled, so that the electrical, thermal, optical and mechanical properties of the graphene and the graphite can be regulated and controlled; and the method can also be used for directly preparing graphene or composite materials of graphite and a matrix.
3. The number of graphene layers obtained by the method is 1-10, the thickness of the graphite film is from several nanometers to several micrometers, the size of crystal grains is 1 nm-100 mu m, and the appearance and the size depend on the shape and the size of a used matrix.
4. The invention provides a premise for the large-scale application of the graphene and the graphite film in the fields of electronic devices, optoelectronic devices, electrochemical energy storage, anticorrosion and wear-resistant coatings, transparent conductive films, electromagnetic shielding, high-strength and high-conductivity composite materials, heat management and the like.
Description of the drawings:
FIG. 1: schematic diagram of ultra-fast preparation of graphene and graphite film quenching method.
FIG. 2: and (3) quenching the prepared graphene by platinum foil with the thickness of 150 mu m and the initial temperature of 1050 ℃ in absolute ethyl alcohol at room temperature. a picture is transferred to SiO after growing on a platinum foil substrate2Optical micrograph of graphene on/Si substrate, b picture is transferred to SiO2The graph c is a light Transmittance curve of the graphene (in the graph, the abscissa wavelet represents the Wavelength nm, and the ordinate Transmittance represents the light Transmittance%), and the graph d is a Raman spectrum of different positions in the graph a (in the graph, the abscissa Raman Shift represents the Raman Shift cm-1The ordinate Intensity represents the relative Intensity a.u.), the plot e is a spherical aberration corrected transmission electron micrograph, the plot f is an atomic structure inside the graphene crystal grains, the plot g is a statistic of the graphene crystal Grain size (in the figure, the abscissa gain size represents the crystal Grain size nm, and the ordinate percent represents the Percentage of different crystal Grain sizes).
FIG. 3: a, c, e are graphs of graphene prepared by quenching a platinum foil with the thickness of 150 μm and the initial temperature of 1000 ℃ in absolute ethanol at room temperature: a picture is transferred to SiO after growing on a platinum foil substrate2Raman spectra on/Si substrate (in the figure, the abscissa Raman Shift represents the Raman Shift cm-1Ordinate Intensity represents relative Intensity a.u.), c is a spherical aberration-corrected transmission electron micrograph of graphene (in the figure, Polymer Residue represents PMMA Residue), and e is a Grain size statistic of graphene (in the figure, abscissa Grain size representsTable grain size nm, the ordinate Percentage represents the Percentage of different grain sizes%). b, d, f are graphene prepared by quenching platinum foil with the thickness of 150 μm and the starting temperature of 950 ℃ in absolute ethyl alcohol at room temperature: b picture is transferred to SiO after growing on a platinum foil substrate2Raman spectra on a/Si substrate (in the figure, the abscissa RamanShift represents the Raman shift cm-1The ordinate Intensity represents the relative Intensity a.u.), d is a spherical aberration corrected transmission electron micrograph of graphene (in the figure, Polymer Residue represents PMMA Residue), and f is the Grain size statistics of graphene (in the figure, the abscissa Grain size represents the Grain size nm and the ordinate percent represents the Percentage of different Grain sizes).
FIG. 4: and (3) quenching the prepared graphene by a platinum foil with the thickness of 150 mu m and the initial temperature of 900 ℃ in absolute ethyl alcohol at room temperature. a picture is transferred to SiO after growing on a platinum foil substrate2Optical micrograph of graphene on/Si substrate, b picture is transferred to SiO2The graph c is a light Transmittance curve of the graphene (in the graph, the abscissa wavelet represents the Wavelength nm, and the ordinate Transmittance represents the light Transmittance%), and the graph d is a Raman spectrum of different positions in the graph a (in the graph, the abscissa Raman Shift represents the Raman Shift cm-1The ordinate Intensity represents the relative Intensity a.u.), the plot e is a spherical aberration corrected transmission electron micrograph of graphene (in the figure, Polymer Residue represents PMMA Residue), the plot f is an atomic structure inside the graphene grains, and the plot g is a Grain size statistic of graphene (in the figure, the abscissa Grain size represents the Grain size nm and the ordinate percent represents the Percentage of different Grain sizes).
FIG. 5: the graphite film is prepared by quenching a nickel foil with the thickness of 100 mu m and the starting temperature of 1200 ℃ in absolute ethyl alcohol at the temperature of 0 ℃. The picture a is an optical photo after the nickel foil growth, and the picture b is a graph of the graphite film transferred to SiO grown on the nickel foil substrate2And c is a transmission electron microscope photograph of the folded part of the graphite film, and d is a transmission electron microscope photograph of spherical aberration correction of the graphite film. The e-diagram is an XRD (in the diagram, the abscissa 2 theta represents the diffraction angle degree, and the ordinate Intensity represents the relative Intensity)a.u.), and f is a Raman spectrum of the graphite film (in the figure, the abscissa Raman Shift represents the Raman Shift cm-1And the ordinate Intensity represents the relative Intensity a.u.).
FIG. 6: and (3) quenching the foamed nickel with the initial temperature of 1000 ℃ in absolute ethanol at room temperature to prepare the multilayer graphene foam. The a diagram is an optical photograph of the nickel foam before growth and the graphene foam/nickel foam after growth (in the figure, Ni foam represents nickel foam, G @ Ni foam represents graphene foam/nickel foam), and the b diagram is a Raman spectrum of multilayer graphene grown on the nickel foam (in the figure, the abscissa Raman Shift represents Raman Shift cm)-1And the ordinate Intensity represents the relative Intensity a.u.).
FIG. 7: the graph a is a growth schematic diagram of graphene coated nickel powder, the graph b is a scanning electron microscope photo of the graphene coated nickel powder, the graph c is a scanning electron microscope photo of graphene on the surface of the nickel powder, and the graph d is a Raman spectrum of the graphene grown on the nickel powder (in the graph, the abscissa Raman Shift represents Raman Shift cm-1And the ordinate Intensity represents the relative Intensity a.u.).
The specific implementation mode is as follows:
in the specific implementation process, the substrate is firstly heated to the preset temperature under the protection of gas, the adopted heating method comprises high-frequency electromagnetic induction heating, resistance wire heating, electric heating furnace heating and the like, then the high-temperature substrate is placed into a liquid carbon source for rapid cooling (quenching), a graphene or graphite film grows on the surface of the substrate by utilizing carbon atoms generated by decomposition of the liquid carbon source in the quenching process, and then the graphene or graphite film is separated from the surface of the substrate by an etching method or a gas bubbling method or is directly used together with the substrate.
The present invention will be described in more detail below with reference to examples and the accompanying drawings.
Example 1
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.150 μm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. And (3) after the temperature of the platinum foil is raised to 1050 ℃, rapidly cooling (quenching) the platinum foil in ethanol (absolute ethyl alcohol, analytically pure) at room temperature, and depositing graphene on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2And (2) dissolving the PMMA on a/Si substrate by using acetone at the temperature of 50 ℃ to remove the PMMA, and completing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are characterized by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is uniform single-layer nanocrystalline graphene, and the average domain size is 10.3 nm.
Example 2
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.150 μm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. After the temperature of the platinum foil is raised to 1000 ℃, the platinum foil is placed in ethanol (absolute ethyl alcohol, analytical pure) at room temperature for rapid cooling (quenching), and graphene is deposited on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2On a/Si substrate, dissolving and removing PMMA by using acetone at the temperature of 50 ℃,and finishing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are characterized by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is uniform single-layer nanocrystalline graphene, and the average domain size is 8.0 nm.
Example 3
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.150 μm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. After the temperature of the platinum foil is raised to 950 ℃, the platinum foil is placed in ethanol (absolute ethyl alcohol, analytical pure) at room temperature for rapid cooling (quenching), and graphene is deposited on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2And (2) dissolving the PMMA on a/Si substrate by using acetone at the temperature of 50 ℃ to remove the PMMA, and completing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are characterized by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is uniform single-layer nanocrystalline graphene, and the average domain size is 5.8 nm.
Example 4
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.150 μm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. After the temperature of the platinum foil is raised to 900 ℃, the platinum foil is placed in ethanol (absolute ethyl alcohol, analytical pure) at room temperature for rapid cooling (quenching), and graphene is deposited on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2And (2) dissolving the PMMA on a/Si substrate by using acetone at the temperature of 50 ℃ to remove the PMMA, and completing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are characterized by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is uniform single-layer nanocrystalline graphene, and the average domain size is 3.6 nm.
Example 5
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.150 μm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. After the temperature of the platinum foil is raised to 1100 ℃, the platinum foil is placed in ethanol (absolute ethyl alcohol, analytical pure) at room temperature for rapid cooling (quenching), and graphene is deposited on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2On a/Si substrate, dissolving and removing PMMA by using acetone at the temperature of 50 ℃ to complete the transfer of graphene。
The uniformity, the number of layers and the domain size of the graphene are characterized by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is single-layer dominant nanocrystalline graphene, and the average domain size is 18.9 nm.
Example 6
First, in this example, a nickel-plated molybdenum foil (nickel-plated layer thickness of 200nm, molybdenum foil size of 20 mm. times.10 mm. times.250 μm, purity of 99.99 wt%) was placed on the upper part of a high-frequency induction heating coil, and heated by high-frequency electromagnetic induction in an argon atmosphere. After the nickel-plated molybdenum foil is heated to 1200 ℃, the nickel-plated molybdenum foil is placed in ethanol (absolute ethyl alcohol, analytical pure) at room temperature for rapid cooling (quenching), and graphene is deposited on the surface of the nickel-plated molybdenum foil in the quenching process. And taking out the nickel-plated molybdenum foil after the temperature of the nickel-plated molybdenum foil is reduced to room temperature, and drying the nickel-plated molybdenum foil in a nitrogen atmosphere.
Then, the surface of the nickel-plated molybdenum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm by using a spin coater, and then the surface is baked at 180 ℃ for 20 minutes and then naturally cooled. Taking the PMMA/graphene-covered nickel-plated molybdenum foil as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode), separating the PMMA/graphene from the nickel-plated molybdenum foil by using hydrogen bubbles generated on the surface of the nickel-plated molybdenum foil under the current of 0.15A, and transferring the PMMA/graphene to SiO2And (2) dissolving the PMMA on a/Si substrate by using acetone at the temperature of 50 ℃ to remove the PMMA, and completing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are represented by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is uniform single-layer nanocrystalline graphene, the average domain size is larger and is 55.2nm
Example 7
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.1 mm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. And (3) after the temperature of the platinum foil is raised to 1050 ℃, rapidly cooling (quenching) the platinum foil in ethanol (absolute ethyl alcohol, analytically pure) at room temperature, and depositing graphene on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2And (2) dissolving the PMMA on a/Si substrate by using acetone at the temperature of 50 ℃ to remove the PMMA, and completing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are characterized by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is a graphene film with double layers as main materials, and the light transmittance at 550nm is 94.6%.
Example 8
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.150 μm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. And (3) after the temperature of the platinum foil is raised to 1050 ℃, rapidly cooling (quenching) the platinum foil in benzene (super grade pure) at room temperature, and depositing graphene on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2On a/Si substrate, then with CAnd (3) dissolving the ketone at the temperature of 50 ℃ to remove PMMA, and completing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are represented by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is a thicker multi-layer graphene film.
Example 9
First, the present example uses a general vertical furnace (the bottom of the quartz tube of the vertical furnace is connected to a glass container filled with ethanol by a flange) to realize the ultrafast growth of the graphite film. An argon gas inlet is arranged at the upper end of the vertical furnace, a nickel foil (30mm multiplied by 40mm multiplied by 100 mu m, the purity is 99.95 wt%) is put down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the nickel foil is raised to 1200 ℃ in an argon gas atmosphere, the nickel foil is made to fall into a glass container filled with 0 ℃ ethanol (absolute ethyl alcohol, analytically pure) to be rapidly cooled (quenched), and the growth of a graphite film is completed in the quenching process. And taking out the nickel foil after the temperature of the nickel foil is reduced to room temperature, and drying the nickel foil in a nitrogen atmosphere.
Then, the surface of the nickel foil on which the graphite film was grown was covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then baked at 180 ℃ for 20 minutes and then naturally cooled. Taking the nickel foil covered with the PMMA/graphite film as the cathode of an electrolytic cell (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, the anode is a platinum electrode), separating the PMMA/graphite film from the nickel foil by using hydrogen bubbles generated on the surface of the nickel foil under the current of 0.03A, and transferring the PMMA/graphite film to SiO2And on a substrate of/Si, PET, PEN and the like, dissolving and removing PMMA by using acetone at the temperature of 50 ℃ to complete the transfer of the graphite film.
The quality, the uniformity and the layer number of the graphite film are characterized by an optical microscope and a Raman spectrometer, and the obtained graphite film is a high-quality graphite film with the average thickness of 77 nm.
Example 10
First, the present example uses a general vertical furnace (the bottom of the quartz tube of the vertical furnace is connected to a glass container filled with ethanol by a flange) to realize the ultrafast growth of the graphite film. An argon gas inlet is arranged at the upper end of the vertical furnace, a nickel foil (30mm multiplied by 40mm multiplied by 100 mu m, the purity is 99.95 wt%) is put down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1100 ℃), after the nickel foil is raised to 1100 ℃ in an argon gas atmosphere, the nickel foil is made to fall into a glass container filled with 0 ℃ ethanol (absolute ethyl alcohol, analytically pure) to be rapidly cooled (quenched), and the growth of a graphite film is completed in the quenching process. And taking out the nickel foil after the temperature of the nickel foil is reduced to room temperature, and drying the nickel foil in a nitrogen atmosphere.
Then, the surface of the nickel foil on which the graphite film was grown was covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then baked at 180 ℃ for 20 minutes and then naturally cooled. Taking the nickel foil covered with the PMMA/graphite film as the cathode of an electrolytic cell (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, the anode is a platinum electrode), separating the PMMA/graphite film from the nickel foil by using hydrogen bubbles generated on the surface of the nickel foil under the current of 0.03A, and transferring the PMMA/graphite film to SiO2And on a substrate of/Si, PET, PEN and the like, dissolving and removing PMMA by using acetone at the temperature of 50 ℃ to complete the transfer of the graphite film.
The quality, the uniformity and the layer number of the graphite film are characterized by an optical microscope and a Raman spectrometer, and the obtained graphite film is a high-quality graphite film with the average thickness of 50 nm.
Example 11
First, the present example uses a general vertical furnace (the bottom of the quartz tube of the vertical furnace is connected to a glass container filled with ethanol by a flange) to realize the ultrafast growth of the graphite film. An argon gas inlet is arranged at the upper end of the vertical furnace, a nickel foil (30mm multiplied by 40mm multiplied by 100 mu m, the purity is 99.95 wt%) is put down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1000 ℃), after the nickel foil is raised to 1000 ℃ in an argon atmosphere, the nickel foil is made to fall into a glass container filled with 0 ℃ ethanol (absolute ethyl alcohol, analytically pure) to be rapidly cooled (quenched), and the growth of a graphite film is completed in the quenching process. And taking out the nickel foil after the temperature of the nickel foil is reduced to room temperature, and drying the nickel foil in a nitrogen atmosphere.
Then, the surface of the nickel foil on which the graphite film was grown was covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then baked at 180 ℃ for 20 minutes and then naturally cooled. Taking the nickel foil covered with the PMMA/graphite film as the cathode of an electrolytic cell (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, the anode is a platinum electrode), separating the PMMA/graphite film from the nickel foil by using hydrogen bubbles generated on the surface of the nickel foil under the current of 0.03A, and transferring the PMMA/graphite film to SiO2And on a substrate of/Si, PET, PEN and the like, dissolving and removing PMMA by using acetone at the temperature of 50 ℃ to complete the transfer of the graphite film.
The quality, the uniformity and the layer number of the graphite film are characterized by an optical microscope and a Raman spectrometer, and the obtained graphite film is a high-quality graphite film with the average thickness of 26 nm.
Example 12
First, in this example, a platinum foil (platinum foil 20 mm. times.10 mm. times.1 mm, purity: 99.99 wt%) was placed on the upper portion of a high-frequency induction heating coil, and heated in an argon atmosphere using high-frequency electromagnetic induction. After the temperature of the platinum foil is raised to 1200 ℃, the platinum foil is placed in ethanol (absolute ethyl alcohol, analytical pure) at room temperature for rapid cooling (quenching), and graphene is deposited on the surface of the platinum foil in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil on which the graphene is grown is covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%), and is uniformly spin-coated for 60 seconds at 2000 rpm using a spin coater, and then the platinum foil is baked at 180 ℃ for 20 minutes and then naturally cooled. Separating PMMA/graphene from platinum foil by using platinum foil covered with PMMA/graphene as an electrolytic cell cathode (NaOH aqueous solution with the molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) under the current of 0.15A and by using hydrogen bubbles generated on the surface of the platinum foil, transferring the PMMA/graphene to SiO2And (2) dissolving the PMMA on a/Si substrate by using acetone at the temperature of 50 ℃ to remove the PMMA, and completing the transfer of the graphene.
The uniformity, the number of layers and the domain size of the graphene are represented by an optical microscope, a transmission electron microscope and a Raman spectrometer, and the obtained graphene is few-layer graphene, and the average domain size is hundreds of nanometers.
Example 13
First, this example will foam nickel (320 g/m)220mm × 10mm × 6.4mm) was placed on the upper end of the high-frequency induction heating coil, and was heated using high-frequency electromagnetic induction in an argon atmosphere. After the temperature of the foamed nickel is raised to 1000 ℃, the foamed nickel is placed in ethanol (absolute ethyl alcohol, analytically pure) to be rapidly cooled (quenched). And finishing the growth of the three-dimensional network graphene macroscopic body in the quenching process. And taking out the foamed nickel after the temperature of the foamed nickel is reduced to the room temperature, and drying the foamed nickel in the nitrogen atmosphere.
Then, the three-dimensional graphene surface was covered with an ethyl lactate solution of polymethyl methacrylate (PMMA) (polymethyl methacrylate accounts for 4 wt%). Baking and heating at 180 ℃ for 30 minutes, and forming a PMMA protective layer on the surface of the graphene after drying and curing. Next, the foamed nickel with the PMMA protective layer is put into hydrochloric acid solution or FeCl with the molar concentration of 3M3In (1M)/HCl (1M) aqueous solution, at 80 ℃ for 3 hours to dissolve the nickel foam matrix. And obtaining the graphene foam with the three-dimensional connected network.
The quality, the uniformity and the number of layers of the three-dimensional network graphene macroscopic body are represented by an optical microscope, a scanning electron microscope and a Raman spectrometer, and the obtained graphene is few-layer graphene and almost has no various defects.
Example 14
First, in this embodiment, an ordinary vertical furnace (the bottom of a quartz tube of the vertical furnace is connected to a glass container filled with ethanol by a flange) is used to realize the ultra-fast preparation of the graphene-coated nickel powder. The upper end of the vertical furnace is provided with an argon inlet, and in order to avoid severe sintering of nickel powder, alumina powder is used as a space blocking agent. Uniformly mixing nickel powder and alumina powder according to a mass ratio of 1:3 (the sizes of the two powders are both 100 meshes, and the purity is 99.99 wt%), placing the uniformly mixed powder in a molybdenum boat, putting the molybdenum boat at the center of a hearth by using a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the temperature of the powder is raised to 1200 ℃ in an argon atmosphere, enabling the powder to fall into a glass container filled with 0 ℃ ethanol (absolute ethyl alcohol, analytically pure) for rapid cooling (quenching), and finishing the growth of graphene on the surface of the nickel powder in the quenching process. And subsequently, separating the nickel powder coated by the graphene by using a magnet to obtain the nickel powder coated by the graphene.
And then, putting the nickel powder coated by the graphene into a hydrochloric acid solution with the molar concentration of 1M, and reacting at the temperature of 90 ℃ for 2 hours to dissolve and remove the nickel powder matrix. Graphene powder is obtained by filtering a hydrochloric acid solution, and then is dried in a vacuum oven at a constant temperature of 90 ℃, so that graphene powder is successfully obtained. The optical microscope, the scanning electron microscope and the Raman spectrometer are used for representing the quality, the uniformity and the number of layers of the graphene powder, and the obtained graphene powder is few-layer graphene and is high in quality. The optical microscope, the scanning electron microscope and the Raman spectrometer are used for representing the quality, the uniformity and the number of layers of the graphene on the surface of the nickel powder, and the obtained graphene is few-layer graphene and almost has no various defects.
Example 15
First, in this embodiment, an ordinary vertical furnace (the bottom of the quartz tube of the vertical furnace is connected to the glass container filled with ethanol by a flange) is used to realize the ultra-fast preparation of graphene-coated alumina powder. An argon gas inlet is arranged at the upper end of the vertical furnace, alumina powder (100 meshes, the purity is 99.99 wt%) is placed in a molybdenum boat and is placed at the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1500 ℃), after the temperature of the powder is raised to 1500 ℃ in an argon atmosphere, the powder falls into a glass container filled with 0 ℃ ethanol (absolute ethyl alcohol, analytically pure) to be rapidly cooled (quenched), and the growth of graphene is completed in the quenching process. And when the temperature of the alumina powder is reduced to room temperature, placing the alumina powder in an oven with a nitrogen protective atmosphere to dry at 100 ℃ to obtain the graphene-coated alumina powder.
Then, putting the graphene-coated alumina powder into a 3M sodium hydroxide aqueous solution with a molar concentration, and reacting at 90 ℃ for 2 hours to dissolve and remove the alumina powder matrix. Graphene powder is obtained by filtering a sodium hydroxide aqueous solution, and then is dried in a vacuum oven at a constant temperature of 90 ℃, so that graphene powder is successfully obtained. The optical microscope, the scanning electron microscope and the Raman spectrometer are used for representing the quality, the uniformity and the number of layers of the graphene powder, and the obtained graphene powder is few-layer graphene and is high in quality.
As shown in fig. 1, a schematic diagram of ultra-fast preparation of graphene and graphite film quenching method. And heating the substrate to a preset temperature under the protection of inert gas, then placing the heated substrate in a liquid carbon source, rapidly cooling (quenching) to room temperature, and rapidly growing a graphene or graphite film on the surface of the substrate.
As shown in fig. 2, the graphene obtained in example 1 is a single layer, has good uniformity, and has an average domain size of 10.3 nm.
As shown in fig. 3, it can be seen from the raman spectrum and the spherical aberration correction electron microscope that the graphenes obtained in examples 2 and 3 are all nanocrystalline graphenes, and the grain sizes are 8.0nm and 5.8nm, respectively.
As shown in fig. 4, it can be seen from the raman spectrum and the spherical aberration correction electron microscope that the graphene obtained in example 4 is single-layer nanocrystalline graphene, and the crystal grain sizes are 3.6nm respectively.
As shown in fig. 5, example 9 illustrates that the method can produce a high quality graphite film.
As shown in fig. 6, example 13 illustrates that the method can prepare high quality three-dimensional graphene foam.
As shown in fig. 7, the growth process of graphene coated nickel powder is as follows: uniformly mixing nickel powder and alumina powder according to the mass ratio of 1:3, heating the uniformly mixed powder to 1200 ℃ in an argon atmosphere, rapidly cooling (quenching) the powder in ethanol at 0 ℃, and finishing the growth of graphene on the surface of the nickel powder in the quenching process. And subsequently, separating the nickel powder coated by the graphene by using a magnet to obtain the nickel powder coated by the graphene. Example 14 illustrates that the method can produce high quality graphene coated nickel powder.
The results show that the graphene or graphite film can be rapidly grown by rapidly cooling (quenching) the high-temperature matrix in the liquid carbon source, and then the graphene or graphite film is obtained by bubbling separation or etching the matrix, or is directly used together with the matrix. The film, the powder and the three-dimensional macroscopic body can be prepared by using the matrixes with different shapes, and the number of layers and the grain size of the graphene and the graphite film can be regulated and controlled by changing the components, the thickness and the initial temperature of the matrixes and the type and the temperature of the liquid carbon source. The invention has the characteristics of simple process, high efficiency, low requirement on equipment, convenient operation, low cost, adjustable product thickness and grain size, suitability for large-area preparation and batch preparation and the like. The product of the invention has potential application in electronic devices, optoelectronic devices, anticorrosion coatings, energy storage, wear-resistant coatings, transparent conductive films, electromagnetic shielding, thermal management and thermoelectricity.
Claims (7)
1. A method for preparing graphene or a graphite film ultra-fast is characterized in that a high-temperature matrix is adopted, the graphene or the graphite film is rapidly cooled in a liquid carbon source through quenching under the protection of gas, and the graphene or the graphite film grows on the surface of the matrix by utilizing the cracking of the liquid carbon source in the quenching process.
2. The method for ultrafast preparing graphene or graphite thin film according to claim 1, wherein the substrate is one or more of metal, carbide, nitride, and oxide, and has any shape of foil, porous foam, or powder; wherein: the metal is one or more than two of copper, platinum, nickel, cobalt, gold, ruthenium, palladium, molybdenum, tungsten, aluminum, copper-nickel alloy and molybdenum-nickel alloy; the carbide is one or more than two of silicon carbide, tungsten carbide and molybdenum carbide; the nitride is one or more than two of silicon nitride, tungsten nitride and molybdenum nitride; the oxide is one or more of silicon oxide, aluminum oxide, magnesium oxide, copper oxide and nickel oxide.
3. The method of claim 1, wherein the liquid carbon source is one or more liquid carbon-containing compounds selected from the group consisting of methanol, ethanol, isopropanol, acetone, benzene, toluene, cyclohexane, acetaldehyde, diethyl ether, acetic acid, ethyl acetate, and carbon disulfide; alternatively, the liquid carbon source is a carbon-containing compound which is dissolved in a solvent or is in a molten state and is solid at room temperature, and includes, but is not limited to, paraffin or a high molecular polymer, and the high molecular polymer is one or more of polymethyl methacrylate, polycarbonate, polystyrene, polyethylene and polypropylene.
4. The method for ultrafast preparation of graphene or graphite thin film according to claim 1, wherein the initial temperature of the high temperature substrate is between the decomposition temperature of the liquid carbon source and the melting point of the substrate, and the temperature of the liquid carbon source is between the solidification temperature and the vaporization temperature.
5. The method for ultrafast preparing graphene or graphite film according to claim 1, wherein the shielding gas is nitrogen or inert gas or a mixture of the nitrogen and inert gases during the preparation process.
6. The method for ultrafast preparation of graphene or graphite thin film according to claim 1, wherein the control of the thickness, grain size and crystallinity of the graphene or graphite thin film is achieved by changing the composition, thickness, starting temperature of the matrix and the kind and temperature of the liquid carbon source.
7. The method for ultrafast preparation of graphene or graphite film according to claim 1, wherein the graphene or graphite film grown on the surface of the substrate by quenching is separated from the surface of the substrate by etching or electrochemical gas bubbling, or is used together with the substrate.
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