CN108840322B - Foaming carbon film and preparation method thereof - Google Patents

Foaming carbon film and preparation method thereof Download PDF

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CN108840322B
CN108840322B CN201810753782.4A CN201810753782A CN108840322B CN 108840322 B CN108840322 B CN 108840322B CN 201810753782 A CN201810753782 A CN 201810753782A CN 108840322 B CN108840322 B CN 108840322B
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film
graphene
transfer agent
temperature
solid transfer
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CN108840322A (en
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高超
彭蠡
刘一晗
郭燕
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Zhejiang University ZJU
Hangzhou Gaoxi Technology Co Ltd
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Zhejiang University ZJU
Hangzhou Gaoxi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/24—Thermal properties

Abstract

The invention discloses a foaming carbon film and a preparation method thereof, wherein the thickness of the carbon film is 70-200nm, and a layer of continuous bubbles is arranged inside the carbon film; the inner wall surface of the bubble is composed of graphene sheets with the sheet layer spacing of 0.34nm, the outer wall surface is composed of diamond, and the diamond layer is attached to the graphene layer; few defects in the graphene sheet of the inner wall surface, ID/IGIs less than 0.01. The film can be applied to an acoustic wave detection and generation device.

Description

Foaming carbon film and preparation method thereof
Technical Field
The invention relates to a high-performance nano material and a preparation method thereof, in particular to a foaming carbon film and a preparation method thereof.
Background
In 2010, Andre GeiM and Konstantin Novoselov, two professors of Manchester university in England, raised the worldwide hot trend of graphene research because of the first successful separation of stable graphene to obtain the Nobel prize of physics. The graphene has excellent electrical properties (the electron mobility can reach 2 multiplied by 105cM2/Vs at room temperature), outstanding properties (5000W/(MK), extraordinary specific surface area (2630M2/g), Young modulus (1100GPa) and breaking strength (125GPa), excellent electric and heat conducting properties completely exceeding those of metal, and simultaneously has the advantages of high temperature resistance and corrosion resistance, and the good mechanical properties and the lower density of the graphene enable the graphene to have the potential of replacing metal in the field of electric heating materials.
The graphene film of macroscopically assembled graphene oxide or graphene nanosheets is the main application form of nanoscale graphene, and common preparation methods are a suction filtration method, a scraping method, a spin-coating method, a spraying method, a dip-coating method and the like. Through further high-temperature treatment, the defects of graphene can be repaired, the conductivity and the thermal conductivity of the graphene film can be effectively improved, and the graphene film can be widely applied to portable electronic equipment such as sound production, sound wave detection, smart phones, intelligent portable hardware, tablet computers and notebook computers.
However, due to the existence of edge defects and the weak interaction force between graphene layers, the strength of the graphene film sintered at high temperature is generally not too high, less than 100MPa, which is not favorable for practical application. In addition, the cross-linked structure between graphene layers is similar to that of a diamond structure, so that heat conduction is not damaged, and the heat conduction performance of the graphene film is not seriously influenced.
To date, graphene films have begun to be applied to sound-producing devices, such as laser-produced PI-based graphene films, chemically reduced graphene films. However, the films of the two have inevitable defects, namely large structural defects and low heating speed; secondly, the thickness is very high, the cooling speed is slow, and therefore the sound production definition is poor; thirdly, the temperature resistance of the film is poor, and the sound adjustment degree is poor; fourth, the vertical thermal conductivity of films such as graphene or carbon tubes is extremely poor, which is not favorable for heat dissipation in the cooling process and seriously affects the further improvement of tone quality.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a foaming carbon film and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: a foaming carbon film, the thickness of the carbon film is 70-200nm, have a layer of continuous bubbles inside; the inner wall surface of the bubble is composed of graphene sheets with the sheet layer spacing of 0.34nm, the outer wall surface is composed of diamond, and the diamond layer is attached to the graphene layer; few defects in the graphene sheet of the inner wall surface, ID/IG＜0.01。
A method for preparing a carbon foam film comprises the following steps:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and performing suction filtration to form a film by taking Anodic Aluminum Oxide (AAO) as a substrate, wherein the thickness is 200-600 nm;
(2) placing the graphene oxide film attached to the AAO film in a closed container, and fumigating HI steam at a high temperature of 60-100 ℃ for 1-10 h;
(3) uniformly coating the solid transfer agent on the surface of the graphene film, and heating at a temperature lower than the melting point of the solid transfer agent by 5 ℃ to solidify the solid transfer agent;
(4) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film;
(5) slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at the temperature of volatilizing the solid transfer agent to obtain an independent self-supported reduced graphene oxide film;
(6) respectively spraying a layer of metal titanium, molybdenum or cobalt and the like on the front surface and the back surface of the reduced graphene oxide film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nanoparticles is not more than 30% of that of carbon atoms in the graphene film;
(7) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(8) and (3) placing the chlorinated graphene film in a high-temperature furnace for high-temperature annealing at 2400-3000 ℃, maintaining for 1-12h, and raising the temperature at a rate of not higher than 20 ℃/min.
Further, in the step 4, the AAO film which is not separated from the graphene film is etched away by using 1-10% phosphoric acid, and the etching time is 1-10 min.
Further, the solid transfer agent is selected from small molecule solid substances which can be sublimated or volatilized under certain conditions, such as paraffin, camphor, aluminum chloride, iodine, naphthalene, arsenic trioxide, phosphorus pentachloride, acrylamide, ferric chloride, sulfur, red phosphorus, ammonium chloride, ammonium bicarbonate, potassium iodide, norbornene, caffeine, melamine, water, rosin, tert-butyl alcohol, sulfur trioxide, and the like.
Further, the sublimation temperature of the solid transfer agent is controlled below 320 ℃.
Further, the chlorination treatment refers to: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
The invention has the beneficial effects that: the film is applied to sound wave detection and has the following advantages: firstly, the film structure is perfect, the structure and stacking defects are few, the conductivity is high, and the temperature rise speed is high; secondly, the thickness of the film wall is below 100nm, the heat conductivity is high, and the heat dissipation is fast; thirdly, the existence of the diamond film greatly increases the vertical thermal conductivity of the graphene film and promotes the heat dissipation in the cooling process; above graphene membrane temperature rise and fall speed is fast, and cooling rate is better, and two decide this film jointly and have fabulous tone quality, and the sound definition is high. Fourthly, the graphene film has few defects, is internally crosslinked, has good thermal stability, can resist the high temperature of 520 ℃ in the air, and has good sound volume adjustability; and fourthly, the graphene film has high thermal conductivity and lower sound production voltage. Meanwhile, the film can also be used as an acoustic wave detector: the film is of a porous structure, and under the action of external sound pressure, the hole wall is contacted up and down, so that the resistance is reduced, and the current is increased; the continuous sound pressure forms a continuously varying current signal. In conclusion, the cross-linked porous structure not only promotes the sound quality of the sounding of the carbon film, but also can be used as an acoustic detector.
Drawings
Fig. 1 is a nano-graphene film (200nm) with the solid state transfer agent removed.
Fig. 2 shows the surface morphology of a nano graphene film subjected to 3000-degree annealing treatment.
FIG. 3 is a temperature rise and decrease curve of the film obtained in example 1.
Fig. 4 is a temperature curve along the direction of the straight line of the two electrodes at the time T ═ 1 s.
Detailed Description
Example 1:
(1) graphene oxide is prepared into a graphene oxide aqueous solution with the concentration of 0.5ug/mL, and the graphene oxide aqueous solution is subjected to suction filtration to form a film with the thickness of 600nm by taking Anodic Aluminum Oxide (AAO) as a substrate.
(2) The graphene oxide membrane attached to the AAO membrane was placed in a closed container and fumigated with HI steam at 60 ℃ for 10 h.
(3) And (3) uniformly coating the solid transfer agent camphor on the surface of the graphene film by using a sublimation evaporation method at 100 ℃, and heating for a period of time at a temperature below 5 ℃ lower than the melting point of the solid transfer agent. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) And slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at the temperature of slowly volatilizing the solid transfer agent to obtain the independent self-supported reduced graphene oxide film.
(5) And respectively spraying a layer of metal titanium on the front surface and the back surface of the reduced graphene oxide film in a magnetron sputtering mode. By controlling sputtering parameters, the sputtering amount of the two layers is equal, and the molar weight of the finally sputtered metal nano particles is 18.4% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 800 degrees celsius, so that the titanium nanoparticles escape as chlorides. The chlorination treatment refers to: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 10% for heating treatment for 0.1 h.
(7) And (3) placing the chlorinated graphene film in a high-temperature furnace for high-temperature annealing at 3000 ℃, maintaining for 1h and heating at a rate of 20 ℃/min.
The obtained graphene film can be independently self-supported in the air, and the transparency is 46%; the thickness is 70nm, and only one layer of continuous bubbles is arranged inside the film; the wall surface of the bubble is composed of graphene sheets with the sheet layer spacing of 0.34nm, the defects of the graphene sheets are very few, and the I of the bubble isD/IGLess than 0.01; the AB stacking rate is more than 80 percent, and no folds are formed on the sheet layer.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 3.7% as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The prepared graphene film has the strength of 9.8GPa and the density of 2.2g/cm3。
The left side and the right side of the film obtained in the embodiment are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film reaches 503 ℃ only within 0.7 second under the direct current voltage of 10V in the atmospheric environment, and after the graphene film is powered off, the temperature of the film is reduced to be close to the room temperature within 0.7 second due to the excellent thermal conductivity of the graphene film. As shown in fig. 3; and (3) obtaining a surface temperature distribution diagram of the film by using an infrared detector, wherein the temperature of the graphene film is stable along the straight line direction of the two electrodes, as shown in fig. 4.
The film obtained in this example was measured at 2X 2cm2The graphene film is laid on a polyimide substrate (with the thermal conductivity of 0.35W/mK), silver colloid electrodes are coated at two ends of the graphene film, and the two silver colloid electrodes are respectively connected with the anode and the cathode of the electric signal input unit to form a nano-scale sound wave generator. Because the film has high electrical conductivity, the film can release heat and raise temperature violently under the condition of external voltage, the external voltage is removed, the heat dissipation speed of the film is extremely high due to good thermal conductivity and thin thickness, and the film can quickly raise and lower the temperature under the combined action, so that the thermal shock of the air at the film is caused, and the film can sound. The input voltage is adjusted, so that the air thermal vibration amplitude can be adjusted, namely the pitch is adjusted; the thermal vibration frequency of the air can be adjusted by adjusting the frequency of the input signal, so that the frequency of the sounding is changed to send different sounds.
The film obtained in this example was measured at 2X 2cm2The graphene film is laid on a polyimide substrate (with the thermal conductivity of 0.35W/mK), silver colloid electrodes are coated at two ends of the graphene film, and the two silver colloid electrodes are respectively connected with a digital source meter; the film obtained in the embodiment is placed in a quiet environment to play a sound signal with a known waveform, and the film is in a porous structure, so that the hole wall is contacted up and down under the action of external sound pressure, so that the resistance is reduced, the current is increased, and the current signal is subjected to sound wave vibration. The digital source meter collects the electric signal change in real time, and the waveform of the electric signal is basically consistent with that of the sound signal.
Example 2:
(1) graphene oxide is prepared into a graphene oxide aqueous solution with the concentration of 10ug/mL, and the graphene oxide aqueous solution is subjected to suction filtration to form a film with the thickness of 200nm by taking Anodic Aluminum Oxide (AAO) as a substrate.
(2) The graphene oxide membrane attached to the AAO membrane was placed in a closed container and fumigated with HI steam at 100 ℃ for 1 h.
(3) The reduced graphene oxide film is uniformly coated with the solid transfer agent paraffin on the surface of the graphene film by a low-temperature melting coating (52 ℃) method, and is heated for a period of time at a temperature below 5 ℃ lower than the melting point of the solid transfer agent. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) Slowly volatilizing the solid transfer agent from the graphene film supported by the obtained solid transfer agent at 120 ℃ to obtain an independent self-supported reduced graphene oxide film; if the reduction is not uniform in the step 2, or hydrogen iodide vapor directly contacts the AAO film, the graphene cannot be automatically separated from the AAO film in the process of transferring the solid transfer agent, and at the moment, the AAO film needs to be etched by 1% phosphoric acid, and the etching time is 10 min.
(5) And respectively spraying a layer of metal titanium on the front surface and the back surface of the reduced graphene oxide film in a magnetron sputtering mode. By controlling sputtering parameters, the sputtering amount of the two layers is equal, and the molar weight of the finally sputtered metal nano particles is 28.6% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 1200 degrees celsius, allowing the titanium nanoparticles to escape as chlorides. The chlorination treatment refers to: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 0.5% for heating treatment for 4 h.
(7) And (3) placing the chlorinated graphene film in a high-temperature furnace for high-temperature annealing, wherein the annealing temperature is 2400 ℃, the maintaining time is 12h, and the heating rate is 15 ℃/min.
The obtained graphene film can be independently self-supported in the air, and the transparency is 31%; the thickness is 138nm, and only one layer of continuous bubbles is arranged inside the film; the wall surface of the bubble is composed of graphene sheets with the sheet layer spacing of 0.34nm, the defects of the graphene sheets are very few, and the I of the bubble isD/IGLess than 0.01; the AB stacking rate is more than 80 percent, and no folds are formed on the sheet layer.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 2.2%, as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The prepared graphene film has the strength of 9.6GPa and the density of 2.0g/cm3。
The left side and the right side of the film obtained in the embodiment are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film reaches 503 ℃ only within 0.7 second under the direct current voltage of 10V in the atmospheric environment, and after the graphene film is powered off, the temperature of the film is reduced to be close to the room temperature within 0.7 second due to the excellent thermal conductivity of the graphene film. The graphene film is stable in temperature along the linear direction of the two electrodes.
The film obtained in this example was measured at 2X 2cm2The graphene film is laid on a polyimide substrate (with the thermal conductivity of 0.35W/mK), silver colloid electrodes are coated at two ends of the graphene film, and the two silver colloid electrodes are respectively connected with the anode and the cathode of the electric signal input unit to form a nano-scale sound wave generator.
The film obtained in this example was measured at 2X 2cm2The graphene film is laid on a polyimide substrate (with the thermal conductivity of 0.35W/mK), silver colloid electrodes are coated at two ends of the graphene film, and the two silver colloid electrodes are respectively connected with a digital source meter; the film obtained in the embodiment is placed in a quiet environment, a sound signal with a known waveform is played, the digital source meter collects the electric signal change in real time, and the waveform of the electric signal is basically consistent with that of the sound signal.
Example 3:
(1) graphene oxide is prepared into a graphene oxide aqueous solution with the concentration of 2ug/mL, and the graphene oxide aqueous solution is subjected to suction filtration to form a film with the thickness of 280nm by taking Anodic Aluminum Oxide (AAO) as a substrate.
(2) The graphene oxide membrane attached to the AAO membrane was placed in a closed container with HI steam at 80 ℃ for 9 h.
(3) The method for coating the reduced graphene oxide film solution uniformly coats the solid transfer agent aluminum chloride on the surface of the graphene film, and heats the graphene film for a period of time at a temperature below 5 ℃ lower than the melting point of the solid transfer agent. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) Slowly volatilizing the solid transfer agent from the graphene film supported by the solid transfer agent at the temperature of slowly volatilizing at 180 ℃ to obtain an independent self-supported reduced graphene oxide film; if the reduction is not uniform in the step 2, or hydrogen iodide vapor directly contacts the AAO film, the graphene cannot be automatically separated from the AAO film in the process of transferring the solid transfer agent, and at the moment, the AAO film needs to be etched by 10% phosphoric acid, and the etching time is 1 min.
(5) And respectively spraying a layer of metal cobalt on the front surface and the back surface of the reduced graphene oxide film in a magnetron sputtering mode, controlling sputtering parameters to ensure that the sputtering amounts of the two layers are equal, and the molar weight of finally sputtered metal nano particles is 15.9% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 1000 degrees celsius, allowing the cobalt nanoparticles to escape as chlorides. The chlorination treatment refers to: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 5% for heating treatment for 1 h.
(7) And (3) placing the chlorinated graphene film in a high-temperature furnace for high-temperature annealing at 2600 ℃, maintaining for 2h and at a heating rate of 10 ℃/min.
The obtained graphene film can be independently self-supported in the air, and the transparency is 15%; the thickness is 198nm, and only one layer of continuous bubbles is arranged inside the film; the wall surface of the bubble is composed of graphene sheets with the sheet layer spacing of 0.34nm, the defects of the graphene sheets are very few, and the I of the bubble isD/IGLess than 0.01; the AB stacking rate is more than 80 percent, and no folds are formed on the sheet layer.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 1.1% as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. Prepared graphiteThe strength of the olefin film is 7.6GPa, and the density is 2.0g/cm3。
The left side and the right side of the film obtained in the embodiment are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film reaches 503 ℃ only within 0.7 second under the direct current voltage of 10V in the atmospheric environment, and after the graphene film is powered off, the temperature of the film is reduced to be close to the room temperature within 0.7 second due to the excellent thermal conductivity of the graphene film. The graphene film is stable in temperature along the linear direction of the two electrodes.
The film obtained in this example was measured at 2X 2cm2The nano-scale acoustic wave generator is formed by paving the graphene film on a polyimide substrate (with the thermal conductivity of 0.35W/mK), coating silver colloid electrodes at two ends of the graphene film, and respectively connecting the two silver colloid electrodes with the positive electrode and the negative electrode of an electric signal input unit.
The film obtained in this example was measured at 2X 2cm2The graphene film is laid on a polyimide substrate (with the thermal conductivity of 0.35W/mK), silver colloid electrodes are coated at two ends of the graphene film, and the two silver colloid electrodes are respectively connected with a digital source meter; the film obtained in the embodiment is placed in a quiet environment, a sound signal with a known waveform is played, the digital source meter collects the electric signal change in real time, and the waveform of the electric signal is basically consistent with that of the sound signal.
Example 4:
(1) graphene oxide is prepared into a graphene oxide aqueous solution with the concentration of 10ug/mL, and the graphene oxide aqueous solution is subjected to suction filtration to form a film with the thickness of 400nm by taking Anodic Aluminum Oxide (AAO) as a substrate.
(2) The graphene oxide membrane attached to the AAO membrane was placed in a closed container with HI steam at 60 ℃ for 8 h.
(3) The reduced graphene oxide film is uniformly coated with the solid transfer agent sulfur on the surface of the graphene film by a high-temperature casting (130 ℃) method, and is heated for a period of time at a temperature lower than the melting point of the solid transfer agent by 5 ℃. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) Slowly volatilizing the solid transfer agent from the graphene film supported by the obtained solid transfer agent by adopting low-pressure sublimation to obtain an independent self-supporting reduced graphene oxide film; if the reduction is not uniform in the step 2, or hydrogen iodide vapor directly contacts the AAO film, the graphene cannot be automatically separated from the AAO film in the process of transferring the solid transfer agent, and at the moment, the AAO film needs to be etched by 5% phosphoric acid, and the etching time is 2 min.
(5) And respectively spraying a layer of metal titanium on the front surface and the back surface of the reduced graphene oxide film in a magnetron sputtering mode, controlling sputtering parameters to ensure that the sputtering amounts of the two layers are equal, and the molar weight of finally sputtered metal nano particles is 25.4% of the molar weight of carbon atoms in the graphene film.
(6) The graphene film sputtered with the metal is chlorinated at 1100 degrees celsius, allowing the titanium nanoparticles to escape as chlorides. The chlorination treatment refers to: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with the chlorine content of 2% for heating treatment for 2 hours.
(7) And (3) placing the chlorinated graphene film in a high-temperature furnace for high-temperature annealing at 2500 ℃, maintaining for 8h and heating at a rate of 20 ℃/min.
The obtained graphene film can be independently self-supported in the air, and the transparency is 22%; the thickness is 90nm, and only one layer of continuous bubbles is arranged inside the film; the wall surface of the bubble is composed of graphene sheets with the sheet layer spacing of 0.34nm, the defects of the graphene sheets are very few, and the I of the bubble isD/IGLess than 0.01; the AB stacking rate is more than 80 percent, and no folds are formed on the sheet layer.
Through Raman test, the graphene film with the graphene mold having a plurality of cross-linked structures has stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (the degree of crosslinking is sp3 carbon content-percent by mass) was 1.9%, as measured by the ID/IG area ratio; the interlayer spacing of the electron diffraction fringes of the graphene film with the crosslinked structure is smaller than that of the normal graphene film. The prepared graphene film has the strength of 11GPa and the density of 2.1g/cm3。
The left side and the right side of the film obtained in the embodiment are connected with two electrodes, the temperature change of the graphene electrothermal film is measured by using a temperature control sensor, the stable temperature of the graphene film reaches 503 ℃ only within 0.7 second under the direct current voltage of 10V in the atmospheric environment, and after the graphene film is powered off, the temperature of the film is reduced to be close to the room temperature within 0.7 second due to the excellent thermal conductivity of the graphene film. The graphene film is stable in temperature along the linear direction of the two electrodes.
The film obtained in this example was measured at 2X 2cm2The graphene film is laid on a polyimide substrate (with the thermal conductivity of 0.35W/mK), silver colloid electrodes are coated at two ends of the graphene film, and the two silver colloid electrodes are respectively connected with the anode and the cathode of the electric signal input unit to form a nano-scale sound wave generator.
The film obtained in this example was measured at 2X 2cm2The graphene film is laid on a polyimide substrate (with the thermal conductivity of 0.35W/mK), silver colloid electrodes are coated at two ends of the graphene film, and the two silver colloid electrodes are respectively connected with a digital source meter; the film obtained in the embodiment is placed in a quiet environment, a sound signal with a known waveform is played, the digital source meter collects the electric signal change in real time, and the waveform of the electric signal is basically consistent with that of the sound signal.

Claims (5)

1. The preparation method of a carbon foam film is characterized in that the thickness of the carbon foam film is 70-200nm, and a layer of continuous bubbles is arranged inside the carbon foam film; the inner wall surface of the bubble is composed of graphene sheets with the sheet layer spacing of 0.34nm, the outer wall surface is composed of diamond, and the diamond layer is attached to the graphene layer; few defects in the graphene sheet of the inner wall surface, ID/IGLess than 0.01; the preparation method comprises the following steps:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and performing suction filtration to form a film with the thickness of 200-600nm by taking anodic aluminum oxide as a substrate;
(2) placing the graphene oxide film attached to the AAO film in a closed container, and fumigating HI steam at a high temperature of 60-100 ℃ for 1-10 h;
(3) uniformly coating a solid transfer agent on the surface of a graphene film, and heating at a temperature lower than the melting point of the solid transfer agent by 5 ℃ to solidify the solid transfer agent;
(4) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film;
(5) slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at the temperature of volatilizing the solid transfer agent to obtain an independent self-supported reduced graphene oxide film;
(6) respectively spraying a layer of metal titanium, molybdenum or cobalt and the like on the front surface and the back surface of the reduced graphene oxide film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nanoparticles is not more than 30% of that of carbon atoms in the graphene film;
(7) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(8) and (3) placing the chlorinated graphene film in a high-temperature furnace for high-temperature annealing at 2400-3000 ℃, maintaining for 1-12h, and raising the temperature at a rate of not higher than 20 ℃/min.
2. The method according to claim 1, wherein in the step (4), the AAO film which is not separated from the graphene film is etched away with 1-10% phosphoric acid for 1-10 min.
3. The method of claim 1, wherein the solid transfer agent is selected from the group consisting of paraffin, camphor, and rosin.
4. The method of claim 1, wherein the sublimation temperature of the solid transfer agent is controlled to be less than 320 ℃.
5. The method according to claim 1, wherein the chlorination treatment is: and (3) placing the graphene film sputtered with the metal nano particles in an environment with the chlorine content of 0.5-10% for heating treatment for 0.1-4 h.
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