CN108871547B - Graphene film-based low-frequency acoustic detector - Google Patents
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Abstract
The invention discloses a graphene film-based low-frequency acoustic wave detector, which takes a high-strength graphene film as a main detection device and forms a capacitor with two electrodes of a graphene/conductive substrate through assembly design. The sound wave vibration causes the vibration of the graphene film, changes the distance between the graphene film and the conductive substrate, and further causes capacitance change to generate a current signal. The high-strength graphene is obtained through the steps of etching and hole making, vacuum filtration and film forming, chemical reduction, solid phase transfer, metal spraying, medium-temperature carbonization, chlorine chlorination, high-temperature graphitization and the like. The whole film is of a graphene structure, and a large number of interlayer cross-linked structures are arranged among the sheets. The thickness of the whole film is 20-50 nm. The graphene film has controllable conductivity and adjustable strength, and can be used as a low-frequency sound wave detection device.
Description
Technical Field
The invention relates to a high-performance device, in particular to a graphene film-based low-frequency acoustic wave detector.
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 10 at room temperature)5cM2Vs), outstanding thermal conductivity (5000W/(MK), extraordinary specific surface area (2630M)2In g), its Young's modulus (1100GPa) and breaking strength (125 GPa). The excellent electric and heat conducting performance of the graphene completely exceeds that of metal, and meanwhile, the graphene has the advantages of high temperature resistance and corrosion resistance, and has good mechanical property and lower performanceThe density further provides the potential for replacing metals 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 smart phones, intelligent portable hardware, tablet computers and notebook computers.
Because of the existence of edge defects and 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. Therefore, the graphene film has the advantages that the two structures are compounded together, and the strength of the graphene film is improved under the condition that the thermal conductivity of the graphene film is slightly damaged.
At present, a graphene-based acoustic wave detector is mainly based on single-layer graphene, but the absolute mechanics is low and the graphene-based acoustic wave detector is easy to damage; the micron-thick graphene is too thick, is insensitive to sound waves, is too low in strength and is not suitable for sound wave detection; the nano-thick graphene is between the two, has the advantages of both, but still has insufficient strength. In addition, too high intensity can only detect high frequency sound waves and cannot generate obvious response to low frequency sound waves. For this reason, the intensity of the film must be controlled within a certain range to control the frequency of sound wave detection to a band suitable for human ears.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a graphene film-based low-frequency acoustic wave detector.
The purpose of the invention is realized by the following technical scheme: a graphene film-based low-frequency acoustic wave detector is characterized in that a signal collecting part of the detector consists of a graphene film and a conductive substrate which are parallel to each other to form a capacitor structure; under the action of sound waves, the graphene film vibrates, and the sound wave detector generates corresponding capacitance change; the thickness of the graphene film is 20-50nm, the graphene layers are crosslinked, the degree of crosslinking is 1-5%, and the graphene film is prepared by the following steps:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of less than 4mg/mL, slowly adding fuming nitric acid with the volume of 10-50% into the graphene oxide aqueous solution, refluxing at 100-120 ℃ for 1-6 hours, and then performing centrifugal washing to obtain the porous graphene oxide. Preparing porous graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and filtering to form a film;
(2) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating at the high temperature of 80-100 ℃ from the bottom to the top for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and slowly cooling at room temperature until the film is separated from the substrate;
(4) heating the reduced graphene oxide film treated in the step 3 to sublimate or volatilize the solid transfer agent;
(5) spraying a layer of metal such as titanium, molybdenum or cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nanoparticles is not more than 30% of the molar weight of carbon atoms in the graphene film;
(6) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(7) and (3) placing the chlorinated graphene film in a high-temperature furnace, heating to 1500 ℃ at 5-20 ℃ per minute, and then heating to 2000 ℃ at 2-5 ℃ per minute to obtain the interlayer crosslinked graphene film.
Further, the graphene film is supported on the conductive substrate through a non-conductive ring structure, and the height of the ring structure is not more than 10 um.
Further, the solid transfer agent is selected from the group consisting of paraffin, naphthalene, arsenic trioxide, camphor, sulfur, norbornene, rosin, and other small molecule solid substances insoluble in water that can sublime or volatilize under certain conditions.
Further, the sublimation temperature of the solid transfer agent is controlled below 320 ℃.
Further, the chlorination treatment means: 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.
Currently, a significant drawback of graphene films is strength. According to the invention, an etched porous graphene oxide film is used for forming a film, and an ultrathin graphene film is obtained in a solid transfer mode, so that a foundation is laid for the high resistance of a device; further, the surface wrinkles of the graphene film are increased through slow heating (1 ℃/min), and the area of the graphene film in a unit space is expanded; and then heating at a speed of 10 ℃/min and placing at 2000 ℃ to remove most of atomic defects in the graphene, but not recovering the stacking structure in the graphene. Further sputtering metal particles on the surface of the ultrathin graphene film, and reacting the metal particles with the graphene at high temperature to form metal carbide; then metal carbide forms metal chloride and the loss under the effect of chlorine, and simultaneously, the carbon structure is to the diamond structure transformation, has promoted the intensity and the thermal stability of membrane greatly, and 2000 degrees high temperature treatment for graphite alkene membrane structure obtains very big degree's recovery, but can not influence the crosslinked structure between the layer and can not form AB and pile up the structure. Carbon atoms are lost in the etching process, graphene is in the presence of holes, and after the carbon atoms are lost, the modulus of the graphene is reduced in the presence of the holes, so that the graphene can be actuated under the condition of low sound intensity or weak sound waves, the capacitance change is caused, and the low-frequency detection is realized; after the subsequent film is chlorinated, graphene layers are crosslinked, so that the ultimate breaking strength of the graphene film is greatly increased, and the film can easily bear high-strength sound waves without breaking.
Drawings
Fig. 1 is a raman spectrum of a non-crosslinked graphene film after treatment at 2000 degrees celsius.
Fig. 2 is a raman spectrum of the cross-linked graphene film after 2000 degrees celsius treatment.
Fig. 3 is a transmission spectrum of a non-crosslinked graphene film at 2000 degrees celsius treatment.
Fig. 4 is a transmission spectrum of a cross-linked graphene film processed at 2000 degrees celsius.
FIG. 5 is a schematic representation of a capacitor formed by the combination of a cross-linked graphene film and a conductive substrate. Wherein, 1 is a graphene film, 2 is a conductive substrate, and 3 is a support.
Detailed Description
Example 1:
(1) preparing 4mg/mL graphene oxide aqueous solution, adding 10% fuming nitric acid, refluxing at 100 ℃ for 6 hours, and then centrifuging and washing to obtain the porous graphene oxide. The carbon atom content was measured to be 11.4% less than that before etching.
Preparing the porous graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5ug/mL, and performing suction filtration to form a membrane by taking the hydrophilic polytetrafluoroethylene membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the hydrophilic polytetrafluoroethylene membrane in a closed container, and fumigating the graphene oxide membrane from the bottom to the top for 1h at a high temperature of 80 ℃.
(3) And uniformly coating the melted solid transfer agent camphor on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, slowly cooling at room temperature, and separating the film from the substrate.
(4) And slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at 40 ℃ to obtain the independent self-supported graphene film.
(5) And spraying a layer of metallic titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles 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 titanium chloride. Specifically, the chlorination treatment means: 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) carrying out 2000-degree high-temperature treatment on the chlorinated graphene film, wherein the temperature rise process in the 2000-degree high-temperature process is as follows: below 1500 ℃ and 20 ℃ per minute; above 1500 ℃, 5 ℃ per minute; graphene films with a thickness of 19nm were obtained.
Comparing FIGS. 1 and 2, the graphene film having a plurality of crosslinked structures has a stronger sp3Carbon bonding Peak (1360 cm)-1) The degree of crosslinking (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 4.8%; in fig. 3 and 4, 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 strength of the graphene film prepared by the method is 8.4 GPa.
As shown in fig. 5, the graphene membrane was supported on a platinum substrate by a circular ring structure (diameter 2cm, height 5um) made of teflon. Under certain sound wave frequency and intensity, the graphene film can vibrate to cause capacitance change, and the capacitance can be measured by using the LCR measurer, so that the frequency and the intensity of the sound wave can be judged. Through tests, the sound wave detection range of the sound wave detector is 5-28KHZ, and the sensitivity reaches 0.3 HZ.
Example 2:
(1) preparing a 2mg/mL graphene oxide aqueous solution, slowly adding 50% fuming nitric acid, refluxing at 120 ℃ for 1 hour, and then centrifuging and washing to obtain the porous graphene oxide. The carbon atom content was found to be 36.8% less than that before etching.
(2) Preparing the porous graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a film by taking the PC film as a substrate.
(2) And (3) putting the graphene oxide film attached to the PC film into a closed container, and fumigating the graphene oxide film at the high temperature of 100 ℃ from the bottom to the top for 0.1 h.
(3) And uniformly coating the melted solid transfer agent naphthalene on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 80 ℃ to obtain the independent self-supporting graphene film.
(5) And spraying a layer of metallic titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles 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 titanium chloride. Specifically, the chlorination treatment means: 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) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 5 ℃ per minute; above 1500 ℃, 2 ℃ per minute; keeping the temperature at 2000 ℃ for 1 h; obtaining the graphene film with the thickness of 48 nm.
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 (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 1.1%; 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 strength of the prepared graphene film is 6.3 GPa.
The graphene film is supported on the platinum substrate by a circular ring structure (diameter of 2cm, height of 10um) made of polytetrafluoroethylene. Under certain sound wave frequency and intensity, the graphene film can vibrate to cause capacitance change, and the capacitance can be measured by using the LCR measurer, so that the frequency and the intensity of the sound wave can be judged. Through tests, the sound wave detection range of the sound wave detector is 5-58KHZ, and the sensitivity reaches 0.3 HZ.
Example 3:
(1) preparing a 3mg/mL graphene oxide aqueous solution, slowly adding fuming nitric acid with the volume of 20% into the graphene oxide aqueous solution, refluxing for 5 hours at 100 ℃, and then centrifugally washing to obtain the porous graphene oxide.
(2) Preparing the porous graphene oxide into a graphene oxide aqueous solution with the concentration of 1ug/mL, and performing suction filtration to form a membrane by taking the AAO membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating at high temperature of 90 ℃ for 0.5h from the bottom to the top.
(3) And uniformly coating the molten solid transfer agent sulfur on the surface of the reduced graphene oxide film by using a method such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 120 ℃ to obtain the independent self-supporting graphene film.
(5) And (2) spraying a layer of metal cobalt on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of the finally sputtered metal nanoparticles is 15.9% of the molar weight of carbon atoms in the graphene film by controlling sputtering parameters.
(6) The graphene film sputtered with the metal is chlorinated at 1000 degrees celsius, so that the cobalt nanoparticles escape as cobalt chloride. Specifically, the chlorination treatment means: 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) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃ and 10 ℃ per minute; above 1500 ℃, 3 ℃ per minute; keeping the temperature at 2000 ℃ for 0.5 h; graphene films with a thickness of 28nm were obtained.
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 (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 1.9%; 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 strength of the prepared graphene film is 9.8 GPa.
The graphene film is supported on the platinum substrate by a circular ring structure (diameter of 2cm, height of 5um) made of polytetrafluoroethylene. Under certain sound wave frequency and intensity, the graphene film can vibrate to cause capacitance change, and the capacitance can be measured by using the LCR measurer, so that the frequency and the intensity of the sound wave can be judged. Through tests, the sound wave detection range of the sound wave detector is 5-47KHZ, and the sensitivity reaches 0.3 HZ.
Example 4:
(1) preparing a 3mg/mL graphene oxide aqueous solution, slowly adding fuming nitric acid with the volume of 20% into the graphene oxide aqueous solution, refluxing for 5 hours at 100 ℃, and then centrifugally washing to obtain the porous graphene oxide.
(2) Preparing the porous graphene oxide into a graphene oxide aqueous solution with the concentration of 3ug/mL, and performing suction filtration to form a membrane by taking the AAO membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating the graphene oxide membrane at the high temperature of 100 ℃ from the bottom to the top for 0.2 h.
(3) And uniformly coating the melted solid transfer agent paraffin on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the graphene film supported by the solid transfer agent at 200 ℃ to obtain the independent self-supporting graphene film.
(5) And (2) spraying a layer of metal titanium on the surface of the chemically reduced graphene film in a magnetron sputtering mode, wherein the molar weight of the finally sputtered metal nanoparticles is 25.4% of the molar weight of carbon atoms in the graphene film by controlling sputtering parameters.
(5) The graphene film sputtered with the metal is chlorinated at 1100 degrees celsius, allowing the titanium nanoparticles to escape as titanium chloride. Specifically, the chlorination treatment means: 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.
(6) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 12 ℃ per minute; above 1500 ℃, 4 ℃ per minute; and keeping the temperature at 2000 ℃ for 1h to obtain the graphene film with the thickness of 33 nm.
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 (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 2.2%; 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 strength of the prepared graphene film is 9.1 GPa.
The graphene film is supported on the platinum substrate by a circular ring structure (diameter of 2cm, height of 5um) made of polytetrafluoroethylene. Under certain sound wave frequency and intensity, the graphene film can vibrate to cause capacitance change, and the capacitance can be measured by using the LCR measurer, so that the frequency and the intensity of the sound wave can be judged. Tests prove that the sound wave detection range of the sound wave detector is 5-37KHZ, and the sensitivity reaches 0.3 HZ.
Example 5:
(1) preparing a 3mg/mL graphene oxide aqueous solution, slowly adding fuming nitric acid with the volume of 20% into the graphene oxide aqueous solution, refluxing for 5 hours at 100 ℃, and then centrifugally washing to obtain the porous graphene oxide.
(2) Preparing the porous graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a membrane by taking the AAO membrane as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating at the high temperature of 80 ℃ for 0.8h from the bottom to the top.
(3) And uniformly coating the melted solid transfer agent norbornene on the surface of the reduced graphene oxide film by using methods such as evaporation, tape casting and the like, and slowly cooling at room temperature.
(4) And slowly volatilizing the obtained graphene film supported by the solid transfer agent at 60 ℃ under 2 atmospheric pressures to obtain the independent self-supported graphene film.
(4) And spraying a layer of metal molybdenum on the surface of the chemically reduced graphene film in a magnetron sputtering mode. By controlling the sputtering parameters, the molar weight of the finally sputtered metal nanoparticles is 22.8% of the molar weight of carbon atoms in the graphene film.
(5) The graphene film sputtered with the metal is chlorinated at 800 ℃ so that the molybdenum nanoparticles escape as molybdenum chloride. Specifically, the chlorination treatment means: and (3) placing the graphene film sputtered with the metal nanoparticles in an environment with chlorine content of 6% for heating treatment for 3 h.
(6) The chlorinated graphene film is subjected to high-temperature treatment at 2000 ℃, and specifically comprises the following steps: below 1500 ℃, 7 ℃ per minute; and (3) preserving heat for 1h at the temperature of more than 1500 ℃, 2 ℃ per minute and 2000 ℃, so as to obtain the graphene film with the thickness of 33 nm.
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 (said degree of crosslinking being sp) as determined by the ID/IG area ratio3Carbon content-mass percentage) was 3.7%; 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 strength of the prepared graphene film is 7.9 GPa.
The graphene film is supported on the platinum substrate by a circular ring structure (diameter of 2cm, height of 5um) made of polytetrafluoroethylene. Through tests, the sound wave detection range of the sound wave detector is 4-22KHZ, and the sensitivity reaches 0.3 HZ.
Claims (5)
1. A graphene film-based low-frequency acoustic wave detector is characterized in that a detector signal collecting part is composed of a graphene film and a conductive substrate, and the graphene film and the conductive substrate are parallel to form a capacitor structure; under the action of sound waves, the graphene film vibrates, and the sound wave detector generates corresponding capacitance change; the graphene film is 20-50nm in thickness, the graphene layers are crosslinked, the degree of crosslinking is 1-5%, and nanoscale holes are formed in the graphene layers, and the graphene film is prepared by the following steps:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of less than 4mg/mL, adding fuming nitric acid with the volume of 10-50% relative to the graphene oxide aqueous solution into the graphene oxide aqueous solution, refluxing at 100-120 ℃ for 1-6 hours, and then performing centrifugal washing to obtain porous graphene oxide; preparing porous graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10 mug/mL, and filtering to form a film;
(2) putting the graphene oxide film attached to the suction filtration substrate into a closed container, and fumigating hydrogen iodide HI at a high temperature of 80-100 ℃ from the bottom to the top for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and slowly cooling at room temperature until the film is separated from the substrate;
(4) heating the reduced graphene oxide film treated in the step (3) to sublimate or volatilize the solid transfer agent;
(5) spraying a layer of metal titanium, molybdenum or cobalt on the surface of the reduced graphene oxide film in a magnetron sputtering mode, wherein the molar weight of sputtered metal nano particles is not more than 30% of the molar weight of carbon atoms in the graphene film;
(6) chloridizing the graphene film sputtered with the metal at 800-1200 ℃, and dissipating the metal nanoparticles in the form of chloride;
(7) and (3) placing the chlorinated graphene film in a high-temperature furnace, heating to 1500 ℃ at 5-20 ℃ per minute, and then heating to 2000 ℃ at 2-5 ℃ per minute to obtain the interlayer crosslinked graphene film.
2. The graphene film-based low frequency acoustic wave sensor of claim 1, wherein the graphene film is supported on the conductive substrate by a non-conductive annular structure, the height of the annular structure being no greater than 10 μm.
3. The graphene film-based low-frequency acoustic wave sensor according to claim 1, wherein the solid transfer agent is paraffin, naphthalene, arsenic trioxide, camphor, sulfur, norbornene, or rosin.
4. The graphene film-based low frequency acoustic wave sensor of claim 1, wherein the sublimation temperature of the solid transfer agent is controlled to be less than 320 ℃.
5. The graphene film-based low-frequency acoustic wave sensor 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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