CN109928387A - A kind of electro-catalysis prepares the method and application of zero defect unrest layer stacked graphene nanometer film - Google Patents
A kind of electro-catalysis prepares the method and application of zero defect unrest layer stacked graphene nanometer film Download PDFInfo
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Classifications
-
- 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
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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
-
- 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
Abstract
The invention discloses a kind of method that electro-catalysis prepares zero defect unrest layer stacked graphene nanometer film, which is obtained by the graphene film of independent self-supporting through Overheating Treatment, electric treatment.The graphene film of independent self-supporting is gradually warming up to 2000 degree, (1-60 degree is per minute) maintains 1-2 hours, repaired most defect sturcture, maintains the folded state of graphene sheet layer unrest layer heap.Then it is powered to film, activated carbon promotes carbon atom flowing, to further repair atomic structure defect.The two collective effect, the defect sturcture for greatly reducing graphene film repair temperature.The thermal conductivity for the horizontal direction that the graphene film has reaches 2500W/mK, and conductivity reaches 2.1MS/m, and the wave-length coverage of photodetection reaches Terahertz, has and is widely applied.
Description
Technical field
The present invention relates to high-performance nano materials and preparation method thereof more particularly to a kind of electro-catalysis to prepare zero defect unrest
The method and application of layer stacked graphene nanometer film, the zero defect unrest layer heap that can obtain nanometer grade thickness by this method are folded
Graphene nano film.
Background technique
2010, two professor Andre GeiM and Konstantin Novoselov of Univ Manchester UK because
It is successfully separated out stable graphene for the first time and obtains Nobel Prize in physics, has started the upsurge that graphene is studied in the whole world.
Graphene has excellent electric property, and (electron mobility is up to 2 × 10 at room temperature5cM2/ Vs), heating conduction outstanding
(5000W/ (MK), extraordinary specific surface area (2630 M2/ g), Young's modulus (1100GPa) and breaking strength (125GPa).
The excellent electrical and thermal conductivity performance of graphene is well beyond metal, while graphene has the advantages that corrosion-and high-temp-resistant, and its is good
Good mechanical performance and lower density more allows it to have the potentiality in thermo electric material field substituted metal.
The graphene film of macroscopic view assembling graphene oxide or graphene nanometer sheet is the main application of nanoscale graphite alkene
Form, common preparation method are suction methods, scrape embrane method, spin-coating method, spray coating method and dip coating etc..Pass through further high temperature
Processing, can repair the defect of graphene, can effectively improve the electric conductivity and thermal conductance of graphene film, can answer extensively
For in smart phone, intelligence with oneself the accompanied electronics equipment such as hardware, tablet computer, laptop.
But currently, the graphene film thickness crossed of high temperature sintering generally in 1um or more, many gas of enclosed inside,
During high pressure compacting, closed stomata is remained in the form of fold, and the graphene film degree of orientation is caused to be deteriorated, close
Degree becomes smaller, and interlayer AB stacking degree is poor, has seriously affected further increasing for graphene film performance.In addition, there is presently no
The preparation of nanoscale graphite alkene film of the work report based on graphene oxide.Under normal conditions, nanoscale graphite alkene film refers generally to
Be chemical vapor deposition method preparation polycrystalline graphite alkene film, using wet process or dry method transfer after be fixed on some
In substrate, independent self-supporting in air can not achieve.This graphene film itself is polycrystalline structure, and performance is by crystal boundary
It influences very big.
Most of all, the graphene of AB accumulation is prepared more demanding (higher temperature and hold time), and photoelectricity
Non- AB structure is more advantageous to photoelectronic migration in, and there is presently no the graphene films that random layer heap stack structure is dominated.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of zero defect unrest layer stacked graphene nanometer film
Preparation method and application.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of electro-catalysis prepares zero defect unrest layer heap piling and layout of stones
The method of black alkene nanometer film, steps are as follows:
(1) graphene film of independent self-supporting is prepared；The number of plies of thickness direction, graphene film is not more than 200；
(2) graphene film is gradually warming up to 2000 DEG C, heating rate is not more than 60 DEG C/min, maintains 1-2 hours, so
It is powered afterwards to film, size of current 1-20A maintains 1-4h.
Further, the graphene film of independent self-supporting is prepared using solid transfer method.
Further, the solid transfer method includes the following steps:
(1.1) graphene oxide is configured to concentration is 0.5-10ug/mL graphene oxide water solution, to mix fiber
Plain ester (MCE) is that substrate filters film forming.
(1.2) graphene oxide membrane for being attached at MCE film is placed in closed container, 60-100 degree HI high temperature fumigation 1-
10h。
(1.3) the solid transfer agent even application of thawing is cold in redox graphene film surface, and at room temperature
But.
(1.4) graphene film for being coated with solid transfer agent is placed in the good solvent of MCE film, etches away MCE film.
(1.5) graphene film that solid transfer agent obtained above supports is waved at a temperature of solid transfer agent volatilizees
Hair falls solid transfer agent, obtains the graphene film of independent self-supporting.
Further, the solid transfer agent is selected from following substance, such as paraffin, aluminium chloride, iodine, naphthalene, three oxidations
Two arsenic, phosphorus pentachloride, acrylamide, ferric trichloride, sulphur, red phosphorus, ammonium chloride, ammonium hydrogen carbonate, potassium iodide, norbornene, coffee
The small molecule solid-state that cause, melamine, water, rosin, the tert-butyl alcohol, sulfur trioxide etc. can distil or volatilize under certain conditions
Substance.
Further, the good solvent of the MCE film is selected from one of acetone, n-butanol, ethyl alcohol, isopropanol or a variety of.
Further, the graphene film of independent self-supporting is prepared using water stripping means, the preparation method is as follows:
(1.1) graphene film is removed from AAO basilar memebrane, specifically: surface is fitted with to the AAO base of graphene film
Counterdie is placed on the water surface with face-up where graphene film；AAO basilar memebrane is pressed, so that AAO basilar memebrane sinks, graphene
Film floats on the water surface.
(1.2) graphene film for floating on the water surface is picked up from the bottom up using a substrate, so that graphene film is laid in
Substrate surface, and there is one layer of aqueous medium between graphene film and substrate.
(1.3) substrate that surface is loaded with graphene film is freeze-dried, graphene film self-supporting, and divided with substrate
From.
Further, the porosity on the surface of the AAO basilar memebrane is not less than 40%.
Further, substrate described in step 2 is hydrophobic substrate.
Further, the upper surface of substrate described in step 2 has sunk area.
In above-mentioned steps 1, pressing position is the edge of AAO basilar memebrane.The thickness of the graphene film can achieve 4nm.
Graphene film can be the graphene oxide membrane after graphene oxide membrane or reduction.
The application of zero defect unrest layer stacked graphene nanometer film are as follows: be applied to nanoscale sonic generator etc..Described receives
Meter level sonic generator includes substrate of the thermal conductivity lower than 200W/mK, the zero defect unrest layer stacked graphene being laid in substrate
Nanometer film and electrical signal input unit and two tone currents input elargol electrodes, two elargol electrodes are separately positioned on
The both ends of sound generating membranes, sound generating membranes, two elargol electrodes and electrical signal input unit series connection forming circuit；Institute
It states in zero defect unrest layer stacked graphene nanometer film, graphene sheet layer is conjugated structure, zero defect；Interlayer stack manner is disorderly
The unordered stacking of layer.
The beneficial effects of the present invention are: the graphene film of independent self-supporting is gradually warming up to 2000 degree by the present invention,
(1-60 degree is per minute) maintains 1-2 hours, has repaired most defect sturcture, maintained graphene sheet layer unrest layer heap
Folded state.Then it is powered to film, activated carbon promotes carbon atom flowing, lacks to further repair atomic structure
It falls into.The two collective effect, the defect sturcture for greatly reducing graphene film repair temperature.Non- ab structure makes interlaminar action power
Weaken, reduces phonon in the conduction of vertical direction and increase the thermal conductivity of horizontal direction to increase horizontal transport.Zero defect knot
Structure is conducive to the transmission of electronics and phonon, not will form resistance and thermal resistance.Temperature rate is fast, and it is fabulous to determine that this film has
Sound quality, sound articulation is high.The present invention ensure that great conductivity and mechanics load while guaranteeing transparent
Can, tension force effect of the battery in discharge process and cell flexible bending process can be born.In use, the film is as light
Anode, to electrode etc.；In comparison, graphene has higher electron mobility, and deposits without heavy metal pollution problem
It is reducing costs, is improving phototransformation efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the graphene film of independent self-supporting prepared by embodiment 1；
Fig. 2 is the Raman figure of film prepared by embodiment 1；
Fig. 3 is the TEM figure of film prepared by embodiment 1；
Fig. 4 is the flow diagram of AAO substrate film stripping graphene film.
Fig. 5 is the experimentation figure of embodiment 4AAO substrate film stripping graphene film.
Fig. 6 is the photo for the self-supporting graphene film that embodiment 4 is prepared.
Fig. 7 is the atomic force microscopy diagram for the self-supporting graphene film that embodiment 4 is prepared.
Fig. 8 is the substrate schematic diagram of embodiment 5, and in figure, the substrate being recessed centered on 1,2 be graphene film, and 3 be water.
Specific embodiment
Embodiment 1:
(1) graphene oxide is configured to concentration is 0.5ug/mL graphene oxide water solution, to mix cellulose esters
(MCE) film forming is filtered for substrate.
(2) graphene oxide membrane for being attached at MCE film is placed in closed container, 60 degree of HI high temperature fumigation 1h.
(3) use the methods of vapor deposition, curtain coating by the paraffin even application of thawing in redox graphene film surface, and in
Slow cooling at room temperature.
(4) graphene film for being coated with solid transfer agent is slowly washed with ethyl alcohol, dissolves MCE film.
(5) graphene film that solid transfer agent obtained above supports slowly is vapored away into solid transfer under 120 degree
Agent, obtains the graphene film of independent self-supporting, the graphene film with a thickness of 30 atomic layers or so, transparency 95%.
(6) graphene film is gradually warming up to 2000 DEG C, 60 DEG C/min of heating rate, maintains 2 hours, then gives film
It is powered, size of current 1A maintains 4h.
As shown in Figure 1, graphene has a small amount of fold.As can be seen that defect peak is substantially not present in Raman in Fig. 2, demonstrate,prove
The zero defect structure of graphene film is illustrated.Fig. 3 TEM electron diffraction diagram spectrum shows that stack manner is random layer between graphene sheet layer
It stacks.The thermal conductivity of its horizontal direction reaches 2500W/mK, and conductivity reaches 1.5MS/m, and the wave-length coverage of photodetection reaches
Terahertz.
Two electrodes are connected in the left and right sides of graphene film, and measure the temperature of graphene Electric radiant Heating Film with temperature-control senser
Degree variation, this graphene film is under atmospheric environment, under the DC voltage of 10V, it is only necessary to just reach stable temperature within 1.2 seconds
270 DEG C of degree, and after powering off, due to the heat conductivity that graphene film is excellent, the temperature of film is just dropped in 1 second close to room temperature.It is right
The T=1s moment obtains film surface temperature distribution map using infrared detecting set, and the graphene film is along straight line where two electrodes
On direction, temperature is stablized, at 270 DEG C or so.
By above-mentioned 2 × 2cm of graphene film2It is laid on polyimide substrate (thermal conductivity 0.35W/mK), it is thin in graphene
Film both ends coat elargol electrode, and two elargol electrodes are connected with the positive and negative anodes of electrical signal input unit respectively, constitute the present invention
The nanoscale sonic generator.Due to film conductivity height, in applied voltage, the heating of meeting very exothermic, is removed
From applied voltage, film heat dissipation very high speed, the two collective effect allows the quick heating and cooling of film, so as to cause
The temperature vibration of air at film, thus sounding.Therefore, defeated additionally by electric signal by the secondary load of the DC voltage of 8V
Determining air can be obtained to adjust the voltage and change frequency that integrally input by entering the specified audio signal of unit input
Temperature vibration amplitude, i.e. pitch；Air thermal shock dynamic frequency can be adjusted by adjusting frequency input signal, and then the frequency of sounding changes
Become, issues different sound.
Embodiment 2:
(1) graphene oxide is configured to concentration is 10ug/mL graphene oxide water solution, to mix cellulose esters
(MCE) film forming is filtered for substrate.
(2) graphene oxide membrane for being attached at MCE film is placed in closed container, 100 degree of HI high temperature fumigation 10h.
(3) use the methods of vapor deposition, curtain coating by the rosin even application of thawing in redox graphene film surface, and in
Slow cooling at room temperature.
(4) graphene film for being coated with solid transfer agent is placed in acetone, removes MCE film.
(5) graphene film that solid transfer agent obtained above supports slowly is vapored away into rosin under 300 degree, obtained
The graphene film of independent self-supporting, with a thickness of 60 atomic layers or so, transparent is 10%.
(6) graphene film is gradually warming up to 2000 DEG C, 45 DEG C/min of heating rate, maintains 1 hour, then gives film
It is powered, size of current 20A maintains 1h.
After tested, defect peak is substantially not present in Raman, it was demonstrated that the zero defect structure of graphene film.TEM electronic diffraction
Map shows that stack manner is folded for random layer heap between graphene sheet layer.The thermal conductivity of its horizontal direction reaches 2100W/mK, electricity
Conductance reaches 1.3MS/m, and the wave-length coverage of photodetection reaches Terahertz.
Two electrodes are connected in the left and right sides of graphene film, and measure the temperature of graphene Electric radiant Heating Film with temperature-control senser
Degree variation, this graphene film is under atmospheric environment, under the DC voltage of 8V, it is only necessary to just reach equilibrium temperature within 0.9 second
280 DEG C, and after powering off, due to the heat conductivity that graphene film is excellent, the temperature of film is just dropped in 1.2 seconds close to room temperature.It should
Graphene film in the straight direction along two electrode institutes, stablize, at 280 DEG C or so by temperature.
By above-mentioned 2 × 2cm of graphene film2It is laid on polyimide substrate (thermal conductivity 0.35W/mK), it is thin in graphene
Film both ends coat elargol electrode, and two elargol electrodes are connected with the positive and negative anodes of electrical signal input unit respectively, constitute the present invention
The nanoscale sonic generator.Due to film conductivity height, in applied voltage, the heating of meeting very exothermic, is removed
From applied voltage, film heat dissipation very high speed, the two collective effect allows the quick heating and cooling of film, so as to cause
The temperature vibration of air at film, thus sounding.Therefore, defeated additionally by electric signal by the secondary load of the DC voltage of 8V
Determining air can be obtained to adjust the voltage and change frequency that integrally input by entering the specified audio signal of unit input
Temperature vibration amplitude, i.e. pitch；Air thermal shock dynamic frequency can be adjusted by adjusting frequency input signal, and then the frequency of sounding changes
Become, issues different sound.
Embodiment 3:
(1) graphene oxide is configured to concentration is 8ug/mL graphene oxide water solution, to mix cellulose esters
(MCE) film forming is filtered for substrate.
(2) graphene oxide membrane for being attached at MCE film is placed in closed container, 80 degree of HI high temperature fumigation 8h.
(3) with the methods of vapor deposition, curtain coating by the norbornene even application of thawing in redox graphene film surface,
And Slow cooling at room temperature.
(4) graphene film for being coated with solid transfer agent is placed in isopropanol, removes MCE film.
(5) graphene film that solid transfer agent obtained above supports slowly is vapored away into solid transfer under 100 degree
Agent obtains the graphene film of independent self-supporting, with a thickness of 200 atomic layers or so.
(6) graphene film is gradually warming up to 2000 DEG C, 20 DEG C/min of heating rate, maintains 1 hour, then gives film
It is powered, size of current 10A maintains 1h.
After tested, defect peak is substantially not present in Raman, it was demonstrated that the zero defect structure of graphene film.TEM electronic diffraction
Map shows that stack manner is folded for random layer heap between graphene sheet layer.The thermal conductivity of its horizontal direction reaches 1800W/mK, electricity
Conductance reaches 1.1MS/m, and the wave-length coverage of photodetection reaches Terahertz.
After tested, defect peak is substantially not present in Raman, it was demonstrated that the zero defect structure of graphene film.TEM electronic diffraction
Map shows that stack manner is folded for random layer heap between graphene sheet layer.The thermal conductivity of its horizontal direction reaches 1800W/mK, electricity
Conductance reaches 1.1MS/m, and the wave-length coverage of photodetection reaches Terahertz.
Two electrodes are connected in the left and right sides of graphene film, and measure the temperature of graphene Electric radiant Heating Film with temperature-control senser
Degree variation, this graphene film is under atmospheric environment, under the DC voltage of 8V, it is only necessary to just reach equilibrium temperature within 0.6 second
300 DEG C, and after powering off, due to the heat conductivity that graphene film is excellent, the temperature of film is just dropped in 1.3 seconds close to room temperature.It should
Graphene film in the straight direction along two electrode institutes, stablize, at 300 DEG C or so by temperature.
By above-mentioned 2 × 2cm of graphene film2It is laid on polyimide substrate (thermal conductivity 0.35W/mK), it is thin in graphene
Film both ends coat elargol electrode, and two elargol electrodes are connected with the positive and negative anodes of electrical signal input unit respectively, constitute the present invention
The nanoscale sonic generator.Due to film conductivity height, in applied voltage, the heating of meeting very exothermic, is removed
From applied voltage, film heat dissipation very high speed, the two collective effect allows the quick heating and cooling of film, so as to cause
The temperature vibration of air at film, thus sounding.Therefore, defeated additionally by electric signal by the secondary load of the DC voltage of 8V
Determining air can be obtained to adjust the voltage and change frequency that integrally input by entering the specified audio signal of unit input
Temperature vibration amplitude, i.e. pitch；Air thermal shock dynamic frequency can be adjusted by adjusting frequency input signal, and then the frequency of sounding changes
Become, issues different sound.
Embodiment 4:
(1) it by the concentration of control graphene solution, filters to obtain ultra-thin go back in AAO basilar memebrane by suction filtration method
Former graphene oxide membrane；
(2) graphene film is removed from AAO basilar memebrane, specifically: surface is fitted with redox graphene film
AAO basilar memebrane (porosity 40%) is placed on the water surface, such as Figure 4 and 5 a with face-up where graphene film；Press AAO
Substrate film edge, such as Fig. 5 b, AAO basilar memebrane starts to sink, and such as Fig. 5 c, finally, AAO basilar memebrane is sunken to bottom of a cup, graphene film floats
It bubbles through the water column (in virtual coil), such as Fig. 5 b and 5d.
(3) substrate of glass that " Zhejiang University " is printed on using a surface will float on the graphene film of the water surface from the bottom up
It picks up, so that graphene film is laid in substrate surface, and there is one layer of aqueous medium between graphene film and substrate.
(4) substrate that surface is loaded with graphene film is freeze-dried, graphene film self-supporting, as shown in Fig. 6, and
It is separated with substrate.It is tested through atomic force microscope, with a thickness of 4nm, as shown in Figure 7.
(5) graphene film is gradually warming up to 2000 DEG C, 60 DEG C/min of heating rate, maintains 2 hours, then gives film
It is powered, size of current 20A maintains 1h.
After tested, defect peak is substantially not present in Raman, it was demonstrated that the zero defect structure of graphene film.TEM electronic diffraction
Map shows that stack manner is folded for random layer heap between graphene sheet layer.The thermal conductivity of its horizontal direction reaches 2700W/mK (certainly
The test of heating hair), conductivity reaches 1.7MS/m.The wave-length coverage of photodetection reaches Terahertz.
Two electrodes are connected in the left and right sides of graphene film, and measure the temperature of graphene Electric radiant Heating Film with temperature-control senser
Degree variation, this graphene film is under atmospheric environment, under the DC voltage of 12V, it is only necessary to just reach equilibrium temperature within 2 seconds
230 DEG C, and after powering off, due to the heat conductivity that graphene film is excellent, the temperature of film is just dropped in 0.5 second close to room temperature.It should
Graphene film in the straight direction along two electrode institutes, stablize, at 230 DEG C or so by temperature.
By above-mentioned 2 × 2cm of graphene film2It is laid on polyimide substrate (thermal conductivity 0.35W/mK), it is thin in graphene
Film both ends coat elargol electrode, and two elargol electrodes are connected with the positive and negative anodes of electrical signal input unit respectively, constitute the present invention
The nanoscale sonic generator.Due to film conductivity height, in applied voltage, the heating of meeting very exothermic, is removed
From applied voltage, film heat dissipation very high speed, the two collective effect allows the quick heating and cooling of film, so as to cause
The temperature vibration of air at film, thus sounding.Therefore, by the secondary load of the DC voltage of 12V, additionally by electric signal
The specified audio signal of input unit input can obtain determining sky to adjust the voltage and change frequency that integrally input
Gas temperature vibration amplitude, i.e. pitch；Air thermal shock dynamic frequency, and then the frequency of sounding can be adjusted by adjusting frequency input signal
Change, issues different sound.
Embodiment 5
(1) it by the concentration of control graphene solution, filters to obtain ultra-thin oxygen in AAO basilar memebrane by suction filtration method
Graphite alkene film；
(2) graphene film is removed from AAO basilar memebrane, specifically: surface is fitted with to the AAO of graphene oxide membrane
Basilar memebrane (porosity 60%) is placed on the water surface with face-up where graphene film, presses AAO substrate film edge, AAO
Basilar memebrane starts to sink, finally, AAO basilar memebrane is sunken to bottom of a cup, graphene film floats on the water surface, and graphene film is successfully removed.
(3) hydrophilic silicon base (silicon face hydrophilic treated, the central concave, such as figure of " Zhejiang University " are printed on using a surface
Shown in 8) graphene film for floating on the water surface is picked up from the bottom up, so that graphene film is laid in base center position, graphite
There is aqueous medium at the center of alkene film and recess.
(4) substrate that surface is loaded with graphene film is freeze-dried, graphene film self-supporting, and is separated with substrate.
It is tested through atomic force microscope, with a thickness of 14nm.
(5) graphene film is gradually warming up to 2000 DEG C, 4 DEG C/min of heating rate, is maintained 2 hours, it is then logical to film
Electricity, size of current 1A maintain 4h.
After tested, defect peak is substantially not present in Raman, it was demonstrated that the zero defect structure of graphene film.TEM electronic diffraction
Map shows that stack manner is folded for random layer heap between graphene sheet layer.The thermal conductivity of its horizontal direction reaches 2600W/mK, electricity
Conductance reaches 1.5MS/m；The wave-length coverage of photodetection reaches Terahertz.
It should be noted that suction method is the method for most uniformly preparing graphene film generally acknowledged at present, in certain suction filtration
Under liquid measure, concentration can be regulated and controled to control the thickness of graphene film, thickness is minimum to can be one layer of graphene, with
The increase of graphene concentration, under pressure, newly-increased graphene are gradually filled into the gap of first layer graphene, so that
First layer graphene is gradually filled up completely, and then develops into the second layer, constantly repeatedly above step, can prepare thickness across 2
Layer arrives the graphene nano film of up to ten thousand layers of graphene.Therefore, those skilled in the art can be adjusted by simple experiment parameter is
It can get the graphene film with a thickness of 4nm.
Two electrodes are connected in the left and right sides of graphene film, and measure the temperature of graphene Electric radiant Heating Film with temperature-control senser
Degree variation, this graphene film is under atmospheric environment, under the DC voltage of 10V, it is only necessary to just reach stable temperature within 0.8 second
260 DEG C of degree, and after powering off, due to the heat conductivity that graphene film is excellent, the temperature of film is just dropped in 1.1 seconds close to room temperature.
The graphene film in the straight direction along two electrode institutes, stablize, at 270 DEG C or so by temperature.
By above-mentioned 2 × 2cm of graphene film2It is laid on polyimide substrate (thermal conductivity 0.35W/mK), it is thin in graphene
Film both ends coat elargol electrode, and two elargol electrodes are connected with the positive and negative anodes of electrical signal input unit respectively, constitute the present invention
The nanoscale sonic generator.Due to film conductivity height, in applied voltage, the heating of meeting very exothermic, is removed
From applied voltage, film heat dissipation very high speed, the two collective effect allows the quick heating and cooling of film, so as to cause
The temperature vibration of air at film, thus sounding.Therefore, by the secondary load of the DC voltage of 10V, additionally by electric signal
The specified audio signal of input unit input can obtain determining sky to adjust the voltage and change frequency that integrally input
Gas temperature vibration amplitude, i.e. pitch；Air thermal shock dynamic frequency, and then the frequency of sounding can be adjusted by adjusting frequency input signal
Change, issues different sound.
Claims (9)
1. a kind of method that electro-catalysis prepares zero defect unrest layer stacked graphene nanometer film, which is characterized in that steps are as follows:
(1) graphene film of independent self-supporting is prepared；The number of plies of thickness direction, graphene film is not more than 200；
(2) graphene film is gradually warming up to 2000 DEG C, heating rate is not more than 60 DEG C/min, maintains 1-2 hours, then to thin
Film is powered, size of current 1-20A, maintains 1-4h.
2. preparation method according to claim 1, which is characterized in that prepare the stone of independent self-supporting using solid transfer method
Black alkene film.
3. according to the method described in claim 2, it is characterized in that, the solid transfer method includes the following steps:
(1.1) graphene oxide is configured to concentration is 0.5-10ug/mL graphene oxide water solution, to mix cellulose esters
(MCE) film forming is filtered for substrate.
(1.2) graphene oxide membrane for being attached at MCE film is placed in closed container, 60-100 degree HI high temperature fumigation 1-10h.
(1.3) the solid transfer agent even application of thawing is cooled down in redox graphene film surface, and at room temperature.
(1.4) graphene film for being coated with solid transfer agent is placed in the good solvent of MCE film, etches away MCE film.
(1.5) graphene film that solid transfer agent obtained above supports is vapored away at a temperature of solid transfer agent volatilizees solid
Body transfer agent obtains the graphene film of independent self-supporting.
4. method as claimed in claim 3, which is characterized in that the solid transfer agent is selected from following substance, such as stone
Wax, aluminium chloride, iodine, naphthalene, arsenic trioxide, phosphorus pentachloride, acrylamide, ferric trichloride, sulphur, red phosphorus, ammonium chloride, bicarbonate
Ammonium, potassium iodide, norbornene, caffeine, melamine, water, rosin, the tert-butyl alcohol, sulfur trioxide etc. can rise under certain conditions
The small molecule solid matter of China or volatilization；The good solvent of the MCE film in acetone, n-butanol, ethyl alcohol, isopropanol one
Kind is a variety of.
5. the method according to claim 1, wherein preparing the graphene of independent self-supporting using water stripping means
Film, the preparation method is as follows:
(1.1) graphene film is removed from AAO basilar memebrane, specifically: by surface be fitted with the AAO basilar memebrane of graphene film with
It is face-up where graphene film, it is placed on the water surface；AAO basilar memebrane is pressed, so that AAO basilar memebrane sinks, graphene film floating
In the water surface.
(1.2) graphene film for floating on the water surface is picked up from the bottom up using a substrate, so that graphene film is laid in substrate
Surface, and there is one layer of aqueous medium between graphene film and substrate.
(1.3) substrate that surface is loaded with graphene film is freeze-dried, graphene film self-supporting, and is separated with substrate.
6. according to the method described in claim 5, it is characterized in that, the porosity on the surface of the AAO basilar memebrane is not less than
40%.
7. according to the method described in claim 5, it is characterized in that, substrate described in step 2 is hydrophobic substrate.
8. according to the method described in claim 5, it is characterized in that, the upper surface of substrate described in step 2 has depressed area
Domain.
9. the application for the graphene nano film that method as described in claim 1 is prepared, which is characterized in that the application are as follows:
Applied to nanoscale sonic generator.The nanoscale sonic generator includes substrate of the thermal conductivity lower than 200W/mK, tiling
In zero defect unrest layer stacked graphene nanometer film and electrical signal input unit and two tone currents input silver in substrate
Gel electrode, two elargol electrodes are separately positioned on the both ends of sound generating membranes, sound generating membranes, two elargol electrodes and electricity
Signal input unit series connection forming circuit.
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| WO2020187332A1 (en) * | 2019-03-17 | 2020-09-24 | 杭州高烯科技有限公司 | Method for electrocatalytic preparation of defect-free disorderly stacked graphene nanofilms and application |
| CN112071978A (en) * | 2020-09-14 | 2020-12-11 | 杭州高烯科技有限公司 | Preparation method of large-area graphene-based magnetoresistive device |
| CN112179868A (en) * | 2020-09-25 | 2021-01-05 | 杭州高烯科技有限公司 | Preparation method of optical modulation terahertz molecule detection device |
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