CN110407196A - A kind of preparation method of the low defect graphene film based on grapheme foam - Google Patents
A kind of preparation method of the low defect graphene film based on grapheme foam Download PDFInfo
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Abstract
The preparation method of the invention discloses a kind of low defect graphene film based on grapheme foam, described method includes following steps: Step 1: the preparation of anisotropic oxide graphene frozen foam；Step 2: the preparation of anisotropic oxide grapheme foam；Step 3: oxidation graphene film；Step 4: the preparation of graphene carbon film；Step 5: the preparation of the low defect graphene film based on grapheme foam.Present invention process is simple, low in cost, and using graphene oxide as raw material, lamella area is larger and adjustable, and continuous lamellar structure reduces phonon and scatters in the crystal boundary of transmission process, is conducive to the raising of thermal conductivity.The present invention can prepare graphene dispersion uniformly, the low defect graphene film based on grapheme foam of the high thermal conductivity with certain flexibility, high strength, adapt to growth requirement scientific and technical now.
Description
Technical field
The invention belongs to material science and technology field, it is related to a kind of low defect graphene film based on grapheme foam
Preparation method.
Background technique
Graphene is another stable nanometer carbon simple substance after fullerene, carbon nanotube, is one kind Utopian two
Dimensional plane material has excellent electricity, mechanics and thermal property.Transmission of the free electron on graphene is not susceptible to dissipate
It penetrates, electron mobility can achieve 2 × 105Cm/V s is more than 100 times of electron mobility in silicon；Its conductivity is up to 106
S/m is conductive material excellent at room temperature.Graphene elasticity modulus is up to 1 TPa, and breaking strength is 125 GPa, room temperature thermal conductivity
Rate is 5.3 × 103W/mK, specific surface area are 2630 m2/g.Graphene also has excellent optical property, single-layer graphene
Visible-light absorptivity be only 2.3%, the layer of graphene thus can be estimated according to the visible light transmittance of thin graphene
Number.In addition, ultraviolet light has corrasion to graphene, with the increase of ultraviolet light time, the structure of graphene film is not
Disconnected to be destroyed, visible light transmittance and film surface resistance are all rising.This two-dimensional graphene film with height in addition to leading
Electrically and except transmitance, excellent chemical stability and thermal stability are also shown, can be used as replacing for solar energy transparent electrode
For object.Therefore graphene is in fields such as composite material, catalysis material, energy storage material, Gao Gongneng nanometer electronic device, gas sensors
With sizable application value, numerous scholar's expansion is also attracted deeply systematically to study graphene.
Graphene film is one of the macroscopic body that graphene realizes application, assembles raw material used in graphene film at present
Including graphene and graphene oxide.Graphene have good crystallinity, be by mechanically pulling off or CVD method preparation few layer
Graphene defect content is few, has excellent thermally conductive and electric conductivity, but graphene has biggish specific surface area, easily rolls into a ball
It is poly-, leverage the uniformity and properties of graphene film.Therefore graphene film is being prepared often using graphene
Often need to be modified graphene or add organic matter dispersing agent to improve its dispersibility.Due to lacking between graphene nanometer sheet
Few effective interaction, can only be combined by the faint Van der Waals force of piece interlayer, greatly reduce the graphene of assembling
Thin film mechanical performance.Another assembling mode of graphene film is exactly that graphene oxide is utilized to assemble graphene oxide film,
The former is restored again to obtain graphene film.Graphene oxide oxygen-containing functional group rich in, can in organic solvent and
It is evenly dispersed in aqueous solution, improve the dispersion problem of graphene.Graphene oxide is oxygen as another advantage of raw material
Graphite alkene lamella area is larger and adjustable, and continuous lamellar structure reduces phonon and scatters in the crystal boundary of transmission process, has
Conducive to the raising of thermal conductivity, it can interact additionally, due to oxygen-containing functional group abundant in graphene oxide layer and generate hydrogen
The stronger interactions such as key, the big pi bond of conjugation improve the mechanical property of graphene film.
At present prepare the common method of graphene film material mainly have chemical vapour deposition technique (CVD), vacuum filtration method,
Self-assembly method, spin-coating method, epitaxial growth method, spray coating method, micromechanics stripping method, liquid phase stripping method etc., wherein using earliest just
It is chemical vapour deposition technique, substantially belongs to the gaseous state mass transport process of atom scope, the crystalline property prepared by it is good, impurity
It is few, but limited by substrate, thickness can not be improved, and piece interlayer keeps mechanical property poor without interaction.Vacuum filtration method is also
One of common method is general to be filtered using micropore composite fibre film either Anodisk filter.This film quality compared with
High and thinner thickness, but time-consuming for this kind of method, and is limited and can not prepare the film of large area by pumping and filtering device.Just
At present, spin-coating method is more common and efficient method in method for manufacturing thin film, it is typically disposed in planar substrates, is cutting
Under the action of shear force, the film prepared is visibly homogeneous, and the orientation with height, but film is separated with substrate difficulty, and thick
Degree is affected by solution concentration and spin coater speed.Evaporation self-assembly method can large scale prepare film, studies have found that, oxygen
Graphite alkene dispersion liquid is evaporated effect under higher temperature conditions, and lamella can form a film at gas-liquid interface, but dry
Slowly, the period needed for testing is long, and is influenced in evaporation process by Tyndall effect, keeps film lamina size uneven, mechanics
Intensity difference.Epitaxial growth provides the multi-layer graphene sample of high quality and its substrate interacts strongly, however, these are assembled
Graphene film due to difference interlayer knot contact resistance and the fault of construction that is formed in violent removing and reduction process and show
Show relatively poor performance.
In conclusion lacking easy to operate, at low cost, solution graphene dispersion in the preparation method of existing graphene film
Problem, while elevating mechanism intensity, and the method that highly thermally conductive fexible film can be taken into account.
Summary of the invention
In order to solve the problems, such as that existing graphene film exists in terms of mechanical performance and electrical and thermal conductivity performance, the present invention
Provide a kind of preparation method of low defect graphene film based on grapheme foam.This method can prepare graphene dispersion
Uniformly, the high thermal conductivity with certain flexibility, high strength the low defect graphene film based on grapheme foam, adapt to existing
The growth requirement of modern science and technology.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of preparation method of the low defect graphene film based on grapheme foam, includes the following steps:
Step 1: preparing graphene oxide water solution:
Using graphene oxide slurry as raw material, deionized water is added, low whipping speed stirs under conditions of being 100 ~ 700r/min
Then 60 ~ 120min carries out 30 ~ 60min of ultrasonic treatment under conditions of frequency is 10 ~ 100KHz, obtains graphene oxide water
Solution, in which: the concentration of the graphene oxide slurry is 20mg/mL；In the graphene oxide water solution, graphene oxide
Concentration be 1 ~ 10mg/mL, preferably 3 ~ 7mg/mL；
Step 2: the preparation of anisotropic oxide graphene frozen foam:
Freezing is oriented to graphene oxide water solution with liquid nitrogen, obtains that there is anisotropic oxide graphene of different shapes
Frozen foam, in which: the orientation freezing is ice separant induction self-assembly method；
Step 3: the preparation of anisotropic oxide grapheme foam:
Using CO2Supercritical drying dries anisotropic oxide graphene frozen foam, obtains anisotropic oxide graphene
Foam, in which: the drying mode is freeze-drying；
Step 4: oxidation graphene film:
Anisotropic oxide grapheme foam is placed in hot pressure reaction furnace, using hot-press oxidization pretreatment technique oxygen reduction fossil
Black alkene, it may be assumed that when heating to 250 DEG C, carry out mechanical pressurization, control pressure is 20 ~ 30MPa；Continue to be warming up to 350 ~ 400
DEG C, start to cool down after 1 ~ 1.5h of constant temperature, when temperature is down to 250 DEG C, lays down pressure, and continue to cool to room temperature, restored
Graphene oxide film, in which: the preparation method of the oxidation graphene film is known as dimensionality reduction degree method；
Step 5: the preparation of graphene carbon film:
Oxidation graphene film is placed in hot pressure reaction furnace, the carbon of graphene is realized using high-temperature vacuum heat treatment process
Change, it may be assumed that when heating to 250 DEG C, carry out mechanical pressurization, control pressure is 20 ~ 30MPa；Continue to be warming up to 800 ~ 1000
DEG C, start to cool down after 2 ~ 2.5h of constant temperature, when temperature is down to 250 DEG C, lays down pressure, and continue to cool to room temperature, obtain graphite
Olefinic carbon film；
Step 6: the preparation of the low defect graphene film based on grapheme foam:
Graphene carbon film is placed in high temperature graphitization furnace, the graphitization of carbon film is realized using gradient heating, it may be assumed that heating rate
1000 ~ 1200 DEG C are heated to for 20 DEG C/min, heating rate is changed to 10 DEG C/min and is heated to 2000 ~ 2200 DEG C, constant temperature 30 ~
35min, heating rate are changed to 5 DEG C/min, continue to be heated to 2800 ~ 3000 DEG C, drop to room temperature after 115 ~ 120min of constant temperature, obtain
Low defect graphene film based on grapheme foam.
Compared with the prior art, the present invention has the advantage that
1, present invention process is simple, low in cost, and using graphene oxide as raw material, lamella area is larger and can
It adjusts, continuous lamellar structure reduces phonon and scatters in the crystal boundary of transmission process, is conducive to the raising of thermal conductivity；
2, the present invention prepares the three-dimensional oxidation with oriented alignment using ice separant induction self-assembly method and Freeze Drying Technique
Grapheme foam improves the dispersion problem of graphene；
3, the present invention uses dimensionality reduction degree method, at hot-press oxidization pretreatment technique, high-temperature vacuum heat treatment process and graphitization
Science and engineering skill obtains the low defect graphene film based on grapheme foam, establishes effective interfacial contact, generates piece interlayer
Stronger interaction, not only improves the mechanical performance of film, while the perfect thermal conductivity and conductivity of film, makes to lead
Heat, electric conductivity are more stable, excellent；
4, the low defect graphene film based on grapheme foam prepared by the present invention can be by adjusting dispersion liquid concentration, machine
Tool pressure, heat treatment temperature and reaction time control the thickness and flexibility of graphene film.
Detailed description of the invention
Fig. 1 is the anisotropic oxide grapheme foam photo prepared in embodiment 1；
Fig. 2 is the low defect graphene film prepared in embodiment 1 based on grapheme foam and its flexible photo；
Fig. 3 is the preparation flow schematic diagram of the low defect graphene film based on grapheme foam obtained in embodiment 1.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Embodiment 1:
In the present embodiment, as shown in figure 3, the preparation method of the low defect graphene film based on grapheme foam be specifically according to
What following steps carried out:
Step 1: preparing graphene oxide water solution:
Measurement 20mL concentration is 20mg/mL graphene oxide slurry, and deionized water is added；Low whipping speed is the item of 700r/min
Under part, 60min is stirred；Then, under conditions of frequency is 100KHz, ultrasonic treatment 30min is carried out, it is dense to obtain graphene oxide
Degree is the graphene oxide water solution of 5mg/mL.
Step 2: the preparation of anisotropic oxide graphene frozen foam:
Freezing is oriented to graphene oxide water solution with liquid nitrogen, obtains that there is anisotropic oxide graphene of different shapes
Frozen foam.
Step 3: the preparation of anisotropic oxide grapheme foam:
Using CO2Supercritical drying dries anisotropic oxide graphene frozen foam, obtains anisotropic oxide graphene
Foam.
Step 4: oxidation graphene film:
Anisotropic oxide graphene composite foam is placed in hot pressure reaction furnace, using hot-press oxidization pretreatment technique oxygen reduction
Graphite alkene；When heating to 250 DEG C, mechanical pressurization, pressure 25MPa are carried out；Continue to be warming up to 400 DEG C, constant temperature 1h
After start to cool down, when temperature is down to 250 DEG C, lay down pressure；And continue to cool to room temperature, it is thin to obtain redox graphene
Film.
Step 5: the preparation of graphene carbon film:
Oxidation graphene film is placed in hot pressure reaction furnace, the carbon of graphene is realized using high-temperature vacuum heat treatment process
Change；When heating to 250 DEG C, mechanical pressurization, pressure 25MPa are carried out；Continue to be warming up to 1000 DEG C, start after constant temperature 2h
Cooling lays down pressure when temperature is down to 250 DEG C；And continue to cool to room temperature, obtain graphene carbon film.
Step 6: the preparation of the low defect graphene film based on grapheme foam:
Graphene carbon film is placed in high temperature graphitization furnace, the graphitization of carbon film is realized using gradient heating；Heating rate is
20 DEG C/min is heated to 1200 DEG C, and heating rate is changed to 10 DEG C/min and is heated to 2200 DEG C, and constant temperature 30min, heating rate is changed to 5
DEG C/min, continue to be heated to 2800 DEG C, drop to room temperature after constant temperature 120min, obtains the low defect graphene based on grapheme foam
Film.
The anisotropic oxide grapheme foam photo of the present embodiment step 3 preparation is as shown in Figure 1, can from figure
Black gray expandable is presented in anisotropic oxide grapheme foam out, and surfacing, internal oxidation graphene sheet layer is along ice crystal after incision
For the direction of growth in orientation Pipe bundle structure, vertical direction is similar cellular hole configurations, and this structure is to be based on graphite in the later period
The formation of the low defect graphene film of alkene foam has positive influence.
The low defect graphene film and its flexible photo such as Fig. 2 based on grapheme foam of the present embodiment step 6 preparation
Shown, as can be seen from the figure the prepared low defect graphene film surface based on grapheme foam is smooth, is in metal light
Pool, and there is certain flexibility, 180 ° can be bent and be folded into various shapes.
The present embodiment passes through the thermal conductivity and conductivity of test sample, obtains the low defect graphene based on grapheme foam
The thermal conductivity of film is 1150 W m-1 K-1, conductivity is up to 1.25 × 105 S m-1, while based on stone prepared by the present embodiment
The low defect graphene film tensile strength with higher of black alkene foam, reaches 76MPa, compared to now can be with individualism
Graphene film, cost of material is low, and preparation graphene dispersion is uniform, combines higher thermally conductive, electric conductivity and excellent
Different mechanical strength, and there is certain flexibility, meet the practical application request in defense military equipment and smart electronics field.
Embodiment 2:
In the present embodiment, the preparation method of the low defect graphene film based on grapheme foam be specifically according to the following steps into
Capable:
Step 1: preparing graphene oxide water solution:
The graphene oxide slurry that 20mL concentration is 20mg/mL is measured, deionized water is added；Low whipping speed is 700r/min's
Under the conditions of, stir 60min；Then, under conditions of frequency is 100KHz, ultrasonic treatment 30min is carried out, graphene oxide is obtained
Concentration is the graphene oxide water solution of 5mg/mL.
Step 2: the preparation of anisotropic oxide graphene frozen foam:
Freezing is oriented to graphene oxide water solution with liquid nitrogen, obtains that there is anisotropic oxide graphene of different shapes
Frozen foam.
Step 3: the preparation of anisotropic oxide grapheme foam:
Using CO2Supercritical drying dries anisotropic oxide graphene frozen foam, obtains anisotropic oxide graphene
Foam.
Step 4: oxidation graphene film:
Anisotropic oxide graphene composite foam is placed in hot pressure reaction furnace, using hot-press oxidization pretreatment technique oxygen reduction
Graphite alkene；When heating to 250 DEG C, mechanical pressurization, pressure 30MPa are carried out；Continue to be warming up to 400 DEG C, constant temperature 1h
After start to cool down, when temperature is down to 250 DEG C, lay down pressure；And continue to cool to room temperature, it is thin to obtain redox graphene
Film.
Step 5: the preparation of graphene carbon film:
Oxidation graphene film is placed in hot pressure reaction furnace, the carbon of graphene is realized using high-temperature vacuum heat treatment process
Change；When heating to 250 DEG C, mechanical pressurization, pressure 30MPa are carried out；Continue to be warming up to 1000 DEG C, start after constant temperature 2h
Cooling lays down pressure when temperature is down to 250 DEG C；And continue to cool to room temperature, obtain graphene carbon film.
Step 6: the preparation of the low defect graphene film based on grapheme foam:
Graphene carbon film is placed in high temperature graphitization furnace, the graphitization of carbon film is realized using gradient heating；Heating rate is
20 DEG C/min is heated to 1000 DEG C, and heating rate is changed to 10 DEG C/min and is heated to 2000 DEG C, and constant temperature 35min, heating rate is changed to 5
DEG C/min, continue to be heated to 3000 DEG C, drop to room temperature after constant temperature 115min, obtains the low defect graphene based on grapheme foam
Film.
The present embodiment passes through the thermal conductivity and conductivity of test sample, obtains the low defect graphene based on grapheme foam
The thermal conductivity of film is 1050 W m-1 K-1, conductivity is up to 1.2 × 105 S m-1, while prepared by present embodiment based on
The low defect graphene film tensile strength with higher of grapheme foam, reaches 70MPa, compared to can individually deposit now
Graphene film, cost of material is low, preparation graphene dispersion it is uniform, combine higher thermally conductive, electric conductivity and
Excellent mechanical strength, and there is certain flexibility, the practical application for meeting defense military equipment and smart electronics field needs
It asks.
Embodiment 3:
In the present embodiment, the preparation method of the low defect graphene film based on grapheme foam be specifically according to the following steps into
Capable:
Step 1: preparing graphene oxide water solution:
The graphene oxide slurry that 20mL concentration is 20mg/mL is measured, deionized water is added；Low whipping speed is 700r/min's
Under the conditions of, stir 60min；Then, under conditions of frequency is 100KHz, ultrasonic treatment 30min is carried out, graphene oxide is obtained
Concentration is the graphene oxide water solution of 5mg/mL.
Step 2: the preparation of anisotropic oxide graphene frozen foam:
Freezing is oriented to graphene oxide water solution with liquid nitrogen, obtains that there is anisotropic oxide graphene of different shapes
Frozen foam.
Step 3: the preparation of anisotropic oxide grapheme foam:
Using CO2Supercritical drying dries anisotropic oxide graphene frozen foam, obtains anisotropic oxide graphene
Foam.
Step 4: oxidation graphene film:
Anisotropic oxide graphene composite foam is placed in hot pressure reaction furnace, using hot-press oxidization pretreatment technique oxygen reduction
Graphite alkene；When heating to 250 DEG C, mechanical pressurization, pressure 20MPa are carried out；Continue to be warming up to 400 DEG C, constant temperature 1h
After start to cool down, when temperature is down to 250 DEG C, lay down pressure；And continue to cool to room temperature, it is thin to obtain redox graphene
Film.
Step 5: the preparation of graphene carbon film:
Oxidation graphene film is placed in hot pressure reaction furnace, the carbon of graphene is realized using high-temperature vacuum heat treatment process
Change；When heating to 250 DEG C, mechanical pressurization, pressure 20MPa are carried out；Continue to be warming up to 1000 DEG C, start after constant temperature 2h
Cooling lays down pressure when temperature is down to 250 DEG C；And continue to cool to room temperature, obtain graphene carbon film.
Step 6: the preparation of the low defect graphene film based on grapheme foam:
Graphene carbon film is placed in high temperature graphitization furnace, the graphitization of carbon film is realized using gradient heating；Heating rate is
20 DEG C/min is heated to 1200 DEG C, and heating rate is changed to 10 DEG C/min and is heated to 2200 DEG C, and constant temperature 30min, heating rate is changed to 5
DEG C/min, continue to be heated to 2800 DEG C, drop to room temperature after constant temperature 120min, obtains the low defect graphene based on grapheme foam
Film.
The present embodiment passes through the thermal conductivity and conductivity of test sample, obtains the low defect graphene based on grapheme foam
The thermal conductivity of film is 950 W m-1 K-1, conductivity is up to 1.05 × 105 S m-1, while prepared by present embodiment based on
The low defect graphene film tensile strength with higher of grapheme foam, reaches 66MPa, compared to can individually deposit now
Graphene film, cost of material is low, preparation graphene dispersion it is uniform, combine higher thermally conductive, electric conductivity and
Excellent mechanical strength, and there is certain flexibility, the practical application for meeting defense military equipment and smart electronics field needs
It asks.
Embodiment 4:
In the present embodiment, the preparation method of the low defect graphene film based on grapheme foam be specifically according to the following steps into
Capable:
Step 1: preparing graphene oxide water solution:
The graphene oxide slurry that 20mL concentration is 20mg/mL is measured, deionized water is added；Low whipping speed is 100r/min's
Under the conditions of, stir 120min；Then, under conditions of frequency is 10KHz, ultrasonic treatment 60min is carried out, graphene oxide is obtained
Concentration is the graphene oxide water solution of 3mg/mL.
Step 2: the preparation of anisotropic oxide graphene frozen foam:
Freezing is oriented to graphene oxide water solution with liquid nitrogen, obtains that there is anisotropic oxide graphene of different shapes
Frozen foam.
Step 3: the preparation of anisotropic oxide grapheme foam:
Using CO2Supercritical drying dries anisotropic oxide graphene frozen foam, obtains anisotropic oxide graphene
Foam.
Step 4: oxidation graphene film:
Anisotropic oxide graphene composite foam is placed in hot pressure reaction furnace, using hot-press oxidization pretreatment technique oxygen reduction
Graphite alkene；When heating to 250 DEG C, mechanical pressurization, pressure 25MPa are carried out；Continue to be warming up to 350 DEG C, constant temperature
Start to cool down after 1.5h, when temperature is down to 250 DEG C, lays down pressure；And continue to cool to room temperature, obtain redox graphene
Film.
Step 5: the preparation of graphene carbon film:
Oxidation graphene film is placed in hot pressure reaction furnace, the carbon of graphene is realized using high-temperature vacuum heat treatment process
Change；When heating to 250 DEG C, mechanical pressurization, pressure 25MPa are carried out；Continue to be warming up to 800 DEG C, be opened after constant temperature 2.5h
Cooling of beginning lays down pressure when temperature is down to 250 DEG C；And continue to cool to room temperature, obtain graphene carbon film.
Step 6: the preparation of the low defect graphene film based on grapheme foam:
Graphene carbon film is placed in high temperature graphitization furnace, the graphitization of carbon film is realized using gradient heating；Heating rate is
20 DEG C/min is heated to 1000 DEG C, and heating rate is changed to 10 DEG C/min and is heated to 2000 DEG C, constant temperature 35min；Heating rate is changed to 5
DEG C/min, continue to be heated to 3000 DEG C, drop to room temperature after constant temperature 115min, obtains the low defect graphene based on grapheme foam
Film.
The present embodiment passes through the thermal conductivity and conductivity of test sample, obtains the low defect graphene based on grapheme foam
The thermal conductivity of film is 1030 W m-1 K-1, conductivity is up to 1.15 × 105 S m-1, while prepared by present embodiment based on
The low defect graphene film tensile strength with higher of grapheme foam, reaches 73MPa, compared to can individually deposit now
Graphene film, cost of material is low, preparation graphene dispersion it is uniform, combine higher thermally conductive, electric conductivity and
Excellent mechanical strength, and there is certain flexibility, the practical application for meeting defense military equipment and smart electronics field needs
It asks.
Embodiment five:
In the present embodiment, the preparation method of the low defect graphene film based on grapheme foam be specifically according to the following steps into
Capable:
Step 1: preparing graphene oxide water solution:
The graphene oxide slurry that 20mL concentration is 20mg/mL is measured, deionized water is added；Low whipping speed is 100r/min's
Under the conditions of, stir 120min；Then, under conditions of frequency is 10KHz, ultrasonic treatment 60min is carried out, graphene oxide is obtained
Concentration is the graphene oxide water solution of 7mg/mL.
Step 2: the preparation of anisotropic oxide graphene frozen foam:
Freezing is oriented to graphene oxide water solution with liquid nitrogen, obtains that there is anisotropic oxide graphene of different shapes
Frozen foam.
Step 3: the preparation of anisotropic oxide grapheme foam:
Using CO2Supercritical drying dries anisotropic oxide graphene frozen foam, obtains anisotropic oxide graphene
Foam.
Step 4: oxidation graphene film:
Anisotropic oxide graphene composite foam is placed in hot pressure reaction furnace, using hot-press oxidization pretreatment technique oxygen reduction
Graphite alkene；When heating to 250 DEG C, mechanical pressurization, pressure 25MPa are carried out；Continue to be warming up to 350 DEG C, constant temperature
Start to cool down after 1.5h, when temperature is down to 250 DEG C, lays down pressure；And continue to cool to room temperature, obtain redox graphene
Film.
Step 5: the preparation of graphene carbon film:
Oxidation graphene film is placed in hot pressure reaction furnace, the carbon of graphene is realized using high-temperature vacuum heat treatment process
Change；When heating to 250 DEG C, mechanical pressurization, pressure 25MPa are carried out；Continue to be warming up to 800 DEG C, be opened after constant temperature 2.5h
Cooling of beginning lays down pressure when temperature is down to 250 DEG C；And continue to cool to room temperature, obtain graphene carbon film.
Step 6: the preparation of the low defect graphene film based on grapheme foam:
Graphene carbon film is placed in high temperature graphitization furnace, the graphitization of carbon film is realized using gradient heating；Heating rate is
20 DEG C/min is heated to 1200 DEG C, and heating rate is changed to 10 DEG C/min and is heated to 2200 DEG C, constant temperature 30min；Heating rate is changed to 5
DEG C/min, continue to be heated to 2800 DEG C, drop to room temperature after constant temperature 120min, obtains the low defect graphene based on grapheme foam
Film.
The present embodiment passes through the thermal conductivity and conductivity of test sample, obtains the low defect graphene based on grapheme foam
The thermal conductivity of film is 970 W m-1 K-1, conductivity is up to 1.0 × 105 S m-1, while based on stone prepared by present embodiment
The low defect graphene film tensile strength with higher of black alkene foam, reaches 69MPa, compared to now can be with individualism
Graphene film, cost of material is low, and preparation graphene dispersion is uniform, combines higher thermally conductive, electric conductivity and excellent
Different mechanical strength, and there is certain flexibility, meet the practical application request in defense military equipment and smart electronics field.
Claims (10)
1. a kind of preparation method of the low defect graphene film based on grapheme foam, it is characterised in that the method includes such as
Lower step:
Step 1: the preparation of anisotropic oxide graphene frozen foam:
Freezing is oriented to graphene oxide water solution with liquid nitrogen, obtains that there is anisotropic oxide graphene of different shapes
Frozen foam；
Step 2: the preparation of anisotropic oxide grapheme foam:
Using CO2Supercritical drying dries anisotropic oxide graphene frozen foam, obtains anisotropic oxide graphene bubble
Foam；
Step 3: oxidation graphene film:
Anisotropic oxide grapheme foam is placed in hot pressure reaction furnace, using hot-press oxidization pretreatment technique oxygen reduction fossil
Black alkene；
Step 4: the preparation of graphene carbon film:
Oxidation graphene film is placed in hot pressure reaction furnace, the carbon of graphene is realized using high-temperature vacuum heat treatment process
Change；
Step 5: the preparation of the low defect graphene film based on grapheme foam:
Graphene carbon film is placed in high temperature graphitization furnace, the graphitization of carbon film is realized using gradient heating.
2. the preparation method of the low defect graphene film according to claim 1 based on grapheme foam, feature exist
It is as follows in the preparation method of the graphene oxide water solution: using graphene oxide slurry as raw material, deionized water to be added, is stirring
It mixes under conditions of speed is 100 ~ 700r/min and stirs 60 ~ 120min, then surpassed under conditions of frequency is 10 ~ 100KHz
30 ~ 60min of sonication, obtains graphene oxide water solution.
3. the preparation method of the low defect graphene film according to claim 1 or 2 based on grapheme foam, feature
It is in the graphene oxide water solution, the concentration of graphene oxide is 1 ~ 10mg/mL.
4. the preparation method of the low defect graphene film according to claim 3 based on grapheme foam, feature exist
In the graphene oxide concentration be 3 ~ 7mg/mL.
5. the preparation method of the low defect graphene film according to claim 2 based on grapheme foam, feature exist
In the graphene oxide slurry concentration be 20mg/mL.
6. the preparation method of the low defect graphene film according to claim 1 based on grapheme foam, feature exist
Freezing in the orientation is ice separant induction self-assembly method.
7. the preparation method of the low defect graphene film according to claim 1 based on grapheme foam, feature exist
In the drying mode be freeze-drying.
8. the preparation method of the low defect graphene film according to claim 1 based on grapheme foam, feature exist
Using hot-press oxidization pretreatment technique redox graphene, specific step is as follows in described: when heating to 250 DEG C,
Mechanical pressurization is carried out, control pressure is 20 ~ 30MPa；Continue to be warming up to 350 ~ 400 DEG C, starts to cool down after 1 ~ 1.5h of constant temperature, work as temperature
When degree is down to 250 DEG C, pressure is laid down, and continue to cool to room temperature, obtain oxidation graphene film.
9. the preparation method of the low defect graphene film according to claim 1 based on grapheme foam, feature exist
The carbonization of graphene realized in described using high-temperature vacuum heat treatment process specific step is as follows: when heating to 250 DEG C
When, mechanical pressurization is carried out, control pressure is 20 ~ 30MPa；Continue to be warming up to 800 ~ 1000 DEG C, start to cool down after 2 ~ 2.5h of constant temperature,
When temperature is down to 250 DEG C, pressure is laid down, and continue to cool to room temperature, obtain graphene carbon film.
10. the preparation method of the low defect graphene film according to claim 1 based on grapheme foam, feature exist
In it is described use gradient heating realize carbon film graphited specific step is as follows: heating rate is heated to for 20 DEG C/min
1000 ~ 1200 DEG C, heating rate is changed to 10 DEG C/min and is heated to 2000 ~ 2200 DEG C, and 30 ~ 35min of constant temperature, heating rate is changed to 5
DEG C/min, continue to be heated to 2800 ~ 3000 DEG C, drops to room temperature after 115 ~ 120min of constant temperature, obtain based on the low of grapheme foam
Defect graphene film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920236A (en) * | 2021-10-14 | 2022-08-19 | 广东墨睿科技有限公司 | Oriented graphene heat-conducting film and preparation method and application thereof |
| CN115259141A (en) * | 2022-06-10 | 2022-11-01 | 中国航发北京航空材料研究院 | Functional graphene carbon film material and preparation method thereof |
| CN116675221A (en) * | 2023-06-01 | 2023-09-01 | 南京工业大学 | Graphene film with high electrical conductivity and high thermal conductivity as well as preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2778128A1 (en) * | 2013-03-15 | 2014-09-17 | Instytut Technologii Materialów Elektronicznych | Method of thermal reduction of graphene oxide |
| US20160272498A1 (en) * | 2013-11-15 | 2016-09-22 | National University Of Singapore | Hot Press Induced Formation of an Ordered Graphene and Few Layered Graphene Sheets |
| CN106629675A (en) * | 2016-09-28 | 2017-05-10 | 上海理工大学 | Preparation method of high-heat-conduction flexible graphene film |
| CN106853966A (en) * | 2015-12-07 | 2017-06-16 | 株洲时代新材料科技股份有限公司 | The method for preparing high heat conduction graphite film using Graphene doping polyamic acid resin |
| CN106861657A (en) * | 2017-03-21 | 2017-06-20 | 湖南大学 | Double sponge adsorbed films of redox graphene polyurethane and its preparation method and application |
| CN107010618A (en) * | 2017-04-28 | 2017-08-04 | 哈尔滨工业大学 | The preparation method and radiating film of a kind of high starch breeding alkene radiating film |
| WO2018061828A1 (en) * | 2016-09-30 | 2018-04-05 | コニカミノルタ株式会社 | Graphite sheet, heat diffusion sheet, and method for producing graphite sheet |
| CN108910865A (en) * | 2018-07-21 | 2018-11-30 | 哈尔滨工业大学 | A method of preparing graphene/graphene nanobelt mixed film |
| CN109467078A (en) * | 2017-09-07 | 2019-03-15 | 常州富烯科技股份有限公司 | Graphene heat conducting film and preparation method thereof, production equipment |
-
2019
- 2019-08-23 CN CN201910786739.2A patent/CN110407196B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2778128A1 (en) * | 2013-03-15 | 2014-09-17 | Instytut Technologii Materialów Elektronicznych | Method of thermal reduction of graphene oxide |
| US20160272498A1 (en) * | 2013-11-15 | 2016-09-22 | National University Of Singapore | Hot Press Induced Formation of an Ordered Graphene and Few Layered Graphene Sheets |
| CN106853966A (en) * | 2015-12-07 | 2017-06-16 | 株洲时代新材料科技股份有限公司 | The method for preparing high heat conduction graphite film using Graphene doping polyamic acid resin |
| CN106629675A (en) * | 2016-09-28 | 2017-05-10 | 上海理工大学 | Preparation method of high-heat-conduction flexible graphene film |
| WO2018061828A1 (en) * | 2016-09-30 | 2018-04-05 | コニカミノルタ株式会社 | Graphite sheet, heat diffusion sheet, and method for producing graphite sheet |
| CN106861657A (en) * | 2017-03-21 | 2017-06-20 | 湖南大学 | Double sponge adsorbed films of redox graphene polyurethane and its preparation method and application |
| CN107010618A (en) * | 2017-04-28 | 2017-08-04 | 哈尔滨工业大学 | The preparation method and radiating film of a kind of high starch breeding alkene radiating film |
| CN109467078A (en) * | 2017-09-07 | 2019-03-15 | 常州富烯科技股份有限公司 | Graphene heat conducting film and preparation method thereof, production equipment |
| CN108910865A (en) * | 2018-07-21 | 2018-11-30 | 哈尔滨工业大学 | A method of preparing graphene/graphene nanobelt mixed film |
Non-Patent Citations (2)
| Title |
|---|
| WANG, L ET AL: "Microstructure and mechanical properties of nacre-like alumina toughened by graphene oxide", 《CERAMICS INTERNATIONAL》 * |
| 王沙沙: "基于多形态石墨烯的薄膜制备与多功能性研究", 《中国优秀博硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920236A (en) * | 2021-10-14 | 2022-08-19 | 广东墨睿科技有限公司 | Oriented graphene heat-conducting film and preparation method and application thereof |
| CN114920236B (en) * | 2021-10-14 | 2023-10-27 | 广东墨睿科技有限公司 | Oriented graphene heat conduction film and preparation method and application thereof |
| CN115259141A (en) * | 2022-06-10 | 2022-11-01 | 中国航发北京航空材料研究院 | Functional graphene carbon film material and preparation method thereof |
| CN115259141B (en) * | 2022-06-10 | 2023-10-20 | 中国航发北京航空材料研究院 | Functional graphene carbon film material and preparation method thereof |
| CN116675221A (en) * | 2023-06-01 | 2023-09-01 | 南京工业大学 | Graphene film with high electrical conductivity and high thermal conductivity as well as preparation method and application thereof |
| CN116675221B (en) * | 2023-06-01 | 2024-04-09 | 南京工业大学 | Graphene film with high electrical conductivity and high thermal conductivity as well as preparation method and application thereof |
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