CN112479195A - Graphene oxide powder and preparation method thereof, graphene oxide film and preparation method thereof - Google Patents
Graphene oxide powder and preparation method thereof, graphene oxide film and preparation method thereof Download PDFInfo
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- CN112479195A CN112479195A CN201910863136.8A CN201910863136A CN112479195A CN 112479195 A CN112479195 A CN 112479195A CN 201910863136 A CN201910863136 A CN 201910863136A CN 112479195 A CN112479195 A CN 112479195A
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Abstract
The invention provides a preparation method of graphene oxide powder, which comprises the following steps: and drying, crushing and crushing the leftover materials and defective products of the graphene oxide film to obtain graphene oxide powder. According to the invention, the graphene oxide powder is prepared from the graphene oxide leftover and defective products, and the graphene heat-conducting film is prepared from the graphene oxide powder, so that the utilization rate of raw materials is improved, and the manufacturing cost is reduced.
Description
Technical Field
The invention relates to the field of heat conduction materials, in particular to a preparation method of a graphene oxide film.
Background
The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
The graphene heat-conducting film is a highly oriented heat-conducting film formed by stacking multiple layers of graphene, has the characteristics of good mechanical property, high heat conductivity coefficient, light weight, thin material, good flexibility and the like, and provides a whole set of high-quality and economical heat-radiating solution for the industries such as electronics, aerospace, medical treatment and the like.
The preparation of the graphene thermal conductive film is generally carried out by taking graphene oxide as a precursor, firstly preparing graphene oxide from graphite, dispersing the graphene oxide in a solvent to form graphene oxide slurry, defoaming, coating, drying and stripping the graphene oxide slurry to obtain the graphene oxide film, and then carrying out thermal treatment on the graphene oxide film to obtain the graphene thermal conductive film.
When the graphene oxide film is prepared by the method, graphene oxide leftover materials can be generated in the processes of cutting, slitting and the like, and the graphene oxide film with poor appearance can be generated in the manufacturing process, so that the utilization rate of raw materials is reduced, and the manufacturing cost is increased.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
Aiming at one or more problems in the prior art, the invention provides a method for preparing graphene oxide powder by using graphene oxide leftover materials and defective products and preparing a graphene heat-conducting film by using the graphene oxide powder, so that the utilization rate of raw materials is improved, and the manufacturing cost is increased.
The invention provides a preparation method of graphene oxide powder, which comprises the following steps: and drying, crushing and crushing the leftover materials and defective products of the graphene oxide film to obtain graphene oxide powder.
In the process of preparing the graphene oxide film, the inventor finds that the elimination of the leftover materials greatly affects the cost, and the proportion of the leftover materials is not low. In consideration of the potential swelling property of graphene oxide, it was found that graphene oxide can be re-dispersed, and the leftover and defective products of graphene oxide can be reused.
In order to prevent dust in the air from contaminating the graphene oxide film, the graphene oxide film needs to be stored in a timely sealed manner and crushed in a timely manner when leftover materials or defective products of the graphene oxide film are obtained.
According to one aspect of the invention, the drying is performed using a forced air drying oven, a tunnel drying oven or a vacuum drying oven.
Preferably, the temperature of the drying is 40-85 ℃.
Preferably, the drying time is 40min-5 h.
Leftover materials and defective products of the graphene oxide film are influenced by air humidity in a storage environment, 15-20% of moisture is contained inside the graphene oxide film, and if the graphene oxide film is not dried, the leftover materials and the defective products have certain toughness and high strength and are not beneficial to subsequent crushing and smashing. The graphene oxide film after drying preferably has a lower moisture content, but if the moisture content is completely removed, the production cost increases, and in industrial production, the graphene oxide film may be dried to a moisture content of about 5%.
According to one aspect of the invention, the graphene oxide membrane is broken to a sheet diameter D50 of 1-5 cm.
Preferably, the crushing is performed with a crusher, preferably a roll crusher.
According to one aspect of the invention, the method of pulverizing comprises pulverizing the graphene oxide film to a sheet diameter of D50 of 1-3mm, and then pulverizing the graphene oxide film to a sheet diameter of D50 of 5-30 μm to form graphene oxide powder.
Preferably, a cutter disc type grinder is used for grinding the sheet diameter of the graphene oxide film to D50 of 1-3 mm.
Preferably, the graphene oxide film is pulverized by a jet mill to a particle size of D50 of 5-30 μm.
Further preferably, the pressure of the jet milled compressed gas is 0.6-1 MPa.
The graphene oxide membrane is crushed to the diameter D50 of 1-5cm, then crushed to the diameter D50 of 1-3mm, finally crushed to the diameter D50 of 5-30 mu m, and the graphene oxide membrane can be better crushed by adopting a stepped crushing method. The volume and the shape of the graphene oxide film serving as leftover materials or defective products of the graphene oxide film are not fixed, and if a cutter disc type grinder is directly adopted, feeding is easily interrupted, manual assistance is needed, and the graphene oxide film is not beneficial to mass production; the jet mill has a certain range of requirements on the size of the fed particles, and is not suitable for directly adding leftover materials and defective products of graphene oxide. The fragments of the graphene oxide film are firstly crushed by a crusher until the diameter D50 is 1-5cm, and then the fragments are gradually reduced.
According to one aspect of the invention, the fragments of the graphene oxide film are in a sealed environment during the crushing to comminution. Fragments of the graphene oxide film are very fine, and dust overflow easily causes damage to operators.
The invention also provides graphene oxide powder prepared by the preparation method of the graphene oxide powder.
The invention also provides a preparation method of the graphene oxide film, which comprises the following steps:
preparing graphene oxide powder by using the preparation method of the graphene oxide powder;
dispersing graphene oxide powder into a solvent to obtain graphene oxide slurry;
and (3) defoaming, coating, drying and stripping the graphene oxide slurry to obtain the graphene oxide film.
According to one aspect of the invention, the dispersion is carried out by stirring followed by high speed dispersion.
Preferably, the linear velocity of the agitation is from 5 to 20 m/s.
Preferably, the linear velocity of the high-speed dispersion is 100-300 m/s.
According to one aspect of the invention, the solvent is water.
According to one aspect of the present invention, the graphene oxide slurry has a solid content of 1-4%.
Preferably, the viscosity of the graphene oxide slurry is 20000-.
According to one aspect of the invention, the coating has a thickness of 1 to 5 mm.
According to one aspect of the invention, the temperature of the drying is 60-85 ℃.
The raw material of the graphene oxide powder is an assembled graphene oxide film, and although the graphene oxide of the raw material is assembled, the structure of the graphene oxide film is not damaged, and the original dispersion performance and assembly performance of the graphene oxide powder can still be maintained. Therefore, the dispersibility of the prepared graphene oxide slurry is not reduced, and the prepared graphene oxide film has good assembling property and good stacking property.
The invention also provides a graphene oxide film prepared by the preparation method of the graphene oxide film.
According to one aspect of the invention, the grammage of the graphene oxide film is 30-200g/m2。
The invention also provides a preparation method of the graphene heat-conducting film, which is characterized in that leftover materials and defective products of the graphene oxide film are used as raw materials to prepare the graphene heat-conducting film.
The method specifically comprises the following steps:
preparing a graphene oxide film by using the preparation method of the graphene oxide film;
and carrying out high-temperature treatment on the graphene oxide film to obtain the graphene heat-conducting film.
According to one aspect of the invention, the method of high temperature treatment comprises heating the graphene oxide film to 2500-.
Preferably, the temperature rise rate of the high-temperature treatment is 2-5 ℃/min.
According to one aspect of the invention, the graphene thermal conductive film is compacted after the high temperature treatment.
The invention also provides a graphene heat-conducting film prepared by the preparation method of the graphene heat-conducting film.
According to one aspect of the invention, the graphene thermal conductive film has a thickness of 10 μm to 1mm, preferably 15 to 200 μm.
According to one aspect of the invention, the graphene thermal conductive film has a density of 1.95-2.1g/cm3。
According to one aspect of the invention, the thermal conductivity of the graphene thermal conductive film is 1000-1800W/m.K, preferably 1000-1700W/m.K.
The invention has the beneficial effects that:
according to the invention, the leftover materials and defective products of the graphene oxide film are recycled to prepare the graphene oxide film and the graphene heat-conducting film, so that the utilization rate of the raw material of the graphene oxide film is improved, and the cost is reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a pictorial representation of a scrap material of a graphene oxide film;
fig. 2 is a physical diagram of graphene oxide fragments after being crushed by a double-roll crusher;
fig. 3 is a physical diagram of graphene oxide fragments after being crushed by a cutter disc type crusher;
fig. 4 is a physical diagram of graphene oxide fragments after being crushed by a cutter disc type crusher;
FIG. 5 is a diagram of graphene oxide powder;
FIG. 6 is an SEM image of the graphene oxide film of example 1B;
FIG. 7 is an SEM image of the graphene oxide film of example 2B;
fig. 8 is an SEM image of the graphene oxide film of example 3B.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
As a first embodiment of the present invention, a method for preparing graphene oxide powder is presented, which includes the steps of: the leftover and defective products of the graphene oxide film (as shown in fig. 1) are dried, crushed and crushed to obtain graphene oxide powder.
The drying adopts an air-blast drying oven, a tunnel drying oven or a vacuum drying oven. The temperature of drying is 40-85 ℃, for example: 40 ℃, 41 ℃, 42 ℃, 43 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 63 ℃, 65 ℃, 68 ℃, 70 ℃, 73 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 85 ℃ and the like. The drying time is 40min-5h, for example: 40min, 50min, 1h20min, 1h30min, 2h30min, 2h50min, 3h30min, 4h20min, 4h30min, 4h50min, 5h, etc. Leftover materials and defective products of the graphene oxide film are influenced by air humidity in a storage environment, 15-20% of moisture is contained inside the graphene oxide film, and if the graphene oxide film is not dried, the leftover materials and the defective products have certain toughness and high strength and are not beneficial to subsequent crushing and smashing. The graphene oxide film after drying preferably has a lower moisture content, but if the moisture content is completely removed, the production cost increases, and in industrial production, the graphene oxide film may be dried to a moisture content of about 5%.
The sheet diameter D50 of the graphene oxide film is broken to 1-5cm, for example: 1cm, 1.2cm, 1.5cm, 1.8cm, 2cm, 2.2cm, 2.4cm, 2.5cm, 2.8cm, 3cm, 3.3cm, 3.5cm, 3.8cm, 4cm, 4.2cm, 4.5cm, 4.7cm, 4.8cm, 4.9cm, 5cm, etc., as shown in FIG. 2. The crushing is carried out by a crusher, preferably a double-roll crusher.
The crushing method comprises the steps of crushing the sheet diameter of the graphene oxide film to D50 of 1-3mm, for example: 1mm, 1.1mm, 1.2mm, 1.4mm, 1.5mm, 1.7mm, 1.8mm, 2mm, 2.2mm, 2.4mm, 2.5mm, 2.8mm, 2.9mm, 3mm, etc., as shown in fig. 3 and 4; and then the sheet diameter of the graphene oxide film is reduced to D50 of 5-30 μm, for example: 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 29 μm, 30 μm, etc., to form a graphene oxide powder, as shown in FIG. 5. And (3) crushing the sheet diameter of the graphene oxide film to 1-3mm of D50 by adopting a cutter disc type crusher. And (3) crushing the sheet diameter of the graphene oxide film to D50 of 5-30 mu m by adopting a jet milling mode. The pressure of the jet-milled compressed gas is from 0.6 to 1MPa, for example: 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1MPa, etc. The graphene oxide membrane is crushed to the diameter D50 of 1-5cm, then crushed to the diameter D50 of 1-3mm, finally crushed to the diameter D50 of 5-30 mu m, and the graphene oxide membrane can be better crushed by adopting a stepped crushing method. The volume and the shape of the graphene oxide film serving as leftover materials or defective products of the graphene oxide film are not fixed, and if a cutter disc type grinder is directly adopted, feeding is easily interrupted, manual assistance is needed, and the graphene oxide film is not beneficial to mass production; the jet mill has a certain range of requirements on the size of the fed particles, and is not suitable for directly adding leftover materials and defective products of graphene oxide. The fragments of the graphene oxide film are firstly crushed by a crusher until the diameter D50 is 1-5cm, and then the fragments are gradually reduced.
During the process of crushing to pulverization, fragments of the graphene oxide film are in a sealed environment. Fragments of the graphene oxide film are very fine, and dust overflow easily causes damage to operators.
As a second embodiment of the present invention, a graphene oxide powder prepared by the method for preparing a graphene oxide powder according to the first embodiment is shown.
As a third embodiment of the present invention, a method for preparing a graphene oxide film is presented, which includes the steps of:
preparing graphene oxide powder by using the method for preparing graphene oxide powder according to the first embodiment;
dispersing graphene oxide powder into a solvent to obtain graphene oxide slurry;
and (3) defoaming, coating, drying and stripping the graphene oxide slurry to obtain the graphene oxide film.
The raw material of the graphene oxide powder is an assembled graphene oxide film, and although the graphene oxide of the raw material is assembled, the structure of the graphene oxide film is not damaged, and the original dispersion performance and assembly performance of the graphene oxide powder can still be maintained. Therefore, the dispersibility of the prepared graphene oxide slurry is not reduced, and the prepared graphene oxide film has good assembling property and good stacking property.
The dispersion adopts a mode of firstly stirring and then dispersing at a high speed. The linear speed of stirring is from 5 to 20m/s, for example: 5m/s, 6m/s, 7m/s, 8m/s, 10m/s, 12m/s, 14m/s, 15m/s, 17m/s, 18m/s, 19m/s, 20m/s, and the like. The linear velocity of high-speed dispersion is 100-300m/s, for example: 100m/s, 110m/s, 120m/s, 130m/s, 150m/s, 160m/s, 180m/s, 200m/s, 220m/s, 240m/s, 250m/s, 270m/s, 280m/s, 290m/s, 300m/s, and the like.
The solvent is water. The solid content of the graphene oxide slurry is 1-4%, for example: 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.4%, 3.5%, 3.8%, 3.9%, 4%, etc. The viscosity of the graphene oxide slurry is 20000-: 20000 mPas, 22000 mPas, 24000 mPas, 25000 mPas, 30000 mPas, 35000 mPas, 40000 mPas, 45000 mPas, 50000 mPas, 55000 mPas, 58000 mPas, 590000 mPas, 60000 mPas, etc.
The thickness of the coating is 1 to 5mm, for example: 1mm, 1.2mm, 1.5mm, 1.8mm, 2mm, 2.2mm, 2.5mm, 2.8mm, 3mm, 3.2mm, 3.4mm, 3.6mm, 3.8mm, 4mm, 4.1mm, 4.3mm, 4.5mm, 4.8mm, 4.9mm, 5mm, etc. The temperature of drying is 60-85 ℃, for example: 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 79 ℃, 80 ℃, 82 ℃, 84 ℃, 85 ℃ and the like.
As a fourth embodiment of the present invention, a graphene oxide film produced by the method for producing a graphene oxide film according to the third embodiment is shown. The gram weight of the graphene oxide film is 30-200g/m2For example: 30g/m2、40g/m2、50g/m2、60g/m2、70g/m2、80g/m2、90g/m2、100g/m2、120g/m2、140g/m2、150g/m2、180g/m2、190g/m2、200g/m2And so on.
As a fifth embodiment of the present invention, a method for preparing a graphene thermal conductive film is presented, which includes the following steps:
preparing a graphene oxide film by using the method for preparing a graphene oxide film according to the third embodiment;
and carrying out high-temperature treatment on the graphene oxide film to obtain the graphene heat-conducting film.
The high temperature treatment method comprises heating the graphene oxide film to 2500-: 2500 deg.C, 2600 deg.C, 2700 deg.C, 2800 deg.C, 2900 deg.C, 3000 deg.C, etc. The temperature rise rate of the high-temperature treatment is 2-5 ℃/min, for example: 2 deg.C/min, 2.5 deg.C/min, 3 deg.C/min, 3.5 deg.C/min, 4 deg.C/min, 4.5 deg.C/min, 5 deg.C/min, etc. And compacting the graphene heat-conducting film after high-temperature treatment.
As a sixth embodiment of the present invention, a graphene thermal conductive film prepared by the method for preparing a graphene thermal conductive film according to the fifth embodiment is shown. The thickness of the graphene heat conduction film is 10 μm-1mm, for example: 10 μm, 15 μm, 20 μm, 30 μm, 50 μm, 80 μm, 90 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 950 μm, 980 μm, 990 μm, 1mm, and the like. As a preferred embodiment, the thickness of the graphene thermal conductive film is 15-200 μm, for example: 15 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 43 μm, 45 μm, 47 μm, 49 μm, 50 μm, 51 μm, 55 μm, 58 μm, 59 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 120 μm, 140 μm, 150 μm, 170 μm, 180 μm, 190 μm, 195 μm, 198 μm, 199 μm, 200 μm, and the like. The density of the graphene heat-conducting film is 1.95-2.1g/cm3For example: 1.95g/cm3、1.96g/cm3、1.97g/cm3、1.98g/cm3、1.99g/cm3、2.0g/cm3、2.01g/cm3、2.03g/cm3、2.05g/cm3、2.08g/cm3、2.09g/cm3、2.1g/cm3And so on. The thermal conductivity of the graphene thermal conductive film is 1000-1800W/m.K, for example: 1000W/mK, 1050W/mK, 1100W/mK, 1150W/mK, 1200W/mK, 1250W/mK, 1300W/mK, 1350W/mK, 1400W/mK. 1450W/mK, 1500W/mK, 1550W/mK, 1600W/mK, 1650W/mK, 1700W/mK, 1750W/mK, 1800W/mK, etc. In a preferred embodiment, the thermal conductivity of the graphene thermal conductive film is 1000-: 1000W/mK, 1100W/mK, 1200W/mK, 1300W/mK, 1400W/mK, 1500W/mK, 1600W/mK, 1700W/mK, etc.
The advantages of the invention are illustrated by the following examples:
example 1A:
the embodiment shows a preparation process of graphene oxide powder, which comprises the following steps:
step 1): and drying 10kg of graphene oxide leftover materials by adopting an electric heating air blowing oven, wherein the drying temperature is 50 ℃, and the drying time is 5 hours.
Step 2): and (3) crushing the dried graphene oxide leftover materials by using an electric crusher until the size of D50 of the diameter of the graphene oxide leftover materials is 1-3 cm.
Step 3): crushing the fragments obtained in the step 2) by using a cutter disc type crusher to obtain fragments with the diameter D50 of 2 mm; and then, adopting a jet milling mode, wherein the pressure of jet milled compressed gas is 0.6MPa, and obtaining the graphene oxide powder with the D50 of 30 mu m.
Example 1B:
the embodiment shows a preparation process of a graphene oxide film, which comprises the following steps:
step 1): graphene oxide powder was prepared using the method of example 1A.
Step 2): adding 4kg of graphene oxide powder into 96kg of deionized water, and stirring by a planetary stirrer with the linear speed of 7 m/s; after stirring, dispersing by a high-speed dispersion machine of 200m/s to obtain graphene oxide slurry with the solid content of 4% and the viscosity of 36000 mPas;
step 3): defoaming the graphene oxide slurry obtained in the step 2), and coating the slurry on a base material, wherein the base material is PET (polyethylene terephthalate) cloth, and the thickness of the coating is 2.5 mm; drying at 78 deg.C to obtain a product with a gram weight of 100g/m2The graphene oxide film of (1). The SEM image of the graphene oxide film is shown in FIG. 6, and it can be seen that the graphite oxide film is formed of graphite oxideThe lamination of the olefin film is good.
Example 1C:
the embodiment shows a preparation process of a graphene heat-conducting film, which comprises the following steps:
step 1): a graphene oxide film was prepared using the method of example 1B.
Step 2): carrying out high-temperature treatment on the graphene oxide film, wherein the temperature of the high-temperature treatment is 2800 ℃, the heating rate is 4 ℃/min, compacting to obtain the graphene oxide film with the thickness of 26 mu m and the density of 2.03g/cm3And the thermal conductivity coefficient is 1430W/m.K.
Example 2A:
the embodiment shows a preparation process of graphene oxide powder, which comprises the following steps:
step 1): 100kg of graphene oxide leftover materials with the thickness of 5cm are flatly paved and placed in a hot air oven with a length of 20m of an electric heating tunnel for continuous drying, the drying temperature is 75 ℃, and the speed of a conveyor belt is 0.2 m/min.
Step 2): and continuously feeding the dried graphene oxide leftover materials into an electric crusher, and crushing until the size D50 of the sheet diameter is 1-3 cm.
Step 3): continuously feeding the crushed graphene oxide fragments into a cutter disc type crusher, and crushing the fragments to obtain fragments with the diameter D50 of 2 mm; and (3) automatically feeding the materials into a jet mill system by a cutter disc type mill, wherein the pressure of jet milled compressed gas is 0.8MPa, and obtaining the graphene oxide powder with the D50 of 15 mu m.
Example 2B:
the embodiment shows a preparation process of a graphene oxide film, which comprises the following steps:
step 1): graphene oxide powder was prepared using the method of example 2A.
Step 2): adding 10kg of graphene oxide powder into 490kg of deionized water, and stirring by a planetary stirrer with the linear speed of 20 m/s; after stirring, dispersing by a high-speed dispersion machine of 300m/s to obtain graphene oxide slurry with the solid content of 2% and the viscosity of 28000mPa & s;
step 3): mixing the graphite oxide obtained in the step 2)Defoaming the olefin slurry, and coating the olefin slurry on a base material, wherein the base material is PET (polyethylene terephthalate) cloth, and the thickness of the coating is 3.5 mm; drying at 70 deg.C to obtain a product with a gram weight of 70g/m2The graphene oxide film of (1). The SEM image of the graphene oxide film is shown in fig. 7, and it can be seen that the graphene oxide film is well stacked.
Example 2C:
the embodiment shows a preparation process of a graphene heat-conducting film, which comprises the following steps:
step 1): a graphene oxide film was prepared using the method of example 2B.
Step 2): carrying out high-temperature treatment on the graphene oxide film, wherein the temperature of the high-temperature treatment is 2850 ℃, the heating rate is 5 ℃/min, compacting is carried out, and the obtained product has the thickness of 16 mu m and the density of 2.0g/cm3And the thermal conductivity coefficient is 1700W/m.K.
Example 3A:
the embodiment shows a preparation process of graphene oxide powder, which comprises the following steps:
step 1): 100kg of graphene oxide leftover materials with the thickness of 5cm are flatly paved and placed in a hot air oven with a length of 20m of an electric heating tunnel for continuous drying, the drying temperature is 85 ℃, and the speed of a conveyor belt is 0.5 m/min.
Step 2): and continuously feeding the dried graphene oxide leftover materials into an electric crusher, and crushing until the size D50 of the sheet diameter is 2-5 cm.
Step 3): continuously feeding the crushed graphene oxide fragments into a cutter disc type crusher, and crushing the fragments to obtain fragments with the diameter D50 of 3 mm; and (3) automatically feeding the materials into a jet mill system by a cutter disc type mill, wherein the pressure of jet milled compressed gas is 1.0MPa, and obtaining graphene oxide powder with the D50 of 8 mu m.
Example 3B:
the embodiment shows a preparation process of a graphene oxide film, which comprises the following steps:
step 1): graphene oxide powder was prepared using the method of example 3A.
Step 2): adding 20kg of graphene oxide powder into 480kg of deionized water, and stirring by a planetary stirrer with the linear speed of 12 m/s; after stirring, dispersing by a high-speed dispersion machine of 100m/s to obtain graphene oxide slurry with the solid content of 4% and the viscosity of 48000mPa & s;
step 3): defoaming the graphene oxide slurry obtained in the step 2), and coating the slurry on a base material by using a coating machine, wherein the base material is PP cloth, the thickness of the coating is 3mm, and the coating speed is 1.5 m/min; and continuously drying, wherein the number of the drying ovens is 18, and the temperature of each drying oven is respectively as follows: 60 deg.C, 65 deg.C, 68 deg.C, 72 deg.C, 75 deg.C, 78 deg.C, 85 deg.C, 78 deg.C, 70 deg.C, 65 deg.C, 60 deg.C to obtain a gram weight of 120g/m2The graphene oxide film of (1). The SEM image of the graphene oxide film is shown in fig. 8, and it can be seen that the graphene oxide film is well stacked.
Example 3C:
the embodiment shows a preparation process of a graphene heat-conducting film, which comprises the following steps:
step 1): a graphene oxide film was prepared using the method of example 3B.
Step 2): overlapping two graphene oxide films together, performing high-temperature treatment at 2850 ℃, heating at a rate of 2 ℃/min, compacting to obtain a composite film with a thickness of 60 mu m and a density of 1.95g/cm3And the thermal conductivity coefficient is 1300W/m.K.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the graphene oxide powder is characterized by comprising the following steps: and drying, crushing and crushing the leftover materials and defective products of the graphene oxide film to obtain graphene oxide powder.
2. The method for preparing graphene oxide powder according to claim 1, wherein the drying is performed by using a forced air drying oven, a tunnel drying oven or a vacuum drying oven;
preferably, the temperature of the drying is 40-85 ℃;
preferably, the drying time is 40min-5 h;
preferably, the graphene oxide membrane is crushed to a sheet diameter D50 of 1-5 cm;
preferably, the crushing is performed by a crusher, preferably a roll crusher;
preferably, the crushing method comprises crushing the graphene oxide film to a diameter D50 of 1-3mm, and then crushing the graphene oxide film to a diameter D50 of 5-30 μm to form graphene oxide powder; preferably, a cutter disc type pulverizer is adopted for pulverizing the sheet diameter of the graphene oxide film to D50 of 1-3 mm; preferably, the graphene oxide film is subjected to jet milling by crushing the sheet diameter of the graphene oxide film to D50 of 5-30 μm; further preferably, the pressure of the jet milled compressed gas is 0.6-1 MPa;
preferably, the fragments of the graphene oxide film are in a sealed environment during the crushing to comminution.
3. Graphene oxide powder, characterized in that the graphene oxide powder is prepared by the method of claim 1 or 2.
4. A graphene oxide film preparation method is characterized by comprising the following steps:
preparing graphene oxide powder by the method of claim 1 or 2;
dispersing the graphite oxide powder into a solvent to obtain graphene oxide slurry;
and (3) defoaming, coating, drying and stripping the graphene oxide slurry to obtain the graphene oxide film.
5. The method for preparing a graphene oxide film according to claim 4, wherein the dispersion is carried out by stirring and then high-speed dispersion; preferably, the linear velocity of the stirring is 5 to 20 m/s; preferably, the linear velocity of the high-speed dispersion is 100-300 m/s;
preferably, the solvent is water;
preferably, the solid content of the graphene oxide slurry is 1-4%;
preferably, the viscosity of the graphene oxide slurry is 20000-;
preferably, the thickness of the coating is 1-5 mm;
preferably, the temperature of the drying is 60-85 ℃.
6. A graphene oxide film, wherein the graphene oxide film is prepared by the method of claim 4 or 5;
preferably, the gram weight of the graphene oxide film is 30-200g/m2。
7. A preparation method of a graphene heat conduction film is characterized in that graphene oxide leftover materials and defective products are used as raw materials to prepare the graphene heat conduction film;
preferably comprising the steps of:
preparing a graphene oxide film by the method of claim 4 or 5;
and carrying out high-temperature treatment on the graphene oxide film to obtain the graphene heat-conducting film.
8. The method for preparing the graphene thermal conductive film according to claim 7, wherein the high temperature treatment method comprises heating the graphene oxide film to 2500-3000 ℃;
preferably, the heating rate of the high-temperature treatment is 2-5 ℃/min;
preferably, the graphene heat conduction film is compacted after the high-temperature treatment.
9. A graphene thermal conductive film, wherein the graphene thermal conductive film is prepared by the method of claim 7 or 8;
preferably, the thickness of the graphene heat conduction film is 10 μm-1mm, preferably 15-200 μm;
preferably, the density of the graphene heat conduction film is 1.95-2.1g/cm3；
Preferably, the thermal conductivity of the graphene thermal conductive film is 1800W/m.K of 1000-.
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