CN114906843A - Preparation method of graphene oxide film - Google Patents
Preparation method of graphene oxide film Download PDFInfo
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- CN114906843A CN114906843A CN202210423272.7A CN202210423272A CN114906843A CN 114906843 A CN114906843 A CN 114906843A CN 202210423272 A CN202210423272 A CN 202210423272A CN 114906843 A CN114906843 A CN 114906843A
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Abstract
The invention provides a preparation method of a graphene oxide film, which comprises the following steps: (1) dispersing organic molecules in a solvent to obtain a modification liquid; (2) slowly adding the modifying liquid obtained in the step (1) into the graphene oxide aqueous slurry to be uniformly dispersed to obtain modified graphene oxide slurry; (3) and (3) coating the modified graphene oxide slurry obtained in the step (2) on a substrate, and drying to obtain the graphene oxide film. The invention also provides a flexible graphene film prepared by applying the graphene oxide film, which is obtained by carrying out heat treatment on the graphene oxide film. The graphene film has good flexibility and a heat dissipation function, and can be widely applied to folding mobile phones and wearable equipment.
Description
The patent application of the invention is divisional application, and the application number of the parent application is as follows: 202110147837.9, the name is: a flexible graphene film and a method for preparing the same.
Technical Field
The invention belongs to the technical field of material synthesis and application, and particularly relates to a preparation process for modifying graphene oxide slurry by using an additive.
Background
Graphene is a two-dimensional nanomaterial structure of a hexagonal honeycomb lattice consisting of only carbon atoms. Since the discovery, it has attracted extensive attention and research due to its excellent mechanical, optical, electrical, and thermal properties. Graphene Oxide (GO) is an oxide corresponding to graphene, and is formed by bonding oxygen-containing functional groups such as hydroxyl, carboxyl, carbonyl, epoxy and the like to graphene sheets. Just because the graphene oxide sheet layers contain a large number of functional groups, the graphene oxide sheet layers can be stacked by self-assembly such as hydrogen bonding to form a macroscopic membrane material. And thermally reducing the graphene oxide film to obtain the graphene film with certain flexibility.
However, for future mainstream flexible electronic devices, the flexibility of the existing graphene film cannot meet the application of the graphene film in folding mobile phones and wearable devices. Therefore, it is crucial to design a graphene film having high flexibility.
Empirically and in known technology, methods for preparing flexible graphene films can be divided into several categories: first, one-dimensional carbon materials, such as carbon nanotubes, carbon fibers, etc., are added. Adding the carbon nanotube dispersion liquid into the graphene oxide dispersion liquid, uniformly stirring, coating to form a graphene oxide film, and performing high-temperature heat treatment to obtain the graphene film compounded by the carbon nanotubes and the graphene. By adding the chain-like material into the graphene oxide, the graphene oxide film can play a role in bridging among graphene film layers, so that the mechanical properties of the graphene film, such as bending resistance, stretching resistance and the like, are improved. Meanwhile, the one-dimensional carbon material can form a heat conduction channel at the lap joint of the graphene segments and can be filled in an air bag cavity formed when the graphene film is subjected to thermal reduction, so that the heat conduction channel in the graphene film is obviously improved, and the heat conduction coefficient of the graphene film is improved. However, carbon nanotubes and carbon fibers, which are used as hydrophobic carbon materials, have poor dispersibility in graphene oxide dispersion liquid, and the finally obtained graphene film has uneven distribution of carbon nanotubes and carbon fibers, and the flexibility of the graphene film cannot be significantly improved. Second, a graphene film is prepared using large-sized graphene oxide sheets. For example, professor in "ultra high Thermal Conductive layer Superflexible Graphene Films" mentioned the use of large-diameter Graphene oxide to increase the flexibility of Graphene Films. The preparation process of the large-size graphene oxide is complex, harsh redox process conditions are required, and the preparation mode is only limited to a laboratory stage. Third, the use of micro-folds improves the flexibility of the film. The 16-year stone height full professor creates a plurality of huge folds on the surface of the graphene film by using a macroscopic template assembly method, achieves high-fold stretching of the graphene film, but needs an elastic substrate, is troublesome to operate, and has unclear flexibility due to the structural design of the film, so that the application of the graphene film in flexible devices is limited. Therefore, from the perspective of large-scale preparation of flexible graphene films, no mature scheme can be applied to the industrial preparation process at present.
Disclosure of Invention
In order to prepare a graphene film with high flexibility, the problems that an existing heat conducting film is poor in flexibility and less in folding times are solved. In the invention, organic molecules are introduced to modify Graphene Oxide (GO) so as to further prepare the flexible graphene film. Specifically, organic molecules and GO slurry are mixed and stirred uniformly before film coating, and then the film coating is carried out and drying is carried out, so as to obtain the modified GO film. The method for adding and doping is convenient and quick, and has strong controllability and wide selection range of modified substances. These modified materials can be intercalated between graphene oxide layers, so that the interaction force between layers is enhanced, and GO is promoted to be self-assembled more easily to obtain a tightly stacked GO membrane. In the finally prepared graphene film, substances for improving flexibility are intercalated between layers, and the effect of improving strength and bending resistance is achieved in the bending process.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a graphene oxide film, which comprises the following steps:
(1) dispersing organic molecules in a solvent to obtain a modification liquid;
(2) slowly adding the modifying liquid obtained in the step (1) into the graphene oxide aqueous slurry to be uniformly dispersed, so as to obtain modified graphene oxide slurry;
(3) and (3) coating the modified graphene oxide slurry obtained in the step (2) on a substrate, and drying to obtain the graphene oxide film.
Preferably, in the step (1), the organic molecule is polyacrylonitrile, polyacrylate or polyacrylamide; and/or
The molecular weight of the organic molecule is 10000-;
the solvent is deionized water, alcohols, acetone or N, N-dimethylformamide.
The reason for selecting polyacrylonitrile, polyacrylate or polyacrylamide as the organic molecule is: the organic molecules are obtained by free radical polymerization of monomer acrylonitrile or a monomer of a derivative thereof, and form a chain structure to connect graphene sheets and sheets, so that the interaction force between the graphene film inner sheet layers is enhanced.
Preferably, in the step (2), the organic molecules account for 0.1-20% of the dry weight of the graphene oxide; preferably, the organic molecules account for 1-10% of the graphene oxide dry weight; most preferably the organic molecules constitute 5% of the graphene oxide dry weight; and/or
The weight percentage concentration of the graphene oxide aqueous slurry is 1-8%.
Preferably, in the step (3), the thickness of the coating film at the time of coating is 1-5 mm; and/or
The drying temperature is 60-120 deg.C, and the drying time is 30-300 min.
Preferably, the dispersion in each step is one or more of stirring, ultrasound and shaking.
The invention modifies GO by adding organic molecules to GO slurry. The substances can be intercalated in GO sheets to play a role in bridging the sheets between the layers, so that the interaction force between the GO sheets is enhanced, graphene oxide is promoted to be self-assembled to obtain a GO membrane which is tightly stacked well, the GO membrane is attached between the layers after heat treatment, additives such as polyacrylonitrile and the like are intercalated between the finally prepared graphene membrane layers, the flexibility of the prepared graphene membrane is enhanced, and the bending resistance of the graphene membrane is improved. Meanwhile, the prepared graphene film keeps the high heat conductivity coefficient of the original graphene film, and can play a good role in heat dissipation performance in the field of flexible devices. The graphene film with good flexibility can be widely applied to folding mobile phones and wearable equipment. The application of the graphene film in the field of flexible electronic devices is expanded, and the market share of the graphene film is improved.
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 an optical photograph of the flexible graphene film prepared in example 1 after being bent 20,000 times.
Fig. 2 is an optical photograph of the flexible graphene film prepared in example 2 after being bent 20,000 times.
Fig. 3 is an optical photograph of the flexible graphene film prepared in example 3 after being bent 30,000 times.
Fig. 4 is an optical photograph of the flexible graphene film prepared in example 4 after being bent 40,000 times.
Fig. 5 is an optical photograph of the flexible graphene film prepared in example 5 after being bent 200,000 times.
Fig. 6 is an optical photograph of the flexible graphene film prepared in example 6 after being bent 20,000 times.
Fig. 7 is an optical photograph of the flexible graphene film prepared in example 7 after being bent 20,000 times.
Fig. 8 is an optical photograph of the flexible graphene film prepared in example 8 after being bent 20,000 times.
Fig. 9 is an optical photograph of the graphene film prepared in comparative example 1 after being bent 20,000 times.
Fig. 10 is an optical photograph of the graphene film prepared in comparative example 2 after being bent 20,000 times.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from conventional biochemicals, unless otherwise specified. The quantitative tests in the following examples, all set up three replicates and the results averaged. In the present invention, "%" is a weight percentage.
Experimental drugs used in the present invention: the GO filter cake is synthesized by a Hummers method. Wherein the graphite raw material is purchased from Aladdin, the purity is 99.9%, and the particle size is 325 meshes; 99.2 percent of concentrated sulfuric acid and 36 to 38 percent of dilute hydrochloric acid by mass, and purchasing the concentrated sulfuric acid and the dilute hydrochloric acid in a Chinese medicine reagent network; potassium permanganate is purchased from a traditional Chinese medicine reagent network; polyacrylonitrile, polyacrylate and polyacrylamide are purchased from the reagent net of traditional Chinese medicine, and the molecular weight is 10000-200000.
Flexibility test methods in examples of the invention: and (3) carrying out bending experiments on the sample by adopting a YUASA tension-free U-shaped folding machine, observing the crease of the bent sample, and observing the crease by adopting a Mingmei MP41 optical microscope.
The thermal conductivity test method in the embodiment of the invention comprises the following steps: the heat conductivity was measured using a German relaxation-resistant laser flash thermal conductivity apparatus (Netzsch, LFA-467).
The preparation method of the modified GO membrane and the graphene membrane prepared from the modified GO membrane comprises the following steps:
(1) preparation of organic molecule modified GO slurry
Preparing graphene oxide into a 1-8% aqueous GO solution by using deionized water, and dispersing uniformly to obtain GO aqueous slurry. For uniform dispersion, one or a combination of several methods commonly used in the prior art, such as stirring at a rotation speed of 200-500rpm for 1-10h, ultrasonic treatment for 30-120min or shaking by a shaking machine for 30-120min, can be adopted here as long as the dispersion is uniform.
The organic molecules are polyacrylonitrile, polyacrylate or polyacrylamide, and the organic molecules account for 0.1-20% of the dry weight of GO, such as 0.1%, 0.2%, 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, etc. of the dry weight of GO. Dispersing organic molecules in deionized water, alcohols, acetone and N, N-Dimethylformamide (DMF) solvent for later use to prepare a modification solution. For uniform dispersion, one or a combination of several methods commonly used in the prior art, such as ultrasonic stirring at 30-90min, 200-600rpm stirring for 1-10h or shaking for 30-120min, can be adopted here as long as the dispersion is uniform.
And slowly adding the modifying liquid into the GO aqueous slurry to be uniformly dispersed, so as to obtain the modified GO slurry. For uniform dispersion, one or more of the conventional methods in the prior art, such as ultrasonic stirring at 600rpm for 1-10h or shaking at 200-120 min for 30-90min, can be adopted, so long as the dispersion is uniform.
(2) Preparation of modified GO membranes
Coating the modified GO slurry on a PET substrate, wherein the thickness of the film is 1-5mm, such as 1mm, 1.5mm, 2mm, 3mm, 4mm, 5mm and the like, and placing the PET substrate in an oven at 60-120 ℃ for drying for 30-300 min, such as the oven temperature of 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and 120 ℃; drying for 30min, 40min, 50min, 60min, 80min, 100min, 120min, 150min, 180min, 210min, 250min, 300min to obtain the modified GO membrane.
(3) Preparation of graphene films
And reducing the GO membrane into a graphene membrane through stage heat treatment, wherein the heat treatment stage is divided into three stages, the first stage is 300-500 ℃, the treatment time is 1-10h, the second stage is heated to 1000-1500 ℃, the heat treatment is carried out for 1-10h, the third stage is heated to 2000-3000 ℃, the heat treatment is carried out for 10-30 h, and the graphene membrane is obtained, and the thickness is 10-60 mu m.
(4) Graphene film flexibility test
And (3) with the bending radius R being 1mm, the bending angle being 180 degrees and the bending speed being 60R/min, bending for 1 ten thousand to 20 ten thousand times, and observing the number and the depth of folds at the bending part of the heat-conducting film by using an optical microscope to judge the flexibility of the graphene film.
(5) Graphene film thermal conductivity test
The thermal conductivity of the graphene film is measured by a laser flash method, and the unit is W/mK.
Example 1
1) Preparing a GO aqueous slurry: dispersing 40gGO (dry weight) in 960mL of water, stirring for 3 hours at the rotating speed of 300rpm by a stirrer, and then shaking for 30min to obtain uniformly dispersed GO water-based slurry with the solid content of 4%;
2) preparing a modifying liquid: adding 5g of polyacrylonitrile powder (molecular weight of 30000) into 95ml of deionized water, stirring at 400rpm for 10h, and uniformly stirring to prepare a modification solution with the concentration of 5%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 20mL of the modification solution at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 3mm membrane, and treating at 70 ℃ for 120min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is at 300 ℃, the treatment time is 10 hours, the second section is heated to 1000 ℃ for heat treatment for 10 hours, and the third section is heated to 2000 ℃ for heat treatment for 10 hours to obtain the graphene film.
5) Flexibility test: the obtained graphene film is bent by 180 degrees at R1, the bending experiment is carried out by testing the testing parameters with the speed of 60R/min, and the folded area of the sample is observed by an optical microscope.
6) Heat conduction property test: setting the laser voltage of the heat conduction instrument to be 260V and the pulse frequency to be 200s -1 Testing the heat conductivity coefficient of the heat-conducting film, wherein the heat conductivity coefficient is as follows: 1191W/mK.
FIG. 1 is an optical photograph of the flexible graphene film prepared in example 1 after being bent 20,000 times (a, before bending; b, after bending).
Example 2
1) Preparing a GO aqueous slurry: dispersing 60gGO (dry weight) in 940mL of water, stirring for 3h at the rotating speed of 300rpm by a stirrer, and then oscillating for 30min to obtain uniformly dispersed GO water-based slurry with the solid content of 6%;
2) preparing a modifying liquid: adding 10g of polyacrylate powder (molecular weight of 50000) into 90ml of acetone, stirring at 400rpm for 6h, and uniformly stirring to obtain a modification solution with the concentration of 10%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 50mL of the modification solution at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 2mm membrane, and treating at 70 ℃ for 90min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, the first section is 350 ℃, the treatment time is 5 hours, the second section is heated to 1200 ℃ for heat treatment for 3 hours, and the third section is heated to 2900 ℃ for heat treatment for 12 hours to obtain the graphene film.
5) Flexibility test: the test method was the same as in example 1.
6) Heat conduction property test: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1225W/mK.
Fig. 2 is an optical photograph of the flexible graphene film prepared in example 2 after being bent 20,000 times.
Example 3
1) Preparing a GO aqueous slurry: dispersing 45gGO (dry weight) in 955mL of water, stirring for 3h at 300rpm by a stirrer, and then shaking for 60min to obtain uniformly dispersed GO water-based slurry with solid content of 4.5%;
2) preparing a modifying liquid: adding 6g of polyacrylamide powder (molecular weight is 200000) into 94ml of deionized water, stirring at 500rpm for 5h, and stirring uniformly to obtain a modification liquid with concentration of 6%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 50mL of the modification solution at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 2.5mm membrane, and treating at 70 ℃ for 90min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is 500 ℃, the treatment time is 1h, the second section is heated to 1500 ℃ for heat treatment for 2h, and the third section is heated to 2500 ℃ for heat treatment for 20h to obtain the graphene film.
5) Flexibility test: the test method was the same as in example 1.
6) Heat conduction property test: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1205W/mK.
Fig. 3 is an optical photograph of the flexible graphene film prepared in example 3 after being bent 30,000 times.
Example 4
1) Preparing a GO aqueous slurry: dispersing 30gGO (dry weight) in 970mL of water, stirring for 3 hours at the rotating speed of 300rpm by a stirrer, and then performing ultrasonic treatment for 30min to obtain uniformly dispersed GO water-based slurry with the solid content of 3.0%;
2) preparing a modifying liquid: adding 10g of polyacrylamide powder (with molecular weight of 150000) into 90ml of deionized water, stirring at 500rpm for 10h, and uniformly stirring to prepare a modification solution with the concentration of 10%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 30mL of the modification solution at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 4mm membrane, and treating at 70 ℃ for 120min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, the first section is at 400 ℃, the treatment time is 5h, the second section is heated to 1500 ℃ for heat treatment for 3h, and the third section is heated to 2800 ℃ for heat treatment for 8h to obtain the graphene film.
5) Flexibility test: the test method was the same as in example 1.
6) Heat conduction property test: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1152W/mK.
Fig. 4 is an optical photograph of the flexible graphene film prepared in example 4 after being bent 40,000 times.
Example 5
1) Preparing a GO aqueous slurry: dispersing 10gGO (dry weight) in 990mL of water, stirring for 5h at 500rpm by a stirrer, and then performing ultrasonic treatment for 30min to obtain uniformly dispersed GO aqueous slurry with a solid content of 1%.
2) Preparing a modifying liquid: adding 5g of polyacrylonitrile powder (molecular weight of 150000) into 95ml of ethanol, stirring at 500rpm for 6h, and stirring uniformly to obtain a modification solution with a concentration of 5%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 10mL of the modification solution at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 5mm membrane, and treating at 70 ℃ for 120min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is at 300 ℃, the treatment time is 1h, the second section is heated to 1200 ℃ for heat treatment for 2h, and the third section is heated to 2600 ℃ for heat treatment for 18h to obtain the graphene film.
5) Flexibility test: the test method was the same as in example 1.
6) Testing heat conductivity: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1211W/mK.
Fig. 5 is an optical photograph of the flexible graphene film prepared in example 5 after being bent 200,000 times.
Example 6
1) Preparing a GO aqueous slurry: 80gGO (dry weight) is dispersed in 920mL of water, and the mixture is stirred for 5 hours at the rotating speed of 500rpm by a stirrer and then is shaken for 90 minutes to obtain the GO water-based slurry with uniform dispersion, wherein the solid content is 8%.
2) Preparing a modifying liquid: adding 10g of polyacrylamide powder (with molecular weight of 150000) into 90ml of deionized water, stirring at 500rpm for 6h, and uniformly stirring to obtain a modification liquid with the concentration of 10%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 8mL of the modification solution at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 5mm membrane, and treating at 70 ℃ for 120min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is at 300 ℃, the treatment time is 1h, the second section is heated to 1200 ℃ for heat treatment for 2h, and the third section is heated to 2600 ℃ for heat treatment for 18h to obtain the graphene film.
5) Flexibility test: the test method was the same as in example 1.
6) Heat conduction property test: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1105W/mK.
Fig. 6 is an optical photograph of the flexible graphene film prepared in example 6 after being bent 20,000 times.
Example 7
1) Preparing a GO aqueous slurry: dispersing 10gGO (dry weight) in 990mL of water, stirring for 5 hours at the rotating speed of 500rpm by a stirrer, and then vibrating for 90min to obtain uniformly dispersed GO water-based slurry with the solid content of 1%;
2) preparing a modifying liquid: adding 0.1g of polyacrylonitrile (molecular weight of 30000) into 99.9ml of deionized water, stirring at 500rpm for 6h, and stirring uniformly to obtain a modification liquid with the concentration of 0.1%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 10mL of the modification solution at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 5mm membrane, and treating at 70 ℃ for 120min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is at 300 ℃, the treatment time is 1h, the second section is heated to 1200 ℃ for heat treatment for 2h, and the third section is heated to 2600 ℃ for heat treatment for 18h to obtain the graphene film.
5) Flexibility testing: the test method was the same as in example 1.
6) Heat conduction property test: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1194W/mK.
Fig. 7 is an optical photograph of the flexible graphene film prepared in example 7 after being bent 20,000 times.
Example 8
1) Preparing a GO aqueous slurry: dispersing 80gGO (dry weight) in 920mL of water, stirring for 5h at 500rpm by a stirrer, and then oscillating for 90min to obtain uniformly dispersed GO water-based slurry with a solid content of 8%;
2) preparing a modifying liquid: adding 20g of polyacrylonitrile (molecular weight of 30000) into 180ml of deionized water, stirring at 500rpm for 6h, and uniformly stirring to prepare a modification solution with the concentration of 10%;
3) preparation of GO membrane: and taking 1000mL of the GO aqueous slurry, and stirring 160mL of the modification solution uniformly at 400rpm for 1h to obtain the modified GO slurry. Coating the modified GO slurry on a PET substrate to form a 3mm membrane, and treating at 70 ℃ for 120min to obtain a dry modified GO membrane.
4) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is at 300 ℃, the treatment time is 1h, the second section is heated to 1200 ℃ for heat treatment for 2h, and the third section is heated to 2600 ℃ for heat treatment for 18h to obtain the graphene film.
5) Flexibility test: the test method was the same as in example 1.
6) Testing heat conductivity: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1250W/mK.
Fig. 8 is an optical photograph of the flexible graphene film prepared in example 8 after being bent 20,000 times.
Comparative example 1
1) Preparing a GO aqueous slurry: dispersing 30gGO (dry weight) in 970mL of water, stirring for 5 hours at the rotating speed of 500rpm by a stirrer, and then oscillating for 90min to obtain uniformly dispersed GO water-based slurry with the solid content of 3%;
2) preparation of GO membrane: coating 1000mL of the GO aqueous slurry on a PET substrate to form a 4mm film, and treating at 70 ℃ for 120min to obtain the GO film.
3) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is at 300 ℃, the treatment time is 1h, the second section is heated to 1200 ℃ for heat treatment for 2h, and the third section is heated to 2600 ℃ for heat treatment for 18h to obtain the graphene film.
4) Flexibility testing: the test method was the same as in example 1.
5) Heat conduction property test: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1200W/mK.
Fig. 9 is a photo of the graphene film prepared in comparative example 1 after being bent 20,000 times (a, before bending; b, after bending).
Comparative example 2
1) Preparing a GO aqueous slurry: dispersing 10gGO (dry weight) in 990mL of water, stirring for 5h at 500rpm by a stirrer, and then shaking for 90min to obtain uniformly dispersed GO water-based slurry with a solid content of 1%.
2) Preparation of GO membrane: coating 1000mL of the GO aqueous slurry on a PET substrate to form a 5mm film, and treating at 70 ℃ for 120min to obtain the GO film.
3) Preparing a graphene film: and reducing the GO membrane into a graphene membrane through stage heat treatment. The heat treatment stage is divided into three sections, wherein the first section is at 300 ℃, the treatment time is 1h, the second section is heated to 1200 ℃ for heat treatment for 2h, and the third section is heated to 2600 ℃ for heat treatment for 18h to obtain the graphene film.
4) Flexibility test: the test method was the same as in example 1.
5) Heat conduction property test: the thermal conductivity measurement method was the same as in example 1, and the thermal conductivity was: 1231W/mK.
Fig. 10 is an optical photograph of the flexible graphene film prepared in comparative example 2 after being bent 20,000 times.
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 (6)
1. A method for preparing a graphene oxide film, comprising: the method comprises the following steps:
(1) dispersing organic molecules in a solvent to obtain a modification liquid;
(2) slowly adding the modifying liquid obtained in the step (1) into the graphene oxide aqueous slurry to be uniformly dispersed, so as to obtain modified graphene oxide slurry;
(3) and (3) coating the modified graphene oxide slurry obtained in the step (2) on a substrate, and drying to obtain the graphene oxide film.
2. The method for preparing a graphene oxide film according to claim 1, wherein: in the step (1), the organic molecule is polyacrylonitrile, polyacrylate or polyacrylamide; and/or
The molecular weight of the organic molecule is 10000-;
the solvent is deionized water, alcohols, acetone or N, N-dimethylformamide.
3. The method for preparing a graphene oxide film according to claim 1, wherein: in the step (2), the organic molecules account for 0.1-20% of the dry weight of the graphene oxide; preferably, the organic molecules account for 1-10% of the graphene oxide dry weight; most preferably the organic molecules comprise 5% of the graphene oxide dry weight; and/or
The weight percentage concentration of the graphene oxide aqueous slurry is 1-8%.
4. The method for preparing a graphene oxide film according to claim 1, wherein: in the step (3), the thickness of the coating film during coating is 1-5 mm; and/or
The drying temperature is 60-120 deg.C, and the drying time is 30-300 min.
5. The method for preparing a graphene oxide film according to claim 1, wherein: the dispersion in each step is one or more of stirring, ultrasound and shaking.
6. A graphene oxide film prepared by the method of any one of claims 1 to 5.
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| CN107840330A (en) * | 2017-10-18 | 2018-03-27 | 复旦大学 | A kind of preparation method of carbon/carbon composite radiating film |
| CN108404689A (en) * | 2018-04-28 | 2018-08-17 | 青岛大学 | A kind of graphene oxide/polyacrylamide combined filtration film and its preparation and application |
| CN108530073A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting |
| CN111921388A (en) * | 2020-07-17 | 2020-11-13 | 河海大学 | Borate intercalation modified graphene oxide composite nanofiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530073A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting |
| CN107840330A (en) * | 2017-10-18 | 2018-03-27 | 复旦大学 | A kind of preparation method of carbon/carbon composite radiating film |
| CN108404689A (en) * | 2018-04-28 | 2018-08-17 | 青岛大学 | A kind of graphene oxide/polyacrylamide combined filtration film and its preparation and application |
| CN111921388A (en) * | 2020-07-17 | 2020-11-13 | 河海大学 | Borate intercalation modified graphene oxide composite nanofiltration membrane and preparation method thereof |
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