CN106744841B - Preparation method of three-dimensional porous graphene film constructed by single-layer graphene - Google Patents
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Abstract
A preparation method and application of a three-dimensional graphene film constructed by utilizing single-layer graphene. The method is characterized in that: adding ultrasonic crushing and ball milling stripping processes in an improved Hummer method process for preparing graphene to obtain single-layer or few-layer graphene, mixing organic solvents to prepare graphene slurry, printing the graphene slurry with different thicknesses on a substrate by a screen printing method, placing the substrate printed with the graphene slurry in a muffle furnace, and removing the organic slurry by a high-temperature heat treatment method to obtain the interconnected graphene film with a nanoscale porous three-dimensional structure. The film has high specific surface area, and can be used as electrode materials of super capacitors, lithium ion batteries, thin-film solar batteries and the like after being modified by metal oxides and metal sulfides.
Description
Technical Field
The invention relates to the field of materials, in particular to a preparation method and application of a three-dimensional graphene film constructed by utilizing single-layer graphene.
Background
Graphene is a material having a single-layer sheet structure composed of carbon atoms, has a high specific surface area and high electrical conductivity, and excellent mechanical properties, thus making the graphene-based material an extremely promising energy storage active material, particularly as an electrode material for an electric double layer supercapacitor.
However, due to the strong van der waals force between graphene nanosheet layers and the hydrophobic property of graphene, the graphene nanosheets are very easy to stack layer by layer, how to synthesize a high-performance graphene-based adsorption material is a key problem in the research of the graphene-based adsorption material, and the construction of a graphene-based porous three-dimensional framework structure is a very effective method. Compared with original graphene and graphene-based materials with other morphological structures, the graphene-based material with the three-dimensional framework structure shows more excellent physicochemical properties based on the three-dimensional network and the porous structure characteristics. The three-dimensional graphene material is structurally different from two-dimensional graphene, and effectively overcomes the defects that the two-dimensional graphene is easy to agglomerate and difficult to disperse and is difficult to obtain high specific surface area, so that the three-dimensional graphene material is more suitable to be used as an electrode material of a double electric layer super capacitor. The three-dimensional graphene has a three-dimensional hollow porous reticular structure, the network wall is graphene, and the graphene is graphite with a laminated structure and porous graphite carbon foam, and has the advantages of ultralow-density-degree surface area, high heat conductivity, high temperature resistance, corrosion resistance, good ductility, good flexibility and the like.
The preparation method of the graphene mainly comprises the following steps: physical methods, mechanical exfoliation methods, chemical vapor deposition methods, thermal expansion exfoliation methods, electrochemical methods, redox methods, and the like. Chemical Vapor Deposition (CVD) is one of the important methods for preparing high-quality graphene thin films, and with the development of preparation technology, the yield of the CVD method can also meet the requirement of mass production. The CVD method can use a gaseous, liquid, or solid substance as a carbon source to grow the graphene thin film. However, the method is complicated and the cost is high. The oxidation-reduction method comprises the steps of oxidizing graphite to obtain graphite oxide, and then reducing the graphite oxide by a reduction method to prepare graphene nanosheets of different specifications. However, due to the limitation of the redox method, the prepared graphene has low quality (for example, the conductivity is only more than 1500S/m), and the performance of the graphene is seriously affected due to many defects of the graphene.
At present, the preparation methods of three-dimensional graphene in the prior art are not ideal, and the invention provides a preparation method of a three-dimensional graphene film constructed by utilizing single-layer graphene, wherein the prepared film has high specific surface area, and can be used as electrode materials of super capacitors, lithium ion batteries, thin-film solar batteries and the like after being modified by metal oxides and metal sulfides.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of a three-dimensional graphene film constructed by utilizing single-layer graphene. The method is characterized in that: adding ultrasonic crushing and ball milling stripping processes in an improved Hummer method process for preparing graphene to obtain single-layer or few-layer graphene, mixing organic solvents to prepare graphene slurry, printing the graphene slurry with different thicknesses on a substrate by a screen printing method, placing the substrate printed with the graphene slurry in a muffle furnace, and removing the organic slurry by a high-temperature heat treatment method to obtain the interconnected graphene film with a nanoscale porous three-dimensional structure. The film has high specific surface area, and can be used as electrode materials of super capacitors, lithium ion batteries, thin-film solar batteries and the like after being modified by metal oxides and metal sulfides.
The technical scheme of the invention is as follows:
a preparation method of a three-dimensional graphene film constructed by utilizing single-layer graphene comprises the following steps:
(1) improved Hummer method for preparing redox graphene
And (3) low-temperature reaction: weighing concentrated sulfuric acid, pouring the concentrated sulfuric acid into a conical flask, putting the conical flask into an ice water bath for cooling, pouring natural graphite and sodium nitrate into the conical flask, carrying out ultrasonic treatment for a period of time, slowly adding 3g of potassium permanganate, and stirring for 2 hours at the temperature lower than 10 ℃.
And (3) medium-temperature reaction: the flask was moved to a 38 ℃ water bath and the reaction was stirred for 2 hours.
High-temperature reaction: adding the obtained solution into 100ml of low-temperature deionized water, carrying out water bath at 80 ℃ for 0.5 hour, and then adding 60ml of deionized water to terminate the reaction; subsequently, 25ml of 30% by volume hydrogen peroxide solution were added, and after 15min 40ml of 10% by volume hydrochloric acid solution were added. Centrifuging at 1000 r/min to remove acid radical ions, and detecting with barium chloride to obtain no white precipitate.
And (3) reduction of graphene oxide: drying in a drying oven at 45 deg.C to obtain sheet sample, grinding into powder, and placing into a crucible. The crucible was placed in a muffle furnace at 300 ℃ for 2 min. Obtaining fluffy graphene powder.
Ball milling treatment: 1) accurately weighing 0.02g of dried fluffy graphene powder, adding the fluffy graphene powder into an organic solvent or pure water, stirring, and ultrasonically dispersing in an ultrasonic cleaner for 10min to uniformly disperse the graphene powder in the solvent. 2) And (3) putting the graphene powder suspension uniformly dispersed in the solvent and zirconia grinding balls into a ball milling tank, and placing the ball milling tank into a planetary ball mill for ball milling. The rotation speed is controlled to reduce the impact ratio of the grinding balls in the normal direction, and the shearing force is enhanced. And finally, carrying out suction filtration and drying on the ball-milled graphene dispersion liquid to obtain single-layer graphene powder.
(2) Preparation of three-dimensional graphene film
Preparing graphene slurry: preparing ethyl cellulose ethanol solution with the mass fraction of 5% -15%, stirring uniformly, and then adding 9.6g of terpineol and 9.2g of absolute ethyl alcohol. And finally adding 0.05-0.1g of prepared single-layer graphene powder subjected to ball milling. Magnetically stirring for 20-30min, and ultrasonically dispersing for 20min, and alternating for 3-5 times. Then stirring and evaporating the dry absolute ethyl alcohol. Then 0.6ml of acetylacetone and 0.6ml of OP emulsifier are added and stirred evenly to obtain graphene slurry.
And (3) a screen printing counter electrode method, wherein a plurality of layers of graphene slurry are printed on the cleaned FTO glass conductive surface, and the FTO glass conductive surface is placed in a forced air drying oven for pretreatment for 20min at the temperature of 80-120 ℃. The printing is then repeated. Finally curing at the temperature of 150 ℃ at 100 ℃. And printing graphene slurry with different layers. Finally, heat treatment is carried out in a muffle furnace at different temperatures of 100 ℃ and 400 ℃.
And (3) introducing an ultrasonic crushing technology in the low-temperature reaction stage, weighing 23ml of concentrated sulfuric acid, pouring the concentrated sulfuric acid into a conical flask, putting the conical flask into an ice water bath, cooling to 4-0 ℃, pouring 1g of natural graphite and 0.5g of sodium nitrate into the conical flask, starting ultrasonic treatment, and stopping ultrasonic treatment after 0.5-2 hours. Finally, redox graphene powder is prepared.
The oxidation-reduction graphene powder is stripped by ball milling, the mass ratio of cobalt oxide ball milling beads to the ball material of the oxidation-reduction graphene powder is about 2000:1 to 10000:1, the rotating speed is 200 plus 400 r/min, and the ball milling time is 10-30 h.
Preparing graphene slurry by using OP emulsifier, terpineol, acetylacetone and ethyl cellulose as organic solvent;
placing the conductive substrate printed with the graphene slurry in an air-blast drying oven for pretreatment at the temperature of 80-120 ℃;
placing the conductive substrate printed with the graphene slurry in a muffle furnace, wherein the temperature of heat treatment is 100-400 ℃;
the three-dimensional graphene film obtained by the invention has a porous three-dimensional interconnected structure, and has high specific surface area, high transmittance and low resistivity. The graphene film can be directly used as an electrode material of a super capacitor, a lithium ion battery, a thin film solar battery, a dye-sensitized solar battery and the like.
The graphene film modified by some metal oxides or metal sulfides can be used as electrode materials of super capacitors, lithium ion battery films, solar cells, dye-sensitized solar cells and the like.
Drawings
FIG. 1 is a TEM photograph of single-layer graphene
FIG. 2 is a graph of thickness of single layer graphene
FIG. 3 is a cross-sectional SEM image of a three-dimensional graphene film
FIG. 4 is a surface SEM image of a three-dimensional graphene film
Detailed Description
(1) Improved Hummer method for preparing redox graphene
And (3) low-temperature reaction: weighing 23ml of concentrated sulfuric acid, pouring the concentrated sulfuric acid into a conical flask, putting the conical flask into an ice water bath to cool the concentrated sulfuric acid to below 4 ℃, pouring 1g of natural graphite and 0.5g of sodium nitrate into the conical flask, turning on ultrasonic treatment, turning off the ultrasonic treatment after one hour, slowly adding 3g of potassium permanganate, and stirring the mixture for 2 hours at the temperature of below 10 ℃.
And (3) medium-temperature reaction: the flask was moved to a 38 ℃ water bath and the reaction was stirred for 2 hours.
High-temperature reaction: adding the obtained solution into 100ml of low-temperature deionized water, carrying out water bath at 80 ℃ for 0.5 hour, and then adding 60ml of deionized water to terminate the reaction; subsequently, 25ml of 30% by volume hydrogen peroxide solution were added, and after 15min 40ml of 10% by volume hydrochloric acid solution were added. Centrifuging at 1000 r/min to remove acid radical ions, and detecting with barium chloride to obtain no white precipitate.
And (3) reduction of graphene oxide: drying in a drying oven at 45 deg.C to obtain sheet sample, grinding into powder, and placing into a crucible. The crucible was placed in a muffle furnace at 300 ℃ for 2 min. Obtaining fluffy graphene powder.
Ball milling treatment: 1) accurately weighing 0.02g of dried graphene powder, adding the dried graphene powder into 80ml of ethanol solvent or pure water, stirring, and then ultrasonically dispersing in an ultrasonic cleaner for 10min to uniformly disperse the graphene powder in the organic solvent. 2) And (3) putting the graphene microchip suspension uniformly dispersed in the organic solvent and zirconia grinding balls into a ball milling tank (the mass ratio of the balls to the materials is about 20000:1), and placing the ball milling tank into a planetary ball mill for ball milling. The rotating speed is controlled at 300 revolutions per minute to reduce the impact rate of the grinding balls in the normal direction and enhance the shearing force; the ball milling time is 30 h. And finally, carrying out suction filtration and drying on the ball-milled graphene dispersion liquid to obtain single-layer graphene powder.
(2) Preparation of three-dimensional graphene film
Preparing graphene slurry: preparing ethyl cellulose ethanol solution with the mass fraction of 5% -15%, stirring uniformly, and then adding 9.6g of terpineol and 9.2g of absolute ethyl alcohol. And finally adding 0.05-0.1g of prepared single-layer graphene powder. Magnetically stirring for 20-30min, and ultrasonically dispersing for 20min, and alternating for 3-5 times. Then stirring and evaporating the dry absolute ethyl alcohol. Then 0.6ml of acetylacetone and 0.6ml of OP emulsifier are added and stirred evenly to obtain graphene slurry.
And (3) a screen printing counter electrode method, wherein a plurality of layers of graphene slurry are printed on the cleaned FTO glass conductive surface, and the FTO glass conductive surface is placed in a forced air drying oven for pretreatment for 20min at the temperature of 80-120 ℃. The printing is then repeated. Finally curing at the temperature of 150 ℃ at 100 ℃. And printing graphene slurry with different layers. Finally, heat treatment is carried out in a muffle furnace at different temperatures of 100 ℃ and 400 DEG C
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (5)
1. A preparation method of a three-dimensional graphene film constructed by utilizing single-layer graphene is characterized by comprising the following steps:
(1) preparing redox graphene by improving a Hummer method: carrying out low-temperature reaction, medium-temperature reaction and high-temperature reaction on natural graphite and sodium nitrate to obtain graphene oxide;
the low-temperature reaction: weighing 23ml of concentrated sulfuric acid, pouring into a conical flask, putting into an ice water bath, cooling to 4-0 ℃, pouring 1g of natural graphite and 0.5g of sodium nitrate into the conical flask, starting ultrasound, and stopping ultrasound after 0.5-2 h; slowly adding 3g of potassium permanganate, and stirring for 2 hours at the temperature lower than 10 ℃; the medium-temperature reaction: moving the conical flask to a 38 ℃ water bath kettle, and stirring for reaction for 2 hours; the high-temperature reaction: adding the obtained solution into 100ml of low-temperature deionized water, carrying out water bath at 80 ℃ for 0.5 hour, and then adding 60ml of deionized water to terminate the reaction; then 25ml of hydrogen peroxide solution with the volume ratio of 30 percent is added, and 40ml of hydrochloric acid solution with the volume ratio of 10 percent is added after 15 min; centrifuging at 1000 r/min to remove acid radical ions, and detecting with barium chloride to remove white precipitate;
and (3) reduction of graphene oxide: drying at 45 ℃ in a drying oven to obtain a sheet sample, grinding the sheet sample into powder, putting the powder into a crucible, and putting the crucible into a muffle furnace at 300 ℃ for 2min to obtain fluffy graphene powder;
ball milling treatment: 1) accurately weighing 0.02g of dried graphene powder, adding the dried graphene powder into ethanol or pure water, stirring, and ultrasonically dispersing in an ultrasonic cleaner for 10min to uniformly disperse the graphene powder in a solvent; 2) putting the graphene powder suspension uniformly dispersed in the solvent and zirconia grinding balls into a ball milling tank, and placing the ball milling tank in a planetary ball mill for ball milling; the rotating speed is controlled to reduce the impact rate of the grinding balls in the normal direction and enhance the shearing force; finally, carrying out suction filtration and drying on the ball-milled graphene dispersion liquid to obtain single-layer graphene powder;
(2) preparation of three-dimensional graphene film
Preparing graphene slurry: preparing an ethanol solution of ethyl cellulose with the mass fraction of 5-15%, uniformly stirring, and then adding 9.6g of terpineol and 9.2g of absolute ethyl alcohol; finally, adding 0.05-0.1g of prepared single-layer graphene powder; magnetically stirring for 20-30min, and ultrasonically dispersing for 20min, and alternating for 3-5 times; then stirring and evaporating the dry absolute ethyl alcohol; then adding 0.6ml of acetylacetone and 0.6ml of emulsifier, and uniformly stirring to obtain graphene slurry;
a screen printing counter electrode method, wherein a plurality of layers of graphene slurry are printed on a cleaned FTO glass conductive surface, and the FTO glass conductive surface is placed in a forced air drying oven to be pretreated for 20min at 80-120 ℃; then, repeatedly printing; finally, curing at 100 ℃ and 150 ℃; printing graphene slurry with different layers; finally, the heat treatment is carried out in a muffle furnace at the temperature of 100 ℃ and 400 ℃.
2. The method for preparing a three-dimensional graphene film constructed by using single-layer graphene according to claim 1, wherein the method comprises the following steps: stripping the redox graphene powder by ball milling, wherein the mass ratio of cobalt oxide ball milling beads to the redox graphene powder is (2000-10000): 1, the rotating speed is 200-.
3. The three-dimensional graphene thin film prepared by the preparation method according to claim 1 or 2.
4. The application of the three-dimensional graphene film constructed by using the single-layer graphene according to claim 3, wherein the graphene film can be directly used as an electrode material of a super capacitor, a lithium ion battery, a thin-film solar battery and a dye-sensitized solar battery.
5. The application of the three-dimensional graphene film constructed by using the single-layer graphene, according to claim 3, wherein the graphene film modified by some metal oxides or metal sulfides can be an electrode material of a super capacitor, a lithium ion battery, a thin film solar cell and a dye-sensitized solar cell.
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| CN110739155B (en) * | 2019-09-24 | 2021-10-19 | 广东工业大学 | Nickel sulfide/graphene composite film and preparation method and application thereof |
| CN113068280B (en) * | 2020-01-02 | 2023-03-24 | 中国科学院福建物质结构研究所 | Graphene heating film and preparation method and application thereof |
| CN112945997A (en) * | 2021-02-01 | 2021-06-11 | 天津艾克凯胜石墨烯科技有限公司 | Sample preparation method for aqueous graphene slurry before scanning electron microscope |
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