CN108249424B - Preparation method of bromine-doped high-conductivity ultrathin graphene film - Google Patents
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- CN108249424B CN108249424B CN201810061894.3A CN201810061894A CN108249424B CN 108249424 B CN108249424 B CN 108249424B CN 201810061894 A CN201810061894 A CN 201810061894A CN 108249424 B CN108249424 B CN 108249424B
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Abstract
The invention discloses a preparation method of a bromine-doped high-conductivity ultrathin graphene film, wherein the graphene film is prepared by filtering and pumping graphene oxide into a film, carrying out chemical reduction, carrying out solid-liquid synchronous transfer, carrying out high-temperature graphitization, carrying out bromine doping and the like. The graphene film is formed by physically crosslinking a single layer of oxidized/reduced graphene oxide. The graphene film has a thickness of 10-2000 atomic layers. The graphene oxide film has a small thickness and a large number of defects inside, and thus has excellent transparency and excellent flexibility. After chemical reduction, most of the functional groups disappear, and the graphene film begins to conduct electricity; high-temperature reduction, graphene structure repair and electron mobility improvement; the graphene carrier concentration is improved after bromine doping. The graphene film can be used as a highly flexible transparent conductive device.
Description
Technical Field
The invention relates to a high-performance nano material and a preparation method thereof, in particular to a preparation method of a bromine-doped high-conductivity ultrathin graphene film.
Background
The graphene film of macroscopically assembled graphene oxide or graphene nanosheets is the main application form of nanoscale graphene, and common preparation methods are a suction filtration method, a scraping method, a spin-coating method, a spraying method, a dip-coating method and the like. Through further high-temperature treatment, the defects of graphene can be repaired, the conductivity and the thermal conductivity of the graphene film can be effectively improved, and the graphene film can be widely applied to portable electronic equipment such as smart phones, intelligent portable hardware, tablet computers and notebook computers.
However, at present, the thickness of the graphene film after high-temperature sintering is generally more than 1um, a lot of gas is sealed in the graphene film, and in the process of high-pressure pressing, sealed gas holes are reserved in a wrinkle form, so that the orientation degree of the graphene film is deteriorated, the density is reduced, and the interlayer AB stacking degree is poor, which seriously affects the further improvement of the performance of the graphene film.
The conductivity of the graphene film reported at present is still 10 due to structural defects6And (5) S/m. There is also a large distance from the metal. For this reason, we raised the conductivity of graphene films to 18.9x10 by a method of structure and composition control6S/m, the conductivity is improved by nearly 20 times, which is comparable to metal. The graphene film prepared by the method can completely meet the requirement of most high electric conductionThe demand of devices opens a new door for the conductive design of graphene films.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a bromine-doped high-conductivity ultrathin graphene film.
The purpose of the invention is realized by the following technical scheme: a preparation method of a bromine-doped high-conductivity ultrathin graphene film comprises the following steps:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO into a closed container, and fumigating at the high temperature of 80-100 ℃ for 0.1-1h from the bottom to the top.
(3) And uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film by using methods such as evaporation, casting and the like, and naturally cooling at room temperature until the basement membrane naturally falls off.
(4) And volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at the temperature of volatilizing the solid transfer agent to obtain the independent self-supported graphene film.
(5) And (3) placing the independent self-supporting graphene film in a high-temperature furnace, heating to 3000 ℃, repairing the graphene film structure, and removing internal defects.
(6) Placing the graphene film treated in the step 5 and a certain amount of liquid bromine in the same sealed container, wherein the amount m of the liquid bromine and the volume v of the container meet the following conditions: m/v is 1g/L, and the whole container is then frozen in liquid nitrogen and evacuated until the air is completely evacuated. Naturally unfreezing at room temperature (20-30 ℃), and then putting into an oven at 30-40 ℃ for heating for 12-24 hours to obtain the bromine-doped graphene film.
Further, the solid transfer agent is selected from materials such as paraffin, naphthalene, arsenic trioxide, camphor, sulfur, norbornene, rosin and other small molecule solid materials which can be sublimated or volatilized under certain conditions and are insoluble in water.
Further, the sublimation temperature of the solid transfer agent is controlled below 320 ℃; the sublimation pressure and the ambient oxygen content depend on the physical properties.
Further, the temperature rise process is as follows: 0-2000 ℃ and 5-20 ℃ per minute; 2000-.
The invention has the beneficial effects that: at present, the common solid transfer agent in the common technology is a macromolecule because of the characteristics of easy operation and easy fitting, and can be removed by solution etching or high-temperature sintering. However, the graphene film is torn by the surface tension when the solution is etched, and a substrate support is also needed when the graphene film is taken out of the solution. The existence of the solution enables the graphene film not to exist independently in a self-supporting mode and only to be attached to the surface of the base. High temperature sintering can cause the graphene film to shrink, can not maintain the morphology of the graphene itself, and can also cause the graphene to adhere to the substrate. The invention removes the substrate by using surface tension; and the easy-to-sublimate solid-state transfer agent is used, so that the nano-scale graphene film can be independently self-supported in the air. In the process, the solid-state transfer agent is removed according to the sublimation principle, and the problem of surface tension does not exist, so that the graphene film cannot be mutually adhered to the substrate. The graphite substrate bears the graphene film, and the graphene film is assisted to finish high-temperature annealing at 3000 ℃. The thickness of the obtained graphene film is controllable, the graphene is highly oriented, defects are hardly generated in the sheets, the sheets are mainly stacked from AB, and all the structures lay the foundation for the excellent performance of the graphene film. According to the thickness of the graphene film, the graphene film has certain transparency, and the smaller the thickness is, the better the transparency is, which undoubtedly expands the potential application of the graphene film. Further, bromine atoms provide electrons for the graphene conjugated structure through bromine doping, so that on one hand, the graphene band gap is opened; on the other hand, the electron density of the graphene film is increased, the conductivity is improved, and the application of the graphene film in the photoelectric field is greatly facilitated.
Drawings
Fig. 1 is an atomic force microscope image of a bromine-doped graphene film prepared in example 1;
fig. 2 is a physical representation of the bromine-doped graphene film prepared in example 1;
fig. 3 is a raman plot of the bromine-doped graphene film prepared in example 1.
Fig. 4 is a xps diagram of bromine-doped graphene film prepared in example 1;
fig. 5 is a graph of the conductivity of graphene films with different bromine doping levels.
Detailed Description
Example 1:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO into a closed container, and fumigating the graphene oxide membrane at the high temperature of 80 ℃ from the bottom to the top for 1 h.
(3) And uniformly coating the melted solid transfer agent camphor on the surface of the reduced graphene oxide film by using an evaporation method, and slowly cooling at room temperature until the base film naturally falls off.
(4) And slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at 60 ℃ to obtain the independent self-supported graphene film.
(5) The independent self-supporting graphene film is placed in a high-temperature furnace, the temperature is raised to 2000 ℃ at the speed of 5 ℃ per minute, and then the temperature is raised to 3000 ℃ at the speed of 2 ℃ per minute, so that the graphene film structure is repaired, and internal defects are removed.
(6) And (3) placing the graphene membrane treated in the step (5) and 0.5g of liquid bromine in a container with the volume of 500 milliliters, freezing the whole container by using liquid nitrogen, and vacuumizing until air is completely pumped out. Naturally unfreezing at room temperature (20-30 ℃), and then heating in an oven at 30 ℃ to obtain the bromine-doped graphene film. The bromine content gradually increased with increasing heating time, and when heated to 12 hours, the bromine content reached 0.07 wt%, which was found to have an electrical conductivity of 19.1 MS/m. After heating for 24 hours, the conductivity reached 19.9 MS/m. As shown in fig. 5. The atomic force scan of the graphene film is shown in fig. 1, and it can be seen from the figure that the thickness of the graphene film is 36nm, and as can be seen from the actual figure of fig. 2, the graphene film with the thickness of 36nm is completely self-supporting. Xps data show that bromine atoms exist in the graphite film, RamanData are shown at 0-1000cm-1Three raman peaks are located.
Example 2:
a preparation method of a bromine-doped high-conductivity ultrathin graphene film comprises the following steps:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 10ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO into a closed container, and fumigating the graphene oxide membrane from the bottom to the top for 0.1h at a high temperature of 100 ℃.
(3) And uniformly coating the molten solid transfer agent rosin on the surface of the reduced graphene oxide film by using a tape casting method, and naturally cooling at room temperature until the base film naturally falls off.
(4) Volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at 120 ℃ to obtain the independent self-supported graphene film.
(5) And (2) placing the independent self-supporting graphene film in a high-temperature furnace, heating to 2000 ℃ at the rate of 20 ℃ per minute, and then heating to 3000 ℃ at the rate of 5 ℃ per minute to repair the graphene film structure and remove internal defects.
(6) And (3) placing the graphene membrane treated in the step (5) and 0.5g of liquid bromine in a 500-milliliter container, freezing the whole container by using liquid nitrogen, and vacuumizing until air is completely pumped out. Naturally unfreezing at room temperature (20-30 ℃), and then heating in an oven at 40 ℃ for 12 hours to obtain the bromine-doped graphene film. The thickness of the material is 40nm, the material can realize independent self-support, and the conductivity is 16.9 MS/m.
Example 3:
a preparation method of a bromine-doped high-conductivity ultrathin graphene film comprises the following steps:
(1) preparing the graphene oxide into a graphene oxide aqueous solution with the concentration of 1ug/mL, and performing suction filtration to form a film by taking the AAO film as a substrate.
(2) The graphene oxide membrane attached to the AAO was placed in a closed container and fumigated from the bottom up for 30 minutes at a high temperature of 100 ℃.
(3) And uniformly coating the molten solid transfer agent rosin on the surface of the reduced graphene oxide film by using a tape casting method, and naturally cooling at room temperature until the base film naturally falls off.
(4) Volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at 120 ℃ to obtain the independent self-supported graphene film.
(5) The independent self-supporting graphene film is placed in a high-temperature furnace, the temperature is increased to 2000 ℃ at the rate of 10 ℃ per minute, and the temperature is increased to 3000 ℃ at the rate of 4 ℃ per minute, so that the graphene film structure is repaired, and internal defects are removed.
(6) And (3) placing the graphene film treated in the step (5) and 5g of liquid bromine in the same 500-milliliter sealed container, freezing the whole container by using liquid nitrogen, and vacuumizing until air is completely pumped out. Naturally unfreezing at room temperature (20-30 ℃), and then putting into an oven at 30-40 ℃ for heating for 15 hours to obtain the bromine-doped graphene film. The thickness of the material is 50nm, the material can realize independent self-support, and the conductivity is 15.9 MS/m.
Claims (5)
1. A preparation method of a bromine-doped high-conductivity ultrathin graphene film is characterized by comprising the following steps:
(1) preparing graphene oxide into a graphene oxide aqueous solution with the concentration of 0.5-10 mug/mL, and performing suction filtration to form a film by taking an AAO film as a substrate;
(2) putting the graphene oxide film attached to the AAO into a closed container, and fumigating at the high temperature of 80-100 ℃ from the bottom to the top for 0.1-1 h;
(3) uniformly coating the melted solid transfer agent on the surface of the reduced graphene oxide film, and naturally cooling at room temperature until the base film naturally falls off;
(4) volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent at the temperature of volatilizing the solid transfer agent to obtain an independent self-supported graphene film;
(5) placing the independent self-supporting graphene film in a high-temperature furnace, heating to 3000 ℃, repairing the graphene film structure, and removing internal defects;
(6) placing the graphene film treated in the step (5) and a certain amount of liquid bromine in the same sealed container, wherein the amount m of the liquid bromine and the volume v of the container meet the following conditions: m/v =1g/L, then the whole container is frozen with liquid nitrogen and evacuated until the air is completely evacuated; naturally unfreezing at room temperature, and then putting the film into an oven at the temperature of 30-40 ℃ to heat for 12-24 hours to obtain the bromine-doped graphene film.
2. The method of claim 1 wherein said solid transfer agent is selected from the group consisting of paraffin, naphthalene, camphor, norbornene, rosin.
3. The method of claim 1, wherein the sublimation temperature of the solid transfer agent is controlled to be less than 320 degrees; the sublimation pressure and the ambient oxygen content depend on the physical properties.
4. The method according to claim 1, wherein the temperature raising in the step (5) is as follows: 0-2000 ℃ and 5-20 ℃ per minute; 2000-.
5. The method according to claim 1, wherein in the step (3), the melted solid transfer agent is uniformly applied to the surface of the reduced graphene oxide film by evaporation or casting.
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