CN107651673B - Nano-scale thickness independent self-supporting folded graphene film and preparation method thereof - Google Patents
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Abstract
The invention discloses a nano-scale thickness independent self-supporting folded graphene film and a preparation method thereof. The graphene film is formed by physically crosslinking single-layer graphene, wherein the graphene elementary structure is complete, no obvious defect exists, the graphene film is rich in wrinkles, and the content of an interlamellar disordered layer structure exceeds 30%. It is extremely thin (16-130nm) and has a large number of wrinkles on the surface, and thus has excellent flexibility.
Description
Technical Field
The invention relates to a high-performance nano material and a preparation method thereof, in particular to a nano-scale thickness independent self-supporting folded graphene film and a preparation method thereof.
Background
In 2010, Andre GeiM and Konstantin Novoselov, two professors of Manchester university in England, raised the worldwide hot trend of graphene research because of the first successful separation of stable graphene to obtain the Nobel prize of physics. The graphene has excellent electrical properties (the electron mobility can reach 2 multiplied by 10 at room temperature)5cM2Vs), outstanding thermal conductivity (5000W/(MK), extraordinary specific surface area (2630M)2In g), its Young's modulus (1100GPa) and breaking strength (125 GPa). The excellent electric and heat conducting performance of the graphene completely exceeds that of metal, meanwhile, the graphene has the advantages of high temperature resistance and corrosion resistance, and the good mechanical property and the low density of the graphene enable the graphene to have the potential of replacing metal in the field of electric heating materials.
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 sintered at high temperature is generally more than 1um, a lot of gas is sealed in the graphene film, and the sealed gas holes are remained in a wrinkle form in the process of high-pressure pressing, so that the orientation degree of the graphene film is deteriorated, and the density is reduced. In addition, the regular stacking of graphene can make the graphene film easily bubble at high temperature, and the introduction of wrinkles can adjust the thickness of the graphene film at which the graphene film starts to bubble.
Furthermore, no work has been reported to prepare graphene oxide-based nanoscale graphene films. Generally, a nano-scale graphene film generally refers to a polycrystalline graphene film prepared by a chemical vapor deposition method, which is fixed on a certain substrate after being transferred by a wet method or a dry method and cannot be independently self-supported in the air. The graphene film is a polycrystalline structure, and the performance of the graphene film is greatly influenced by grain boundaries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a graphene film with independent self-supporting folds and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: an independent self-supporting folded graphene film with a nanoscale thickness, wherein the graphene film is 16-130nm thick and has a transparency of less than 50%; the graphene sheet is composed of randomly folded graphene sheets, and the AB stacking rate is 50-70%; few defects in graphene sheets, ID/IG＜0.01。
A graphene membrane with independent self-supporting folds and nanoscale thickness and a preparation method thereof comprise the following steps:
(1) preparing graphene oxide into a graphene oxide organic solution with the concentration of 0.5-10ug/mL, precipitating graphene oxide sheets by using a poor solvent, and finally performing suction filtration to form a film by using Anode Alumina (AAO) as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating HI steam at a high temperature of 60-100 ℃ for 1-10 h.
(3) The solid transfer agent is uniformly coated on the surface of the graphene film by using methods such as evaporation, casting and the like, and is heated at a temperature lower than the melting point of the solid transfer agent by 5 ℃ or lower, so that the solid transfer agent is cured.
(4) And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(5) And volatilizing the solid transfer agent from the graphene film supported by the solid transfer agent at the temperature of volatilizing the solid transfer agent to obtain the independent self-supported reduced graphene oxide film.
(6) And (3) placing the independent self-supporting reduced graphene oxide film in a high-temperature furnace for high-temperature annealing at 2400-3000 ℃, maintaining for 1-12h and raising the temperature at a rate of not more than 20 ℃/min.
Further, in the step 1, the organic solution is acetone, tetrahydrofuran, DMF, methanol, ethanol, ethylene glycol, NMP, DMSO; the poor solvent is ethyl acetate, toluene, o-xylene, acetonitrile, ethyl acetate, diethyl ether, n-hexane, etc.
Further, in the step 4, the AAO film which is not separated from the graphene film is etched away by using 1-10% phosphoric acid, and the etching time is 1-10 min.
Further, the solid transfer agent is selected from small molecule solid substances which can be sublimated or volatilized under certain conditions, such as paraffin, camphor, aluminum chloride, iodine, naphthalene, arsenic trioxide, phosphorus pentachloride, acrylamide, ferric chloride, sulfur, red phosphorus, ammonium chloride, ammonium bicarbonate, potassium iodide, norbornene, caffeine, melamine, water, rosin, tert-butyl alcohol, sulfur trioxide, and the like.
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.
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 and in a self-supporting mode, and only can 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. According to the invention, the easy-to-sublimate solid transfer agent is used, so that the nano-scale graphene film can be independently 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 obtained graphene film is mainly stacked from AB, the stacking degree can be adjusted through the folding degree of graphene oxide, 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.
Drawings
Fig. 1 is a nano-graphene film (10nm) with the solid state transfer agent removed.
Fig. 2 is a nano-graphene film annealed at 3000 degrees.
Detailed Description
Example 1:
(1) preparing graphene oxide into a graphene oxide DMF solution with the concentration of 0.5ug/mL, slowly precipitating graphene oxide sheets by using ethyl acetate, and performing suction filtration to form a film by using Anode Alumina (AAO) as a substrate.
(2) And (3) placing the graphene oxide membrane attached to the AAO membrane in a closed container, and fumigating for 1h by HI steam at 60 ℃.
(3) And (3) uniformly coating the solid transfer agent camphor on the surface of the graphene film by using a sublimation evaporation method at 100 ℃, and heating for a period of time at a temperature below 5 ℃ lower than the melting point of the solid transfer agent. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) And slowly volatilizing the solid transfer agent from the graphene film supported by the solid transfer agent at room temperature to obtain the independent self-supported reduced graphene oxide film.
(5) And (3) placing the independent self-supporting reduced graphene oxide film in a high-temperature furnace for high-temperature annealing, wherein the annealing temperature is 3000 ℃, the holding time is 1h, and the heating rate is 20 ℃/min.
The obtained graphene film can be independently self-supported in the air, the thickness of the graphene film is 130nm, and the transparency of the graphene film is 47%; from randomly-folded stonesGraphene sheet composition, AB stacking rate 50%; few defects in graphene sheets, ID/IG＜0.01。
Example 2:
(1) preparing graphene oxide into a graphene oxide DMSO solution with the concentration of 10ug/mL, slowly precipitating graphene oxide sheets by using ethyl acetate, and performing suction filtration to form a film by using Anode Alumina (AAO) as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating for 5 hours at 100 ℃ by using HI steam.
(3) The reduced graphene oxide film is uniformly coated on the surface of the graphene film by using a low-temperature melting coating (52 ℃), and the graphene film is heated for a period of time at a temperature below 5 ℃ below the melting point of the solid transfer agent. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) Slowly volatilizing the solid transfer agent from the graphene film supported by the obtained solid transfer agent at 120 ℃ to obtain an independent self-supported reduced graphene oxide film; if the reduction is not uniform in the step 2, or hydrogen iodide vapor directly contacts the AAO film, the graphene cannot be automatically separated from the AAO film in the process of transferring the solid transfer agent, and at the moment, the AAO film needs to be etched by 5% phosphoric acid, and the etching time is 2 min.
(5) And (3) placing the independent self-supporting reduced graphene oxide film in a high-temperature furnace for high-temperature annealing, wherein the annealing temperature is 2400 ℃, the maintaining time is 12h, and the heating rate is 20 ℃/min.
The obtained graphene film can be independently self-supported in the air, the thickness of the graphene film is 16nm, and the transparency of the graphene film is 48%; consists of randomly folded graphene sheets, and the AB stacking rate is 70%; few defects in graphene sheets, ID/IG＜0.01。
Example 3:
(1) preparing graphene oxide into a graphene oxide allyl ketone solution with the concentration of 2ug/mL, slowly precipitating graphene oxide sheets by using normal hexane, and performing suction filtration to form a film by using Anode Alumina (AAO) as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating for 10 hours at 80 ℃ by using HI steam.
(3) The method for coating the reduced graphene oxide film by using the solution uniformly coats the solid transfer agent aluminum chloride on the surface of the graphene film, and heats the graphene film for a period of time at a temperature lower than the melting point of the solid transfer agent by 5 ℃. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) Slowly volatilizing the solid transfer agent from the graphene film supported by the obtained solid transfer agent at 180 ℃ to obtain an independent self-supported reduced graphene oxide film; if the reduction is not uniform in the step 2, or hydrogen iodide vapor directly contacts the AAO film, the graphene cannot be automatically separated from the AAO film in the process of transferring the solid transfer agent, and the AAO film needs to be etched by 1-10% phosphoric acid for 1-10 min.
(5) And (3) placing the independent self-supporting reduced graphene oxide film in a high-temperature furnace for high-temperature annealing, wherein the annealing temperature is 2600 ℃, the holding time is 2h, and the heating rate is 10 ℃/min.
The obtained graphene film can be independently self-supported in the air, the thickness of the graphene film is 39nm, and the transparency of the graphene film is 36%; consists of randomly folded graphene sheets, and has an AB stacking rate of 66%; few defects in graphene sheets, ID/IG＜0.01。
Example 4:
(1) preparing graphene oxide into a graphene oxide tetrahydrofuran solution with the concentration of 10ug/mL, slowly precipitating graphene oxide sheets by using toluene, and performing suction filtration to form a film by using Anode Alumina (AAO) as a substrate.
(2) And (3) putting the graphene oxide membrane attached to the AAO membrane into a closed container, and fumigating for 10 hours at 90 ℃ by using HI steam.
(3) The reduced graphene oxide film is uniformly coated with the solid transfer agent sulfur on the surface of the graphene film by a high-temperature casting (130 ℃) method, and is heated for a period of time at a temperature below 5 ℃ lower than the melting point of the solid transfer agent. And (3) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film.
(4) Slowly volatilizing the solid transfer agent from the obtained graphene film supported by the solid transfer agent by adopting a low-pressure sublimation method to obtain an independent self-supported reduced graphene oxide film; if the reduction is not uniform in the step 2, or hydrogen iodide vapor directly contacts the AAO film, the graphene cannot be automatically separated from the AAO film in the process of transferring the solid transfer agent, and the AAO film needs to be etched by 1-10% phosphoric acid for 1-10 min.
(5) And (3) placing the independent self-supporting reduced graphene oxide film in a high-temperature furnace for high-temperature annealing, wherein the annealing temperature is 2500 ℃, the maintaining time is 12h, and the heating rate is 10 ℃/min.
The obtained graphene film can be independently self-supported in the air, the thickness of the graphene film is 109nm, and the transparency of the graphene film is 41%; consists of randomly folded graphene sheets, with an AB stacking rate of 59%; few defects in graphene sheets, ID/IG＜0.01。
Claims (6)
1. A preparation method of a graphene film with independent self-supporting folds and nanometer-scale thickness is characterized by comprising the following steps:
(1) preparing graphene oxide into a graphene oxide organic solution with the concentration of 0.5-10 mug/mL, precipitating graphene oxide sheets by using a poor solvent, and finally performing suction filtration to form a film by using Anode Alumina (AAO) as a substrate;
(2) placing the graphene oxide film attached to the AAO film in a closed container, and fumigating HI steam at a high temperature of 60-100 ℃ for 1-10 h;
(3) uniformly coating the solid transfer agent on the surface of the graphene film by using an evaporation and casting method, and heating at a temperature lower than the melting point of the solid transfer agent by 5 ℃ to solidify the solid transfer agent;
(4) placing the graphene film coated with the solid transfer agent at room temperature, and automatically separating the graphene film from the AAO film;
(5) volatilizing the solid transfer agent from the graphene film supported by the obtained solid transfer agent at the temperature of volatilizing the solid transfer agent to obtain an independent self-supported reduced graphene oxide film;
(6) placing the independent self-supporting reduced graphene oxide film in a high-temperature furnace for high-temperature annealing at 2400-3000oC, maintaining for 1-12h, and raising the temperature at a rate not greater than 20oC/min。
2. The method according to claim 1, wherein in step 1, the solvent in the organic solution is acetone, tetrahydrofuran, DMF, methanol, ethanol, ethylene glycol, NMP, DMSO; the poor solvent is ethyl acetate, toluene, o-xylene, acetonitrile, ethyl acetate, diethyl ether and n-hexane.
3. The method according to claim 1, wherein in the step 4, the AAO film which is not separated from the graphene film is etched away by using 1-10% phosphoric acid for 1-10 min.
4. The method of claim 1 wherein said solid transfer agent is selected from the group consisting of paraffin, camphor, aluminum chloride and sulfur.
5. The method of claim 1, wherein the sublimation temperature of the solid transfer agent is controlled to be less than 320 ℃; the sublimation pressure and the ambient oxygen content depend on the physical properties.
6. The graphene film with the independent self-supporting folds and the nano-scale thickness prepared by the method of claim 1, wherein the graphene film has the thickness of 16-130nm and the transparency of less than 50%, consists of graphene sheets with random folds, the AB stacking rate is 50 ~ 70%, the defects of the graphene sheets are few, and the I of the graphene sheets is ID/IG＜0.01。
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| CN201710955058.5A CN107651673B (en) | 2017-10-13 | 2017-10-13 | Nano-scale thickness independent self-supporting folded graphene film and preparation method thereof |
| RU2020115707A RU2753510C1 (en) | 2017-10-13 | 2018-05-08 | Independent freely located graphene film and method for production thereof |
| PCT/CN2018/086085 WO2019071943A1 (en) | 2017-10-13 | 2018-05-08 | Independent self-supporting graphene film and preparation method therefor |
| JP2020510549A JP2020531387A (en) | 2017-10-13 | 2018-05-08 | Self-supporting graphene film and its manufacturing method |
| EP18866208.4A EP3620435B1 (en) | 2017-10-13 | 2018-05-08 | Independent free-standing graphene film and preparation method therefor |
| KR1020207006088A KR102316218B1 (en) | 2017-10-13 | 2018-05-08 | Independent self-supporting graphene film and method for manufacturing the same |
| US16/476,117 US11834336B2 (en) | 2017-10-13 | 2018-05-08 | Independent free-standing graphene film and method of preparing the same |
| JP2021086043A JP7186464B2 (en) | 2017-10-13 | 2021-05-21 | Free-standing graphene film and method for producing same |
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| US11834336B2 (en) | 2017-10-13 | 2023-12-05 | Zhejiang University | Independent free-standing graphene film and method of preparing the same |
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