CN109775697B - High-conductivity foldable graphene film and preparation method and application thereof - Google Patents
High-conductivity foldable graphene film and preparation method and application thereof Download PDFInfo
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- CN109775697B CN109775697B CN201910200703.1A CN201910200703A CN109775697B CN 109775697 B CN109775697 B CN 109775697B CN 201910200703 A CN201910200703 A CN 201910200703A CN 109775697 B CN109775697 B CN 109775697B
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Abstract
The invention discloses a high-conductivity foldable graphene film and a preparation method thereof. The few-layer graphene in the graphene film is formed by connecting chemically reduced graphene oxide with each other through physical crosslinking and filling gaps. The graphene element is uniformly combined with the polycondensation polymer through a surface functional group, and a heat conduction crosslinking network is formed between the graphene sheet and the graphene sheet through physical crosslinking. The graphene film has good conductivity of 1000-2000S/cm and high folding flexibility (10 ten thousand times of bending), and is suitable for high-conductivity flexible films.
Description
Technical Field
The invention relates to a high-performance nano material and a preparation method thereof, in particular to a high-conductivity foldable graphene film and a preparation method thereof.
Background
The graphene has excellent electrical properties (the electron mobility can reach 2 × 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 electric conductivity and the low density of the graphene enable the graphene to have the potential of replacing metal in the field of electric heating materials.
However, the defect-free macroscopic assembled graphene film is prepared by high-temperature calcination, the film has excellent conductivity and flexibility, but the preparation requires 3000 ℃ high temperature, the cost is high, and the time is long. The graphene film directly pressed without calcination has moderate performance and poor flexibility, but the preparation method is extremely simple and has low cost.
Therefore, a novel graphene material and a preparation method thereof are urgently needed, wherein the novel graphene material can not only improve the excellent electrical properties and flexibility of graphene, but also reduce the processing cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-conductivity foldable graphene film and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: the high-conductivity foldable graphene film consists of few-layer graphene sheets and single-layer reduced graphene oxide sheets, wherein the number of the few-layer graphene sheets is less than or equal to 20, the transverse dimension is 0.1-20 mu m, the internal structure is complete, and IDI is less than or equal to 0.2; the reduced graphene oxide sheet is a full single layer, the oxygen-carbon ratio is 1.8-2, and the transverse dimension is 0.1-100 um. Few-layer graphene sheets are stacked into the graphene film, the reduced graphene oxide sheets are positioned between the few-layer graphene sheets, the stacked gaps of the few-layer graphene sheets are filled, and the few-layer graphene sheets realize crosslinking through single-layer graphene
A preparation method of a high-conductivity foldable graphene film comprises the following steps:
(1) uniformly dispersing the few-layer graphene, the single-layer graphene oxide and the reducing agent in a solvent.
(2) And (5) spreading the mixed solution on a film, and naturally drying.
(3) And pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film.
Further, the mass ratio of the few-layer graphene to the single-layer graphene oxide is as follows: 83-67: 10-30.
Further, the chemical reducing agent is hydroiodic acid, hydrazine hydrate, vitamin C and the like.
Further, the few-layer graphene is obtained by mechanical exfoliation.
Further, the hot pressing temperature is 60-100 ℃, the time is 0.5-2h, and the pressure is 20-60MPa
Further, the prepared graphene film has the conductivity of 1000-2000S/cm, can be folded for more than 10 ten thousand times, and the conductivity is reduced within 20% after the graphene film is folded.
The invention has the beneficial effects that: the method comprises the step of blending single-layer graphene oxide and few-layer graphene to form a film, wherein the few-layer graphene is stacked to form the film, so that the single-layer graphene oxide is positioned between few-layer graphene sheets, stacked gaps of the few-layer graphene sheets are filled, and the few-layer graphene sheets are crosslinked through the single-layer graphene. After hot pressing under certain conditions, the graphene oxide is reduced to form a conductive path, so that the conductivity of the graphene film is ensured. The hot pressing process also keeps the folds in the graphene oxide uniformly mixing process, the crosslinking effect of the single-layer graphene and the fold structure of the single-layer graphene, and guarantees the mechanical property of the graphene.
The film is used as a photo-anode, a counter electrode and the like; in comparison, the graphene has higher electron mobility, and the problem of heavy metal pollution does not exist, so that the cost is reduced, and the light conversion efficiency is improved.
Detailed Description
Example 1:
1. using less-layer graphene (the number of layers of less-layer graphene sheets is less than or equal to 20, the transverse dimension is 0.1-20um, the internal structure is complete, IDI is less than or equal to 0.2), single-layer graphene oxide (a full single layer, the oxygen-carbon ratio is 1.8-2, the transverse dimension is 0.1-100um) and reducing agent hydrazine hydrate are uniformly mixed and dispersed in deionized water, wherein the mixing time of graphene (8.3 wt%), graphene oxide (1.0 wt%) and reducing agent (0.3 wt%) is 0.5h, and the rotating speed is 2000 r/min.
2. And (5) spreading the mixed solution on a film, and naturally drying.
3. And pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film. The hot pressing temperature is 60 ℃, the time is 0.5h, and the pressure is 20 MPa.
The prepared graphene film has the density of 2.0, the conductivity of 1000S/cm, can be folded for more than 10 ten thousand times, and the conductivity of the folded graphene film is reduced by about 19 percent.
Comparative example 1
1. Dispersing few-layer graphene (from the same source as in example 1) in deionized water, wherein the mass percentage is 9.3 wt%, the mixing time is 0.5h, and the rotating speed is 2000 r/min.
2. And (5) spreading the mixed solution on a film, and naturally drying.
3. And pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film. The hot pressing temperature is 60 ℃, the time is 0.5h, and the pressure is 20 MPa.
The density of the prepared graphene film is 1.8, the conductivity of the graphene film is 600S/cm, and after the graphene film is folded for 4 times, the conductivity of the graphene film is reduced to about 10% after the graphene film is broken.
Example 2:
1. the number of the layers of the few-layer graphene sheets is less than or equal to 20, the transverse dimension is 0.1-20um, the internal structure is complete, IDI is less than or equal to 0.2), single-layer graphene oxide (a full single layer, the oxygen-carbon ratio is 1.8-2, the transverse dimension is 0.1-100um) and a reducing agent hydroiodic acid are uniformly mixed and dispersed in deionized water, wherein the mixing time of the graphene (6.7%), the graphene oxide (3.0%) and the reducing agent (0.7%) is 2 hours, and the rotating speed is 200 r/min.
2. And (5) spreading the mixed solution on a film, and naturally drying.
3. And pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film. The hot pressing temperature is 100 ℃, the time is 2h, and the pressure is 60 MPa.
The prepared graphene film has the density of 2.1, the conductivity of 2000S/cm, the graphene film can be folded for more than 10 ten thousand times, and the conductivity of the graphene film is reduced by 12% after the graphene film is folded.
Comparative example 2
1. Dispersing few-layer graphene (from the same source as in example 2) in deionized water, wherein the mass percentage is 10.7 wt%, the mixing time is 2h, and the rotating speed is 200 r/min.
2. And (5) spreading the mixed solution on a film, and naturally drying.
3. And pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film. The hot pressing temperature is 100 ℃, the time is 2h, and the pressure is 60 MPa.
The density of the prepared graphene film is 1.9, the conductivity of the graphene film is 800S/cm, and the conductivity of the graphene film is reduced to about 12% after the graphene film is folded for 6 times.
Example 3:
1. the number of the layers of the few-layer graphene sheets is less than or equal to 20, the transverse dimension is 0.1-20um, the internal structure is complete, IDI is less than or equal to 0.2), single-layer graphene oxide (a full single layer, the oxygen-carbon ratio is 1.8-2, and the transverse dimension is 0.1-100um) and a reducing agent vitamin C are uniformly mixed and dispersed in deionized water, wherein the percentage of graphene (7.5%), the percentage of graphene oxide (2.0%) and the percentage of reducing agent (0.4%); the mixing time is 1h, and the rotating speed is 1000 r/min.
2. And (5) spreading the mixed solution on a film, and naturally drying.
3. And pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film. The hot pressing temperature is 80 ℃, the time is 1h, and the pressure is 40 MPa.
The density of the prepared graphene film is 2.0, the conductivity of the graphene film is 1200S/cm, the graphene film can be folded for more than 10 ten thousand times, and the conductivity of the graphene film is reduced by 16% after the graphene film is folded.
Comparative example 3
1. Dispersing few-layer graphene (from the same source as in example 3) in deionized water, wherein the mass percentage is 9.5 wt%, the mixing time is 1h, and the rotating speed is 1000 r/min.
2. And (5) spreading the mixed solution on a film, and naturally drying.
3. And pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film. The hot pressing temperature is 80 ℃, the time is 1h, and the pressure is 40 MPa.
The density of the prepared graphene film is 1.81, the conductivity of the graphene film is 710S/cm, and the conductivity of the graphene film is reduced to about 9% after the graphene film is folded for 4 times.
As described above, the single layer of graphene oxide is located between the few graphene sheets, and the few graphene sheets fill the stacking gap, thereby increasing the density of the graphene film. The reduced single-layer graphene oxide provides a passage between the few-layer graphene sheets, and the conductivity of the film is improved. The crosslinking effect of the single-layer graphene also lays a foundation for the folding performance of the graphene film.
Claims (8)
1. The high-conductivity foldable graphene film is characterized by comprising few-layer graphene sheets and single-layer reduced graphene oxide sheets, wherein the number of the few-layer graphene sheets is less than or equal to 20, the transverse dimension is 0.1-20um, the internal structure is complete, and IDI is less than or equal to 0.2; the reduced graphene oxide sheet is a full single layer, the oxygen-carbon ratio is 1.8-2, and the transverse dimension is 0.1-100 um; and stacking the few-layer graphene sheets into the graphene film, wherein the reduced graphene oxide sheets are positioned between the few-layer graphene sheets, filling the stacking gaps of the few-layer graphene sheets, and the few-layer graphene sheets realize crosslinking through single-layer graphene.
2. The method for preparing the highly conductive foldable graphene film according to claim 1, comprising the following steps:
(1) uniformly dispersing few-layer graphene, single-layer graphene oxide and a reducing agent in a solvent;
(2) spreading a membrane on the mixed solution, and naturally drying;
(3) and pressing the obtained graphene film at low temperature to obtain the final flexible high-conductivity foldable graphene film.
3. The preparation method according to claim 2, wherein the mass ratio of the few-layer graphene to the single-layer graphene oxide is: 83-67: 10-30.
4. The method of claim 2, wherein the chemical reducing agent is hydroiodic acid, hydrazine hydrate, vitamin C.
5. The method of claim 2, wherein the few-layer graphene is obtained by mechanical exfoliation.
6. The method according to claim 2, wherein the low-temperature pressing is performed at a temperature of 60 to 100 degrees centigrade, for 0.5 to 2 hours, and under a pressure of 20 to 60 MPa.
7. The preparation method of claim 2, wherein the prepared graphene film has a conductivity of 1000-.
8. Use of the graphene film of claim 1 in the preparation of a flexible device comprising a flexible solar cell, a flexible acoustic wave generator.
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