CN107555419B - A kind of low corrugation density graphene film and preparation method thereof - Google Patents
A kind of low corrugation density graphene film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of low corrugation density graphene film and preparation method thereof, the graphene film by graphene oxide by solution film forming, electronation, Low Temperature Heat Treatment, high temperature hot pressing and etc. obtain.The graphene film is made up of low fold graphene physical crosslinking, and piece interlayer slip, therefore has high flexibility.Its graphene sheet layer perfect structure, and seldom containing defective, by a high temperature hot pressing process, the graphene sheet layer degree of orientation is high, and fold is less, and structure is closely knit, electric conductivity and thermal conductivity with superelevation.This high flexibility graphene heat conducting film is resistant to bend repeatedly 600 times or more, elongation at break 4-12%, conductivity 8000-10000S/cm, and thermal conductivity 1600-1800W/mK can be used as high flexibility thermal conductivity device.
Description
Technical field
The present invention relates to novel heat-conducting material and preparation method thereof more particularly to a kind of low corrugation density graphene film and its
Preparation method.
Background technique
2010, two professor Andre GeiM and Konstantin Novoselov of Univ Manchester UK because
It is successfully separated out stable graphene for the first time and obtains Nobel Prize in physics, has started the upsurge that graphene is studied in the whole world.
Graphene has excellent electric property, and (electron mobility is up to 2 × 10 at room temperature5cM2/ Vs), heating conduction (5000W/ outstanding
(MK), extraordinary specific surface area (2630M2/ g), Young's modulus (1100GPa) and breaking strength (125GPa).Graphene is excellent
Different electrical and thermal conductivity performance is well beyond metal, while graphene has the advantages that corrosion-and high-temp-resistant, and its good machinery
Performance and lower density more allow it to have the potentiality in thermo electric material field substituted metal.
The graphene film of macroscopic view assembling graphene oxide or graphene nanometer sheet is the main application of nanoscale graphite alkene
Form, common preparation method are suction methods, scrape embrane method, spin-coating method, spray coating method and dip coating etc..At further high temperature
Reason, can repair the defect of graphene, can effectively improve the electric conductivity and thermal conductance of graphene film, can be widely applied to
Smart phone, intelligence are with oneself in the high radiating requirements accompanied electronic equipment such as hardware, tablet computer, laptop.
But currently, many gas of graphene film enclosed inside that high temperature sintering is crossed, in the process of high pressure compacting
In, closed stomata cannot be excluded outside film in the rolling process, cause graphene film that cannot continuously produce on a large scale.Separately
Outside, direct high-pressure process can make graphene sheet layer generate many folds, reduce the thermal conductivity of graphene film, together
When reduce graphene film density.This patent is by the method for high temperature hot pressing, and regulation bubble generates, into adjust the close of fold
Degree, and it is finally reached regulation calorifics, the purpose of electricity and mechanical performance.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of low corrugation density graphene film and its preparation side
Method.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of low corrugation density graphene film, the high flexibility
The density of graphene film is 2-2.2g/cm3, pass through the pi-conjugated effect of π in 50 μm of graphene film by the average-size of planar orientation
Mutually it is formed by overlapping.Graphene sheet layer corrugation density is 50-300mm/mm2, and the defect of graphene film is few, ID/TG<
0.01。
A kind of preparation method of low corrugation density graphene film, comprises the following steps:
(1) average-size is configured to concentration greater than 50 μm of graphene oxide is that 6~30mg/mL graphene oxide is water-soluble
Liquid, naturally dry after solution film forming, is then restored with reducing agent；
(2) graphene film after reduction is warming up to 200-400 DEG C with the rate of 0.1-5 DEG C/min, keeps the temperature 0.5-
2h and Temperature fall.
(3) above-mentioned graphene film is warming up to 2400-3000 DEG C under inert gas protection with the rate of 1-10 DEG C/min,
Keep the temperature 0.5h-8；Apply pressure 5-60MPa in whole process.
(4) after Temperature fall, by graphene film, (200-300MPa) roll-in compacting can obtain low fold and lead under high pressure
Hot graphene film, the speed ratio of two of them roller system are 1.05:1.
Further, the reducing agent includes vitamin C, ascorbic acid, hydrogen iodide.
By the present invention in that graphene defect is repaired in perfection, and drops to internal flaw most with the mode of high-temperature process
It is low, perfect big conjugated structure is formed, ensure that the unimpeded of graphene thermal conducting path；Further, in high-temperature annealing process,
Regulate and control the growth course of micro- air bag, and then adjust the quantity of fold inside graphene film, adjusts graphene film eventually by fold
Calorifics, electricity, mechanical property.
Detailed description of the invention
Fig. 1 is graphene membrane surface fold situation under different pressures.
Fig. 2 is the stress strain curve of graphene film under different pressures.
Specific embodiment
By the way that experimental results demonstrate the pressure born on graphene film is higher, and the graphene film degree of orientation is higher, thermally conductive to lead
Electricity is better, linear.However, the graphene film prepared at elevated pressures, graphene film fold quantity is few, and degree ratio is unfolded
The phenomenon that lower, after certain extensibility, fold is not reinflated, at this time entire film uniform stressed, shows stress hardening.
Micro- fold of the graphene film prepared at low pressures, graphene film gradually stretches expansion, this process is continued until graphene
Film damages under stress concentration.Finally graphene film is heat-treated the present invention by determination in 5-60MPa, then in 200-
Roll-in is suppressed under the pressure of 300MPa, obtains that electrical and thermal conductivity is good, and the graphene film of excellent in mechanical performance.
The present invention will be further described with reference to the examples below.The present embodiment is served only for doing further the present invention
Illustrate, should not be understood as limiting the scope of the invention, those skilled in the art makes according to the content of foregoing invention
Some nonessential changes and adjustment, all belong to the scope of protection of the present invention.
Embodiment 1:
(1) it is 6mg/mL graphene oxide water solution that the graphene oxide by average-size greater than 50 μm, which is configured to concentration,
Naturally dry after solution film forming, is then restored with reducing agent；
(2) graphene film after reduction is warming up to 400 degree with the rate of 5 DEG C/min, keeps the temperature 2h and Temperature fall.
(3) above-mentioned graphene film is warming up to 2400 DEG C under inert gas protection with the rate of 1 DEG C/min, heat preservation
0.5h；Apply pressure 5MPa in whole process.
(5) after Temperature fall, by graphene film, (200MPa) rolling compacting can obtain the low thermally conductive stone of fold under high pressure
Black alkene film, the speed ratio of two roller systems are 1.05:1.
Prepared graphene film density is 2-2.2g/cm3, ID/TG< 0.01, corrugation density 294mm/mm2, fracture
Elongation 13.6%, intensity 57MPa are resistant to bend repeatedly 600 times or more, conductivity 9300S/cm, thermal conductivity 1698W/
mK。
Embodiment 2:
(1) it is 16mg/mL graphene oxide water solution that the graphene oxide by average-size greater than 50 μm, which is configured to concentration,
Naturally dry after solution film forming, is then restored with reducing agent；
(2) graphene film after reduction is warming up to 350 degree with the rate of 1 DEG C/min, keeps the temperature 1h and Temperature fall.
(3) above-mentioned graphene film is warming up to 3000 DEG C under inert gas protection with the rate of 5 DEG C/min, heat preservation
0.5h；Apply pressure 15MPa in whole process.
(5) after Temperature fall, by graphene film, (250MPa) rolling compacting can obtain the low thermally conductive stone of fold under high pressure
Black alkene film, the speed ratio of two roller systems are 1.05:1.
Prepared graphene film density is 2-2.2g/cm3, ID/TG< 0.01, corrugation density 189mm/mm2, fracture
Elongation 10.5%, intensity 64MPa are resistant to bend repeatedly 600 times or more, conductivity 8920S/cm, thermal conductivity 1722W/
mK。
Embodiment 3:
(1) it is 30mg/mL graphene oxide water solution that the graphene oxide by average-size greater than 50 μm, which is configured to concentration,
Naturally dry after solution film forming, is then restored with reducing agent；
(2) graphene film after reduction is being warming up to 300 degree with the rate of 0.1 DEG C/min, keeps the temperature 2h and dropped naturally
Temperature.
(3) above-mentioned graphene film is warming up to 3000 DEG C under inert gas protection with the rate of 10 DEG C/min, heat preservation
0.5h；Apply pressure 40MPa in whole process.
(5) after Temperature fall, by graphene film, (300MPa) rolling compacting can obtain the low thermally conductive stone of fold under high pressure
Black alkene film, the speed ratio of two roller systems are 1.05:1.
Prepared graphene film density is 2-2.2g/cm3, ID/TG< 0.01, corrugation density 115mm/mm2, fracture
Elongation 7%, intensity 93MPa are resistant to bend repeatedly 600 times or more, conductivity 8600S/cm, thermal conductivity 1784W/mK.
Embodiment 4:
(1) it is 30mg/mL graphene oxide water solution that the graphene oxide by average-size greater than 50 μm, which is configured to concentration,
Naturally dry after solution film forming, is then restored with reducing agent；
(2) graphene film after reduction is being warming up to 200 degree with the rate of 0.1 DEG C/min, keeps the temperature 2h and dropped naturally
Temperature.
(3) above-mentioned graphene film is warming up to 3000 DEG C under inert gas protection with the rate of 8 DEG C/min, heat preservation
0.5h；Apply pressure 60MPa in whole process.
(5) after Temperature fall, by graphene film, (300MPa) rolling compacting can obtain the low thermally conductive stone of fold under high pressure
Black alkene film, the speed ratio of two roller systems are 1.05:1.
Prepared graphene film thickness is 2-2.2g/cm3, ID/TG< 0.01, corrugation density 52-300mm/mm2, fracture
Elongation 11.4%, intensity 71MPa are resistant to bend repeatedly 600 times or more, conductivity 9100S/cm, thermal conductivity 1626W/
mK。
Claims (3)
1. a kind of preparation method of low corrugation density graphene film, which is characterized in that comprise the following steps:
(1) it is 6 ~ 30mg/mL graphene oxide water solution that the graphene oxide by average-size greater than 50 μm, which is configured to concentration,
Naturally dry after solution film forming, is then restored with reducing agent；
(2) by the graphene film after reduction with 0.1-5oThe rate of C/min is warming up to 200-400oC keeps the temperature 0.5-2h simultaneously certainly
So cooling；
(3) above-mentioned graphene film is warming up to 2400-3000 under inert gas protection with the rate of 1-10 DEG C/minoC, heat preservation
0.5h；Apply pressure 5-60MPa in whole process；
(4) after Temperature fall, by graphene film, 200-300MPa roll-in compacting can obtain low fold heat conductive graphite under high pressure
Alkene film, the speed ratio of two of them roller system are 1.05:1.
2. the low corrugation density graphene film that a kind of method as described in claim 1 is prepared, which is characterized in that the low fold
The density of density graphite alkene film is 2-2.2g/cm3, it is total in 50 μm of graphene film by π π by the average-size of planar orientation
Yoke effect is mutually formed by overlapping；Graphene sheet layer corrugation density is 50-300mm/mm2, and the defect of graphene film is few, ID/
TG< 0.01.
3. a kind of preparation method of low corrugation density graphene film as described in claim 1, which is characterized in that the reduction
Agent includes ascorbic acid, hydrogen iodide.
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| CN112028058B (en) * | 2020-08-28 | 2021-10-19 | 清华大学深圳国际研究生院 | Preparation method of graphene composite heat-conducting film |
| CN115043397B (en) * | 2022-06-29 | 2023-06-02 | 内蒙古工业大学 | Method for preparing graphene and heat conducting film based on 18-mesh extra-large flake graphite |
| CN115353867A (en) * | 2022-08-25 | 2022-11-18 | 江苏斯迪克新材料科技股份有限公司 | Preparation method of graphene-based composite heat-conducting film |
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| CN104556013A (en) * | 2015-01-08 | 2015-04-29 | 浙江伟星新型建材股份有限公司 | Preparation method of large-size self-supporting graphene film |
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