CN107555419A - 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 is obtained by graphene oxide by steps such as solution film forming, electronation, Low Temperature Heat Treatment, high temperature hot pressings.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, has the electric conductivity and thermal conductivity of superelevation.This high flexibility graphene heat conducting film is resistant to bend repeatedly more than 600 times, and elongation at break is 4 12%, and conductance is 8000 10000S/cm, and thermal conductivity is 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 technology
2010, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov because
Stable graphene is successfully separated out first and obtains Nobel Prize in physics, has started the upsurge that the whole world is studied graphene.
Graphene has excellent electric property, and (electron mobility is up to 2 × 10 at room temperature5cM2/ Vs), prominent heat conductivility (5000W/
(MK), extraordinary specific surface area (2630M2/ g), its Young's modulus (1100GPa) and fracture strength (125GPa).Graphene is excellent
Different electrical and thermal conductivity performance is well beyond metal, while graphene has the advantages of corrosion-and high-temp-resistant, and its good machinery
Performance and relatively low density more allow it to possess 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, conventional preparation method is suction method, scrape embrane method, spin-coating method, spraying process and dip coating etc..At further high temperature
Reason, the defects of graphene can be repaired, the electric conductivity and thermal conductance of graphene film can be effectively improved, can be widely applied to
Smart mobile phone, intelligence are with oneself in the high radiating requirements accompanied electronic equipment such as hardware, tablet personal computer, notebook computer.
But at present, many gas of graphene film enclosed inside that high temperature sintering is crossed, in the process of high pressure compacting
In, the stomata of closing can not be excluded outside film in rolling process, cause graphene film continuously can not produce on a large scale.Separately
Outside, direct high-pressure process can cause graphene sheet layer to produce many folds, reduce the thermal conductivity of graphene film, together
When reduce graphene film density.This patent regulation and control bubble generation, is entered to adjust the close of fold by the method for high temperature hot pressing
Degree, and regulation and control calorifics is finally reached, the purpose of electricity and mechanical performance.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of low corrugation density graphene film and its preparation side
Method.
The purpose of the present invention is 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 effects of π in 50 μm of graphene film by the average-size of planar orientation
Mutually overlap joint forms.Graphene sheet layer corrugation density is 50-300mm/mm2, and few the defects of graphene film, its ID/TG＜
0.01。
A kind of preparation method of low corrugation density graphene film, is comprised the following steps：
(1) it is that 6~30mg/mL graphene oxides are water-soluble graphene oxide of the average-size more than 50 μm to be configured into concentration
Liquid, naturally dry after solution film forming, is then reduced with reducing agent；
(2) graphene film after reduction is warming up to 200-400 DEG C with 0.1-5 DEG C/min speed, is incubated 0.5-
2h and Temperature fall.
(3) above-mentioned graphene film is warming up to 2400-3000 DEG C under inert gas shielding with 1-10 DEG C/min speed,
It is incubated 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 which roller system is 1.05:1.
Further, described reducing agent includes vitamin C, ascorbic acid, hydrogen iodide.
By the present invention in that with the mode of high-temperature process, graphene defect is repaired in perfection, and internal flaw is dropped to most
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, graphene film is adjusted eventually through fold
Calorifics, electricity, mechanical property.
Brief description of the drawings
Fig. 1 is graphene membrane surface fold situation under different pressures.
Fig. 2 is the stress strain curve of graphene film under different pressures.
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, and heat conduction is led
Electricity is better, linear.However, the graphene film prepared at elevated pressures, graphene film fold quantity is few, deploys degree ratio
Relatively low, after certain extensibility, fold is not reinflated, now whole film uniform stressed, shows the phenomenon of stress hardening.
The graphene film prepared at low pressures, micro- fold of graphene film gradually stretch expansion, and this process is continued until graphene
Film damages under stress concentration.The present invention finally determines graphene film being heat-treated in 5-60MPa, then in 200-
Roll-in is suppressed under 300MPa pressure, obtains that electrical and thermal conductivity is good, and the graphene film of excellent in mechanical performance.
With reference to embodiment, the invention will be further described.The present embodiment is served only for doing further the present invention
Explanation, it is impossible to be interpreted 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, belong to protection scope of the present invention.
Embodiment 1：
(1) it is 6mg/mL graphene oxide water solutions graphene oxide of the average-size more than 50 μm to be configured into concentration,
Naturally dry after solution film forming, is then reduced with reducing agent；
(2) graphene film after reduction is warming up to 400 degree with 5 DEG C/min speed, is incubated 2h and Temperature fall.
(3) above-mentioned graphene film is warming up to 2400 DEG C under inert gas shielding with 1 DEG C/min speed, insulation
0.5h；Apply pressure 5MPa in whole process.
(5) after Temperature fall, by graphene film, (200MPa) rolling compacting can obtain low fold heat conduction stone under high pressure
Black alkene film, the speed ratio of two roller systems is 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, it is resistant to bend repeatedly more than 600 times, conductance 9300S/cm, thermal conductivity 1698W/
mK。
Embodiment 2：
(1) it is 16mg/mL graphene oxide water solutions graphene oxide of the average-size more than 50 μm to be configured into concentration,
Naturally dry after solution film forming, is then reduced with reducing agent；
(2) graphene film after reduction is warming up to 350 degree with 1 DEG C/min speed, is incubated 1h and Temperature fall.
(3) above-mentioned graphene film is warming up to 3000 DEG C under inert gas shielding with 5 DEG C/min speed, insulation
0.5h；Apply pressure 15MPa in whole process.
(5) after Temperature fall, by graphene film, (250MPa) rolling compacting can obtain low fold heat conduction stone under high pressure
Black alkene film, the speed ratio of two roller systems is 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, it is resistant to bend repeatedly more than 600 times, conductance 8920S/cm, thermal conductivity 1722W/
mK。
Embodiment 3：
(1) it is 30mg/mL graphene oxide water solutions graphene oxide of the average-size more than 50 μm to be configured into concentration,
Naturally dry after solution film forming, is then reduced with reducing agent；
(2) graphene film after reduction is being warming up to 300 degree with 0.1 DEG C/min speed, is being incubated 2h and drops naturally
Temperature.
(3) above-mentioned graphene film is warming up to 3000 DEG C under inert gas shielding with 10 DEG C/min speed, insulation
0.5h；Apply pressure 40MPa in whole process.
(5) after Temperature fall, by graphene film, (300MPa) rolling compacting can obtain low fold heat conduction stone under high pressure
Black alkene film, the speed ratio of two roller systems is 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, it is resistant to bend repeatedly more than 600 times, conductance 8600S/cm, thermal conductivity 1784W/mK.
Embodiment 4：
(1) it is 30mg/mL graphene oxide water solutions graphene oxide of the average-size more than 50 μm to be configured into concentration,
Naturally dry after solution film forming, is then reduced with reducing agent；
(2) graphene film after reduction is being warming up to 200 degree with 0.1 DEG C/min speed, is being incubated 2h and drops naturally
Temperature.
(3) above-mentioned graphene film is warming up to 3000 DEG C under inert gas shielding with 8 DEG C/min speed, insulation
0.5h；Apply pressure 60MPa in whole process.
(5) after Temperature fall, by graphene film, (300MPa) rolling compacting can obtain low fold heat conduction stone under high pressure
Black alkene film, the speed ratio of two roller systems is 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, it is resistant to bend repeatedly more than 600 times, conductance 9100S/cm, thermal conductivity 1626W/
mK。
Claims (3)
1. a kind of low corrugation density graphene film, it is characterised in that the density of the high flexibility graphene film is 2-2.2g/cm3, by
The average-size of planar orientation is formed in 50 μm of graphene film by the pi-conjugated effects of π mutually overlap joint.Graphene sheet layer fold is close
Spend for 50-300mm/mm2, and few the defects of graphene film, its ID/TG＜ 0.01.
2. a kind of preparation method of low corrugation density graphene film, it is characterised in that comprise the following steps：
(1) it is 6~30mg/mL graphene oxide water solutions graphene oxide of the average-size more than 50 μm to be configured into concentration,
Naturally dry after solution film forming, is then reduced with reducing agent；
(2) graphene film after reduction is being warming up to 200-400 DEG C with 0.1-5 DEG C/min speed, insulation 0.5-2h is simultaneously
Temperature fall.
(3) above-mentioned graphene film is warming up to 2400-3000 DEG C under inert gas shielding with 1-10 DEG C/min speed, insulation
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 conduction stone under high pressure
Black alkene film, the speed ratio of two of which roller system is 1.05:1.
3. a kind of preparation method of super flexible high heat conduction graphene film as claimed in claim 2, it is characterised in that described
Reducing agent includes vitamin C, ascorbic acid, hydrogen iodide.
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Cited By (7)
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| CN108493397A (en) * | 2018-04-24 | 2018-09-04 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene anode pole piece, preparation method and aluminium-graphene battery |
| CN109334155A (en) * | 2018-10-25 | 2019-02-15 | 张家港展博电子科技有限公司 | Graphene-copper composite heat dissipation film and its preparation method and application |
| CN109824033A (en) * | 2019-03-06 | 2019-05-31 | 华南理工大学 | A low-cost method for preparing high thermal conductivity graphene film |
| CN110040724A (en) * | 2019-05-23 | 2019-07-23 | 科炭(厦门)新材料有限公司 | A kind of preparation method and its electromagnetic shielding material of fold graphene |
| CN112028058A (en) * | 2020-08-28 | 2020-12-04 | 清华大学深圳国际研究生院 | Preparation method of graphene composite heat-conducting film |
| CN115043397A (en) * | 2022-06-29 | 2022-09-13 | 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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| CN109334155A (en) * | 2018-10-25 | 2019-02-15 | 张家港展博电子科技有限公司 | Graphene-copper composite heat dissipation film and its preparation method and application |
| CN109334155B (en) * | 2018-10-25 | 2021-10-15 | 张家港展博电子科技有限公司 | Graphene-copper composite heat dissipation film and its preparation method and application |
| CN109824033A (en) * | 2019-03-06 | 2019-05-31 | 华南理工大学 | A low-cost method for preparing high thermal conductivity graphene film |
| CN110040724A (en) * | 2019-05-23 | 2019-07-23 | 科炭(厦门)新材料有限公司 | A kind of preparation method and its electromagnetic shielding material of fold graphene |
| CN110040724B (en) * | 2019-05-23 | 2021-08-24 | 科炭(厦门)新材料有限公司 | Preparation method of folded graphene and electromagnetic shielding material thereof |
| CN112028058A (en) * | 2020-08-28 | 2020-12-04 | 清华大学深圳国际研究生院 | Preparation method of graphene composite heat-conducting film |
| 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 |
| CN115043397A (en) * | 2022-06-29 | 2022-09-13 | 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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