CN107140619A - A kind of graphene thick film of high heat conduction and preparation method thereof - Google Patents
A kind of graphene thick film of high heat conduction and preparation method thereof Download PDFInfo
- Publication number
- CN107140619A CN107140619A CN201710391092.4A CN201710391092A CN107140619A CN 107140619 A CN107140619 A CN 107140619A CN 201710391092 A CN201710391092 A CN 201710391092A CN 107140619 A CN107140619 A CN 107140619A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene oxide
- hot pressing
- thick film
- heat conduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Abstract
The invention discloses a kind of high heat conduction graphene thick film and preparation method thereof.By one layer of liquid of graphene oxide membrane surface even application, multiple graphene oxide membranes are bonded together by surface after being swelled, treat that it is dried rear oxidation graphene film and can realize self-adhesive by the active force at bonding interface, cause to bond more consolidation between every layer of graphene oxide membrane by further low temperature and pressure, low-temperature heat prereduction is eventually passed through, it is the graphene composite film that can obtain high heat conduction that defect is repaired in HTHP heat treatment.The compound thickness of the graphene of the high heat conduction is more than 50 μm, is 1000~2000W/mK towards thermal conductivity, has larger prospect of the application in high-frequency high heat flux device.
Description
Technical field
The present invention relates to graphene thick film and its preparation side of novel heat-conducting material and method, more particularly to a kind of high heat conduction
Method.
Background technology
, two of Univ Manchester UK professor Andre GeiM and Konstantin Novoselov in 2010 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 (Graphene), also known as mono-layer graphite, a kind of flat film being made up of carbon atom are peeled off from graphite material, only
There is the thickness of a carbon atom, be the two-dimensional material by single layer of carbon atom in honeycomb lattice arrangement form.The structure of graphene is non-
Often stable, carbon-carbon bond (carbon-carbon bond) is onlyThe connection between carbon atom inside graphene is very soft
It is tough, when applying external force in graphene, carbon atom face meeting flexural deformation so that carbon atom need not be rearranged to adapt to external force,
So as to which holding structure is stable.The lattice structure of this stabilization makes graphene have outstanding thermal conductivity, and thermal conductivity factor is up to
5300W/mK, higher than CNT and diamond.Graphene has excellent electric property, and (electron mobility is up to 2 at room temperature
×105cM2/ Vs), prominent heat conductivility (5000W/ (MK), extraordinary specific surface area (2630M2/ g), its Young's modulus
(1100GPa) and fracture strength (125GPa).Graphene has the advantages that corrosion-and high-temp-resistant simultaneously, and its good mechanicalness
It can be more allowed to possess the potentiality in thermo electric material field substituted metal with relatively low density.
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, can repair the defect of graphene, can effectively improve the electric conductivity and thermal conductance of graphene film, 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, the usual thickness of macroscopic view assembling graphene film of high heat conduction is 5 μm~30 μm, and thickness is at hundreds of microns
More than graphene thick film or graphene bulk due to graphene film interlamellar spacing therein it is bigger than normal or uneven the problems such as, its face
400~800W/mK is generally only to thermal conductivity.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of graphene thick film of high heat conduction and its preparation side
Method.
The purpose of the present invention is achieved through the following technical solutions：A kind of graphene thick film of high heat conduction, it is prepared
The thickness of graphene thick film is more than 50 μm, and porosity is 5~40%；Graphene sheet layer corrugation density is controlled in 50-500mm/
mm2, and the defect of graphene film is few, its ID/TG ＜ 0.02, is 1000~2000W/mK towards thermal conductivity.Graphene thick film without
Lamination, the lamella of the adjacent graphene film of any two is smaller than 20nm.
Further, the preparation method is comprised the following steps：
(1) it is that 1~20mg/mL graphene oxides are water-soluble the graphene oxide that average-size is more than 50 μm to be configured into concentration
Dried naturally after liquid, solution film forming, obtain graphene oxide membrane.
(2) multiple graphene oxide membranes are combined, and are specially：Even application liquid is carried out on graphene oxide membrane surface
Body, is allowed to surface and is swelled, and then multiple graphene oxide membrane through-thickness bond together.
(3) the graphene oxide composite membrane after bonding is placed on oven for drying, the temperature of baking oven is less than 40 DEG C.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, with 0.1~5 DEG C/min speed
Rate, which is warming up to after 200 DEG C, carries out hot pressing, repetition following hot pressing 8-10 times：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge
Pressure to 0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100~10KPa；Then again with 0.1~5 DEG C/min speed
300 DEG C of heating, is incubated 0.5h, then carries out hot pressing, repetition following hot pressing 4-6 times：Pressure 60MPa is maintained, 1h is maintained, by
Gradually release pressure to 0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100~10KPa；Hot pressing drops naturally after terminating
Temperature.
(5) graphene oxide membrane after step 4 hot pressing is heated up under atmosphere of inert gases with 1~20v/min speed
Further hot pressing, 0.5~8h of heat-insulation pressure keeping are carried out to 1800~3000 DEG C；Pressure is 60MPa.After cooling, high heat conduction is obtained
Graphene thick film.
Further, the thickness of graphene oxide membrane prepared by the step 1 is 1~30 μm.
Further, the film build method in the step 1 is selected from suction method, scrapes embrane method, spin-coating method, spraying process and dip coating
Deng.
Further, the carbon-to-oxygen ratio 1.8~2.1 of graphene oxide membrane prepared by described step 1.
Further, described step 2 spray used in liquid be：Deionized water, concentration is 1~10mg/mL oxygen
Graphite aqueous solution, or other solution containing deionized water.
The beneficial effects of the present invention are：After the present invention is by the way that graphene oxide membrane surface is swelled so that multiple oxidations
Graphene film bonds together, and treats that it is dried rear oxidation graphene film and can realize self-adhesive by the active force at bonding interface,
Cause to bond more consolidation between graphene oxide membrane by further low temperature and pressure, realize the preparation of graphene oxide thick film.
Low-temperature heat prereduction, then the mode that high temperature hot pressing is handled are eventually passed through, graphene film fault of construction is repaired, controls graphene
Lamella corrugation density, improves the degree of orientation of graphene film so that the formation three-dimensional graphite structure of graphene film top,
The unimpeded of graphene thermal conducting path is ensure that, the graphene thick film of high heat conduction is can obtain.The graphene thick film of the high heat conduction has
Flexibility, bent, heat conductivility is high.
Brief description of the drawings
Fig. 1 is the SEM sectional views for the graphene thick film being bonded using deionized water；
Fig. 2 is the SEM sectional views for the graphene thick film being bonded using graphene oxide water solution.
Embodiment
The invention discloses a kind of self-adhesiveness of utilization graphene oxide can prepare high heat conduction graphene thick film and its
Preparation method.To realize the bonding of graphene oxide membrane, the present invention by one layer of water of graphene oxide membrane surface even application or
Dilute graphene oxide solution, surface bonds together multiple graphene oxide membranes after being swelled, so that graphene oxide is thin
By hydrogen bond and van der Waals interaction between film, the interface that can be bonded in film is realized between self-adhesive, graphene oxide membrane
Combine together, the interface between film and film almost disappears.Pass through further low temperature and pressure, high temperature hot pressing annealing reduction so that
Graphene film fold is few, and defect almost all is repaired on graphene sheet layer, forms perfect three-dimensional graphite structure, contacts with each other
Graphene sheet layer between have certain fusion, finally give thickness and be more than 50 μm of high heat conduction graphene thick film.After tested, hole
Gap rate is 5~40%；Graphene sheet layer corrugation density is controlled in 50~500mm/mm2, and the defect of graphene film is few, its ID/
TG ＜ 0.02, are 1000~2000W/mK towards thermal conductivity.Graphene thick film is without lamination, the adjacent graphene of any two
The lamella of piece is smaller than 20nm, with very big actual application value.
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.The present embodiment be served only for being the present invention into
The explanation of one step, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according in foregoing invention
Appearance makes some nonessential changes and adjustment, belongs to protection scope of the present invention.
Embodiment 1：
(1) graphene oxide that average-size is more than 50 μm is configured to concentration for 7mg/mL graphene oxide water solutions,
With embrane method is scraped, paving thickness obtains graphene oxide membrane to be dried naturally after 5mm graphene oxide solution film forming.
(2) two sizes are combined for 8cm*8cm graphene oxide membrane with liquid coating, are specially：In oxidation
Graphene membrane surface carries out the graphene oxide water solution that uniform one layer of concentration of coating is 4mg/mL, then by multiple graphite oxides
Alkene film through-thickness bonds together.
(3) the graphene oxide composite membrane after bonding is placed on oven for drying, the temperature of baking oven is 40 DEG C.
(4) the compound and former graphene film of graphene oxide after drying is respectively placed in the hot pressing chamber of hot press, with 2
DEG C/min speed is warming up to after 200 DEG C and carries out hot pressing, repeats following hot pressing 10 times：Pressure 20MPa is maintained, 1h is maintained；
Gradually release pressure to 0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Then again with 2 DEG C/min speed liter
300 DEG C of temperature, is incubated 0.5h, then carries out hot pressing, the following hot pressing of repetition 5 times：Pressure 60MPa is maintained, 1h is maintained, gradually releases
Power is bled off pressure to 0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Hot pressing terminates rear Temperature fall.
(5) film after step 4 hot pressing is warming up to 2800 DEG C with 5 DEG C/min speed under atmosphere of inert gases and enters traveling
One step hot pressing, heat-insulation pressure keeping 2h；Pressure is 60MPa.After cooling, the graphene film of high heat conduction is obtained.
By above step, graphene oxide membrane is merged by the active force at viscous place, forms overall structure.By further
Low temperature and pressure, high temperature hot pressing annealing reduction, finally gives the graphene composite film of high heat conduction.And it is molten by coating graphene oxide
The graphene composite film that liquid is bonded, because graphene oxide therein can be with blind at, therefore defect is less, and structure is more
It is closely knit complete.After tested, the thickness of former graphene film is 26 μm, and graphene sheet layer corrugation density is 92mm/mm2, and graphene
The defect of piece is few, and its ID/TG=0.004, porosity is 8.6%, and density is 2.01g/cm3, it is towards thermal conductivity
1613.2W/mK；After above-mentioned processing, the thickness of graphene composite film is 53 μm, and graphene sheet layer corrugation density is 113mm/
mm2, and the defect of graphene film is few, its ID/TG=0.005, porosity is 9.0%, and density is 1.99g/cm3, porosity,
It is 1563.9W/mK towards thermal conductivity.Graphene thick film is without lamination, the piece interlamellar spacing of the adjacent graphene film of any two
Less than 20nm.
Embodiment 2：
(1) graphene oxide that average-size is more than 50 μm is configured to concentration for 7mg/mL graphene oxide water solutions,
With embrane method is scraped, paving thickness obtains graphene oxide membrane to be dried naturally after 5mm graphene oxide solution film forming.
(2) ten sizes are combined with different liquids coating respectively for 8cm*8cm graphene oxide membrane, specifically
For：Even application deionized water is carried out on graphene oxide membrane surface, surface is allowed to and is swelled, then by multiple graphene oxide membranes
Through-thickness bonds together, and the sample that the method is made is labeled as sample A；Uniformly applied on graphene oxide membrane surface
The graphene oxide water solution that one layer of concentration is 4mg/mL is covered, multiple graphene oxide membrane through-thickness are then bonded in one
Rise, the sample that the method is made is labeled as sample B.
(3) the graphene oxide composite membrane after two kinds are bonded is placed on oven for drying, and the temperature of baking oven is less than 40 DEG C.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, heated up with 2 DEG C/min speed
Hot pressing, the following hot pressing of repetition 10 times are carried out after to 200 DEG C：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge pressure extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Then heated up 300 DEG C with 2 DEG C/min speed again, insulation
0.5h, then carries out hot pressing, the following hot pressing of repetition 5 times：Pressure 60MPa is maintained, 1h is maintained, gradually pressure is discharged extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Hot pressing terminates rear Temperature fall.
(5) the graphene oxide composite membrane after step 4 hot pressing is heated up under atmosphere of inert gases with 5 DEG C/min speed
Further hot pressing, heat-insulation pressure keeping 2h are carried out to 2800 DEG C；Pressure is 60MPa.After cooling, the graphene thick film of high heat conduction is obtained.
By above step, graphene oxide membrane is merged by the active force at viscous place, forms overall structure.By further
Low temperature and pressure, high temperature hot pressing annealing reduction, finally gives the graphene composite thick film of high heat conduction.And by coating graphene oxide
The graphene composite thick film that solution is bonded, because graphene oxide therein can be with blind at, therefore the less structure of defect
It is more closely knit complete.After tested, sample A thickness is 279 μm, and graphene sheet layer corrugation density is 143mm/mm2, and graphene film
Defect it is few, its ID/TG=0.008, porosity is 11.8%, and density is 1.94g/cm3, as shown in figure 1, graphene thick film
Without lamination, the lamella of the adjacent graphene film of any two is smaller than 20nm.Thermal conductivity is 1448.9W/mK.Sample B
Thickness is 291 μm, and graphene sheet layer corrugation density is 134mm/mm2, and the defect of graphene film is few, its ID/TG=
0.007, porosity is 11.4%, and density is 1.95g/cm3, as shown in Fig. 2 graphene thick film is without lamination, any two
The lamella of adjacent graphene film is smaller than 20nm, and thermal conductivity is 1495.8W/mK.
Embodiment 3：
(1) average-size is more than the graphene oxide of 50 μm of high oxidation degree and the graphene oxide point of suboxides degree
7mg/mL graphene oxide water solution is not configured to, with embrane method is scraped, is spread after the graphene oxide solution film forming that thickness is 5mm certainly
So dry the graphene oxide membrane of the graphene oxide membrane for obtaining high oxidation degree and suboxides degree.
(2) graphene oxide membrane of the graphene oxide membrane of ten high oxidation degree and suboxides degree is answered respectively
Close, be specially：Even application deionized water is carried out on graphene oxide membrane surface, surface is allowed to and is swelled, then aoxidize multiple
Graphene film through-thickness bonds together.Graphene oxide film can realize self-adhesion by the active force at bonding interface
Knot, obtains the graphene oxide composite membrane of high oxidation degree and the graphene oxide composite membrane of suboxides degree, is respectively labeled as
Sample C and sample D.
(3) two graphene oxide composite membranes after bonding are placed on oven for drying, the temperature of baking oven is less than 40 DEG C, and
Gradually bring some pressure to bear in the drying process.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, heated up with 2 DEG C/min speed
Hot pressing, the following hot pressing of repetition 10 times are carried out after to 200 DEG C：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge pressure extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Then heated up 300 DEG C with 2 DEG C/min speed again, insulation
0.5h, then carries out hot pressing, the following hot pressing of repetition 5 times：Pressure 60MPa is maintained, 1h is maintained, gradually pressure is discharged extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Hot pressing terminates rear Temperature fall.
(5) the graphene oxide composite membrane after step 4 hot pressing is heated up under atmosphere of inert gases with 5 DEG C/min speed
Further hot pressing, heat-insulation pressure keeping 2h are carried out to 2800 DEG C；Pressure is 60MPa.After cooling, the graphene thick film of high heat conduction is obtained.
By above step, graphene oxide membrane is merged by the active force at viscous place, forms overall structure.By further
Low temperature and pressure, high temperature hot pressing annealing reduction, finally gives the graphene composite thick film of high heat conduction.And due to the oxygen of high oxidation degree
Graphite alkene is due to more functional group so that by the graphene oxide film of high oxidation degree in uniformly one layer of water of coating
After bonding, the hydrogen bond and van der Waals interaction of interface are bigger so that more preferably, structure is more densely cross-linked for bond effect.After tested, sample
Product C thickness is 261 μm, and graphene sheet layer corrugation density is 151mm/mm2, and the defect of graphene film is few, its ID/TG=
0.008, porosity is 12.3%, and density is 1.93g/cm3, it is 1466.9W/mK towards thermal conductivity, graphene thick film is without layering
Phenomenon, the lamella of the adjacent graphene film of any two is smaller than 20nm.Sample B thickness is 255 μm, graphene sheet layer fold
Density is 139mm/mm2, and the defect of graphene film is few, its ID/TG=0.09, porosity is 13.2%, and density is
1.91g/cm3, thermal conductivity is 1418.7W/mK, and graphene thick film is without lamination, the piece of the adjacent graphene film of any two
Interlamellar spacing is less than 20nm.
Embodiment 4：
(1) graphene oxide that average-size is more than 50 μm is configured to 7mg/mL graphene oxide water solution respectively,
With embrane method is scraped, the oxygen for obtaining two kinds of thickness is dried naturally after the graphene oxide membrane that thickness is 5mm and 2.5mm, film forming are spread respectively
Graphite alkene film.
(2) five thicker graphene oxide membranes and ten relatively thin graphene oxide membranes are combined respectively, specifically
For：The graphene oxide water solution that uniform one layer of concentration of coating is 4mg/mL is carried out on graphene oxide membrane surface, then will be many
Open graphene oxide membrane through-thickness to bond together, obtain two different graphene oxide composite membranes, be respectively labeled as
Sample E and sample F.
(3) two graphene oxide composite membranes after bonding are placed on oven for drying, the temperature of baking oven is less than 40 DEG C, and
Gradually bring some pressure to bear in the drying process.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, heated up with 2 DEG C/min speed
Hot pressing, the following hot pressing of repetition 10 times are carried out after to 200 DEG C：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge pressure extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Then heated up 300 DEG C with 2 DEG C/min speed again, insulation
0.5h, then carries out hot pressing, the following hot pressing of repetition 5 times：Pressure 60MPa is maintained, 1h is maintained, gradually pressure is discharged extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -50KPa；Hot pressing terminates rear Temperature fall.
(5) the graphene oxide composite membrane after step 4 hot pressing is heated up under atmosphere of inert gases with 5 DEG C/min speed
Further hot pressing, heat-insulation pressure keeping 2h are carried out to 2800 DEG C；Pressure is 60MPa.After cooling, the graphene thick film of high heat conduction is obtained.
By above step, graphene oxide membrane is merged by the active force at viscous place, forms overall structure.By further
Low temperature and pressure, high-temperature heat treatment repairs defect, finally gives the graphene thick film of high heat conduction.After tested, sample E thickness is 135 μ
M, graphene sheet layer corrugation density is 121mm/mm2, and the defect of graphene film is few, its ID/TG=0.009, porosity is
12.7%, density is 1.92g/cm3, thermal conductivity is 1518.4W/mK, and graphene thick film is without lamination, and any two is adjacent
The lamella of graphene film is smaller than 20nm；Sample F thickness is 138 μm, and graphene sheet layer corrugation density is 118mm/mm2, and
The defect of graphene film is few, and its ID/TG=0.009, porosity is 13.2%, and density is 1.91g/cm3, thermal conductivity is
1521.7W/mK, graphene thick film is without lamination, and the lamella of the adjacent graphene film of any two is smaller than 20nm.
Embodiment 5：
(1) graphene oxide that average-size is more than 50 μm is configured to concentration for 7mg/mL graphene oxide water solutions,
With embrane method is scraped, paving thickness obtains graphene oxide membrane to be dried naturally after 5mm graphene oxide solution film forming.
(2) 100 sizes are combined for 4cm*4cm graphene oxide membrane, are specially：In graphene oxide membrane
Surface carries out the graphene oxide water solution that uniform one layer of concentration of coating is 4mg/mL, then that multiple graphene oxide membranes edge is thick
Degree direction bonds together.
(3) the graphene oxide composite membrane after bonding is placed on oven for drying, the temperature of baking oven is less than 40 DEG C.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, heated up with 2 DEG C/min speed
Hot pressing, the following hot pressing of repetition 10 times are carried out after to 200 DEG C：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge pressure extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100~10KPa；Then heated up 300 DEG C with 2 DEG C/min speed again,
0.5h is incubated, hot pressing, the following hot pressing of repetition 5 times is then carried out：Pressure 60MPa is maintained, 1h is maintained, gradually pressure is discharged extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100~10KPa；Hot pressing terminates rear Temperature fall.
(5) the graphene oxide composite membrane after step 4 hot pressing is heated up under atmosphere of inert gases with 5 DEG C/min speed
Further hot pressing, heat-insulation pressure keeping 2h are carried out to 2500 DEG C；Pressure is 60MPa.After cooling, the graphene thick film of high heat conduction is obtained.
By above step, graphene oxide in active force fusion and applying liquid of the graphene oxide membrane by viscous place
Blind, formed overall structure.By further low temperature and pressure, high temperature hot pressing annealing reduction finally gives high heat conduction
Graphene composite thick film.After tested, the thickness of the graphene film is 2.93mm, and graphene sheet layer corrugation density is 310mm/mm2,
And the defect of graphene film is few, its ID/TG=0.018, porosity is 20.1%, and density is 1.74g/cm3, thermal conductivity is
1287.1W/mK, graphene thick film is without lamination, and the lamella of the adjacent graphene film of any two is smaller than 20nm.
Embodiment 6：
(1) graphene oxide that average-size is more than 100 μm is configured to concentration for 1mg/mL graphene oxide water solutions,
Dried naturally after solution film forming, obtain graphene oxide membrane.The thickness of graphene oxide membrane is 15 μm, the carbon of graphene oxide membrane
Oxygen compares 1.8.
(2) multiple graphene oxide membranes are combined, are specially：Even application is carried out on graphene oxide membrane surface
Water, is allowed to surface and is swelled, and then multiple graphene oxide membrane through-thickness bond together.
(3) the graphene oxide composite membrane after bonding is placed on oven for drying, the temperature of baking oven is 40 DEG C.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, with 0.1 DEG C/min speed liter
Hot pressing, the following hot pressing of repetition 8 times are carried out after warm to 200 DEG C：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge pressure extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100KPa；Then heated up 300 DEG C, protected with 0.1 DEG C/min speed again
Warm 0.5h, then carries out hot pressing, the following hot pressing of repetition 4 times：Pressure 60MPa is maintained, 1h is maintained, gradually pressure is discharged extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100KPa；Hot pressing terminates rear Temperature fall.
(5) graphene oxide membrane after step 4 hot pressing is warming up under atmosphere of inert gases with 1 DEG C/min speed
1800 DEG C carry out further hot pressing, heat-insulation pressure keeping 8h；Pressure is 60MPa.After cooling compacting, the graphene for obtaining high heat conduction is thick
Film.
After tested, the thickness of prepared graphene thick film is 54 μm, and density is 2.1g/cm3, porosity is 5%；Heat conduction
Rate is 1987.1W/mK, graphene sheet layer corrugation density position 50mm/mm2, and the defect of graphene film is few, its ID/TG=
0.005, graphene thick film is without lamination, and the lamella of the adjacent graphene film of any two is smaller than 20nm.
Embodiment 7：(1) graphene oxide that average-size is more than 50 μm is configured to concentration for 20mg/mL graphite oxides
Dried naturally after aqueous solution, solution film forming, obtain graphene oxide membrane, thickness is 50 μm, carbon-to-oxygen ratio 2.1.
(2) multiple graphene oxide membranes are combined, are specially：It is dense that even application is carried out on graphene oxide membrane surface
The graphene oxide water solution for 1mg/mL is spent, surface is allowed to and is swelled, then multiple graphene oxide membrane through-thickness are glued
It is connected together.
(3) the graphene oxide composite membrane after bonding is placed on oven for drying, the temperature of baking oven is 30 DEG C.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, heated up with 5 DEG C/min speed
Hot pressing, the following hot pressing of repetition 10 times are carried out after to 200 DEG C：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge pressure extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -10KPa；Then heated up 300 DEG C with 5 DEG C/min speed again, insulation
0.5h, then carries out hot pressing, the following hot pressing of repetition 6 times：Pressure 60MPa is maintained, 1h is maintained, gradually pressure is discharged extremely
0MPa, hot pressing chamber is vacuumized 5min to vacuum be -10KPa；Hot pressing terminates rear Temperature fall.
(5) graphene oxide membrane after step 4 hot pressing is warming up under atmosphere of inert gases with 20 DEG C/min speed
3000 DEG C carry out further hot pressing, heat-insulation pressure keeping 0.5h；Pressure is 10MPa.After cooling compacting, the graphene for obtaining high heat conduction is thick
Film.
After tested, the thickness of prepared graphene thick film is 4.56mm, and porosity is 40%；Graphene sheet layer fold is close
Spend for 500mm/mm2Left and right, and the defect of graphene film is few, its ID/TG=0.02, graphene thick film is without lamination, arbitrarily
The lamella of two adjacent graphene films is smaller than 20nm.
Claims (6)
1. a kind of graphene thick film of high heat conduction, it is characterised in that the thickness of prepared graphene thick film is more than 50 μm, hole
Rate is 5~40%, is 1000~2000W/mK towards thermal conductivity,；Graphene sheet layer corrugation density is controlled in 50~500mm/
mm2, and the defect of graphene film is few, its ID/TG ＜ 0.02, graphene thick film is without lamination, the adjacent graphite of any two
The lamella of alkene piece is smaller than 20nm.
2. the graphene thick film of a kind of high heat conduction according to claim 1, it is characterised in that the preparation method is comprising such as
Lower step：
(1) graphene oxide that average-size is more than 50 μm is configured to concentration for 1~20mg/mL graphene oxide water solutions,
Dried naturally after solution film forming, obtain graphene oxide membrane.
(2) multiple graphene oxide membranes are combined, are specially：Even application liquid is carried out on graphene oxide membrane surface,
It is allowed to surface to be swelled, then multiple graphene oxide membrane through-thickness bonds together.
(3) the graphene oxide composite membrane after bonding is placed on oven for drying, the temperature of baking oven is not higher than 40 DEG C.
(4) the graphene oxide composite membrane after drying is placed in the hot pressing chamber of hot press, with 0.1~5 DEG C/min speed liter
Hot pressing, repetition following hot pressing 8-10 times are carried out after warm to 200 DEG C：Pressure 20MPa is maintained, 1h is maintained；Gradually discharge pressure
To 0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100~10KPa；Then heated up again with 0.1~5 DEG C/min speed
300 DEG C, 0.5h is incubated, hot pressing, repetition following hot pressing 4-6 times is then carried out：Pressure 60MPa is maintained, 1h is maintained, gradually releases
Power is bled off pressure to 0MPa, hot pressing chamber is vacuumized 5min to vacuum be -100~10KPa；Hot pressing terminates rear Temperature fall.
(5) graphene oxide membrane after step 4 hot pressing is warming up under atmosphere of inert gases with 1-20 DEG C/min speed
1800~3000 DEG C carry out further hot pressing, 0.5~8h of heat-insulation pressure keeping；Pressure is 10~60MPa.After cooling compacting, height is obtained
The graphene thick film of heat conduction.
3. a kind of preparation method of high heat conduction graphene thick film according to claim 2, it is characterised in that the step 1
The thickness of the graphene oxide membrane of preparation is 1 μm~30 μm.
4. a kind of preparation method of high heat conduction graphene thick film according to claim 2, it is characterised in that the step 1
In film build method be selected from suction method, scrape embrane method, spin-coating method, spraying process and dip coating etc..
5. a kind of preparation method of the graphene thick film of high heat conduction according to claim 2, it is characterised in that described step
The carbon-to-oxygen ratio 1.8~2.1 of rapid 1 graphene oxide membrane prepared.
6. the preparation method of the graphene thick film of a kind of high heat conduction according to claim 2, it is characterised in that described
Step 2 spray used in liquid be：Deionized water, concentration is 1~10mg/mL graphene oxide water solution, or other
Solution containing deionized water.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710391092.4A CN107140619B (en) | 2017-05-27 | 2017-05-27 | A kind of graphene thick film of high thermal conductivity and preparation method thereof |
| US16/617,531 US11542411B2 (en) | 2017-05-27 | 2018-03-13 | Method for preparing composites on basis of graphene bonding |
| JP2019565907A JP6952134B2 (en) | 2017-05-27 | 2018-03-13 | Method of manufacturing composite material based on graphene adhesive |
| PCT/CN2018/078765 WO2018219008A1 (en) | 2017-05-27 | 2018-03-13 | Method for preparing composites on basis of graphene bonding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710391092.4A CN107140619B (en) | 2017-05-27 | 2017-05-27 | A kind of graphene thick film of high thermal conductivity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107140619A true CN107140619A (en) | 2017-09-08 |
| CN107140619B CN107140619B (en) | 2019-09-03 |
Family
ID=59779245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710391092.4A Active CN107140619B (en) | 2017-05-27 | 2017-05-27 | A kind of graphene thick film of high thermal conductivity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107140619B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555419A (en) * | 2017-10-13 | 2018-01-09 | 杭州高烯科技有限公司 | A kind of low corrugation density graphene film and preparation method thereof |
| CN107705871A (en) * | 2017-09-27 | 2018-02-16 | 武汉理工大学 | A kind of superelevation electrical conductivity large-size graphene film and frequency microwave device |
| CN107892295A (en) * | 2017-09-30 | 2018-04-10 | 珠海聚碳复合材料有限公司 | A kind of preparation method of heat conducting film and a kind of heat conducting film |
| CN108383112A (en) * | 2018-04-11 | 2018-08-10 | 杭州牛墨科技有限公司 | A kind of high heat graphene heating film and preparation method thereof |
| WO2018219008A1 (en) * | 2017-05-27 | 2018-12-06 | 杭州高烯科技有限公司 | Method for preparing composites on basis of graphene bonding |
| CN109318564A (en) * | 2018-09-10 | 2019-02-12 | 成都紫苑华光新材料科技有限公司 | A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film |
| CN109609040A (en) * | 2018-12-11 | 2019-04-12 | 苏州鸿凌达电子科技有限公司 | A method of it being bonded double-layer graphite piece using graphene nano gel as adhesive layer |
| CN109694055A (en) * | 2018-12-28 | 2019-04-30 | 常州富烯科技股份有限公司 | High-density graphite alkene foam film and preparation method thereof |
| CN110550625A (en) * | 2019-10-24 | 2019-12-10 | 宁波石墨烯创新中心有限公司 | Graphene film repairing solution, repairing method and repairing film |
| CN111302332A (en) * | 2020-04-21 | 2020-06-19 | 福建永安市永清石墨烯研究院有限公司 | Ultrahigh-thermal-conductivity graphene thick film and preparation method thereof |
| CN111392722A (en) * | 2020-06-04 | 2020-07-10 | 山东海科创新研究院有限公司 | High-heat-conductivity high-temperature-resistant graphene heat dissipation film and preparation method thereof |
| CN112279239A (en) * | 2020-09-21 | 2021-01-29 | 宁波华丰包装有限公司 | Method for preparing graphene film in batch and graphene film prepared by method |
| CN114751404A (en) * | 2022-04-29 | 2022-07-15 | 上海大学 | High-thermal-conductivity graphene thick film and preparation method thereof |
| CN115367744A (en) * | 2022-09-14 | 2022-11-22 | 上海大学 | Secondary-formed high-thermal-conductivity graphene thick film and preparation method thereof |
| CN115744884A (en) * | 2022-11-07 | 2023-03-07 | 厦门大学 | Continuous preparation method and system of graphene film with directional heat conduction function |
| US11618682B2 (en) * | 2019-09-06 | 2023-04-04 | Changzhou Fuxi Technology Co., Ltd | Mixed slurry of strong and weak graphene oxides and preparation method of mixed slurry, and composite film of strong and weak graphene oxides and preparation method of composite film |
| CN116606144A (en) * | 2023-05-22 | 2023-08-18 | 南京工业大学 | Method for preparing graphene heat-conducting thick film through chemical pre-reduction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502368A (en) * | 2015-12-30 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Graphene film and preparation method thereof |
| CN106629675A (en) * | 2016-09-28 | 2017-05-10 | 上海理工大学 | Preparation method of high-heat-conduction flexible graphene film |
-
2017
- 2017-05-27 CN CN201710391092.4A patent/CN107140619B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502368A (en) * | 2015-12-30 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Graphene film and preparation method thereof |
| CN106629675A (en) * | 2016-09-28 | 2017-05-10 | 上海理工大学 | Preparation method of high-heat-conduction flexible graphene film |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018219008A1 (en) * | 2017-05-27 | 2018-12-06 | 杭州高烯科技有限公司 | Method for preparing composites on basis of graphene bonding |
| CN107705871A (en) * | 2017-09-27 | 2018-02-16 | 武汉理工大学 | A kind of superelevation electrical conductivity large-size graphene film and frequency microwave device |
| CN107705871B (en) * | 2017-09-27 | 2020-01-14 | 武汉理工大学 | Ultrahigh-conductivity large-size graphene film and radio frequency microwave device |
| CN107892295A (en) * | 2017-09-30 | 2018-04-10 | 珠海聚碳复合材料有限公司 | A kind of preparation method of heat conducting film and a kind of heat conducting film |
| CN107555419A (en) * | 2017-10-13 | 2018-01-09 | 杭州高烯科技有限公司 | A kind of low corrugation density graphene film and preparation method thereof |
| CN108383112A (en) * | 2018-04-11 | 2018-08-10 | 杭州牛墨科技有限公司 | A kind of high heat graphene heating film and preparation method thereof |
| CN109318564A (en) * | 2018-09-10 | 2019-02-12 | 成都紫苑华光新材料科技有限公司 | A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film |
| CN109609040A (en) * | 2018-12-11 | 2019-04-12 | 苏州鸿凌达电子科技有限公司 | A method of it being bonded double-layer graphite piece using graphene nano gel as adhesive layer |
| CN109694055B (en) * | 2018-12-28 | 2021-12-03 | 常州富烯科技股份有限公司 | High-density graphene foam film and preparation method thereof |
| CN109694055A (en) * | 2018-12-28 | 2019-04-30 | 常州富烯科技股份有限公司 | High-density graphite alkene foam film and preparation method thereof |
| US11618682B2 (en) * | 2019-09-06 | 2023-04-04 | Changzhou Fuxi Technology Co., Ltd | Mixed slurry of strong and weak graphene oxides and preparation method of mixed slurry, and composite film of strong and weak graphene oxides and preparation method of composite film |
| CN110550625A (en) * | 2019-10-24 | 2019-12-10 | 宁波石墨烯创新中心有限公司 | Graphene film repairing solution, repairing method and repairing film |
| CN111302332A (en) * | 2020-04-21 | 2020-06-19 | 福建永安市永清石墨烯研究院有限公司 | Ultrahigh-thermal-conductivity graphene thick film and preparation method thereof |
| CN111392722B (en) * | 2020-06-04 | 2020-12-18 | 山东海科创新研究院有限公司 | High-heat-conductivity high-temperature-resistant graphene heat dissipation film and preparation method thereof |
| CN111392722A (en) * | 2020-06-04 | 2020-07-10 | 山东海科创新研究院有限公司 | High-heat-conductivity high-temperature-resistant graphene heat dissipation film and preparation method thereof |
| CN112279239A (en) * | 2020-09-21 | 2021-01-29 | 宁波华丰包装有限公司 | Method for preparing graphene film in batch and graphene film prepared by method |
| CN114751404A (en) * | 2022-04-29 | 2022-07-15 | 上海大学 | High-thermal-conductivity graphene thick film and preparation method thereof |
| CN115367744A (en) * | 2022-09-14 | 2022-11-22 | 上海大学 | Secondary-formed high-thermal-conductivity graphene thick film and preparation method thereof |
| CN115744884A (en) * | 2022-11-07 | 2023-03-07 | 厦门大学 | Continuous preparation method and system of graphene film with directional heat conduction function |
| CN116606144A (en) * | 2023-05-22 | 2023-08-18 | 南京工业大学 | Method for preparing graphene heat-conducting thick film through chemical pre-reduction |
| CN116606144B (en) * | 2023-05-22 | 2023-11-21 | 南京工业大学 | Method for preparing graphene heat-conducting thick film through chemical pre-reduction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107140619B (en) | 2019-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107140619B (en) | A kind of graphene thick film of high thermal conductivity and preparation method thereof | |
| CN107555419B (en) | A kind of low corrugation density graphene film and preparation method thereof | |
| CN106082186B (en) | A kind of heat conduction film and preparation method thereof of graphene-nanometer carbon/carbon-copper composite material | |
| CN107651673B (en) | Nano-scale thickness independent self-supporting folded graphene film and preparation method thereof | |
| CN106847767A (en) | A kind of graphite Copper Foil heat sink compound | |
| CN108217627B (en) | Preparation method of independent self-supporting graphene carbon tube composite membrane | |
| TW201241843A (en) | Method for manufacturing a carbon nanotube composite and application | |
| CN105491695A (en) | Two-dimensional nano carbon heating body, and flexible electric heating module and preparation method therefor | |
| CN105692600B (en) | A kind of preparation method of super soft light graphite alkene Electric radiant Heating Film | |
| CN105110312B (en) | CNT graphite composite material and preparation method thereof and device | |
| CN104477892A (en) | Preparation method of flake graphene and flake graphene device prepared by same | |
| CN104475316A (en) | Preparing method of graphene coating | |
| CN107162594A (en) | A kind of polyimide-based compound carbon film of high heat conduction and preparation method thereof | |
| CN111302332B (en) | Ultrahigh-thermal-conductivity graphene thick film and preparation method thereof | |
| CN104229729A (en) | Method for transferring carbon nanotube vertical array to flexible polymer substrate | |
| CN107651671A (en) | A kind of method of catalyzed graphitization and a kind of preparation method of super flexible high heat conduction graphene film | |
| WO2018219000A1 (en) | Polyimide-based composite carbon film with high thermal conductivity and preparation method therefor | |
| CN105489748B (en) | A kind of preparation method of the high-temperature flexible thermo-electric device based on graphene | |
| CN107758644B (en) | A kind of method that super-pressure thermal reduction prepares graphene film | |
| CN110324920A (en) | A kind of preparation method of thermal-insulating type graphene Electric radiant Heating Film | |
| CN113401892A (en) | Preparation method of ultra-thick heat-conducting graphene film | |
| CN206947325U (en) | A kind of graphite copper foil heat sink compound | |
| CN110964219B (en) | Nano cellulose membrane with high thermal conductivity and preparation method thereof | |
| CN106219532B (en) | A kind of nanometer carbon pipe array/graphite composite heat conduction film and preparation method thereof | |
| CN205498197U (en) | Scattered heat recombination membrane of high -efficient thermal current direction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |