CN106010469A - Carbon nanotube array/graphene paper heat-conducting composite material and preparation method - Google Patents
Carbon nanotube array/graphene paper heat-conducting composite material and preparation method Download PDFInfo
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Abstract
The invention relates to a carbon nanotube array/graphene paper heat-conducting composite material and a preparation method. The composite material is formed by stacking and compositing vertical orientation carbon nanotube arrays and horizontal orientation graphene paper layers. Carbon nanotube array and graphene paper combinations serve as structural units for lamination and accumulation of the structural units in the vertical direction. The carbon nanotube array layers and the graphene paper layers are alternately and vertically connected with flaky solid heat-conducting gaskets layer by layer, the flaky solid heat-conducting gaskets are obtained through horizontal orientation stacking, and the layers are combined through adhesion force of an intermediate phase asphalt-base graphite material to form a composite heat-conducting structure. According to the composite material, a heat-conducting passage in the thickness direction is provided for the composite material by the orientation carbon nanotube array structures, and heat-conducting performance in the plane direction is provided for flaky graphene paper. Heat conductivity of graphene heat-conducting pieces in the plane direction reaches 500 W/(m.K), and heat conductivity of the graphene heat-conducting pieces in the thickness direction reaches 20 W/(m.K).
Description
Technical field
The present invention relates to carbon nano pipe array/graphene paper heat-conductive composite material and preparation method, specifically a kind of at Graphene
Carbon nano pipe array the preparation method of high-temperature thermo-compression formation conductive graphite sheet is grown on paper.
Background technology
Since 21st century, science and technology achieves development at a high speed, and efficient conduction of heat and heat radiation become thermal management materials neck
The critical problem in territory.Such as during heat generating device arrangement works, because of the resistance of device itself, thermal resistance, electronics eddy current
Etc. effect, building up amount of heat, the position particularly high in component density, heat-dissipating space is narrow, heat flow density can spy
Not big, thus cause integral member temperature the most uneven.Major part microelectronic chip surface temperature must be maintained at relatively low water
Just can ensure that (such as silicon device 100 DEG C) under Ping that its high performance operation, many electronic units need ability at a temperature of 40～60 DEG C
Can normally work, this proposes the highest requirement to Heat Conduction Material, and can device heat production discharge in time, device heat radiation is
No uniform high-efficiency be electronic device can fast and stable work deciding factor, greatly have impact on performance and the matter of electronic equipment
Amount.In order to be derived by these heats in time, need the heat conduction that development quality is lighter, thermal conductivity is higher, performance is more excellent in a hurry
New material.
Graphene is a kind of planar sheet nano material obtained through peroxidating, intercalation, stripping by natural flake graphite.Graphene
Owing to having regular orderly graphite atomic layer, the obstruction of phonon conduction is less, and in-plane defects is less, and heat transfer efficiency is the highest, because of
And utilize Graphene or graphene paper to prepare carbon back highly heat-conductive material and become the emphasis of people's research, also occur in that similar patent
Authorize or open.State Intellectual Property Office of the People's Republic of China's grant number is CN103449421B, CN103805144A,
The patents of invention such as CN102573413A disclose the technology utilizing graphene paper to prepare thermally-conductive sheet.
Above-described patent of invention disclose only traditional graphene paper preparation method and combination process, only obtains to have and leads
The graphene paper Heat Conduction Material of thermal anisotropy.And for graphene sheet layer, the lattice vibrations of carbon atom are the bases of material conducts heat,
Therefore in graphene paper material, phonon transmission carries out travel at high speeds only along graphite crystal face, and between graphite wafer surface layer due to away from
From too far, have a strong impact on the conduction of phonon.After graphene filter membrane PROCESS FOR TREATMENT, Graphene crystal face is edge under hot pressing function
In-plane is orientated, thus only has high heat conductance along in-plane (more than 1000 in Graphene conducting strip
W/ (m K)), and through-thickness thermal conductivity is the lowest, less than 20W/ (m K) (Balandin A A.Thermal properties of
graphene and nanostructured carbon materials.[J].Nature Material,2011,10(10):569-81.).China
The thermal conductivity of graphene paper heat-conducting plate through-thickness of the announcement such as patent application CN103449421B, CN103805144A
All at 10W/ (m K) below.Therefore, the through-thickness heat conductivity of existing the obtained material of published patent of invention is remote not
The requirement to the Heat Conduction Material capacity of heat transmission such as mainframe computer, highly integrated electronic device can be met, on material with carbon element existing advantage basis
Upper exploitation is a kind of to be had simultaneously and is particularly important along thickness and the high heat conduction of in-plane, the material of less anisotropy.
Summary of the invention
The present invention is directed to existing cool molded graphite alkene or graphite paper conducting strip through-thickness thermal conductivity prepared by expanded graphite is too low not
Foot, it is provided that a kind of be respectively provided with high thermal conductivity along plane and thickness direction can the thermal conductivity graphite composite material of the lowest anisotropic heat conductivity
And preparation method thereof.500W/ (m K) and the graphite heat-conducting fin of 20W/ (m K) is respectively reached along plane and thickness direction thermal conductivity,
As it is shown in figure 1, composite is by vertical orientated carbon nano pipe array, folded being combined is constituted with the graphene paper layer stack of horizontal alignment.
A kind of preparation method of the carbon nano pipe array/graphene paper heat-conductive composite material of the present invention, step is as follows:
1) graphene oxide paper is immersed in ethyl orthosilicate solvent and carry out vacuum impregnation 12～24 hours, then inserting forced air drying
Machine；
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.02～0.05g/ml, by step 1) obtain
Graphene oxide paper be placed in the flat-temperature zone of vacuum tube furnace, be passed through argon after being evacuated to below 10Pa as protection gas, with
10～15 DEG C/min speed is warming up to 700～800 DEG C, pushes in vacuum tube furnace by complex catalyst precursor liquid, is oriented CNT
The growth of array；
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to disk, select 2～10 layers of carbon nano pipe array/
Graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes dipping solution, by standby CNT
Array/graphene paper composite sample disk immerses in impregnation liquid vacuum impregnation 24～inserts vacuum drying oven after 48 hours and carry out room temperature
It is dried 24～36 hours；Carbon nano pipe array/the graphene paper obtained after being completed by dipping/mesophase pitch composite sample disk is inserted
In mould, carry out hot-forming with 1000～1500 DEG C and 5～20MPa pressure in argon gas atmosphere, and pressurize 0.5～5 hours；
Obtain carbon nano pipe array/graphene paper heat-conductive composite material.
Described step 1) drying condition be 60～80 DEG C be dried 24～36 hours.
Described step 2) complex catalyst precursor liquid pushes in vacuum tube furnace with 0.2～0.6ml/min speed and stably insulation 5～80 points
Clock.
Described step 2) growth length that it is characterized in that directional carbon nanotube array is 20～80 μm, array density is 2 × 108～2
×109cm-2。
Described step 3) disk diameter 3～5cm.
Described step 3) to be dissolved in xylene concentration be 0.3～0.7mg/ml to dipping solution mesophase pitch.
Preferential oxidation graphene paper preparation method of the present invention is: join in deionized water by graphene oxide powder, with
The power room temperature of 200～300W carries out ultrasonic disperse in ultrasonic 0.5～2 hour；Use vacuum filter membrane that graphene oxide dispersion is carried out
Sucking filtration, separates Graphene filter cake and vacuum filter membrane, filter cake is inserted vacuum drying oven and carries out normal temperature drying 18～24 hours, obtaining
Thickness is the graphene oxide paper of 0.1～0.3mm.
Described vacuum filter sizes is 0.2～1 μm.Vacuum filtration with vacuum-impregnated vacuum degree condition is: instrument internal gas pressure
≤20Pa。
The present invention, with carbon nano pipe array-graphene paper coalition as construction unit, carries out the lamination heap of construction unit vertical direction
It is long-pending: carbon nano pipe array layer is connected horizontal alignment layer by layer and stacks the chip solid heat-conducting pad obtained with Graphene ply of paper alternating orthogonal,
The bonding force of intermediate phase pitch-based graphite material is relied on to be bonded composite heat-conducting structure between layers.This composite is by orienting
Carbon nano tube array structure provides the thermal conducting path of composite through-thickness, and is provided composite by flake graphite alkene paper
Heat conductivility along in-plane.
CNT is in growth course, and CNT need not particular orientation technique and density solid matter effect can be relied on to realize nature
Vertical orientation；The growth obtained has carbon nano pipe array as it is shown on figure 3, CNT is piled up with very high-density, by thickness direction
Orientation aligns.
Owing to graphene paper direction along face has high thermal conductivity coefficient, and normal direction heat conductivity is the lowest, orients carbon in its superficial growth
After nano-tube array, during high temperature hot pressing subsequently, carbon nano pipe array will trend towards standing vertically at graphene paper interlayer,
Utilizing its high thermal conductivity vertically to realize the transmission of graphene paper interlayer hot-fluid, this is very beneficial for improving composite along thick
The capacity of heat transmission in degree direction, reduces its anisotropic heat conductivity；
By the graphene paper of above step and the compound of directional carbon nanotube array and high-temperature thermo-compression formation, it is achieved that have vertically
The directional carbon nanotube array having high thermal conductivity is compound, through too high with the graphene paper at in-plane with high thermal conductivity
Warm pressure makes composite densification, obtains thermal conductivity along in-plane more than 500W/ (m K), and through-thickness is more than
The graphite composite heat conducting sheet of 20W/ (m K).
Beneficial effects of the present invention: the matrix material graphene oxide of the present invention is easy to get, and the growth of directional carbon nanotube array is simple
Controlled.Microstructure ordering in the present invention, densification, graphitization and material molding can efficiently complete, and that can obtain has relatively
Low anisotropic heat conductivity can C-base composte material conducting strip, its capacity of heat transmission be far superior to traditional expanded graphite paper web and
Other graphite papers and carbon fibre composite.
Accompanying drawing illustrates:
Fig. 1 is the microcosmic schematic diagram of the conducting strip of the present invention, including complex form and hot pressing direction；
Fig. 2 is macroscopical picture of graphene paper sample；
Fig. 3 is the scanning electron microscopic picture of oriented growth of carbon nanometer tube array.
Detailed description of the invention
7 embodiments of the present invention are given below, are the present invention to be further illustrated rather than limits the scope of the present invention.
Embodiment 1
1) 100mg graphene oxide powder is joined deionized water carries out ultrasonic disperse, surpass with the power room temperature of 200W
Sound 1 hour.Use vacuum filter membrane that graphene oxide dispersion carries out sucking filtration, separate Graphene filter cake and vacuum filter membrane, will filter
Cake is inserted vacuum drying oven and is carried out normal temperature drying 20 hours, obtains the graphene oxide paper that thickness is 0.1mm.By graphite oxide
Alkene paper immerses in ethyl orthosilicate solvent and carries out vacuum impregnation 12 hours, inserts blast drier afterwards and carries out 60 DEG C to be dried 24 little
Time.
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.05g/ml, graphene oxide paper is placed in
The flat-temperature zone of vacuum tube furnace, be passed through after being evacuated to 8Pa argon as protection gas, programme-control heat up, with 10 DEG C/min
At the uniform velocity it is warming up to 800 DEG C, after reaching design temperature, applies injector for medical purpose by complex catalyst precursor under the effect of delicate flow pump
Liquid at the uniform velocity pushes with 0.2ml/min in vacuum tube furnace and is stably incubated 5 minutes, is oriented the growth of carbon nano pipe array,
To a length of 20 μm of directional carbon nanotube array, array density is 2 × 108cm-2。
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to the disk of diameter 3cm, selects 10 layers of carbon nanometer
Pipe array/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes the dipping that concentration is 0.3mg/ml
Solution, immerses above-mentioned carbon nano pipe array/graphene paper composite sample disk vacuum impregnation in impregnation liquid and inserts after 36 hours
Vacuum drying oven carries out normal temperature drying 24 hours, the carbon nano pipe array/graphene paper/mesophase pitch obtained after being completed by dipping
Composite sample disk is inserted in mould, carries out hot-forming with 1000 DEG C and 10MPa pressure in argon gas atmosphere, and pressurize 0.5
Obtaining graphite heat-conducting fin after hour, test is 531.1W/ (m K) along in-plane thermal conductivity, and through-thickness thermal conductivity is
20.8W/(m·K)。
Embodiment 2
1) 200mg graphene oxide powder is joined deionized water carries out ultrasonic disperse, surpass with the power room temperature of 300W
Sound 0.5 hour.Use vacuum filter membrane that graphene oxide dispersion carries out sucking filtration, separate Graphene filter cake and vacuum filter membrane, will
Filter cake is inserted vacuum drying oven and is carried out normal temperature drying 24 hours, obtains the graphene oxide paper that thickness is 0.3mm.Stone will be aoxidized
Ink alkene paper immerses in ethyl orthosilicate solvent and carries out vacuum impregnation 18 hours, inserts blast drier afterwards and carries out 80 DEG C dry 29
Hour.
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.05g/ml, graphene oxide paper is placed in
The flat-temperature zone of vacuum tube furnace, be passed through after being evacuated to 5Pa argon as protection gas, programme-control heat up, with 15 DEG C/min
At the uniform velocity it is warming up to 800 DEG C, after reaching design temperature, applies injector for medical purpose by complex catalyst precursor under the effect of delicate flow pump
Liquid at the uniform velocity pushes with 0.6ml/min in vacuum tube furnace and is stably incubated 30 minutes, is oriented the growth of carbon nano pipe array,
Obtaining a length of 50 μm of directional carbon nanotube array, array density is 2 × 109cm-2。
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to the disk of diameter 5cm, selects 4 layers of carbon nanometer
Pipe array/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes the dipping that concentration is 0.7mg/ml
Solution, immerses above-mentioned carbon nano pipe array/graphene paper composite sample disk vacuum impregnation in impregnation liquid and inserts after 48 hours
Vacuum drying oven carries out normal temperature drying 36 hours, the carbon nano pipe array/graphene paper/mesophase pitch obtained after being completed by dipping
Composite sample disk is inserted in mould, carries out hot-forming with 1500 DEG C and 15MPa pressure in argon gas atmosphere, and pressurize 5
Obtaining graphite heat-conducting fin after hour, test is 864.0W/ (m K) along in-plane thermal conductivity, and through-thickness thermal conductivity is
33.6W/(m·K)。
Embodiment 3
1) 180mg graphene oxide powder is joined deionized water carries out ultrasonic disperse, surpass with the power room temperature of 260W
Sound 1 hour.Use vacuum filter membrane that graphene oxide dispersion carries out sucking filtration, separate Graphene filter cake and vacuum filter membrane, will filter
Cake is inserted vacuum drying oven and is carried out normal temperature drying 18 hours, obtains the graphene oxide paper that thickness is 0.2mm.By graphite oxide
Alkene paper immerses in ethyl orthosilicate solvent and carries out vacuum impregnation 24 hours, inserts blast drier afterwards and carries out 75 DEG C to be dried 36 little
Time.
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.02g/ml, graphene oxide paper is placed in
The flat-temperature zone of vacuum tube furnace, be passed through after being evacuated to 5Pa argon as protection gas, programme-control heat up, with 12 DEG C/min
At the uniform velocity it is warming up to 700 DEG C, after reaching design temperature, applies injector for medical purpose by complex catalyst precursor under the effect of delicate flow pump
Liquid at the uniform velocity pushes with 0.3ml/min in vacuum tube furnace and is stably incubated 80 minutes, is oriented the growth of carbon nano pipe array,
Obtaining a length of 80 μm of directional carbon nanotube array, array density is 2.3 × 108cm-2。
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to the disk of diameter 4cm, selects 2 layers of carbon nanometer
Pipe array/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes the dipping that concentration is 0.5mg/ml
Solution, immerses above-mentioned carbon nano pipe array/graphene paper composite sample disk vacuum impregnation in impregnation liquid and inserts after 24 hours
Vacuum drying oven carries out normal temperature drying 28 hours, the carbon nano pipe array/graphene paper/mesophase pitch obtained after being completed by dipping
Composite sample disk is inserted in mould, carries out hot-forming with 1150 DEG C and 5MPa pressure, and pressurize 1 is little in argon gas atmosphere
Obtaining graphite heat-conducting fin time after, test is 597.5W/ (m K) along in-plane thermal conductivity, and through-thickness thermal conductivity is
22.3W/(m·K)。
Embodiment 4
1) 100mg graphene oxide powder is joined deionized water carries out ultrasonic disperse, surpass with the power room temperature of 280W
Sound 1.5 hours.Use vacuum filter membrane that graphene oxide dispersion carries out sucking filtration, separate Graphene filter cake and vacuum filter membrane, will
Filter cake is inserted vacuum drying oven and is carried out normal temperature drying 24 hours, obtains the graphene oxide paper that thickness is 0.1mm.Stone will be aoxidized
Ink alkene paper immerses in ethyl orthosilicate solvent and carries out vacuum impregnation 21 hours, inserts blast drier afterwards and carries out 60 DEG C dry 24
Hour.
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.05g/ml, graphene oxide paper is placed in
The flat-temperature zone of vacuum tube furnace, be passed through after being evacuated to 3Pa argon as protection gas, programme-control heat up, with 15 DEG C/min
At the uniform velocity it is warming up to 800 DEG C, after reaching design temperature, applies injector for medical purpose by complex catalyst precursor under the effect of delicate flow pump
Liquid at the uniform velocity pushes with 0.6ml/min in vacuum tube furnace and is stably incubated 20 minutes, is oriented the growth of carbon nano pipe array,
Obtaining a length of 30 μm of directional carbon nanotube array, array density is 2 × 109cm-2。
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to the disk of diameter 3cm, selects 3 layers of carbon nanometer
Pipe array/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes the dipping that concentration is 0.3mg/ml
Solution, immerses above-mentioned carbon nano pipe array/graphene paper composite sample disk vacuum impregnation in impregnation liquid and inserts after 28 hours
Vacuum drying oven carries out normal temperature drying 24 hours, the carbon nano pipe array/graphene paper/mesophase pitch obtained after being completed by dipping
Composite sample disk is inserted in mould, carries out hot-forming with 1500 DEG C and 7MPa pressure in argon gas atmosphere, and pressurize 0.8
Obtaining graphite heat-conducting fin after hour, test is 703.9W/ (m K) along in-plane thermal conductivity, and through-thickness thermal conductivity is
39.2W/(m·K)。
Embodiment 5
1) 150mg graphene oxide powder is joined deionized water carries out ultrasonic disperse, surpass with the power room temperature of 260W
Sound 2 hours.Use vacuum filter membrane that graphene oxide dispersion carries out sucking filtration, separate Graphene filter cake and vacuum filter membrane, will filter
Cake is inserted vacuum drying oven and is carried out normal temperature drying 18 hours, obtains the graphene oxide paper that thickness is 0.2mm.By graphite oxide
Alkene paper immerses in ethyl orthosilicate solvent and carries out vacuum impregnation 24 hours, inserts blast drier afterwards and carries out 80 DEG C to be dried 30 little
Time.
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.02g/ml, graphene oxide paper is placed in
The flat-temperature zone of vacuum tube furnace, be passed through after being evacuated to 8Pa argon as protection gas, programme-control heat up, with 13 DEG C/min
At the uniform velocity it is warming up to 740 DEG C, after reaching design temperature, applies injector for medical purpose by complex catalyst precursor under the effect of delicate flow pump
Liquid at the uniform velocity pushes with 0.2ml/min in vacuum tube furnace and is stably incubated 15 minutes, is oriented the growth of carbon nano pipe array,
Obtaining a length of 25 μm of directional carbon nanotube array, array density is 2 × 108cm-2。
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to the disk of diameter 5cm, selects 10 layers of carbon nanometer
Pipe array/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes the dipping that concentration is 0.7mg/ml
Solution, immerses above-mentioned carbon nano pipe array/graphene paper composite sample disk vacuum impregnation in impregnation liquid and inserts after 36 hours
Vacuum drying oven carries out normal temperature drying 36 hours, the carbon nano pipe array/graphene paper/mesophase pitch obtained after being completed by dipping
Composite sample disk is inserted in mould, carries out hot-forming with 1350 DEG C and 5MPa pressure, and pressurize 5 is little in argon gas atmosphere
Obtaining graphite heat-conducting fin time after, test is 657.5W/ (m K) along in-plane thermal conductivity, and through-thickness thermal conductivity is
21.8W/(m·K)。
Embodiment 6
1) 200mg graphene oxide powder is joined deionized water carries out ultrasonic disperse, surpass with the power room temperature of 200W
Sound 2 hours.Use vacuum filter membrane that graphene oxide dispersion carries out sucking filtration, separate Graphene filter cake and vacuum filter membrane, will filter
Cake is inserted vacuum drying oven and is carried out normal temperature drying 22 hours, obtains the graphene oxide paper that thickness is 0.3mm.By graphite oxide
Alkene paper immerses in ethyl orthosilicate solvent and carries out vacuum impregnation 19 hours, inserts blast drier afterwards and carries out 80 DEG C to be dried 33 little
Time.
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.04g/ml, graphene oxide paper is placed in
The flat-temperature zone of vacuum tube furnace, be passed through after being evacuated to 5Pa argon as protection gas, programme-control heat up, with 10 DEG C/min
At the uniform velocity it is warming up to 700 DEG C, after reaching design temperature, applies injector for medical purpose by complex catalyst precursor under the effect of delicate flow pump
Liquid at the uniform velocity pushes with 0.5ml/min in vacuum tube furnace and is stably incubated 80 minutes, is oriented the growth of carbon nano pipe array,
Obtaining a length of 75 μm of directional carbon nanotube array, array density is 2.7 × 108cm-2。
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to the disk of diameter 3cm, selects 3 layers of carbon nanometer
Pipe array/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes the dipping that concentration is 0.5mg/ml
Solution, immerses above-mentioned carbon nano pipe array/graphene paper composite sample disk vacuum impregnation in impregnation liquid and inserts after 24 hours
Vacuum drying oven carries out normal temperature drying 24 hours, the carbon nano pipe array/graphene paper/mesophase pitch obtained after being completed by dipping
Composite sample disk is inserted in mould, carries out hot-forming with 1000 DEG C and 15MPa pressure in argon gas atmosphere, and pressurize 1
Obtaining graphite heat-conducting fin after hour, test is 510.9W/ (m K) along in-plane thermal conductivity, and through-thickness thermal conductivity is
20.7W/(m·K)。
Embodiment 7
1) 100mg graphene oxide powder is joined deionized water carries out ultrasonic disperse, surpass with the power room temperature of 200W
Sound 1.5 hours.Use vacuum filter membrane that graphene oxide dispersion carries out sucking filtration, separate Graphene filter cake and vacuum filter membrane, will
Filter cake is inserted vacuum drying oven and is carried out normal temperature drying 21 hours, obtains the graphene oxide paper that thickness is 0.1mm.Stone will be aoxidized
Ink alkene paper immerses in ethyl orthosilicate solvent and carries out vacuum impregnation 20 hours, inserts blast drier afterwards and carries out 65 DEG C dry 28
Hour.
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.02g/ml, graphene oxide paper is placed in
The flat-temperature zone of vacuum tube furnace, be passed through after being evacuated to 5Pa argon as protection gas, programme-control heat up, with 15 DEG C/min
At the uniform velocity it is warming up to 710 DEG C, after reaching design temperature, applies injector for medical purpose by complex catalyst precursor under the effect of delicate flow pump
Liquid at the uniform velocity pushes with 0.2ml/min in vacuum tube furnace and is stably incubated 18 minutes, is oriented the growth of carbon nano pipe array,
Obtaining a length of 35 μm of directional carbon nanotube array, array density is 2.6 × 108cm-2。
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to the disk of diameter 3cm, selects 8 layers of carbon nanometer
Pipe array/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes the dipping that concentration is 0.4mg/ml
Solution, immerses above-mentioned carbon nano pipe array/graphene paper composite sample disk vacuum impregnation in impregnation liquid and inserts after 27 hours
Vacuum drying oven carries out normal temperature drying 34 hours, the carbon nano pipe array/graphene paper/mesophase pitch obtained after being completed by dipping
Composite sample disk is inserted in mould, carries out hot-forming with 1400 DEG C and 20MPa pressure in argon gas atmosphere, and pressurize 4
Obtaining graphite heat-conducting fin after hour, test is 761.7W/ (m K) along in-plane thermal conductivity, and through-thickness thermal conductivity is
34.5W/(m·K)。
Claims (10)
1. carbon nano pipe array/graphene paper heat-conductive composite material；It is characterized in that composite is by vertical orientated CNT
Array is folded compound composition with the graphene paper layer stack of horizontal alignment.
2. a preparation method for carbon nano pipe array/graphene paper heat-conductive composite material, is characterized in that step is as follows:
1) graphene oxide paper is immersed in ethyl orthosilicate solvent and carry out vacuum impregnation 12～24 hours, then inserting air blast
Drying machine；
2) ferrocene is dissolved in xylene solution and makes the complex catalyst precursor liquid that concentration is 0.02～0.05g/ml, by step 1)
The graphene oxide paper obtained is placed in the flat-temperature zone of vacuum tube furnace, is passed through argon as protection after being evacuated to below 10Pa
Gas, is warming up to 700～800 DEG C with 10～15 DEG C/min speed, pushes in vacuum tube furnace by complex catalyst precursor liquid, carry out
The growth of directional carbon nanotube array；
3) carbon nano pipe array of acquisition/graphene paper composite sample is cut to disk, selects 2～10 layers of carbon nano-pipe array
Row/graphene paper composite sample disk is standby；Mesophase pitch is dissolved in dimethylbenzene, makes dipping solution, by standby carbon
Nano-tube array/graphene paper composite sample disk immerses in impregnation liquid vacuum impregnation 24～inserts vacuum drying after 48 hours
Case carries out normal temperature drying 24～36 hours；Carbon nano pipe array/graphene paper/the mesophase pitch obtained after being completed by dipping is multiple
Close sample disk and insert in mould, carry out hot-forming with 1000～1500 DEG C and 5～20MPa pressure in argon gas atmosphere,
And pressurize 0.5～5 hours；Obtain carbon nano pipe array/graphene paper heat-conductive composite material.
3. method as claimed in claim 2, is characterized in that described step 1) drying condition be 60～80 DEG C to be dried 24～36 little
Time.
4. method as claimed in claim 2, is characterized in that described step 2) complex catalyst precursor liquid pushes away with 0.2～0.6ml/min speed
Enter in vacuum tube furnace and be stably incubated 5～80 minutes.
5. method as claimed in claim 2, is characterized in that described step 2) it is characterized in that the growth of directional carbon nanotube array is long
Degree is 20～80 μm, and array density is 2 × 108～2 × 109cm-2.
6. method as claimed in claim 2, is characterized in that described step 3) disk diameter 3～5cm.
7. method as claimed in claim 2, is characterized in that described step 3) dipping solution mesophase pitch is dissolved in xylene concentration
It is 0.3～0.7mg/ml.
8. method as claimed in claim 2, is characterized in that graphene oxide paper preparation method is: added by graphene oxide powder
In deionized water, the power room temperature with 200～300W carries out ultrasonic disperse in ultrasonic 0.5～2 hour；Use vacuum filter membrane pair
Graphene oxide dispersion carries out sucking filtration, separates Graphene filter cake and vacuum filter membrane, filter cake is inserted vacuum drying oven and carries out often
Temperature is dried 18～24 hours, obtains the graphene oxide paper that thickness is 0.1～0.3mm.
9. method as claimed in claim 8, is characterized in that described vacuum filter sizes is 0.2～1 μm.
10. method as claimed in claim 8, is characterized in that vacuum filtration with vacuum-impregnated vacuum degree condition is: gas in instrument
Pressure≤20Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610322164.5A CN106010469A (en) | 2016-05-16 | 2016-05-16 | Carbon nanotube array/graphene paper heat-conducting composite material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610322164.5A CN106010469A (en) | 2016-05-16 | 2016-05-16 | Carbon nanotube array/graphene paper heat-conducting composite material and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106505200A (en) * | 2016-12-27 | 2017-03-15 | 电子科技大学 | Carbon nano tube/graphene/silicon composite lithium ion battery negative material and preparation method thereof |
| CN106543979A (en) * | 2016-10-26 | 2017-03-29 | 天津大学 | The preparation method of graphite/carbon nanotube fibers beam/Graphene heat conduction laminated film |
| CN106706166A (en) * | 2016-11-14 | 2017-05-24 | 北京临近空间飞行器***工程研究所 | Ceramic wall surface composite plug type heat flux sensor applicable to high-enthalpy, medium and low heat flux environment |
| CN109246977A (en) * | 2018-08-01 | 2019-01-18 | 天津大学 | A kind of preparation method of high thermal conductivity graphite composite material |
| CN109554168A (en) * | 2017-09-22 | 2019-04-02 | 天津大学 | Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof |
| CN110342497A (en) * | 2019-07-05 | 2019-10-18 | 上海大学 | Vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof |
| CN110423432A (en) * | 2019-01-14 | 2019-11-08 | 上海大学 | A kind of vertically-oriented carbon nano pipe array and graphene epoxy resin composite film material and preparation method thereof |
| CN110776319A (en) * | 2018-07-31 | 2020-02-11 | 天津大学 | All-carbon heat-conducting composite material and preparation method thereof |
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| CN106543979A (en) * | 2016-10-26 | 2017-03-29 | 天津大学 | The preparation method of graphite/carbon nanotube fibers beam/Graphene heat conduction laminated film |
| CN106543979B (en) * | 2016-10-26 | 2019-10-22 | 天津大学 | Graphite/carbon nanotube fibers beam/graphene thermally conductive laminated film preparation method |
| CN106706166A (en) * | 2016-11-14 | 2017-05-24 | 北京临近空间飞行器***工程研究所 | Ceramic wall surface composite plug type heat flux sensor applicable to high-enthalpy, medium and low heat flux environment |
| CN106706166B (en) * | 2016-11-14 | 2019-04-30 | 北京临近空间飞行器***工程研究所 | The compound plug heat flow transducer of the ceramic wall surface of low-heat stream environment suitable for high enthalpy |
| CN106505200A (en) * | 2016-12-27 | 2017-03-15 | 电子科技大学 | Carbon nano tube/graphene/silicon composite lithium ion battery negative material and preparation method thereof |
| CN106505200B (en) * | 2016-12-27 | 2019-12-10 | 电子科技大学 | carbon nanotube/graphene/silicon composite lithium battery cathode material and preparation method thereof |
| CN109554168A (en) * | 2017-09-22 | 2019-04-02 | 天津大学 | Carbon nano pipe array/graphene heat-conductive composite material and preparation method thereof |
| CN110776319A (en) * | 2018-07-31 | 2020-02-11 | 天津大学 | All-carbon heat-conducting composite material and preparation method thereof |
| CN109246977A (en) * | 2018-08-01 | 2019-01-18 | 天津大学 | A kind of preparation method of high thermal conductivity graphite composite material |
| CN110423432A (en) * | 2019-01-14 | 2019-11-08 | 上海大学 | A kind of vertically-oriented carbon nano pipe array and graphene epoxy resin composite film material and preparation method thereof |
| CN110342497A (en) * | 2019-07-05 | 2019-10-18 | 上海大学 | Vertical orientation carbon nano pipe array and Graphene composite thin film material and preparation method thereof |
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