CN108251076A - Carbon nanotube-graphene composite radiating film, preparation method and application - Google Patents
Carbon nanotube-graphene composite radiating film, preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of carbon nanotube graphene composite radiating film, preparation method and applications.The preparation method includes：Graphene oxide dispersion with the carbon nano tube dispersion liquid being acidified is uniformly mixed, forms carbon nanotube graphene oxide mixed dispersion liquid；Vacuum filtration processing is carried out to the carbon nanotube graphene oxide mixed dispersion liquid, forms carbon nanotube graphene oxide composite membrane；High temperature thermal reduction processing is carried out to the carbon nanotube graphene oxide composite membrane, forms carbon nanotube graphene composite radiating film.The carbon nanotube graphene composite radiating film of the present invention has many advantages, such as that compound with regular structure does not lose powder, oxygen content is low, favorable orientation, the closely knit and thermal conductivity of interlayer accumulation are high in face, preparation method is simple, condition is easily-controllable, at low cost, has wide application prospect in fields such as heat dissipation from microelectronic devices.
Description
Technical field
Present invention relates particularly to a kind of carbon nanotube-graphene composite radiating film, preparation method and applications, belong to nanometer
Field of material technology.
Background technology
In recent years, with the continuous development of microelectric technique and progress, computer/mobile phone terminal equipment (such as：Tablet electricity
Brain, mobile phone etc.) integrated level, packaging density and the working frequency of equipment chips improve rapidly, make the fast of heat flow density in chip
Speed increases, and causes chip temperature excessively high, so as to seriously affect its working efficiency and system stability.In order to ensure consumer electronics
Reliability and its service life, need thermal conductivity higher, density smaller, more heat safe novel heat-conducting heat sink material.Tradition
Heat sink material be mainly metal material (such as silver, copper), but the density of these materials is larger, coefficient of thermal expansion is high, thermal conductivity
Rate is relatively low (400W/m K or so).Meet the needs of development of modern scientific technology therefore, it is necessary to develop new highly heat-conductive material.It grinds
Study carefully show carbon material have high thermal conductivity (such as：In single-layer graphene face thermal conductivity be 1500~5300W/m K, carbon nanometer
Pipe thermal conductivity is 3000~3500W/m K), excellent mechanical performance, the advantages that low-density and coefficient of thermal expansion are small, one can be used as
The novel highly heat-conductive material of kind.
At present, there are two types of the conduction graphite films sold on the market：One kind is flexible graphite film, has centainly flexible
Property, thermal conductivity is about 200~500W/mK；Another kind be polyimides cracking graphite film, be by by polyimide film in height
The lower cracking of temperature obtains, the higher reachable 1000W/mK of thermal conductivity, still, molecular structure and composition requirement to polyimide film
It is higher, and polyimide film cracking needs longer heating carbonisation and the at high temperature graphitization of (about 3000 DEG C)
Journey, the numerous and diverse harshness of process, cost are higher.
The heat conductivility of graphene film is suitable with polyimides cracking graphite film, but advantage of lower cost.The prior art
In, graphene film can be made by following two methods：A kind of prepared by directly filtering the method for graphene, this side
It is more difficult formation that method, which prepares graphene film, and main cause is that dispersed graphite alkene can generate reunion in the process, cannot be stablized
Graphene suspension.Another method is to prepare graphene oxide film by graphene oxide suspension, using also original place
Reason prepares graphene film.Graphene oxide film prepared by this method is more regular, but is being reduced to graphene film
When be easily broken, lose powder scaling-off, poor orientation in face, interlayer accumulation leakiness (interlayer has " air-pocket ", i.e. airbag), lead
Cause film heat dissipation performance poor.
Invention content
It is a primary object of the present invention to provide a kind of carbon nanotube-graphene composite radiating film, preparation method with answering
With to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of preparation method of carbon nanotube-graphene composite radiating film, including：
(1) graphene oxide dispersion is provided；
(2) carbon nano tube dispersion liquid of acidification is provided；
(3) graphene oxide dispersion is uniformly mixed with the carbon nano tube dispersion liquid being acidified, formation carbon nanotube-
Graphene oxide mixed dispersion liquid；
(4) processing is carried out and (be preferably filtered by vacuum) to the carbon nanotube-graphene oxide mixed dispersion liquid, forms carbon
Nanotube-graphene oxide composite membrane；
(5) high temperature thermal reduction processing is carried out to the carbon nanotube-graphene oxide composite membrane, forms the carbon nanometer
Pipe-graphene composite radiating film.
Further, abovementioned steps (1) can include：Graphene oxide is dispersed in water, forms the oxidation
Graphene dispersing solution.
Preferably, a concentration of 1~5mg/ml of the graphene oxide dispersion.
Further, abovementioned steps (2) can include：The carbon nanotube of acidification is dispersed in water, described in formation
The carbon nano tube dispersion liquid of acidification.
Preferably, a concentration of 1~5mg/ml of the carbon nano tube dispersion liquid of the acidification.
Further, abovementioned steps (4) can include：The carbon nanotube-graphene oxide mixed dispersion liquid is carried out
Vacuum filtration processing, forms carbon nanotube-graphene oxide composite membrane.
Further, step (4) can also include：After the completion of vacuum filtration processing, by filter cake and filter membrane point
From, and processing is dried to filtering, obtain carbon nanotube-graphene oxide composite membrane of self-supporting.
Wherein, mode filter cake detached with filter membrane can there are many, be that industry is known, such as can pass through hand
The mode of work stripping detaches filter cake with filter membrane.
In some embodiments, the miillpore filter that the vacuum filtration processing uses includes filter opening aperture for 0.22 μm
Nylon 6,6 filter membrane, the cellulose mixture filter membrane that filter opening aperture is 0.45 μm or nylon 6,6 filter membrane that filter opening aperture is 0.45 μm
Deng, and it is without being limited thereto.
In some preferred embodiments, the processing of high temperature thermal reduction described in abovementioned steps (5) includes：By the carbon nanometer
Pipe-graphene oxide composite membrane is placed in vacuum environment or protective atmosphere, and 150 are warming up to the heating rate of 1~5 DEG C/min
~400 DEG C, stop heating up and keep the temperature 1~2h, continue to rise to 500~1000 DEG C simultaneously with the heating rate of 5~10 DEG C/min later
1~2h is kept the temperature, room temperature is cooled to, obtains the carbon nanotube-graphene composite radiating film.
Further, aforementioned protective atmosphere include argon gas, hydrogen and nitrogen atmosphere in any one or it is two or more
Combination, it is and without being limited thereto.
Further, foregoing carbon nanotubes-graphene composite radiating film includes 0~50wt% carbon nanotube (carbon nanotubes
Content is not 0, preferably in more than 5Wt%).The content of carbon nanotube can be in foregoing carbon nanotubes-graphene composite radiating film
It is adjusted by the usage ratio for controlling carbon nano tube dispersion liquid of the graphene oxide dispersion with being acidified.
In some more specifically case study on implementation, the preparation method of the carbon nanotube-graphene composite radiating film can
To include step in detail below：
(1) at room temperature, it adds graphene oxide into deionized water, by stirring, ultrasound, obtains graphene oxide
The dispersion liquid of solution, a concentration of 1~5mg/ml of the graphene oxide dispersion；
(2) at room temperature, the carbon nanotube of acidification is added in deionized water, by stirring, being ultrasonically treated, obtained dense
Spend the carbon nano tube dispersion liquid for the finely dispersed acidifications of 1~5mg/ml；
(3) carbon nano tube dispersion liquid of acidification that the graphene oxide dispersion and step (2) obtained step (1) obtains
It is mixed by a certain percentage, by stirring, being ultrasonically treated, obtains finely dispersed graphene-carbon nano tube mixed solution；
(4) mixed solution that step (3) obtains is filtered by vacuum using miillpore filter, obtained filter cake is together with filter membrane
After drying, filter cake from filter membrane is removed and obtains carbon nanotube-graphene oxide composite membrane；
(5) carbon nanotube-graphene composite film is obtained using the method that high temperature heat-treats.
Further, the sonication treatment time described in abovementioned steps (1) can be 1~3 hour.
Further, the sonication treatment time described in abovementioned steps (2) can be 1~3 hour.
Further, the sonification power described in abovementioned steps (3) can be 500w, and the time can be 0.5h.
Further, the thermal reduction of high temperature described in abovementioned steps (5) can include：Carbon nanotube-graphene oxide is thin
Film is sandwiched between two quartz plates, is placed in tube furnace, in vacuum environment or any one in argon gas, nitrogen and hydrogen
In atmosphere, with the heating rate of 1~5 DEG C/min, 150~400 DEG C are warming up to, stops heating, 1~2h is kept the temperature, continues later with 5
The heating rate of~10 DEG C/min rises to 500~1000 DEG C, handles 1~2h, is cooled to room temperature to get carbon nanotube-graphene
Composite radiating film.
Further, aforementioned oxidation graphene and the carbon nanotube of acidification can be obtained from commercial channel, can also be certainly
System.For example, the preparation method of the carbon nanotube of the acidification can include：Carbon nanotube is acidified by nitric acid, sulfuric acid
Processing forms the carbon nanotube of the acidification.
Further, acidic functionality is distributed in the carbon nano tube surface of aforementioned acidification, and the acidic functionality includes carboxylic
Base.
Preferably, the content of carboxyl is 0.73wt%~3.86wt% in the carbon nanotube of the acidification.
Preferably, the outer diameter of the carbon nanotube of the acidification is 30~50nm, and length is 10~40 μm.
In one more specific embodiment, carboxyl-content is 0.73wt% in the carbon nanotube of aforementioned acidification, and outer diameter is
30~50nm, length are 20 μm, and the carbon nanotube of the acidification is in the case of without additionally adding surfactant, you can in water
It is middle to form uniform and stable dispersion liquid.
The embodiment of the present invention additionally provides the carbon nanotube-graphene composite radiating film prepared by aforementioned any method.
The carbon nanotube-graphene composite radiating film is with oxygen content is low, interlayer accumulation is closely knit, favorable orientation, film are regular not in face
The features such as picking and thermal conductivity are high.
Further, the carbon nanotube in the carbon nanotube-graphene composite radiating film is sandwiched to be formed by graphene film
Sandwich structure, make the carbon nanotube-graphene composite radiating film entirety microscopic cross present layer upon layer " concrete is seemingly
Brick structure ", carbon nanotube be similar to reinforcing bar, and graphene be similar to brick.Also, as content of carbon nanotubes increases, carbon
The alleviation phenomenon of the interlayer " air-pocket " of nanotube-graphene alkene composite radiating film becomes apparent.
The embodiment of the present invention additionally provides the purposes of foregoing carbon nanotubes-graphene composite radiating film, such as is dissipated preparing
Purposes in thermal conductivity hot material, heat dissipation heat-transfer device or electronic device.
The carbon nanotube of acidification is introduced between graphene layer by ultrasonic disperse, suction filtration thin film-forming method and obtains carbon by the present invention
Nanotube-graphene oxide film, and reduction is heat-treated in limited space, due between carbon nanotube and graphene compared with
Strong interfacial interaction power, maintains the ordered structure of graphene composite film, effectively overcomes graphene oxide film system
Standby redox graphene heat dissipation film is broken, poor orientation, interlayer accumulate uncompacted technical problem in face.
It is summarized, compared with prior art, carbon nanotube provided by the invention-graphene composite radiating film has oxygen content
Low, compound with regular structure does not lose powder and slag, face in favorable orientation, interlayer accumulation it is closely knit, thermal conductivity is high the advantages that and preparation method it is simple,
Condition is easily-controllable, energy conservation and environmental protection, at low cost, has wide application prospect in heat dissipation from microelectronic devices field.
Description of the drawings
Fig. 1 a- Fig. 1 b are carbon nanotube made from the embodiment of the present invention 1-graphene oxide composite membrane and carbon nanotube-stone
The optical photograph of black alkene composite radiating film；
Fig. 2 is that carbon nanotube made from the embodiment of the present invention 1-graphene oxide composite membrane and carbon nanotube-graphene are multiple
Close the IR collection of illustrative plates of heat dissipation film；
Fig. 3 is that carbon nanotube made from the embodiment of the present invention 1-graphene oxide composite membrane and carbon nanotube-graphene are multiple
Close the XRD spectrum of heat dissipation film；
Fig. 4 a figures-4b is carbon nanotube made from the embodiment of the present invention 1-graphene oxide composite membrane and carbon nanotube-stone
The SEM figures of black alkene composite radiating film；
Fig. 4 c are that the SEM of carbon nanotube made from comparative example 1 of the present invention-graphene composite radiating film schemes.
Specific embodiment
In view of deficiency of the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution.It is further to works such as technical scheme of the present invention, its implementation process and principles below in conjunction with the accompanying drawings and embodiments
Explanation.
The carbon nanotube of graphene oxide and acidification in following examples is that commercial channel obtains.
The scanning electron microscope (SEM) used in following examples, model S4800, Japanese HITACHI companies production.
The powder x-ray diffraction (XRD) (CuK α, λ=0.15406nm) used in following examples, model is
D8Advance, German BrukerAXS companies production.
Thermal diffusion coefficient (α, mm in following examples in thin film planar2/ s) it is dodged using the LFA447 of Nai Chi companies of Germany
Light method heat transfer analysis instrument is tested, density (ρ, g/cm3) obtained by drainage, specific heat capacity (Cp, J/Kg DEG C) value of sample is reason
713J/Kg DEG C of the carbon material thermal capacitance of opinion, thermal conductivity (λ, W/m K) are calculated by the following formula：λ=α × ρ × Cp.
Certainly, according to this specification content, those skilled in the art can also be easy to think of using it is other properly come
Reagent, equipment in the reagent in source and other appropriate sizes, the equipment replacement following examples of model etc..
Embodiment 1
(1) under room temperature, 500mg graphene oxides are added in 100mL deionized waters and are stirred, surpassed by glass bar
Sonication 3h is uniformly mixed, and the graphene oxide dispersion of a concentration of 5mg/mL is made；
(2) under room temperature, by the carbon nanotube of 100mg acidifications, (wherein carboxyl-content is about 0.73wt%, outer diameter 30
~50nm, about 20 μm of average length) it is added in 100mL deionized waters and is stirred by glass bar, is ultrasonically treated 3h and is uniformly mixed,
The carbon nano tube dispersion liquid of the acidification of a concentration of 1mg/mL is made；
(3) by the carbon nanometer of 15mL acidifications made from 17mL graphene oxide dispersions made from step (1) and step (2)
Pipe dispersion liquid by stir, be ultrasonically treated (ultrasonic power 500W, time 0.5h) be uniformly mixed, use later filter opening aperture for
The nylon66 fiber miillpore filter vacuum filtration of 0.45um, after obtained filter cake is together with 60 DEG C of dryings for 24 hours of filter membrane, then by filter cake from filter membrane
Upper stripping obtains carbon nanotube-graphene oxide composite membrane of the carbon nanotube containing 15wt%；
(4) carbon nanotube made from step (3)-graphene oxide composite membrane is subjected to high temperature thermal reduction, specifically included：It will
Carbon nanotube-graphene oxide composite membrane is sandwiched between two quartz plates, is placed in tube furnace, under hydrogen shield, with 2 DEG C/
The heating rate of min is warming up to 300 DEG C, keeps the temperature 2h, continues to rise to 1000 DEG C with the heating rate of 5 DEG C/min later, heat preservation
1h is cooled to room temperature to get carbon nanotube-graphene composite radiating film.
It, can be with referring to the optical photograph that Fig. 1 a- Fig. 1 b are carbon nanotube made from the present embodiment-graphene composite radiating film
To see, carbon nanotube-graphene composite thin film after high temperature heat-treats is become the grey of metallic luster by black, and
And integrality is maintained, smooth surface and with certain flexibility.
It is carbon nanotube-graphene oxide composite membrane made from the present embodiment 1 (lines a) and carbon nanotube-stone referring to Fig. 2
Black alkene composite radiating film (the IR collection of illustrative plates of lines b), it can be seen that after high temperature heat-treats, medium wavelength 3650cm-1(O-H)、
1087cm-1(C-O)、1400cm-1(C-O-H) and 1790cm-1(C=O) peak of oxygen-containing functional group disappears, and the corresponding peaks of C=C
1600cm-1It still has, shows that high temperature thermal reduction processing can effectively remove the oxygen-containing functional group in raw material or even can also repair
SP2The C=C keys of the graphite flake layer of hydridization.
It is the carbon nanotube obtained of this implementation 1-graphene oxide composite membrane (lines a) and carbon nanotube-stone referring to Fig. 3
The black alkene composite radiating film (XRD diagram of lines b), it can be seen that after high temperature heat-treats, diffraction maximum occur in 2 θ=10.6 °, height
There is diffraction maximum at 2 θ=26.2 ° after warm reduction treatment, show that the interlamellar spacing of composite radiating film after heat-treating becomes smaller, develop into
Similar to the structure of graphite.
It is carbon nanotube-graphene oxide composite membrane and carbon nanotube-stone made from the present embodiment 1 referring to Fig. 4 a- Fig. 4 b
The SEM figures of black alkene composite radiating film, without apparent between high temperature thermal reduction treated carbon nanotube-graphene composite radiating film layer
" airbag " phenomenon, favorable orientation in face, accumulation are closely knit.
After tested, the thermal conductivity of carbon nanotube-graphene composite film obtained is 1388W/m K in the embodiment of the present invention 1.
Embodiment 2
(1) under room temperature, 500mg graphene oxides are added in 250mL deionized waters and are stirred, surpassed by glass bar
Sonication 1h is uniformly mixed, and the graphene oxide dispersion of a concentration of 2mg/mL is made；
(2) under room temperature, by the carbon nanotube of 100mg acidifications, (wherein carboxyl-content is about 3.86wt%, outer diameter 10
~20nm, about 10~30 μm of average length) it is added in 50mL deionized waters and is stirred by glass bar, is ultrasonically treated 1h mixing
It is even, the carbon nano tube dispersion liquid of the acidification of a concentration of 2mg/mL is made；
(3) by the carbon of 2.5mL acidifications made from 47.5mL graphene oxide dispersions made from step (1) and step (2)
Nanotube dispersion liquid is uniformly mixed by stirring, being ultrasonically treated (ultrasonic power 500W, time 0.5h), later using filter opening aperture
Nylon66 fiber miillpore filter for 0.22um is filtered by vacuum, after obtained filter cake is together with 60 DEG C of dryings for 24 hours of filter membrane, then by filter cake from filter
Stripping obtains carbon nanotube-graphene oxide composite membrane of the carbon nanotube containing 5wt% on film；
(4) carbon nanotube made from step (3)-graphene oxide composite membrane is subjected to high temperature thermal reduction, specifically included：It will
Carbon nanotube-graphene oxide composite membrane is sandwiched between two quartz plates, is placed in tube furnace, under protection of argon gas, with 1 DEG C/
The heating rate of min is warming up to 150 DEG C, keeps the temperature 1h, continues to rise to 500 DEG C with the heating rate of 8 DEG C/min later, keeps the temperature 1h,
It is cooled to room temperature the carbon nanotube to get the carbon nanotube containing 5wt%-graphene composite radiating film.
After tested, the thermal conductivity of carbon nanotube-graphene composite film obtained is 190W/m K in the embodiment of the present invention 2.
Embodiment 3
(1) under room temperature, 500mg graphene oxides are added in 250mL deionized waters and are stirred, surpassed by glass bar
Sonication 2h is uniformly mixed, and the graphene oxide dispersion of a concentration of 2mg/mL is made；
(2) under room temperature, by the carbon nanotube of 100mg acidifications, (wherein carboxyl-content is about 2.0wt%, outer diameter 30
~50nm, about 20 μm of average length) it is added in 100mL deionized waters and is stirred by glass bar, is ultrasonically treated 2h and is uniformly mixed,
The carbon nano tube dispersion liquid of the acidification of a concentration of 1mg/mL is made；
(3) by the carbon nanometer of 50mL acidifications made from 25mL graphene oxide dispersions made from step (1) and step (2)
Pipe dispersion liquid by stir, be ultrasonically treated (ultrasonic power 500W, time 0.5h) be uniformly mixed, use later filter opening aperture for
The nylon66 fiber miillpore filter vacuum filtration of 0.45um, after obtained filter cake is together with 60 DEG C of dryings for 24 hours of filter membrane, then by filter cake from filter membrane
Upper stripping obtains carbon nanotube-graphene oxide composite membrane of the carbon nanotube containing 50wt%；
(4) carbon nanotube made from step (3)-graphene oxide composite membrane is subjected to high temperature thermal reduction, specifically included：It will
Carbon nanotube-graphene oxide composite membrane is sandwiched between two quartz plates, is placed in tube furnace, under vacuum, with 5 DEG C/
The heating rate of min is warming up to 400 DEG C, keeps the temperature 1h, continues to rise to 1000 DEG C with the heating rate of 10 DEG C/min later, heat preservation
2h is cooled to room temperature the carbon nanotube to get the carbon nanotube containing 50wt%-graphene composite radiating film.
After tested, the thermal conductivity of carbon nanotube-graphene composite film obtained is 780W/m K in the embodiment of the present invention.
Embodiment 4
(1) under room temperature, 500mg graphene oxides are added in 500mL deionized waters and are stirred, surpassed by glass bar
Sonication 2h is uniformly mixed, and the graphene oxide dispersion of a concentration of 1mg/mL is made；
(2) under room temperature, by the carbon nanotube of 100mg acidifications, (wherein carboxyl-content is about 0.73wt%, outer diameter 30
~50nm, about 20 μm of average length) it is added in 50mL deionized waters and is stirred by glass bar, is ultrasonically treated 1h and is uniformly mixed,
The carbon nano tube dispersion liquid of the acidification of a concentration of 2mg/mL is made；
(3) 75mL graphene oxide dispersions made from step (1) and the carbon being acidified of 2.5mL made from step (2) are received
Mitron dispersion liquid by stir, be ultrasonically treated (ultrasonic power 500W, time 0.5h) be uniformly mixed, use later filter opening aperture for
The nylon66 fiber miillpore filter vacuum filtration of 0.45um, after obtained filter cake is together with 60 DEG C of dryings for 24 hours of filter membrane, then by filter cake from filter membrane
Upper stripping obtains carbon nanotube-graphene oxide composite membrane of the carbon nanotube containing 25wt%；
(4) carbon nanotube made from step (3)-graphene oxide composite membrane is subjected to high temperature thermal reduction, specifically included：It will
Carbon nanotube-graphene oxide composite membrane is sandwiched between two quartz plates, is placed in tube furnace, under nitrogen protection, with 2 DEG C/
The heating rate of min is warming up to 400 DEG C, keeps the temperature 1h, continues to rise to 800 DEG C with the heating rate of 6 DEG C/min later, keeps the temperature 1h,
It is cooled to room temperature the carbon nanotube to get the carbon nanotube containing 25wt%-graphene composite radiating film.
After tested, the thermal conductivity of carbon nanotube-graphene composite film obtained is 1100W/m K in the embodiment of the present invention.
Comparative example 1
(1) under room temperature, 500mg graphene oxides are added in 250mL deionized waters and are stirred, surpassed by glass bar
Sonication 2h is uniformly mixed, and the graphene oxide dispersion of a concentration of 2mg/mL is made；
(2) under room temperature, the 100mg carbon nanotubes (same as Example 1) being acidified are added to 50mL deionized waters
In stirred by glass bar, be ultrasonically treated 2h and be uniformly mixed, the carbon nano tube dispersion liquid of the acidification of a concentration of 2mg/ml is made；
(3) 100mL graphene oxide dispersions made from step (1) are ultrasonically treated (ultrasonic power 500W, time
0.5h), filter opening aperture is used to be filtered by vacuum for the nylon66 fiber miillpore filter of 0.45um later, obtained filter cake is together with 60 DEG C of filter membrane
After drying for 24 hours, then filter cake from filter membrane is removed and obtains carbon nanotube-graphene oxide composite membrane of the carbon nanotube containing 0wt%；
(4) carbon nanotube made from step (3)-graphene oxide composite membrane is subjected to high temperature thermal reduction, specifically included：It will
Carbon nanotube-graphene oxide composite membrane is sandwiched between two quartz plates, is placed in tube furnace, under hydrogen shield, with 2 DEG C/
The heating rate of min is warming up to 300 DEG C, keeps the temperature 1h, continues to rise to 1000 DEG C with the heating rate of 5 DEG C/min later, heat preservation
1h is cooled to room temperature the carbon nanotube to get the carbon nanotube containing 0wt%-graphene composite radiating film.
After tested, the thermal conductivity of carbon nanotube-graphene composite film obtained is 742W/m K in the comparative example.
Fig. 4 c are that the SEM of carbon nanotube made from the comparative example-graphene composite radiating film schemes, it can be seen that in high temperature
There is apparent " airbag " phenomenon between thermal reduction treated carbon nanotube-graphene composite radiating film layer, orientation is poor in face, heap
Product is loose.
Comparative example 2
(1) under room temperature, 500mg graphene oxides are added in 250mL deionized waters and are stirred, surpassed by glass bar
Sonication 2h is uniformly mixed, and the graphene oxide dispersion of a concentration of 2mg/mL is made；
(2) under room temperature, common carbon nanotube purchased in market 100mg and 100mg polystyrene dispersion aids are added to
It stirred in 50mL deionized waters by glass bar, be ultrasonically treated 2h and be uniformly mixed, the carbon nanotube dispersion of a concentration of 2mg/m is made
Liquid；
(3) 42.5mL graphene oxide dispersions made from step (1) and the carbon being acidified of 15mL made from step (2) are received
Mitron dispersion liquid is ultrasonically treated (ultrasonic power 500W, time 0.5h), uses filter opening aperture micro- for the nylon66 fiber of 0.22um later
Hole filter membrane vacuum filtration, after obtained filter cake is together with 60 DEG C of dryings for 24 hours of filter membrane, then filter cake from filter membrane is removed and is contained
The carbon nanotube of 15wt% carbon nanotubes-graphene oxide composite membrane；
(4) carbon nanotube made from step (3)-graphene oxide composite membrane is subjected to high temperature thermal reduction, specifically included：It will
Carbon nanotube-graphene oxide composite membrane is sandwiched between two quartz plates, is placed in tube furnace, under hydrogen shield, with 2 DEG C/
The heating rate of min is warming up to 300 DEG C, keeps the temperature 2h, continues to rise to 1000 DEG C with the heating rate of 5 DEG C/min later, heat preservation
1h is cooled to room temperature the carbon nanotube to get the carbon nanotube containing 15wt%-graphene composite radiating film.
After tested, the thermal conductivity of carbon nanotube-graphene composite film obtained is 24.2W/m K in the comparative example.
To sum up, carbon nanotube produced by the present invention-graphene composite radiating film has that oxygen content is low, compound with regular structure does not lose powder
The advantages that closely knit and thermal conductivity is high is accumulated with favorable orientation, interlayer in slag, face.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all
The equivalent change or modification made according to spirit of the invention, should be covered by the protection scope of the present invention.
Claims (11)
1. a kind of preparation method of carbon nanotube-graphene composite radiating film, it is characterised in that including：
(1) graphene oxide dispersion is provided；
(2) carbon nano tube dispersion liquid of acidification is provided；
(3) graphene oxide dispersion with the carbon nano tube dispersion liquid being acidified is uniformly mixed, forms carbon nanotube-oxidation
Graphene mixed dispersion liquid；
(4) processing is filtered to the carbon nanotube-graphene oxide mixed dispersion liquid, forms carbon nanotube-graphite oxide
Alkene composite membrane；
(5) high temperature thermal reduction processing is carried out to the carbon nanotube-graphene oxide composite membrane, forms the carbon nanotube-stone
Black alkene composite radiating film.
2. preparation method according to claim 1, which is characterized in that step (1) includes：Graphene oxide is uniformly dispersed
Yu Shuizhong forms the graphene oxide dispersion；Preferably, a concentration of 1~5mg/ml of the graphene oxide dispersion.
3. preparation method according to claim 1, which is characterized in that step (2) includes：The carbon nanotube of acidification is uniform
It is dispersed in water, forms the carbon nano tube dispersion liquid of the acidification；Preferably, the concentration of the carbon nano tube dispersion liquid of the acidification
For 1~5mg/ml；Preferably, acidic functionality is distributed in the carbon nano tube surface of the acidification, and the acidic functionality includes
Carboxyl；Preferably, the content of carboxyl is 0.73wt%~3.86wt% in the carbon nanotube of the acidification；Preferably, the acid
The outer diameter of the carbon nanotube of change is 10~50nm, and length is 10~40 μm.
4. preparation method according to claim 1, which is characterized in that step (4) includes：To the carbon nanotube-oxidation
Graphene mixed dispersion liquid carries out vacuum filtration processing, forms carbon nanotube-graphene oxide composite membrane.
5. preparation method according to claim 4, which is characterized in that step (4) further includes：In vacuum filtration processing
After the completion, filter cake with filter membrane is detached, and processing is dried to filtering, obtain carbon nanotube-graphene oxide of self-supporting
Composite membrane.
6. preparation method according to claim 4 or 5, it is characterised in that：The micropore filter that the vacuum filtration processing uses
Film includes nylon 6,6 filter membrane, the cellulose mixture filter membrane that filter opening aperture is 0.45 μm or the filter opening hole that filter opening aperture is 0.22 μm
Diameter is 0.45 μm of nylon 6,6 filter membrane.
7. preparation method according to claim 1, which is characterized in that the processing of high temperature thermal reduction described in step (5) includes：
The carbon nanotube-graphene oxide composite membrane is placed in vacuum environment or protective atmosphere, with the heating of 1~5 DEG C/min
Rate is warming up to 150~400 DEG C, stops heating up and keeps the temperature 1~2h, continues to rise to the heating rate of 5~10 DEG C/min later
500~1000 DEG C and 1~2h of heat preservation, room temperature is cooled to, obtains the carbon nanotube-graphene composite radiating film.
8. the preparation method according to claim 1 or 7, it is characterised in that：The protective atmosphere include argon gas, hydrogen and
Any one in nitrogen atmosphere or two or more combinations.
9. preparation method according to claim 1, it is characterised in that：In the carbon nanotube-graphene composite radiating film
The content of carbon nanotube is more than 0 and is less than or equal to 50wt%, preferably 5wt%~50wt%.
10. carbon nanotube-graphene composite radiating the film prepared by any one of claim 1-9 the methods.
11. carbon nanotube described in claim 10-graphene composite radiating film is in preparing, heat dissipation Heat Conduction Material, radiate heat-transfer device
Or the purposes in electronic device.
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|---|---|---|---|---|
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674315A (en) * | 2012-04-25 | 2012-09-19 | 浙江大学 | Graphene-carbon nano tube composite all-carbon ultra-light elastic aerogel and preparation method thereof |
| CN103725263A (en) * | 2013-12-17 | 2014-04-16 | 张家港康得新光电材料有限公司 | Film made from graphene-carbon nanotube composite material and preparation method of film |
| US20150285975A1 (en) * | 2014-04-03 | 2015-10-08 | Samsung Display Co., Ltd. | Window member and display device including the same |
| CN105148990A (en) * | 2015-08-05 | 2015-12-16 | 江南大学 | Preparation method and application of sulfated carbon nanotube/graphene oxide composite catalyst |
| CN105502353A (en) * | 2015-12-14 | 2016-04-20 | 湖南科技大学 | Wrapped monolayer graphene oxide/ carbon nano tube compound and preparation method thereof |
| CN105590757A (en) * | 2014-11-18 | 2016-05-18 | 中国科学院宁波材料技术与工程研究所 | Carbon nanotube/graphene composite gel and preparation method thereof |
| WO2016103784A1 (en) * | 2014-12-26 | 2016-06-30 | リンテック株式会社 | Thermally conductive adhesive sheet, production method therefor, and electronic device using same |
| CN105776185A (en) * | 2014-12-25 | 2016-07-20 | 江南石墨烯研究院 | Preparation method of graphene paper with high thermal conductivity and electrical conductivity |
| CN105948029A (en) * | 2016-05-09 | 2016-09-21 | 东华大学 | Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof |
-
2016
- 2016-12-29 CN CN201611247595.6A patent/CN108251076B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674315A (en) * | 2012-04-25 | 2012-09-19 | 浙江大学 | Graphene-carbon nano tube composite all-carbon ultra-light elastic aerogel and preparation method thereof |
| CN103725263A (en) * | 2013-12-17 | 2014-04-16 | 张家港康得新光电材料有限公司 | Film made from graphene-carbon nanotube composite material and preparation method of film |
| US20150285975A1 (en) * | 2014-04-03 | 2015-10-08 | Samsung Display Co., Ltd. | Window member and display device including the same |
| CN105590757A (en) * | 2014-11-18 | 2016-05-18 | 中国科学院宁波材料技术与工程研究所 | Carbon nanotube/graphene composite gel and preparation method thereof |
| CN105776185A (en) * | 2014-12-25 | 2016-07-20 | 江南石墨烯研究院 | Preparation method of graphene paper with high thermal conductivity and electrical conductivity |
| WO2016103784A1 (en) * | 2014-12-26 | 2016-06-30 | リンテック株式会社 | Thermally conductive adhesive sheet, production method therefor, and electronic device using same |
| CN105148990A (en) * | 2015-08-05 | 2015-12-16 | 江南大学 | Preparation method and application of sulfated carbon nanotube/graphene oxide composite catalyst |
| CN105502353A (en) * | 2015-12-14 | 2016-04-20 | 湖南科技大学 | Wrapped monolayer graphene oxide/ carbon nano tube compound and preparation method thereof |
| CN105948029A (en) * | 2016-05-09 | 2016-09-21 | 东华大学 | Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| S.ASKARI ETAL: "Rheological and thermophysical properties of ultra-stable kerosene-based Fe3O4/Graphene nanofluids for energy conservation", 《ENERGY CONVERSION AND MANAGEMENT》 * |
| 孙康宁: "《碳纳米管复合材料》", 31 December 2009, 机械工业出版社 * |
| 赵冬梅等: "石墨烯/碳纳米管复合材料的制备及应用进展", 《化学学报》 * |
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