CN109650892A - A kind of high thermal conductivity graphene film and preparation method thereof - Google Patents
A kind of high thermal conductivity graphene film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of high thermal conductivity graphene films and preparation method thereof, comprising the following steps: A) polyamic acid resin and graphene oxide solution are successively coated on substrate surface, graphene oxide composite membrane is obtained after dry；B it) will be removed on the graphene oxide compound film from substrate, obtain the compound film coiled material of continuous graphene oxide；C) the compound film coiled material of the graphene oxide is heat-treated, the graphene oxide composite membrane after being carbonized；D the graphene oxide composite membrane after carbonization) is subjected to graphitization processing, obtains high thermal conductivity graphene film.The present invention successively forms a film polyamic acid resin with graphene oxide solution, form the structure that graphene oxide membrane is superimposed with polyamide acid film two membranes, the high thermal conductivity of graphene can more fully be played, it can remove to obtain thicker graphene film simultaneously, it can satisfy the specific demand of aerospace field, while also improving the product yield of removing graphene.
Description
Technical field
The invention belongs to Heat Conduction Material technical fields more particularly to a kind of high thermal conductivity graphene film and preparation method thereof.
Background technique
Graphite is that a kind of allotrope formed by carbon due to its perfect molecular structure makes it have uniqueness
The performances such as calorifics, electricity, chemistry, can be widely applied in the industry such as electronics, heat dissipation.The plane thermal conductivity prepared at present
Solves the problems, such as the hot-spot of the small-powers chip such as mobile phone in the high thermal conductivity graphite film of 800~1500W/m.K.But with electricity
Sub- equipment performance is become better and better, and processing speed, frequency are higher and higher.Volume weight is higher and higher, and power is increasing, and electronics is set
Standby fever is increasing, and the requirement to heat dissipation is also just higher and higher.Therefore, common electrographite film is not able to satisfy very much
The demand for heat dissipation of high-end devices, urgent need find a kind of material for having more high thermal conductivity, heat dissipation.
Two of Univ Manchester UK in 2010 professors due to being successfully separated out the graphene being stabilized for the first time and
Nobel Prize in physics is obtained, the whole world has started the research boom to graphene.Graphene is as the substantially single of composition graphite
Member, has excellent heating conduction, and the theoretical thermal conductivity of single-layer graphene can achieve 5000W/m.K or more.Graphene has
The advantages such as high thermal conductivity coefficient, low-density, easy to process, therefore there is very big market potential.
The graphene oxide of pre-treatment is coated on drying removing, carbon in PET film by Chinese patent CN105510794A
Change, be graphitized obtained graphene film.Chinese patent CN105502368A graphite after knifing on matrix by graphene oxide
Change processing rolling and remove matrix and obtains graphene film.Find that current technology is deposited by comparative analysis and practical production experience
In following problems: it is larger that graphene is coated on difficulty when removing again on matrix, and product yield is low, inefficiency；Prepare the ruler of film
Very little, technique is difficult to large-scale production and application；It is unable to the film of continuous production web-like, production efficiency is low.
Summary of the invention
Preparation method the purpose of the present invention is to provide a kind of high thermal conductivity graphene film and preparation method thereof, in the present invention
Simple process, high production efficiency, size is big, and heating conduction is excellent, the high thermal conductivity that can be mass-produced graphene film.
The present invention provides a kind of preparation method of high thermal conductivity graphene film, comprising the following steps:
A polyamic acid resin and graphene oxide solution successively) are coated on substrate surface, obtain graphite oxide after dry
Alkene composite membrane；
B it) will be removed on the graphene oxide compound film from substrate, obtain the compound film coiled material of continuous graphene oxide；
C) the compound film coiled material of the graphene oxide is heat-treated, the graphene oxide composite membrane after being carbonized；
D the graphene oxide composite membrane after carbonization) is subjected to graphitization processing, obtains high thermal conductivity graphene film.
Preferably, the polyamic acid resin carries out polycondensation reaction by dianhydride and diamines in intensive polar solvent and is prepared into
It arrives；
The dianhydride is one or more of biphenyltetracarboxylic dianhydride, pyromellitic acid dianhydride, benzophenone tetracid dianhydride；
The diamines is one or more of diaminodiphenyl ether, p-phenylenediamine, diamino benzophenone.
Preferably, the solid content of the polyamic acid resin is 10~25wt%.
Preferably, the graphene oxide solution is the organic surface active agent solution of graphene oxide powder；
The organic surface active agent is that polyvinylpyrrolidone, polyvinyl alcohol, lauryl sodium sulfate and carboxymethyl are fine
Tie up one or more of element.
Preferably, in the graphene oxide solution, the mass concentration of graphene oxide is 3~10wt%, described organic
The concentration of surfactant is 0.01~0.05wt%；
The viscosity of the graphene oxide solution is 5000~30000cPs.
Preferably, the coating thickness of the polyamic acid resin is 80~400 μm；
The coating thickness of the graphene oxide solution is 200~1000 μm.
Preferably, the step A) in dry temperature be 70~200 DEG C；
The step A) in dry time be 15~30min.
Preferably, the step C) in be heat-treated temperature be 700~1500 DEG C；
The step C) in be heat-treated time be 4~10 hours.
Preferably, the step D) in graphitization processing temperature be 2700~3000 DEG C；
The step D) in graphitization processing time be 3~8 hours.
The present invention provides a kind of high thermal conductivity graphene film, according to preparation method system described in any one of claim 1 to 9
,
The high thermal conductivity graphene film with a thickness of 50~200 μm.
The present invention provides a kind of preparation methods of high thermal conductivity graphene film, comprising the following steps: A) by polyamic acid tree
Rouge and graphene oxide solution are successively coated on substrate surface, obtain graphene oxide composite membrane after dry；B) by the oxidation
Graphene composite film is removed from substrate, obtains the compound film coiled material of continuous graphene oxide；C) graphene oxide is answered
It closes film coiled material to be heat-treated, the graphene oxide composite membrane after being carbonized；D) by the graphene oxide composite membrane after carbonization
Graphitization processing is carried out, high thermal conductivity graphene film is obtained.The present invention by polyamic acid resin and graphene oxide solution successively at
Film, forms the structure that graphene oxide membrane is superimposed with polyamide acid film two membranes, and the height that can more fully play graphene is led
Hot property, while can remove to obtain thicker graphene film, it can satisfy the specific demand of aerospace field, while also mentioning
The high product yield of removing graphene.The experimental results showed that the thermally conductive system of graphene film that the preparation method in the present invention obtains
Number is 1850wW/m.k, tensile strength 38MPa, number > 100,000 times resistant to bending, density 1.92g/m3。
Specific embodiment
The present invention provides a kind of preparation methods of high thermal conductivity graphene film, comprising the following steps:
A polyamic acid resin and graphene oxide solution successively) are coated on substrate surface, obtain graphite oxide after dry
Alkene composite membrane；
B it) will be removed on the graphene oxide compound film from substrate, obtain the compound film coiled material of continuous graphene oxide；
C) the compound film coiled material of the graphene oxide is heat-treated, the graphene oxide composite membrane after being carbonized；
D the graphene oxide composite membrane after carbonization) is subjected to graphitization processing, obtains high thermal conductivity graphene film.
The present invention preferably prepares polyamic acid resin in accordance with the following methods:
Dianhydride and diamines are subjected to polycondensation reaction in intensive polar solvent, obtain polyamic acid resin；
The dianhydride is preferably one or more of biphenyltetracarboxylic dianhydride, pyromellitic acid dianhydride, benzophenone tetracid dianhydride；
The diamines is one or more of diaminodiphenyl ether, p-phenylenediamine, diamino benzophenone；Mole of the dianhydride and diamines
Than being preferably 1:(0.9~1.1), more preferably 1:1.The intensive polar solvent be preferably dimethyl acetamide (DMAC) and/or
N-Methyl pyrrolidone (NMP).
The solid content for the polyamic acid resin that polycondensation reaction obtains is preferably 10~25wt%, more preferably 15~
20wt%.
The present invention is preferably prepared according to the following steps to obtain graphene oxide solution:
Graphene oxide powder is dispersed with stirring containing organic surface active agent using vacuum ultrasonic stirring dispersion machine
In solvent, forms uniform graphene oxide slurry and carry out vacuum defoamation.
In the present invention, the lamella size of the graphene oxide powder is preferably 50~100 μm, more preferably 60~90
μm, most preferably 70~80 μm；The organic surface active agent is preferably polyvinylpyrrolidone (PVP), polyvinyl alcohol
(PVA), one or more of lauryl sodium sulfate (SDS) and carboxymethyl cellulose (CMC).
In the graphene oxide solution, the mass concentration of graphene oxide is preferably 3~10wt%, more preferably 5~
6wt%；The concentration of the organic surface active agent is preferably 0.01~0.05wt%, more preferably 0.02~0.04wt%；Institute
The viscosity for stating graphene oxide solution is preferably 5000~30000cPs, more preferably 10000~25000cPs, most preferably
10000~20000cPs.
It is ready to after polyamic acid resin and graphene oxide solution, the present invention passes through two concatenated coating heads or double
Polyimide acid, graphene oxide solution, are successively coated on substrate and form certain thickness by the coating head for feeding double coating mouths
Graphene oxide composite membrane, be then dried again remove solvent film forming, continuously wound, be made into coiled material.
In the present invention, the substrate is preferably steel band or PET base material, the wet film coating thickness of the polyamic acid resin
Preferably 80~400 μm, more preferably 100~300 μm, most preferably 200~250 μm；The graphene oxide solution it is wet
Film coating thickness is preferably 200~1000 μm, more preferably 300~800 μm, most preferably 500~600 μm.The drying
Temperature is preferably 70~200 DEG C, more preferably 80~160 DEG C, most preferably 140~160 DEG C；The time of the drying is preferably
15~30min, most preferably 25~30min.
After drying, obtained coiled material is the graphene oxide composite membrane on substrate described in composite wood, the graphite oxide
Alkene composite membrane has graphene oxide layer and polyamide acid layer, and the polyamide acid layer is contacted with substrate.
Removing on graphene oxide compound film from substrate is formed continuous graphene oxide using peel-off device by the present invention
Compound film coiled material；In the present invention, the peel-off device includes one or two automatic winding mechanism.If substrate is steel band,
It needs that automatic winding on winding rod will be pasted on after compound film stripping manually；If substrate is PET base material, need manually to shell composite membrane
From and paste automatic winding on two different automatic winding rods.
Graphene oxide membrane in the prior art is mostly one layer of graphene oxide of independent coating, by graphene oxide
It mixes other modified materials to be modified graphene oxide membrane, still, it is exactly oxygen that existing this method, which has a problem that,
Graphite alkene layer can not be coated with too thick, be easy to tear film in strip step if too thin or too thick, influence yield, be not easy
Realize volume production.But in aerospace field, need that there is certain thickness graphene oxide membrane, existing oxidation
Graphene film is unable to satisfy demand of the aerospace field to film thickness.But the graphene oxide membrane in the present invention can not only expire
To the requirement of film thickness in sufficient aerospace field, it can also guarantee excellent performance simultaneously.
The compound film coiled material of graphene oxide that removing obtains is heat-treated by the present invention under protective atmosphere, obtains carbon
The coiled material of change；
In heat treatment process described in the step, at the same carried out high temperature thermal reduction, imidization and carbonization treatment this
Three processes, wherein high temperature thermal reduction makes graphene oxide reduction become grapheme material, and imidization prepares polyamide acid layer
Polyimide layer is obtained, carbonization treatment can restore organic matter and functional group, gas be released, by organic carbon.
In the present invention, the temperature of the heat treatment is preferably 700~1500 DEG C, and more preferably 1200~1500 DEG C；Tool
Body, in an embodiment of the present invention, it can be 1250 DEG C；The time of the heat treatment is preferably 4~10 hours, more preferably
6~8 hours.
In the present invention, the protective atmosphere is preferably inert gas atmosphere or reducing atmosphere, as nitrogen, argon gas,
Helium or hydrogen.
After coiled material after being carbonized, the coiled material after carbonization is carried out graphitization processing by the present invention, obtains high thermal conductivity stone
Black alkene film.
In the present invention, the graphited temperature is preferably 2700~3000 DEG C, and more preferably 2800~2900 DEG C, most
Preferably 2850 DEG C；The graphited time is preferably 3~8 hours, and more preferably 4~7 hours, most preferably 5~6 is small
When.
After graphitization, obtained graphene film is preferably carried out calendering process by the present invention, density is improved, finally according to need
The size wanted is cut out processing.The pressure of the calendering process is preferably 0.5~20MPa, more preferably 5~15MPa, optimal
It is selected as 10~13MPa.
The present invention also provides a kind of high thermal conductivity graphene films, are made according to above-mentioned preparation method, the high thermal conductivity graphite
The thickness of alkene film is preferably 50~200 μm, and more preferably 100~150 μm；The thermally conductive film density of graphene is 0.5~2.1g/
m3；The thermal coefficient of graphene heat conducting film is 1800~2200W/m.K；Graphene heat conducting film tensile strength is 15~50MPa；Stone
Number > resistant to bending 100,000 times of black alkene heat conducting film.
The present invention provides a kind of preparation methods of high thermal conductivity graphene film, comprising the following steps: A) by polyamic acid tree
Rouge and graphene oxide solution are successively coated on substrate surface, obtain graphene oxide composite membrane after dry；B) by the oxidation
Graphene composite film is removed from substrate, obtains the compound film coiled material of continuous graphene oxide；C) graphene oxide is answered
It closes film coiled material to be heat-treated, the graphene oxide composite membrane after being carbonized；D) by the graphene oxide composite membrane after carbonization
Graphitization processing is carried out, high thermal conductivity graphene film is obtained.The present invention by polyamic acid resin and graphene oxide solution successively at
Film, forms the structure that graphene oxide membrane is superimposed with polyamide acid film two membranes, and the height that can more fully play graphene is led
Hot property, while improving mechanical property, additionally it is possible to removing obtains thicker graphene film, can satisfy the spy of aerospace field
Different demand, while also improving the product yield of removing graphene.The experimental results showed that the preparation method in the present invention obtained
Graphene film thermal coefficient is 1850wW/m.k, tensile strength 38MPa, number > 100,000 times resistant to bending, density 1.92g/m3。
In order to further illustrate the present invention, with reference to embodiments to a kind of high thermal conductivity graphene film provided by the invention and
Preparation method is described in detail, but cannot be understood as limiting the scope of the present invention.
Embodiment 1
By biphenyltetracarboxylic dianhydride (BPDA), benzophenone tetracid dianhydride (BTDA) and diaminodiphenyl ether (ODA), p-phenylenediamine
(PPDA) polyimide acid (PAA) matrix tree that solid content is 20% is configured to through polycondensation reaction in intensive polar solvent DMAC
Rouge；
Graphene oxide powder is dispersed in the NMP containing PVA using vacuum ultrasonic stirring dispersion machine, is formed uniform
Graphene oxide slurry simultaneously carries out vacuum defoamation；Wherein the concentration of graphene oxide is in prepared graphene oxide slurry
5wt%, viscosity 10000cPs, organic surface active agent content are 0.02wt%
Above-mentioned polyimide acid matrix resin and graphene oxide solution are passed through into double coating heads for feeding double coating mouths, according to
Secondary polyimide acid, graphene oxide solution are coated on substrate forms certain thickness graphene oxide composite membrane, passes through
Coating machine oven dries and removes solvent and film process, then is continuously wound, and coiled material is made into；The substrate is PET；It is described
The wet film coating thickness of PAA resin is 200 μm；Graphene oxide solution wet film coating thickness is 500 μm；Coating machine oven is dry
Temperature is 150 DEG C, and wet film drying time is 30min；
Graphene oxide composite membrane is removed and is wound to form continuous oxygen from PET by above-mentioned coiled material by peel-off device
The compound film coiled material of graphite alkene；
The compound film coiled material of obtained graphene oxide is put into the high temperature furnace that 1250 DEG C have under nitrogen atmosphere protection and is carried out
Thermal reduction, imidization and carbonization treatment 6h；
Material after obtained carbonization is put into progress graphitization processing 6h in 2850 DEG C of graphitizing furnace；
Obtained graphene film is subjected to calendering process, improves density, and carries out trimming etc. and be processed into the stone of required size
Black alkene film；Wherein control calender pressure is 10MPa.
The thermally conductive film density of graphene manufactured in the present embodiment is 1.92g/m3, with a thickness of 50 μm, thermal coefficient 1850W/
M.K, tensile strength 38MPa, number > 100,000 times resistant to bending.
Embodiment 2
By biphenyltetracarboxylic dianhydride (BPDA), benzophenone tetracid dianhydride (BTDA) and diaminodiphenyl ether (ODA), p-phenylenediamine
(PPDA) polyimide acid (PAA) matrix tree that solid content is 15% is configured to through polycondensation reaction in intensive polar solvent DMAC
Rouge；
Graphene oxide powder is dispersed in the NMP containing PVA using vacuum ultrasonic stirring dispersion machine, is formed uniform
Graphene oxide slurry simultaneously carries out vacuum defoamation；Wherein the concentration of graphene oxide is in prepared graphene oxide slurry
7wt%, viscosity 20000cPs, organic surface active agent content are 0.03wt%
Above-mentioned polyimide acid matrix resin and graphene oxide solution are passed through into double coating heads for feeding double coating mouths, according to
Secondary polyimide acid, graphene oxide solution are coated on substrate forms certain thickness graphene oxide composite membrane, passes through
Coating machine oven dries and removes solvent and film process, then is continuously wound, and coiled material is made into；The substrate is PET；It is described
The wet film coating thickness of PAA resin is 240 μm；Graphene oxide solution wet film coating thickness is 600 μm；Coating machine oven is dry
Temperature is 140 DEG C, and wet film drying time is 25min；
Graphene oxide composite membrane is removed and is wound to form continuous oxygen from PET by above-mentioned coiled material by peel-off device
The compound film coiled material of graphite alkene；
The compound film coiled material of obtained graphene oxide is put into the high temperature furnace that 1200 DEG C have under helium atmosphere protection and is carried out
Thermal reduction, imidization and carbonization treatment 4h；
Material after obtained carbonization is put into progress graphitization processing 5h in 2750 DEG C of graphitizing furnace；
Obtained graphene film is subjected to calendering process, improves density, and carries out trimming etc. and be processed into the stone of required size
Black alkene film；Wherein control calender pressure is 7MPa.
The thermally conductive film density of graphene manufactured in the present embodiment is 1.72g/m3, with a thickness of 60 μm, thermal coefficient 1350W/
M.K, tensile strength 21MPa, number < 50,000 times resistant to bending.
Embodiment 3
By biphenyltetracarboxylic dianhydride (BPDA), benzophenone tetracid dianhydride (BTDA) and diaminodiphenyl ether (ODA), p-phenylenediamine
(PPDA) polyimide acid (PAA) matrix tree that solid content is 12% is configured to through polycondensation reaction in intensive polar solvent DMAC
Rouge；
Graphene oxide powder is dispersed in the NMP containing PVA using vacuum ultrasonic stirring dispersion machine, is formed uniform
Graphene oxide slurry simultaneously carries out vacuum defoamation；Wherein the concentration of graphene oxide is in prepared graphene oxide slurry
10wt%, viscosity 28000cPs, organic surface active agent content are 0.04wt%
Above-mentioned polyimide acid matrix resin and graphene oxide solution are passed through into double coating heads for feeding double coating mouths, according to
Secondary polyimide acid, graphene oxide solution are coated on substrate forms certain thickness graphene oxide composite membrane, passes through
Coating machine oven dries and removes solvent and film process, then is continuously wound, and coiled material is made into；The substrate is PET；It is described
The coating thickness of PAA resin is 250 μm；Graphene oxide solution coating thickness is 300 μm；Coating machine oven drying temperature is
140 DEG C, wet film drying time is 20min；
Graphene oxide composite membrane is removed and is wound to form continuous oxygen from PET by above-mentioned coiled material by peel-off device
The compound film coiled material of graphite alkene；
The compound film coiled material of obtained graphene oxide is put into the high temperature furnace that 1100 DEG C have under helium atmosphere protection and is carried out
Thermal reduction, imidization and carbonization treatment 4h；
Material after obtained carbonization is put into progress graphitization processing 5h in 2700 DEG C of graphitizing furnace；
Obtained graphene film is subjected to calendering process, improves density, and carries out trimming etc. and be processed into the stone of required size
Black alkene film；Wherein control calender pressure is 5MPa.
The thermally conductive film density of graphene manufactured in the present embodiment is 1.52g/m3, with a thickness of 45 μm, thermal coefficient 1200W/
M.K, tensile strength 20MPa, number < 30,000 times resistant to bending.
Provided with 3 comparative examples once, it is arranged according to different key parameters, to protrude the creativeness of the application, please be mend
Fill corresponding parameter and effect data.
Comparative example 1
Graphene film is prepared according to method in embodiment 1, unlike, graphene oxide is directly coated on matrix
Solution is not coated with polyamic acid resin, and the coating thickness of graphene oxide solution is 300 μm.
The thermally conductive film density of graphene of this comparative example preparation is 1.81g/m3, with a thickness of 10 μm, thermal coefficient 1450W/
M.K, tensile strength 15MPa number < 20,000 times resistant to bending, occur a large amount of tearings and damaged existing in removing and calender line
As.
Comparative example 2
Graphene film is prepared according to the method in embodiment 1, unlike, this comparative example is by graphene solution and gathers
It is coated on matrix after the mixing of amide acid resin.
The thermally conductive film density of graphene of this comparative example preparation is 1.76g/m3, with a thickness of 54 μm, thermal coefficient 950W/
M.K, tensile strength 23MPa, number < 50,000 times resistant to bending.
Comparative example 3
Graphene film is prepared according to the method in embodiment 1, unlike, heat is carried out in the application high temperature furnace also
The temperature of former, imidization and carbonization treatment is 600 DEG C.
The thermally conductive film density of graphene of this comparative example preparation is 1.56g/m3, with a thickness of 40 μm, thermal coefficient 690W/
M.K, tensile strength 8MPa, number < 10,000 times resistant to bending.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high thermal conductivity graphene film, comprising the following steps:
A polyamic acid resin and graphene oxide solution successively) are coated on substrate surface, it is multiple that graphene oxide is obtained after dry
Close film；
B it) will be removed on the graphene oxide compound film from substrate, obtain the compound film coiled material of continuous graphene oxide；
C) the compound film coiled material of the graphene oxide is heat-treated, the graphene oxide composite membrane after being carbonized；
D the graphene oxide composite membrane after carbonization) is subjected to graphitization processing, obtains high thermal conductivity graphene film.
2. preparation method according to claim 1, which is characterized in that the polyamic acid resin is by dianhydride and diamines strong
Polycondensation reaction is carried out in polar solvent to be prepared；
The dianhydride is one or more of biphenyltetracarboxylic dianhydride, pyromellitic acid dianhydride, benzophenone tetracid dianhydride；
The diamines is one or more of diaminodiphenyl ether, p-phenylenediamine, diamino benzophenone.
3. preparation method according to claim 1, which is characterized in that the solid content of the polyamic acid resin be 10~
25wt%.
4. preparation method according to claim 1, which is characterized in that the graphene oxide solution is graphene oxide powder
The organic surface active agent solution of body；
The organic surface active agent is polyvinylpyrrolidone, polyvinyl alcohol, lauryl sodium sulfate and carboxymethyl cellulose
One or more of.
5. the preparation method according to claim 4, which is characterized in that in the graphene oxide solution, graphene oxide
Mass concentration be 3~10wt%, the concentration of the organic surface active agent is 0.01~0.05wt%；
The viscosity of the graphene oxide solution is 5000~30000cPs.
6. preparation method according to claim 1, which is characterized in that the coating thickness of the polyamic acid resin be 80~
400μm；
The coating thickness of the graphene oxide solution is 200~1000 μm.
7. preparation method according to claim 1, which is characterized in that the step A) in dry temperature be 70~200
℃；
The step A) in dry time be 15~30min.
8. preparation method according to claim 1, which is characterized in that the step C) in be heat-treated temperature be 700~
1500℃；
The step C) in be heat-treated time be 4~10 hours.
9. preparation method according to claim 1, which is characterized in that the step D) in the temperature of graphitization processing be
2700~3000 DEG C；
The step D) in graphitization processing time be 3~8 hours.
10. a kind of high thermal conductivity graphene film is made according to preparation method described in any one of claim 1 to 9,
The high thermal conductivity graphene film with a thickness of 50~200 μm.
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