CN107293377A - A kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film - Google Patents
A kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film Download PDFInfo
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- CN107293377A CN107293377A CN201710548856.6A CN201710548856A CN107293377A CN 107293377 A CN107293377 A CN 107293377A CN 201710548856 A CN201710548856 A CN 201710548856A CN 107293377 A CN107293377 A CN 107293377A
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Abstract
The invention discloses a kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film.Preparation process is as follows：Wood pulp is distributed in the aqueous solution first, single, a diameter of nano level single fiber beam is peeled off into the presence of liquid phase shearing force.The plain aqueous solution of low-consistency fiber is obtained by high-speed shearing machine processing certain time after single fiber beam is diluted through deionized water.Then industrialized graphene nanometer sheet is evenly spread in the aqueous solution containing dispersant by ultrasonically treated.Then the cellulose aqueous solution prepared is progressively added drop-wise in graphene dispersing solution, then graphene/cellulose laminated film is prepared by processes such as ultrasonic mixing, suction filtration and drying process.Obtained film has preferable pliability, heat conduction and electric conductivity, after hot-pressing processing, and mechanics, calorifics and the electric property of film are further enhanced.Preparation technology of the present invention is simple, with low cost, environmental protection, has wide application value in functional composite material field.
Description
Technical field
The invention belongs to nano material and functional material research field, specially a kind of tough graphene/cellulose is combined
The preparation method of thermal conductivity film.
Background technology
Graphene (Graphene) refers to
0.35 nm single layer of carbon atom carbonaceous material.Carbon atom is connected by α keys with three adjacent carbon atoms in graphene, carbon carbon
Between bond distance be only 0.142 nm, these bond energys very strong C-C keys are mutually 120 ° of bond angle so that graphene turns into the world
Most strong most hard material.The specific surface area of graphene is up to 2630 m2/ g, tensile strength and Young's modulus respectively reach 130GPa
And 1TPa, its theoretical thermal conductivity factor is thermal conductivity factors of the 5300 W/m K far above metal and CNT.Electronics is moved under normal temperature
The cm of shifting rate ＞ 150002/ V s, conductance is up to 6000 S/cm, more than CNT and silicon crystal.If so by graphene
Remolding into thin-film material will be in many field such as ultracapacitor, flexible electrode, solar cell, touch-screen, electronic apparatus
Have a wide range of applications.
Used in current graphene film preparation is single-layer graphene mostly, the graphene film that for example prepared by CVD method
Based on single-layer graphene, this method limits stone due to complex process, harsh condition, low yield and the high shortcoming of cost
The black large-scale commercial application of alkene.Graphene oxide is prepared using chemistry redox method for another example, by being filtered by vacuum
To graphene oxide film, during then obtaining graphene film, the chemical stripping of this method by chemical reduction method again
Used strong oxidizer would generally destroy the planar structure of carbon atom, produce defect, make heat conduction and the electric conductivity of graphene
Decline.Must for single-layer graphene preparation cost it is higher, technology is also immature, it is difficult to realize in field of compound material
Scale application.And i.e. for multi-layer graphene graphene nanometer sheet, it is by several layers of or more than ten layer graphenes stacking
Into, its thickness is less than 10 nm, possesses the excellent heat conduction of single-layer graphene and electric conductivity.This graphene is with aboundresources
Graphite be raw material, can be by " from top to bottom " method, the graphite oxide through microwave radiation or the sour intercalation of thermal expansion realizes industry
Metaplasia is produced, and production cost is relatively low, and this is that grapheme material commercial application has paved road.
Cellulose is degradable green bio resource the abundantest in nature, and the cellulose of nanoscale has excellent
Intensity and modulus, while having preferable pliability.On the premise of performance is met, a kind of inexpensive, many work(of exploitation
Environmental protection graphene/cellulose laminated film of energy is significant.
The content of the invention
It is an object of the invention to provide a kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film,
Industrialized graphene uniform is distributed in solvent first, while wood pulp is peeled off by refiner and cutter scattered
Into the fibre bundle of nanometer diameter, tough thermal conductivity THIN COMPOSITE is then prepared by suction filtration graphene/cellulose mixed solution
Film, so as to further promote graphene in the application in functional composite material field.The present invention for graphene in the composite
Commercial application provides a new approach.
The technical scheme is that：
S1 adds graphene and dispersant in solvent, is configured to the graphene solution that concentration is 0.2 ~ 5 mg/ml, and to stone
Black alkene solution progress is ultrasonically treated, obtains finely dispersed graphene suspension；
Wood pulp is distributed in the aqueous solution by S2, then disperses cellulose by repeatedly circulation liquid phase shearing with refiner
Into single fibre bundle.Further the preferable Nanowire of decentralization is obtained by being mixed with deionized water with high-speed shearing machine is scattered
The plain aqueous solution of dimension；
Cellulose aqueous solution in S2 is slowly added in the graphene aqueous solution in stirring by S3, is then obtained with ultrasonically treated
Even scattered graphene/cellulose mixed liquor；
S4 acts on forming stone using graphene/cellulose mixed liquor described in miillpore filter vacuum filter by self assembly remodeling
Black alkene and cellulose are alternate, the preferable membrane material of the graphene film degree of orientation, and after filtration washing, film is existed together with filter paper
About 24 h are dried at room temperature, then take screening from miillpore filter off, are transferred in vacuum drying oven under 50 ~ 100 oC true
Sky dries 12 ~ 24 h, obtains graphene/cellulose composite membrane material；
Graphene/cellulose composite membrane that S5 obtains S4 passes through hot-pressing processing under certain temperature and pressure, obtains structure more
For closely knit laminated film.
The preparation method of described tough graphene/cellulose composite heat-conducting conductive film, dispersant right and wrong used from
Sub- surfactant：Octyl phenyl polyoxyethylene ether (triton x-100).
The preparation method of described tough graphene/cellulose composite heat-conducting conductive film, configuration alkene nanometer sheet solution institute
Solvent is water, ethanol, acetone, isopropanol, tetrahydrofuran, isopropanol, methanol, 1-METHYLPYRROLIDONE and dimethyl formyl
One kind in amine.
The preparation method of described tough graphene/cellulose composite heat-conducting conductive film, it is characterised in that the stone
Black alkene can be single or multiple lift graphene prepared by intercalation stripping method, solvent stripping method and oxidation-reduction method, and thickness is 1 ~ 10
nm.Piece footpath is 0.5 ~ 200 μm, and concentration is 0.2 ~ 5 mg/ml, and sonication treatment time is 3 ~ 30 min.
The preparation method of described tough graphene/cellulose composite heat-conducting conductive film, for the wooden of circulation shear
Cellulose solid content is 2 ~ 10 wt%, the preparation side of described tough graphene/cellulose composite heat-conducting conductive film in paper pulp
Method, wooden slurry sequentially passes through heavy caliber nozzle and hand line nozzle, a diameter of 350 ~ 500 μm of heavy caliber nozzle, osculum
Footpath nozzle diameter is 150 ~ 250 μm.It it is 40 ~ 60 times by heavy caliber number of processing, small-bore number of processing is 20 ~ 40
It is secondary；Pressure used is 100 ~ 160 MPa.
The preparation method of described tough graphene/cellulose composite heat-conducting conductive film, the rotating speed of high-speed shearing machine is
10000 ~ 15000 rpm, processing time is 3 ~ 20 min.
The preparation method of described tough graphene/cellulose composite heat-conducting conductive film, graphene/cellulose mixing
The content of cellulose is in 0 ~ 60 wt% in liquid, and the ultrasonically treated time is 3 ~ 30 min.
The preparation method of described tough graphene/cellulose composite heat-conducting conductive film, filter process is in vacuum bar
Under part, carried out using microporous barrier.Drying is carried out in vacuum drying chamber, and aridity is 50 ~ 100 oC, and drying time is
12~24 h。
In the preparation method of described tough graphene/cellulose composite heat-conducting conductive film, hot pressing, temperature is
100 ~ 150 oC, pressure is 50 ~ 120 MPa, and the time is 0.5 ~ 3 h.
The preparation method of tough graphene provided by the present invention/cellulose composite heat-conducting conductive film has following excellent
Point：1. use the industrialized graphene nanometer sheet that can be mass produced for raw material, size is controllable, it is possible to achieve graphene
Commercial application of the material in field of compound material.Lignocellulosic is natural macromolecular material, can be degradable, THIN COMPOSITE
Film preparation cost is low, simple to operate, green non-pollution.
2. the dispersant selected is octyl phenyl polyoxyethylene ether (triton x-100), ultrasonically treated by the short time
It graphene uniform is stablized and must be distributed in solvent afterwards, most of dispersant can be removed by flushing after filtering.
3. wooden paper pulp fiber can be completely exfoliated by refiner processing, then can be with by the decentralized processing of cutter
The single fiber-bundles aqueous solution of finely dispersed nanometer diameter is obtained, the flexibility and intensity of cellulose can be given full play to, make graphite
The pliability of alkene/cellulose is improved, and the degree of orientation of graphene film preferably, possesses preferable heat conduction and electric conductivity.
Brief description of the drawings
Fig. 1 is the photo of graphene/cellulose laminated film prepared by the present invention.
Fig. 2 is the electron scanning micrograph of graphene/cellulose laminated film cross section prepared by the present invention.
Embodiment
In a specific embodiment, the preparation method of tough graphene of the invention/cellulose composite heat-conducting conductive film
In, the fibre bundle that finely dispersed graphene in a solvent and finely dispersed nanometer diameter in aqueous are obtained respectively is molten
Liquid, graphene/cellulose laminated film is prepared by vacuum filtration method.It is comprised the following steps that：
1. the preparation of graphene dispersing solution
Graphene used is by taking industrialized graphene nanometer sheet as an example, and thickness is ~ 5 nm, and the number of plies is 10 layers or so, average piece
A diameter of 5 μm of layer, graphene nanometer sheet and dispersant are added in solvent, are configured to the graphene nano that concentration is 1 mg/ml
Piece solution, and ultrasonically treated 3 min is carried out to graphene solution, obtain finely dispersed graphene suspension；
2. the preparation of single fiber-bundles element dispersion liquid
Wood pulp is diluted with water after the slurries that solid content is 5 wt%, dispersed with stirring, at refiner
Reason：By slurries under 145 MPa pressure by bigbore nozzle (400 μm), circular treatment 40 times, then slurry is passed through
Small-bore nozzle (195 μm), circular treatment 30 times.Then obtained slurries water is further diluted and obtains 1mg/ml's
Cellulose aqueous solution, the cellulose aqueous solution that 5 min finally give finely dispersed single beam is handled with high-speed shearing machine；
3. graphene/cellulose mixed solution
Dispersion liquid in 1 and 2 is mixed, ultrasonically treated 5 min obtains finely dispersed mixed solution, then passes through vacuum filter
Mixed solution prepares graphene/cellulose laminated film.
To clearly demonstrate technical scheme, graphene/cellulose THIN COMPOSITE is illustrated with reference to example
The preparation of film.
Embodiment 1:Pure graphene nanometer sheet film
Using 25 ml graphene nanometer sheet suspension described in miillpore filter vacuum filter, graphene film is remolded by self assembly
Filmogen, after filtering, with distilled water by multiple flushing, 24 h are dried at room temperature for by graphene film together with filter paper,
Then screening is taken off from miillpore filter, then sample is put into vacuum drying chamber and dries 24 h.By dried graphite
Alkene nanometer sheet film is placed on hot press the h of pressurize 1 under 65 MPa pressure, obtains the higher graphene nanometer sheet of compactness
Film.
The thickness of this graphene nanometer sheet/cellulose laminated film prepared is 0.095 mm, and mechanical property is poor, no
Easily measure.Its in-plane thermal conductivity and electrical conductivity are respectively 46 W/mK and 18 S/cm.It is worth noting that working as film
Keep measuring the thermal conductivity and electrical conductivity of graphene nanometer sheet/cellulose composite membrane after compacting under 65 MPa pressure after 1 h
Greatly improve respectively to 132 W/mK and 912 S/cm.
Embodiment 2:Content of cellulose is 10 wt% laminated film
The graphene nanometer sheet solution for taking 25 ml concentration to be 1 mg/ml, is then slowly added to 2.8ml's in the state of stirring
Concentration is 1 mg/ml cellulose aqueous solution, is stirred, then ultrasonically treated 5 min under 120 W power, then logical
Cross vacuum filtration, washing, drying and other steps and obtain the laminated film that content of cellulose is 10 wt%.
The thickness of the graphene nanometer sheet prepared using this method/cellulose laminated film be 0.09 mm, tensile strength,
Modulus and elongation at break are respectively 1.5 MPa, 0.19 MPa and 2.5%；In-plane thermal conductivity and electrical conductivity are respectively 58
W/mK and 14 S/cm.Graphene nanometer sheet/the cellulose measured after film keeps 1 h under 65 MPa pressure after compacting is multiple
Tensile strength, modulus and the elongation at break for closing film are respectively 11.4MPa, 3.4 GPa and 1.9%；Thermal conductivity and electrical conductivity difference
Greatly improve to 145 W/mK and 290 S/cm.
Embodiment 3:Content of cellulose is 20 wt% laminated film
The graphene nanometer sheet solution for taking 25 ml concentration to be 1 mg/ml, is then slowly added to 6.25 ml in the state of stirring
Concentration be 1 mg/ml cellulose aqueous solution, stir, then ultrasonically treated 5 min under 120 W power, then
The laminated film that content of cellulose is 20 wt% is obtained by vacuum filtration, washing, drying and other steps.
The thickness of the graphene nanometer sheet prepared using this method/cellulose laminated film be 0.075mm, tensile strength,
Modulus and elongation at break are respectively 6.5 MPa, 1.0 GPa and 3.9%；In-plane thermal conductivity and electrical conductivity are respectively 65.2
W/mK and 9.6 S/cm.Graphene nanometer sheet/cellulose after compacting is measured after film keeps 1 h under 65 MPa pressure
Tensile strength, modulus and the elongation at break of composite membrane are respectively 16.2MPa, 4.6 GPa and 3.3%；Thermal conductivity and electrical conductivity point
Do not greatly improve to 156.6 W/mK and 58 S/cm.
Embodiment 4:Content of cellulose is 40 wt% laminated film
The graphene nanometer sheet solution for taking 25 ml concentration to be 1 mg/ml, is then slowly added to 16.7 ml in the state of stirring
Concentration be 1 mg/ml cellulose aqueous solution, stir, then ultrasonically treated 5 min under 120 W power, then
The laminated film that content of cellulose is 40 wt% is obtained by vacuum filtration, washing, drying and other steps.
The thickness of the graphene nanometer sheet prepared using this method/cellulose laminated film be 0.055 mm, tensile strength,
Modulus and elongation at break are respectively 33.9 MPa, 3.5 MPa and 6.7 %；In-plane thermal conductivity and electrical conductivity are respectively
68.4 W/mK and 0.09 S/cm.Graphene nanometer sheet/fibre after compacting is measured after film keeps 1 h under 65 MPa pressure
Tensile strength, modulus and the elongation at break of the plain composite membrane of dimension are respectively 50.3 MPa, 9.1 GPa and 5.2%；Thermal conductivity and electricity
Conductance is greatly improved to 161 W/mK and 7.74 S/cm respectively.
Embodiment 5:Content of cellulose is 60 wt% laminated film
The graphene nanometer sheet solution for taking 25 ml concentration to be 1 mg/ml, is then slowly added to 37.5 ml in the state of stirring
Concentration be 1 mg/ml cellulose aqueous solution, stir, then ultrasonically treated 5 min under 120 W power, then
The laminated film that content of cellulose is 0 wt% is obtained by vacuum filtration, washing, drying and other steps.
The thickness of the graphene nanometer sheet prepared using this method/cellulose laminated film be 0.06 mm, tensile strength,
Modulus and elongation at break are respectively 44.6 MPa, 6.9 MPa and 5.0%；In-plane thermal conductivity and electrical conductivity are respectively 57.6
W/mK and 0.02 S/cm.Graphene nanometer sheet/cellulose after compacting is measured after film keeps 1 h under 65 MPa pressure
Tensile strength, modulus and the elongation at break of composite membrane are respectively 57.7 MPa, 9.1 GPa and 3.7%；And thermal conductivity and conductance
Rate distinguishes 143 W/mK and 0.02 S/cm.
By embodiment it can be seen that the thickness of graphene nanometer sheet film is in increase of the initial period with content of cellulose
And gradually reduce, this is due to that hydrophilic cellulose can possess moisture, with the drying of composite membrane, and moisture gradually evaporates, fine
Dimension element makes graphene nanometer sheet is even closer must link together, and makes the degree of orientation of graphene film more preferable, so as to cause composite membrane
Material porosity is reduced, and with higher compactness, adds the scanning on the surface and section of the laminated film of 30 wt% celluloses
Electromicroscopic photograph is as depicted in figs. 1 and 2.
The tensile strength and modulus of graphene nanometer sheet/cellulose laminated film are all with the increase of content of cellulose simultaneously
And raise, after overcompaction, the tensile strength and modulus of composite film material are further raised.When content of cellulose is 30%,
Laminated film still has higher heat conduction and electric conductivity.
Embodiment result shows, graphene/cellulose laminated film prepared by the present invention, when the fibre for adding proper content
After dimension element, elongation at break is higher, and the pliability of film preferably, and has remained in that preferable thermal conductivity net between lamella
Network passage, with preferable heat conduction and electric conductivity.The present invention is the large-scale application and multifunctional graphite vinyl for promoting graphene
The preparation of based composites provides new technical thought.
Claims (10)
1. the preparation method of a kind of tough graphene/cellulose composite heat-conducting conductive film, it is characterised in that including following step
Suddenly：
S1 adds graphene and dispersant in solvent, is configured to the graphene solution that concentration is 0.2 ~ 5 mg/ml, and to stone
Black alkene solution progress is ultrasonically treated, obtains finely dispersed graphene suspension.
Wood pulp is distributed in the aqueous solution by S2, then disperses cellulose by repeatedly circulation liquid phase shearing with refiner
Into single fibre bundle.Further the preferable Nanowire of decentralization is obtained by being mixed with deionized water with high-speed shearing machine is scattered
The plain aqueous solution of dimension.
Cellulose aqueous solution in S2 is slowly added in the graphene aqueous solution in stirring by S3, is then obtained with ultrasonically treated
Dispersed graphene/cellulose mixed liquor.
S4 acts on forming stone using graphene/cellulose mixed liquor described in miillpore filter vacuum filter by self assembly remodeling
Black alkene and cellulose are alternate, the preferable membrane material of the graphene film degree of orientation, and after filtration washing, film is existed together with filter paper
About 24 h are dried at room temperature, then take screening from miillpore filter off, are transferred in vacuum drying oven under 50 ~ 100 oC true
Sky dries 12 ~ 24 h, obtains graphene/cellulose composite membrane material.
Obtained graphene/cellulose composite membrane is passed through hot-pressing processing by S5 under certain temperature and pressure, can obtain structure more
For closely knit laminated film.
2. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In described dispersant is nonionic surfactant：Octyl phenyl polyoxyethylene ether (triton x-100).
3. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In the solvent used in the graphene solution is water, ethanol, acetone, isopropanol, tetrahydrofuran, isopropanol, methanol, N- methyl
One kind in pyrrolidones and dimethylformamide.
4. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In the graphene can be single or multiple lift graphene prepared by intercalation stripping method, solvent stripping method and oxidation-reduction method, thick
Spend for 1 ~ 10 nm.Piece footpath is 0.5 ~ 200 μm, and concentration is 0.2 ~ 5 mg/ml, and sonication treatment time is 3 ~ 30 min.
5. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In, for cellulose solid content in the wood pulp of circulation shear be 2 ~ 10 wt%.
6. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In described wooden slurry sequentially passes through heavy caliber nozzle and hand line nozzle, a diameter of 350 ~ 500 μ of heavy caliber nozzle
M, a diameter of 150 ~ 250 μm of hand line nozzle.It is 40 ~ 60 times, small-bore number of processing by heavy caliber number of processing
For 20 ~ 40 times；Pressure used is 100 ~ 160 MPa.
7. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In the rotating speed of the high-speed shearing machine is 10000 ~ 15000 rpm, and processing time is 3 ~ 20 min.
8. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In the content of cellulose is in 0 ~ 60 wt% in the graphene/cellulose mixed liquor, and the ultrasonically treated time is 3 ~ 30 min.
9. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature exists
In the filter process is under vacuum, to be carried out using microporous barrier.Drying is carried out in vacuum drying chamber, is done
Dry temperature is 50 ~ 100 oC, and drying time is 12 ~ 24 h.
10. the preparation method of tough graphene according to claim 1/cellulose composite heat-conducting conductive film, its feature
It is, in described hot pressing, temperature is 100 ~ 150 oC, and pressure is 50 ~ 120 MPa, and the time is 0.5 ~ 3 h.
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