CN108910865A - A method of preparing graphene/graphene nanobelt mixed film - Google Patents
A method of preparing graphene/graphene nanobelt mixed film Download PDFInfo
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- CN108910865A CN108910865A CN201810815799.8A CN201810815799A CN108910865A CN 108910865 A CN108910865 A CN 108910865A CN 201810815799 A CN201810815799 A CN 201810815799A CN 108910865 A CN108910865 A CN 108910865A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/198—Graphene oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
Abstract
Graphene/graphene nanobelt mixed film method is prepared the invention discloses a kind of, steps are as follows for the method：One, after mixing graphene oxide dispersion and stannic oxide/graphene nano band homogeneous dispersion, mixed dispersion liquid is prepared into graphene oxide/stannic oxide/graphene nano band by directly freezed seasoning and mixes sponge；Two, by graphene oxide/stannic oxide/graphene nano band mix sponge close hydrazine steam in restore, obtain graphene/graphene nanobelt and mix sponge；Three, it graphene/graphene nanobelt is mixed into sponge is put into mold and carry out hot pressed sintering, obtain graphene/graphene nanobelt mixed film.The present invention utilizes the excellent properties of graphene carbon nanotube hybrid materials, solve the problems, such as that the contact area between graphene and carbon nanotube is limited, and the electromagnet shield effect of material is improved by introducing interface in graphene film material, improve the not high phenomenon of electromagnetic shielding performance caused by thin-film material is limited because of thickness.
Description
Technical field
The present invention relates to a kind of preparation methods of mixed film material, and in particular to one kind is based on graphene sponge three-dimensional knot
The preparation method of mixed film based on structure.
Background technique
The atomic arrangement of graphene and the monoatomic layer of graphite are identical, are carbon atoms with sp2Hybridized orbit is according to honeycomb crystalline substance
The single layer two dimensional crystal that lattice are arranged to make up.The C-C skeleton of graphene is made of the participation of σ key skeleton, is divided above and below this skeleton
It is furnished with pairs of electron cloud, the Bonding model of this bonding form and phenyl ring is just the same.The special construction of graphene determines
Its unique property.It is its special electronic property that graphene is most wondrous, since the band structure of ideal graphite alkene has been
Holosymmetric taper valence band and conduction band are symmetrically dispersed in fermi level or more, there are dirac point between conduction band and valence band, because
This graphene belongs to zero gap semiconductor.Basically, graphene（The number of plies is 1,2 or 3）Middle many electronic behaviors are similar to
Two-dimensional electron gas, quality only have the 1/10 of free electron.Therefore graphene has high carrier transmission performance, room temperature downloading
It flows transport factor and is greater than 15 000cm2.V-1.s-1, which is not affected by temperature substantially, and maximum is up to 200 000
cm2.V-1.s-1.Other than electric property, graphene also has an excellent optical property, single-layer graphene to visible light there are about
3.2% absorption, graphene also show good nonlinear optical absorption characteristic, i.e., when strong illumination graphene, graphene
There is good absorption to visible and infrared lamp wave band light, the feature of its zero band gap in addition makes graphene be easy to become pair
Light saturation.In terms of calorifics, the heating conduction of graphene depends primarily on phonon transmission therein, the room temperature thermal conductivity of graphene
For（4.84±0.44）×103~（5.30±0.48）×103 W. m-1. K-1, theoretical thermal conductivity is up to 6000W. m-1. K-1With
On.
Graphene nanobelt（Graphene nanoribbon, GNR）It is a kind of quasi-one-dimensional band-like Graphene derivative,
Graphene nanobelt can regard the graphene film of small size as, unlike graphene, due to the dimensional effect of nanometer sheet
So that the band gap of GNR can be not zero, therefore GNR and carbon nanotube（CNT）Equally it is divided into metal mold and semi-conductor type two types.
Common GNR preparation method includes chemical method（Such as chemical vapour deposition technique, organic synthesis method）, ultrasonic method, lithographic methods,
Etching method and CNT chemical cleavage etc., wherein for CNT patterning method because easy to operate, preparation efficiency is high and is widely used.
GNR can also regard CNT as along axially cutting product, and GNR can not only inherit the excellent properties of graphene film, and due to amount
Sub- confinement and edge effect open the band gap of graphene, so that GNR has the performance of CNT simultaneously, before being a kind of great application
The new material of scape.
Due to similar atomic building and structure, so that carbon nanotube（CNT）With graphene（GR）Between can be well
It is combined together by π-π interaction and Van der Waals force, the graphene mixed has also shown very excellent with carbon nanotube
Performance, the big L/D ratio of MWCNTs reunites adjacent graphene film bridging together, avoiding graphene so that
The hybrid materials of the two have excellent mechanical property and thermal property, but due to the tubular structure of carbon nanotube, so that carbon is received
Mitron contacts limited with graphene film, limits the performance boost of hybrid materials.By carbon nanotube using chemical method along axial
It cuts, forms quasi-one-dimensional graphene nano band structure, can effectively improve the contact area of the two, promote material property.
Summary of the invention
Graphene/graphene nanobelt mixed film method is prepared the object of the present invention is to provide a kind of, utilizes graphite
The excellent properties of olefinic carbon nanotube hybrid materials solve the problems, such as that the contact area between graphene and carbon nanotube is limited,
And the electromagnet shield effect of material is improved by introducing interface in graphene film material, improve thin-film material because thickness limits
The not high phenomenon of caused electromagnetic shielding performance.
The purpose of the present invention is what is be achieved through the following technical solutions：
A method of graphene/graphene nanobelt mixed film is prepared, sponge is gone back by way of in-situ hot pressing
Former and hot pressing, prepare with high electromagnetic shielding performance, certain flexibility, densification thermally conductive mixed film.It specifically includes following
Step：
One, graphene oxide/stannic oxide/graphene nano band mixes the preparation of sponge：
By graphene oxide dispersion and stannic oxide/graphene nano band dispersion liquid according to mass ratio 0.5 ~ 1.5:0.5 ~ 1.5 carries out
After even mixing, mixed dispersion liquid is prepared into graphene oxide/stannic oxide/graphene nano band by directly freezed seasoning and is mixed
Sponge；
Two, graphene oxide/stannic oxide/graphene nano band mixes the reduction of sponge：
By step 1 prepare graphene oxide/stannic oxide/graphene nano band mix sponge in 50 ~ 100 DEG C of hydrazine hydrate steam also
20 ~ 30 h of original, obtain graphene/graphene nanobelt and mix sponge；
Three, graphene/graphene nanobelt mixed film preparation：
Graphene/graphene nanobelt that step 2 is prepared mixes sponge and is put into mold, is 1200 ~ 2000 in temperature
DEG C, pressure be 20 ~ 30 Mpa under conditions of carry out hot pressed sintering（Pressure applies at 1000 ~ 1200 DEG C）, after keeping the temperature 0.5 ~ 2 h
Stop heat, until in-furnace temperature is down to room temperature, takes out sample, obtain graphene/graphene nanobelt mixed film.
In the present invention, the graphene oxide dispersion is prepared using chemical method, and specific step is as follows：（1）Weigh 4 g squamas
Piece graphite is placed in a beaker, and pours into and be configured to mixed solution in beaker 400 ~ 500ml concentrated sulfuric acid and 40 ~ 50 ml phosphoric acid, room temperature
30 ~ 60 min of lower stirring；（2）It places the beaker and carries out heating water bath in water-bath, 16 ~ 20 g potassium permanganate point 8 times are added respectively
Enter into solution, and by solution at 60 ~ 70 DEG C heated at constant temperature, take out after 10 ~ 20 h and cool down at room temperature；（3）It is to be cooled to arrive
After room temperature, mixed solution is poured slowly into 600 ~ 700 ml and contains the hydrogen peroxide mixing ice water that 6 ~ 7 ml mass fractions are 30%
In, after standing 20 ~ 30 h, supernatant liquor is filtered off, lower layer's solution is taken to carry out centrifuge washing；（4）The graphene oxide that will have been washed
It is scattered in deionized water, obtains graphene oxide dispersion.
In the present invention, the stannic oxide/graphene nano band dispersion liquid is prepared using chemical cleavage carbon nanotube method, specific to walk
It is rapid as follows：（1）Weigh 1g multi-walled carbon nanotube（MWCNTs）It is placed in a beaker, 160 ~ 200ml concentrated sulfuric acid is added and stirs 1 at room temperature
15 ~ 25 ml phosphoric acid are added into mixed liquor, continue 10 ~ 20 min of stirring by ~ 2h；（2）6 ~ 8g potassium permanganate is weighed, is divided after grinding
Batch is added in mixed liquor（It is added in 1h, it is lasting to stir）, 65 ~ 75 DEG C of 1.5 ~ 2 h of heating stirring of subsequent water-bath are until liquid face
Discoloration is rufous, and the solution after reaction is cooled to room temperature, and pours into 400 ~ 500ml deionized water and 5 ~ 15ml hydrogen peroxide is mixed
It closes and is stood in ice water；（3）Supernatant liquor is filtered off after standing, sediment is washed, and washing process is：10% mixed in hydrochloric acid
150 ~ 250ml of solution is washed 2 ~ 3 times；40 ~ 60ml of dehydrated alcohol is washed 2 ~ 3 times；75 ~ 120ml of deionized water is washed 2 ~ 3 times；（4）
In deionized water by neutral stannic oxide/graphene nano band dispersion, stannic oxide/graphene nano band dispersion liquid is obtained.
In the present invention, the concentration of the graphene oxide dispersion and stannic oxide/graphene nano with dispersion liquid is 5 ~ 15 mg/
mL。
In the present invention, the step of directly freezed seasoning, is as follows：Mixed dispersion liquid is placed in beaker（Or arbitrary shape
The container of shape）In, freezed in the cold well of freeze drier, control cryogenic temperature be -50 ~ -20 DEG C, the time be 20 ~ 40 h with
On, it is subsequently vacuumed out 40 ~ 50 h of freeze-drying.
In the present invention, the specific reduction step that the graphene oxide/stannic oxide/graphene nano band mixes sponge is as follows：It will
80wt% hydrazine hydrate aqueous solution and graphene oxide/stannic oxide/graphene nano band mix sponge and are placed in closed drier, dry
Device places hydrazine hydrate solution below, and top places graphene oxide/stannic oxide/graphene nano band and mixes sponge, is heated to 50 ~ 100
DEG C, using hydrazine hydrate steam to 0 ~ 30 h of sponge reductase 12, the graphene/graphene nanobelt for obtaining Dark grey mixes sponge.
Compared with the prior art, the invention has the advantages that：
1, there is graphene prepared by the present invention/graphene nanobelt mixed film metallic luster and certain flexibility, conduction to lead
Hot property is good.
2, present invention process is simple, low in cost, high production efficiency, and controllability is good, can prepare large scale sample, meets
The needs of different engineerings.
3, stable preparation process of the invention, strong operability, can large-scale industrial production, on electromagnetic shielding field
With considerable application prospect.
4, graphene oxide is assembled into three-dimensional porous structure-graphene oxide sponge by the present invention, by electronation it
Carry out in-situ hot pressing sintering afterwards, obtain compactness it is higher, with multi-functional graphene/graphene nanobelt mixed film,
Improve the not high phenomenon of electromagnet shield effect caused by film is limited because of thickness.
Detailed description of the invention
Fig. 1 is graphene oxide dispersion, stannic oxide/graphene nano band dispersion liquid and the two mixed solution；
Fig. 2 is that graphene/graphene nanobelt mixes sponge；
Fig. 3 is graphene/graphene nanobelt mixed film；
Fig. 4 is graphene/graphene nanobelt mixed film preparation process schematic diagram；
Fig. 5 is graphene/graphene nanobelt mixed film section SEM figure.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Embodiment 1：
The present embodiment prepares graphene/graphene nanobelt mixed film in accordance with the following steps：
One, graphene oxide is prepared：
Graphene oxide is prepared using chemical method：（1）It weighs 4 g crystalline flake graphites to be placed in a beaker, by the 450 ml concentrated sulfuric acids and 50
Ml phosphoric acid pours into and is configured to mixed solution in beaker, stirs 40 min at room temperature.（2）Progress water-bath in water-bath is placed the beaker to add
18 g potassium permanganate points 8 times are added separately in solution by heat, and by solution at 70 DEG C heated at constant temperature, take out after 16 h and exist
It cools down at room temperature.（3）It is to be cooled to after room temperature, it is 30% that mixed solution, which is poured slowly into 700 ml to contain 6 ml mass fractions,
In hydrogen peroxide mixing ice water, after standing 24 h, supernatant liquor is filtered off, lower layer's solution is taken to carry out centrifuge washing.（4）It will finally wash
The graphene oxide washed is scattered in deionized water, obtains the graphene oxide dispersion that concentration is 10 mg/mL, spare.
Two, stannic oxide/graphene nano band is prepared：
Stannic oxide/graphene nano band is prepared using chemical cleavage carbon nanotube method：（1）Weigh 1 g multi-walled carbon nanotube（MWCNTs）
It is placed in a beaker, the 180 ml concentrated sulfuric acids is added and stir 2 h at room temperature, 20 ml phosphoric acid are added into mixed liquor, continue to stir
15min.（2）6 g potassium permanganate are weighed, are added in mixed liquor in batches after grinding（It is added in 1 h, it is lasting to stir）, subsequent water
Bathe 65 DEG C of 2 h of heating stirring until liquid color become rufous, the solution after reaction is cooled to room temperature, 500 ml is poured into and goes
It is stood in ionized water and 10 ml hydrogen peroxide mixing ice water.（3）Supernatant liquor is filtered off after standing, sediment is washed, and is washed
The process of washing is：10% 200 ml of hydrochloric acid mixed solution is washed twice；50 ml of dehydrated alcohol is washed twice；100 ml of deionized water
It washes twice.（4）Finally in deionized water by neutral stannic oxide/graphene nano band dispersion, obtaining concentration is 10 mg/mL's
Stannic oxide/graphene nano band dispersion liquid, it is spare.
Three, graphene oxide/graphene oxide graphene nanobelt mixes sponge preparation：
By graphene oxide dispersion and stannic oxide/graphene nano band dispersion liquid according to mass ratio 1:1 carries out after evenly mixing, will
Mixed dispersion liquid is placed in a beaker, and is freezed 24 h or more in the cold well of freeze drier, is subsequently vacuumed out freeze-drying
48h obtains diameter and is 100 mm, mixes sponge with a thickness of 5 mm, discoid graphene oxide/stannic oxide/graphene nano band.
Four, graphene oxide/stannic oxide/graphene nano band reduction：
Graphene oxide/stannic oxide/graphene nano band is mixed sponge to be removed from the molds, is restored in 90 DEG C of hydrazine hydrate steam
For 24 hours, graphene/graphene nanobelt can be obtained and mix sponge.
Five, graphene/graphene nanobelt mixed film preparation：
Graphene/the graphene nanobelt prepared is mixed sponge to be put into mold, hot pressed sintering is carried out in vacuum environment,
At 1200 DEG C of temperature, applies 30 Mpa of pressure after keeping the temperature 0.5 h, continue to heat up, keep the temperature 0.5h when temperature reaches 1900 DEG C
Stop heating afterwards, until in-furnace temperature is down to room temperature, takes out sample, obtain graphene/graphene nanobelt mixed film.
The present embodiment by the thickness of test sample it is observed that the graphene film prepared it is micro- with a thickness of 40
Rice, sample can be bent, and have metallic luster, and thermal coefficient is 509.34 Wm-1·K-1, conductivity is 7.43 × 104
S.m-1, the dB of electromagnet shield effect SEt=37.
Embodiment 2：
The present embodiment prepares graphene/graphene nanobelt mixed film in accordance with the following steps：
One, graphene oxide is prepared：
Graphene oxide is prepared using chemical method：（1）It weighs 4 g crystalline flake graphites to be placed in a beaker, by the 450 ml concentrated sulfuric acids and 50
Ml phosphoric acid pours into and is configured to mixed solution in beaker, stirs 40 min at room temperature.（2）Progress water-bath in water-bath is placed the beaker to add
18 g potassium permanganate points 8 times are added separately in solution by heat, and by solution at 70 DEG C heated at constant temperature, take out after 16 h and exist
It cools down at room temperature.（3）It is to be cooled to after room temperature, it is 30% that mixed solution, which is poured slowly into 700 ml to contain 6 ml mass fractions,
In hydrogen peroxide mixing ice water, after standing 24 h, supernatant liquor is filtered off, lower layer's solution is taken to carry out centrifuge washing.（4）It will finally wash
The graphene oxide washed is scattered in deionized water, obtains the graphene oxide dispersion that concentration is 10 mg/mL, spare.
Two, stannic oxide/graphene nano band is prepared：
Stannic oxide/graphene nano band is prepared using chemical cleavage carbon nanotube method：（1）Weigh 1 g multi-walled carbon nanotube
（MWCNTs）It is placed in a beaker, the 180 ml concentrated sulfuric acids is added and stir 2 h at room temperature, 20 ml phosphoric acid are added into mixed liquor, continue
Stir 15min.（2）6 g potassium permanganate are weighed, are added in mixed liquor in batches after grinding（It is added in 1 h, it is lasting to stir）, with
Afterwards 65 DEG C of 2 h of heating stirring of water-bath until liquid color become rufous, the solution after reaction is cooled to room temperature, pours into 500
It is stood in ml deionized water and 10 ml hydrogen peroxide mixing ice water.（3）Supernatant liquor is filtered off after standing, and sediment is washed
It washs, washing process is：10% 200 ml of hydrochloric acid mixed solution is washed twice；50 ml of dehydrated alcohol is washed twice；Deionized water
100 ml are washed twice.（4）Finally in deionized water by neutral stannic oxide/graphene nano band dispersion, obtaining concentration is 10
The stannic oxide/graphene nano band dispersion liquid of mg/mL is spare.
Three, graphene oxide/graphene oxide graphene nanobelt mixes sponge preparation：
By graphene oxide dispersion and stannic oxide/graphene nano band dispersion liquid according to mass ratio be 1:1 after evenly mixing, will mix
The dispersion liquid of conjunction is placed in container, freezes 24 h or more in the cold well of freeze drier, is subsequently vacuumed out freeze-drying 48h,
Obtain a length of 100 mm, width is 50 mm, is mixed with a thickness of rectangle graphene oxide/graphene oxide graphene nanobelt of 5mm
Sponge.
Four, graphene oxide/stannic oxide/graphene nano band reduction：
Graphene oxide/graphene oxide graphene nanobelt is mixed sponge to be removed from the molds, in 90 DEG C of hydrazine hydrate steam
Middle reductase 12 4h can be obtained graphene/graphene nanobelt and mix sponge.
Five, graphene/graphene nanobelt mixed film preparation：
The graphene prepared/graphene nanobelt sponge is put into mold, hot pressed sintering is carried out in vacuum environment, in temperature
When spending 1200 DEG C, applies 30 Mpa of pressure after keeping the temperature 0.5 h, continue to heat up, stop after 2 h are kept the temperature when temperature reaches 1600 DEG C
Heating takes out sample, obtains graphene/graphene nanobelt mixed film until in-furnace temperature is down to room temperature.
The present embodiment by the thickness of test sample it is observed that the graphene film prepared it is micro- with a thickness of 35
Rice, sample can be bent, and have metallic luster, and thermal coefficient is 489.21 Wm-1·K-1, conductivity is 7.0 × 104
S.m-1, the dB of electromagnet shield effect SEt=30.
Embodiment 3：
The present embodiment prepares graphene/graphene nanobelt mixed film in accordance with the following steps：
One, graphene oxide is prepared：
Graphene oxide is prepared using chemical method：（1）It weighs 4 g crystalline flake graphites to be placed in a beaker, by the 450 ml concentrated sulfuric acids and 50
Ml phosphoric acid pours into and is configured to mixed solution in beaker, stirs 40 min at room temperature.（2）Progress water-bath in water-bath is placed the beaker to add
18 g potassium permanganate points 8 times are added separately in solution by heat, and by solution at 70 DEG C heated at constant temperature, take out after 16 h and exist
It cools down at room temperature.（3）It is to be cooled to after room temperature, it is 30% that mixed solution, which is poured slowly into 700 ml to contain 6 ml mass fractions,
In hydrogen peroxide mixing ice water, after standing 24 h, supernatant liquor is filtered off, lower layer's solution is taken to carry out centrifuge washing.（4）It will finally wash
The graphene oxide washed is scattered in deionized water, obtains the graphene oxide dispersion that concentration is 10 mg/mL, spare.
Two, stannic oxide/graphene nano band is prepared：
Stannic oxide/graphene nano band is prepared using chemical cleavage carbon nanotube method：（1）Weigh 1 g multi-walled carbon nanotube
（MWCNTs）It is placed in a beaker, the 180 ml concentrated sulfuric acids is added and stir 2 h at room temperature, 20 ml phosphoric acid are added into mixed liquor, continue
Stir 15min.（2）6 g potassium permanganate are weighed, are added in mixed liquor in batches after grinding（It is added in 1 h, it is lasting to stir）, with
Afterwards 65 DEG C of 2 h of heating stirring of water-bath until liquid color become rufous, the solution after reaction is cooled to room temperature, pours into 500
It is stood in ml deionized water and 10 ml hydrogen peroxide mixing ice water.（3）Supernatant liquor is filtered off after standing, and sediment is washed
It washs, washing process is：10% 200 ml of hydrochloric acid mixed solution is washed twice；50 ml of dehydrated alcohol is washed twice；Deionized water
100 ml are washed twice.（4）Finally in deionized water by neutral stannic oxide/graphene nano band dispersion, obtaining concentration is 10
The stannic oxide/graphene nano band dispersion liquid of mg/mL, it is spare.
Three, graphene oxide/graphene oxide graphene nanobelt mixes sponge preparation：
By graphene oxide dispersion and stannic oxide/graphene nano band dispersion liquid according to mass ratio be 1:1 carries out full and uniform mixing
Afterwards, mixed dispersion liquid is placed in container, freezes 24 h or more in the cold well of freeze drier, is subsequently vacuumed out freezing
Dry 48h obtains a length of 100 mm, width is 50 mm, is received with a thickness of rectangle graphene oxide/graphene oxide graphene of 5mm
Rice band mixes sponge.
Four, graphene oxide/stannic oxide/graphene nano band reduction：
Graphene oxide/graphene oxide graphene nanobelt is mixed sponge to be removed from the molds, in 90 DEG C of hydrazine hydrate steam
Middle reductase 12 4h can be obtained graphene/graphene nanobelt and mix sponge.
Five, graphene/graphene nanobelt mixed film preparation：
The graphene prepared/graphene nanobelt sponge is put into mold, hot pressed sintering is carried out in vacuum environment, in temperature
When spending 1000 DEG C, applies 30 Mpa of pressure after keeping the temperature 0.5 h, continue to heat up, stop after 2 h are kept the temperature when temperature reaches 1200 DEG C
Heating takes out sample, obtains graphene/graphene nanobelt mixed film until in-furnace temperature is down to room temperature.
The present embodiment by the thickness of test sample it is observed that the graphene film prepared it is micro- with a thickness of 45
Rice, thermal coefficient are 480.32 Wm-1·K-1, conductivity is 6.3 × 104 S.m-1, electromagnet shield effect SEt=35dB, sample
Product can be bent, and have metallic luster.
Claims (10)
1. a kind of prepare graphene/graphene nanobelt mixed film method, it is characterised in that steps are as follows for the method：
One, graphene oxide/stannic oxide/graphene nano band mixes the preparation of sponge：
By graphene oxide dispersion and stannic oxide/graphene nano band dispersion liquid according to mass ratio 0.5 ~ 1.5:0.5 ~ 1.5 carries out
After even mixing, mixed dispersion liquid is prepared into graphene oxide/stannic oxide/graphene nano band by directly freezed seasoning and is mixed
Sponge；
Two, graphene oxide/stannic oxide/graphene nano band mixes the reduction of sponge：
By step 1 prepare graphene oxide/stannic oxide/graphene nano band mix sponge in 50 ~ 100 DEG C of hydrazine hydrate steam also
20 ~ 30 h of original, obtain graphene/graphene nanobelt and mix sponge；
Three, graphene/graphene nanobelt mixed film preparation：
Graphene/graphene nanobelt that step 2 is prepared mixes sponge and is put into mold, is 1200 ~ 2000 in temperature
DEG C, pressure carry out hot pressed sintering under conditions of being 20 ~ 30 Mpa, stop heat after keeping the temperature 0.5 ~ 2 h, until in-furnace temperature is down to room
Temperature takes out sample, obtains graphene/graphene nanobelt mixed film.
2. according to claim 1 prepare graphene/graphene nanobelt mixed film method, it is characterised in that described
Graphene oxide dispersion is prepared using chemical method.
3. according to claim 2 prepare graphene/graphene nanobelt mixed film method, it is characterised in that described
Specific step is as follows for graphene oxide dispersion：（1）It weighs 4 g crystalline flake graphites to be placed in a beaker, by 400 ~ 500ml concentrated sulfuric acid
It is poured into 40 ~ 50 ml phosphoric acid and is configured to mixed solution in beaker, stir 30 ~ 60 min at room temperature；（2）Place the beaker water-bath
16 ~ 20 g potassium permanganate points 8 times are added separately in solution by middle carry out heating water bath, and by solution at 60 ~ 70 DEG C constant temperature
It heats, takes out after 10 ~ 20 h and cool down at room temperature；（3）It is to be cooled to after room temperature, mixed solution is poured slowly into 600 ~ 700 ml
In the hydrogen peroxide mixing ice water for being 30% containing 6 ~ 7 ml mass fractions, after standing 20 ~ 30 h, supernatant liquor is filtered off, lower layer is taken
Solution carries out centrifuge washing；（4）It disperses the graphene oxide washed in deionized water, obtains graphene oxide dispersion
Liquid.
4. according to claim 1 prepare graphene/graphene nanobelt mixed film method, it is characterised in that described
Stannic oxide/graphene nano band dispersion liquid is prepared using chemical cleavage carbon nanotube method.
5. according to claim 4 prepare graphene/graphene nanobelt mixed film method, it is characterised in that described
Specific step is as follows with dispersion liquid for stannic oxide/graphene nano：（1）1g multi-walled carbon nanotube is weighed to be placed in a beaker, addition 160 ~
The 200ml concentrated sulfuric acid stirs 1 ~ 2h at room temperature, and 15 ~ 25 ml phosphoric acid are added into mixed liquor, continue 10 ~ 20 min of stirring；（2）Claim
6 ~ 8g potassium permanganate is taken, is added in mixed liquor in batches in 1h after grinding, 65 ~ 75 DEG C of 1.5 ~ 2 h of heating stirring of subsequent water-bath are straight
Become rufous to liquid color, the solution after reaction is cooled to room temperature, pours into 400 ~ 500ml deionized water and 5 ~ 15ml mistake
It is stood in hydrogen oxide mixing ice water；（3）Supernatant liquor is filtered off after standing, and sediment is washed；（4）By the oxidation after washing
Graphene nanobelt disperses in deionized water, to obtain stannic oxide/graphene nano band dispersion liquid.
6. according to claim 5 prepare graphene/graphene nanobelt mixed film method, it is characterised in that described
Washing process is：10% 150 ~ 250ml of hydrochloric acid mixed solution is washed 2 ~ 3 times；40 ~ 60ml of dehydrated alcohol is washed 2 ~ 3 times；Go from
Sub- 75 ~ 120ml of water is washed 2 ~ 3 times.
7. according to claim 1, preparing graphene/graphene nanobelt mixed film method described in 3 or 5, feature exists
In the graphene oxide dispersion and stannic oxide/graphene nano, the concentration with dispersion liquid is 5 ~ 15 mg/mL.
8. according to claim 1 prepare graphene/graphene nanobelt mixed film method, it is characterised in that described
The step of directly freezed seasoning, is as follows：Mixed dispersion liquid is placed in container, it is cold in the cold well of freeze drier
Freeze, control cryogenic temperature is -50 ~ -20 DEG C, and the time is 20 ~ 40 h or more, is subsequently vacuumed out 40 ~ 50 h of freeze-drying.
9. according to claim 1 prepare graphene/graphene nanobelt mixed film method, it is characterised in that described
The specific reduction step that graphene oxide/stannic oxide/graphene nano band mixes sponge is as follows：By 80wt% hydrazine hydrate aqueous solution and oxygen
Graphite alkene/stannic oxide/graphene nano band mixes sponge and is placed in closed drier, and drier places hydrazine hydrate solution below,
Top places graphene oxide/stannic oxide/graphene nano band and mixes sponge, 50 ~ 100 DEG C is heated to, using hydrazine hydrate steam to sea
Continuous 0 ~ 30 h of reductase 12, the graphene/graphene nanobelt for obtaining Dark grey mix sponge.
10. according to claim 1 prepare graphene/graphene nanobelt mixed film method, it is characterised in that institute
When stating hot pressed sintering, pressure applies at 1000 ~ 1200 DEG C.
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