CN107253716B - A kind of preparation method of graphene paper - Google Patents
A kind of preparation method of graphene paper Download PDFInfo
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- CN107253716B CN107253716B CN201710445862.9A CN201710445862A CN107253716B CN 107253716 B CN107253716 B CN 107253716B CN 201710445862 A CN201710445862 A CN 201710445862A CN 107253716 B CN107253716 B CN 107253716B
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- C01—INORGANIC CHEMISTRY
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention discloses a kind of preparation methods of graphene paper, comprising the following steps: (1) electro spinning nanometer fiber membrane substrate；(2) EFI combined oxidation graphene film；(3) substrate is removed；(4) redox graphene.Compared to existing method, preparation method operation is simpler, at low cost, resulting graphene paper thickness is uniform, has preferable chemical property, and it is easy to separate with substrate material, the graphene paper of large area can be prepared, the patterning of graphene paper can be directly realized by during the preparation process simultaneously, expand the application field of material.
Description
Technical field
The invention belongs to grapheme material preparation technical fields, and in particular to a kind of preparation method of graphene paper.
Background technique
Graphene is a kind of single layer Two-dimensional Carbon atomic crystal of discovery in 2004, unique two-dimensional layered structure and excellent
The performances such as different electricity, calorifics, mechanics show it in various fields such as flexible electronic, photodetection, energy stores non-
The application prospect of Chang Youyi.It is limited to the preparation method of graphene, prepares the high-quality single-layer graphene sample of large scale at present
There is also difficulties, are limited in micro-meter scale mostly, in order to realize application, how to assemble the grapheme material with macro-scale
One of the hot spot of recent researcher research is become.A kind of graphene macroscopic view of the graphene paper as typical two-dimensional structure
Assembled material especially receives extensively in energy storage field since it is easy to blend with the material manufacturing process of modern popular
Concern.The method of preparation graphene paper mainly has the side such as vacuum filtration, liquid phase electrophoretic deposition and the self assembly of gas-liquid face at present
Method, but in different aspect all there is some limitations, for example, most widely used vacuum filtration method during the preparation process there is also
Energy consumption it is high and the disadvantages of material separates difficulty with filter membrane.In addition, with the wearable device based on flexible electronic
Gradually develop, constructing special construction or patterning is the common strategy for increasing material tensile property, but is preparing pattern at present
It there is no preferable research achievement in terms of the graphene paper of change.
Summary of the invention
The technical problem to be solved by the present invention is overcoming prior art defect, a kind of grapheme material technology of preparing is provided
Field, compared to existing method, preparation method operation is simpler, at low cost, and resulting graphene paper thickness is uniform, has
Preferable chemical property, and be easy to separate with substrate material, the graphene paper of large area can be prepared, while can prepare
It is directly realized by the patterning of graphene paper in the process, expands the application field of material.
To solve the above-mentioned problems, the present invention provides a kind of preparation methods of graphene paper, comprising the following steps:
(1) electro spinning nanometer fiber membrane substrate: preparing high molecular polymer spinning precursor liquid, and gained spinning precursor liquid is added
In the liquid storage mechanism of electrostatic spinning apparatus, high molecular polymer nano fibrous membrane is prepared using method of electrostatic spinning, that is, is collecting bottom
Nano fibrous membrane substrate is obtained on plate；
(2) graphene oxide dispersion EFI combined oxidation graphene film: is placed in the liquid storage machine of electrostatic atomizer
In structure, step (1) nano fibrous membrane substrate is placed on the collecting mechanism of electrostatic atomizer, using electrostatic spraying processes in nanometer
Direct spraying combined oxidation graphene film on tunica fibrosa substrate；
(3) it removes substrate: the nano fibrous membrane substrate of step (2) resulting composite film material being removed, graphite oxide is obtained
Alkene film；
(4) redox graphene: step (3) resulting graphene oxide film is restored up to graphene paper.
Preparation method of the invention is easy to operate, at low cost, and this method is fine with high molecular nanometer prepared by method of electrostatic spinning
Dimension film is substrate, and utilizes electric field force in the compound one layer of dense uniform of substrate fiber surface direct spraying using electrostatic spraying processes
Graphene oxide film, since the nano-fiber film as substrate can be easily by the methods of dissolution, burning removal, most
It can be prepared by graphene paper in homogeneous thickness in oxidation graphene film afterwards, the removal substrate approach is not only simple, and should
The performance of graphene oxide film and pattern allow this method easily to realize graphene paper and substrate without influence in the process
Separation, the problem of being attached on substrate, be not readily separated application in effective solution graphene paper preparation process, meanwhile, warp
Testing the graphene paper has the chemical property for being better than common graphite alkene paper, and applicant guesses that this is derived from two during EFI
The introducing for tieing up moveable platform, causes graphene oxide microplate to disperse in an assembling process more uniform, simultaneously because electric field
The presence of power effect reduces the gap between graphene oxide layer, can all lead to the raising of chemical property；Additionally, due to
Nano fibrous membrane substrate has fibre structure, so that the graphene substrate surface also has the micro- knot complementary with substrate tunica fibrosa
Structure, the difference in this structure may also lead to the promotion of the graphene paper performance.
Preferably, high molecular material described in step (1) is nylon, polyethylene pyrrole network alkanone, polyethylene glycol oxide, gathers inclined fluorine
One of ethylene, polycaprolactone, polystyrene, polymethyl methacrylate are a variety of.
Preferably, the collection bottom plate of the step (1) is the metal plate with pierced pattern.
Preferably, the step (2) is that graphene oxide dispersion is placed in the liquid storage mechanism of electrostatic atomizer,
The collecting mechanism of the electrostatic atomizer is computer-controlled two-dimensional movement platform, by step (1) nano fibrous membrane substrate
It is placed in two-dimensional movement platform together with the collection bottom plate of its bottom, it is straight on nano fibrous membrane substrate using electrostatic spraying processes
Connect spraying combined oxidation graphene film.
As collector there is nano fibrous membrane substrate obtained using the metal plate with pierced pattern in step (1)
Patterned structure, again using the metal plate with pierced pattern as collecting plate connection electrostatic spray dress in step (2)
The high voltage power supply set, in patterned nanofiber film surface EFI graphene oxide film, between spray head and collecting plate not
Under the double action of uniform electric field and patterned nano fibrous membrane, so that the graphene oxide film that substrate surface is formed
With pattern structure, it can be readily available the graphene paper with pattern structure by subsequent processing, meanwhile, two dimension
Mobile platform is controlled by computer, and computer can drive collecting plate by pre-set process control two-dimensional movement platform
Shuttling movement is done on X, Y-direction, thus the even application graphene oxide on nano fibrous membrane substrate, it can be according to practical need
It wants, prepares the graphene paper of large area, cycle-index can also be set on computers, to control the thickness of film forming, expand material
Application field.
Preferably, during the electrostatic spray of the step (2), the vertical distance of spray head and nano fibrous membrane substrate is
The propulsion of 1.5~4cm, 7~10KV of spray voltage, liquid storage mechanism pump 20~40 μ L/min of fltting speed.
Preferably, the solvent of graphene oxide dispersion described in step (2) is n,N-Dimethylformamide (DMF), institute
The graphene oxide concentration contained is 11.7mg/g.
Preferably, the step (3) is the height that step (2) resulting composite film material is dipped in dissolvable step (1)
In the solvent of Molecularly Imprinted Polymer, impregnate until nano fibrous membrane substrate takes out sample after being completely dissolved, after being cleaned with deionized water
Obtain graphene oxide film.
Preferably, the step (3) is that step (2) resulting composite film material carries out at high warm under oxygen atmosphere
Reason takes out sample after burning up nano fibrous membrane substrate to get graphene oxide film.
Preferably, the step (4) is that step (3) resulting graphene oxide film is placed in reducing agent to be gone back
Original reaction, after graphene oxide is reduced to graphene, cleaning, dry gained sample are up to graphene paper.
Preferably, the step (4) is 88wt%'s for step (3) resulting graphene oxide film is dipped in concentration
In hydroiodic acid, heats 100 DEG C and restore 1 hour, graphene oxide is reduced, with deionized water repeated flushing 3-4 times, by gained
Sample is put into vacuum shelf dryer after air drying up to graphene paper.
Preferably, the step (4) is that step (3) resulting graphene oxide film is carried out height under reducing atmosphere
Warm processing, until graphene oxide is reduced to get graphene paper.
The beneficial effects of the present invention are: the present invention provides a kind of grapheme material preparation technical fields, compared to existing
Method, preparation method operation is simpler, at low cost, and resulting graphene paper thickness is uniform, has preferable electrochemistry
Can, and be easy to separate with substrate material, the graphene paper of large area can be prepared, while can be directly realized by during the preparation process
The patterning of graphene paper expands the application field of material.Specifically:
(1) preparation method of the invention is easy to operate, at low cost, the high molecular nanometer that this method is prepared with method of electrostatic spinning
Tunica fibrosa is substrate, and utilizes electric field force in the compound one layer of dense uniform of substrate fiber surface direct spraying using electrostatic spraying processes
Graphene oxide film, due to the nano-fiber film as substrate can easily by dissolution, burning the methods of removal,
Finally can be prepared by graphene paper in homogeneous thickness in oxidation graphene film, the removal substrate approach is not only simple, and
The performance of graphene oxide film and the influence of pattern during this allow this method easily to realize graphene paper and lining
The separation at bottom, the problem of being attached on substrate, be not readily separated application in effective solution graphene paper preparation process, meanwhile,
The graphene paper has the chemical property better than common graphite alkene paper after tested, and applicant guesses that this is derived from during EFI
The introducing of two-dimentional moveable platform causes graphene oxide microplate to disperse in an assembling process more uniform, simultaneously because electric
The presence of field force effect reduces the gap between graphene oxide layer, can all lead to the raising of chemical property；In addition, by
There is fibre structure in nano fibrous membrane substrate, so that the graphene substrate surface also has the micro- knot complementary with substrate tunica fibrosa
Structure, the difference in this structure may be the reason of graphene paper is had excellent performance.
(2) nano fibrous membrane substrate obtained is made as collector using the metal plate with pierced pattern in step (1)
With patterned structure, electrostatic is connected using the metal plate with pierced pattern as collecting plate again in step (2)
The high voltage power supply of mist device, in patterned nanofiber film surface EFI graphene oxide film, in spray head and collecting plate
Between non-uniform electric field and patterned nano fibrous membrane double action under so that substrate surface formed graphene oxide it is thin
Film also has pattern structure, can be readily available the graphene paper with pattern structure by subsequent processing, meanwhile,
Two-dimensional movement platform is controlled by computer, and computer can be driven by pre-set process control two-dimensional movement platform and be collected
Pole plate does shuttling movement on X, Y-direction, thus the even application graphene oxide on nano fibrous membrane substrate, it can be according to reality
Border needs, and prepares the graphene paper of large area, can also set cycle-index on computers, to control the thickness of film forming, expands
The application field of material.
Detailed description of the invention
Fig. 1: the structural schematic diagram of electrostatic atomizer used in embodiment；
Fig. 2: the flow chart of the preparation method of embodiment 1；
Fig. 3: the electron scanning micrograph of graphene paper made from embodiment 1；
Fig. 4: the electron scanning micrograph in the section of the graphene paper of embodiment 1；
Fig. 5: graphene paper electrode constant current charge-discharge curve graph made from embodiment 1；
Fig. 6: the optical microscope photograph of graphene paper made from embodiment 2；
In figure, 1- promotes pump；2- liquid storage mechanism；3- spray head；4- high voltage power supply；5- two-dimensional movement platform；6- computer；7-
Collecting plate；8- perfusion tube.
Specific embodiment
In order to clarify the technical characteristics of the invention, being illustrated below by embodiment to this programme.
The embodiment of the present invention thus electrostatic atomizer structure as shown in Figure 1, the electrostatic atomizer include storage
There is the liquid storage mechanism 2 of graphene oxide dispersion, the liquid storage mechanism 2 is mounted on propulsion pump 1, the liquid storage mechanism
2 connect spray head 3 by perfusion tube 8, and spray head connects the anode of high voltage power supply 4, and the collecting mechanism of the electrostatic atomizer includes two
Mobile platform 5 is tieed up, the collecting plate 7 of connection high voltage power supply (4), the two-dimensional movement are placed in the two-dimensional movement platform 5
Platform 5 is controlled by computer 6, and computer 6 can drive collecting plate by pre-set process control two-dimensional movement platform 5
7 do shuttling movement on X, Y-direction, can set cycle-index on computers, to control the thickness of film forming.
Embodiment 1
As shown in the flowchart of figure 2, a kind of preparation method of graphene paper, comprising the following steps:
(1) electro spinning nanometer fiber membrane substrate: the ratio of nylon and formic acid 3:22 in mass ratio mixing, with magnetic stirring apparatus into
Row stirring obtains uniform spinning precursor liquid in 4 hours, gained spinning precursor liquid is added in the liquid storage mechanism of electrostatic spinning apparatus, with
Aluminium foil prepares nylon nano fiber film as collector, using method of electrostatic spinning, spinning power supply 20kV, spinning distance 12-15cm,
Spinning solution 3ml obtains nano fibrous membrane substrate on aluminium foil；
(2) graphene oxide dispersion EFI combined oxidation graphene film: is placed in electrostatic atomizer shown in FIG. 1
Liquid storage mechanism 2 in, the two-dimensional movement that the aluminium foil for being attached with step (1) nano fibrous membrane substrate is placed in electrostatic atomizer is flat
On platform 5, collecting plate 7 using the aluminium foil as electrostatic atomizer is straight on nano fibrous membrane substrate using electrostatic spraying processes
Spraying combined oxidation graphene film is connect, collecting plate 7 does circulation fortune under the drive of two-dimensional movement platform on X, Y-direction
It is dynamic, graphene oxide film is formed in nano fibrous membrane substrate surface uniform deposition, 4 output voltage of high voltage power supply during this
8KV is promoted and is pumped 1 fltting speed 30ul/min, and the vertical distance of spray head and nano fibrous membrane substrate is 2.5cm, the oxidation
The solvent of graphene dispersing solution is n,N-Dimethylformamide, and contained graphene oxide concentration is 11.7mg/g；
(3) it removes substrate: it is molten that the resulting aluminium foil (collecting plate) for being attached with composite film material of step (2) being dipped in formic acid
In liquid, until graphene oxide film is separated with aluminium foil after dissolving nylon nano fiber film, sample is cleaned with deionized water
Product obtain graphene oxide film；
(4) step (3) resulting graphene oxide film redox graphene: is dipped in the hydrogen iodine that concentration is 88wt%
It in acid, heats 100 DEG C and restores 1 hour, graphene oxide is reduced, and with deionized water repeated flushing 3 times, gained sample is put
Enter in vacuum shelf dryer up to graphene paper after air drying, the thickness of gained graphene paper is about 1-5 μm, and view EFI circulation is secondary
Depending on number, the electron scanning micrograph in resulting graphene paper surface and section is as shown in Figure 3 and Figure 4, by Fig. 3 and Fig. 4
It can be seen that the graphene paper surface has the micro-structure complementary with substrate fiber, while from sectional view it is also seen that by the party
The material of method preparation is graphene film interlayer part folded array made of being added as finely dispersed graphene film layer stackup, piece
Interlayer is combined closely, and gap is small and uniform.
Performance test: taking the graphene paper of a piece of above-mentioned preparation, is cut into about 1 square centimeter of size of circular electric
Graphene electrodes are placed on diaphragm two and surveyed by pole piece, are instilled appropriate KOH aqueous solution (KOH concentration 6mol/L) and are made as electrolyte
Double layer capacitor, and 8 hours are stood, electro-chemical test is carried out in two-electrode system, tests graphene paper electrode in difference
Constant current charge-discharge characteristic under current density, as shown in figure 5, in different discharge current density 1A/g, 2A/g, 5A/g, under 10A/g
Utilize formula:
The specific capacity that electrode can be calculated is respectively 185F/g, 172F/g, 147F/g, 117F/, and high rate performance is preferable.
Fig. 5 is the constant current charge-discharge curve graph that graphene paper makees that electrode of super capacitor carries out electro-chemical test, it can be seen from the figure that
Using this method preparation graphene paper chemical property well, voltage drop very little calculates under 1A/g current density
Specific capacity be 185F/g.Electrode capacity is an important indicator of capacitor quality, compared to the pure graphite of other methods preparation
The volumetric properties of alkene paper are preferable.
Embodiment 2
A kind of preparation method of graphene paper, comprising the following steps:
(1) electro spinning nanometer fiber membrane substrate: the ratio of nylon and formic acid 3:22 in mass ratio mixing, with magnetic stirring apparatus into
Row stirring obtains uniform spinning precursor liquid in 4 hours, gained spinning precursor liquid is added in the liquid storage mechanism of electrostatic spinning apparatus, with
Metal plate with hollow out circular pattern prepares nylon nano fiber film, spinning power supply as collector, using method of electrostatic spinning
20kV, spinning distance 15cm, spinning solution 3ml obtain nano fibrous membrane on the metal sheet surface with hollow out circular pattern
Substrate；
(2) graphene oxide dispersion EFI combined oxidation graphene film: is placed in electrostatic atomizer shown in FIG. 1
Liquid storage mechanism 2 in, the metal plate with hollow out circular pattern for being attached with step (1) nano fibrous membrane substrate is placed in electrostatic
In the two-dimensional movement platform 5 of mist device, collecting plate 7 using the metal plate with hollow out circular pattern as electrostatic atomizer,
Using electrostatic spraying processes, direct spraying combined oxidation graphene film, collecting plate 7 are moved in two dimension on nano fibrous membrane substrate
Shuttling movement is done on X, Y-direction under the drive of moving platform, forms graphite oxide in nano fibrous membrane substrate surface uniform deposition
Alkene film, 4 output voltage 10KV of high voltage power supply during this promote 1 fltting speed 40ul/min of pump, spray head and nano fibrous membrane
The vertical distance of substrate is 4cm, and the solvent of the graphene oxide dispersion is n,N-Dimethylformamide, contained oxidation
Graphene concentration is 11.7mg/g；
(3) substrate is removed: by the composite film material on the resulting collecting plate 7 for being attached with composite film material of step (2)
It is removed from collecting plate 7, composite film material is dipped in formic acid solution, until being spent after dissolving nylon nano fiber film
Ionized water cleaning sample, obtains graphene oxide film；
(4) step (3) resulting graphene oxide film redox graphene: is dipped in the hydrogen iodine that concentration is 88wt%
It in acid, heats 100 DEG C and restores 1 hour, graphene oxide is reduced, and with deionized water repeated flushing 3 times, gained sample is put
Enter in vacuum shelf dryer up to graphene paper after air drying, the thickness of gained graphene paper is about 1-5um, and view EFI circulation is secondary
Depending on number, gained is as shown in Figure 6 with a thickness of the optical microscope photograph of 3 μm of graphene paper.
Embodiment 3
A kind of preparation method of graphene paper, comprising the following steps:
(1) electro spinning nanometer fiber membrane substrate: polyethylene pyrrole network alkanone (PVP) is dissolved in deionized water, with before solution-polymerized SBR
Liquid is driven, the mass fraction of PVP is 12% in spinning precursor liquid, and gained spinning precursor liquid is added to the liquid storage machine of electrostatic spinning apparatus
In structure, using the metal plate with hollow out circular pattern as collector, nylon nano fiber film, spinning are prepared using method of electrostatic spinning
Power supply 20kV, spinning distance 15cm, spinning time 20min obtain nanometer on the metal sheet surface with hollow out circular pattern
Tunica fibrosa substrate；
(2) graphene oxide dispersion EFI combined oxidation graphene film: is placed in electrostatic atomizer shown in FIG. 1
Liquid storage mechanism 2 in, the metal plate with hollow out circular pattern for being attached with step (1) nano fibrous membrane substrate is placed in electrostatic
In the two-dimensional movement platform 5 of mist device, collecting plate 7 using the metal plate with hollow out circular pattern as electrostatic atomizer,
Using electrostatic spraying processes, direct spraying combined oxidation graphene film, collecting plate 7 are moved in two dimension on nano fibrous membrane substrate
Shuttling movement is done on X, Y-direction under the drive of moving platform, forms graphite oxide in nano fibrous membrane substrate surface uniform deposition
Alkene film, 4 output voltage 10KV of high voltage power supply during this promote 1 fltting speed 40ul/min of pump, spray head and nano fibrous membrane
The vertical distance of substrate is 4cm, and the solvent of the graphene oxide dispersion is n,N-Dimethylformamide, contained oxidation
Graphene concentration is 11.7mg/g；
(3) it removes substrate: the resulting collecting plate 7 for being attached with composite film material of step (2) is transferred in Muffle furnace,
Logical oxygen, 500-600 DEG C of temperature control is heat-treated 1 hour, and nano fibrous membrane substrate is burned off, and takes out sample to get pure oxygen graphite
Alkene film；
(4) redox graphene: step (3) resulting graphene oxide film being placed in Muffle furnace, argon gas is passed through,
800 DEG C of temperature control are heat-treated 1 hour, and graphene oxide is reduced, and obtains pure graphene paper.
Embodiment enumerated above is not to technical solution described in the invention only for understanding that the present invention is used
Restriction, the those of ordinary skill in relation to field on the basis of the technical solution described in claim, can also make a variety of changes
Change or deformation, all equivalent variations or deformation should all be covered within the scope of the claims of the present invention.The present invention is not
Place is described in detail, is the well-known technique of those skilled in the art of the present technique.
Claims (10)
1. a kind of preparation method of graphene paper, which comprises the following steps:
(1) electro spinning nanometer fiber membrane substrate: preparing high molecular polymer spinning precursor liquid, and electrostatic is added in gained spinning precursor liquid
In the liquid storage mechanism of device for spinning, high molecular polymer nano fibrous membrane is prepared using method of electrostatic spinning, i.e., on collecting bottom plate
Obtain nano fibrous membrane substrate；
(2) EFI combined oxidation graphene film: graphene oxide dispersion is placed in the liquid storage mechanism of electrostatic atomizer,
Step (1) nano fibrous membrane substrate is placed on the collecting mechanism of electrostatic atomizer, using electrostatic spraying processes in nanofiber
Direct spraying combined oxidation graphene film on film substrate；
(3) it removes substrate: the nano fibrous membrane substrate of step (2) resulting composite film material being removed, it is thin to obtain graphene oxide
Film；
(4) redox graphene: step (3) resulting graphene oxide film is restored up to graphene paper.
2. a kind of preparation method of graphene paper as described in claim 1, which is characterized in that macromolecule described in step (1)
Material is nylon, polyethylene pyrrole network alkanone, polyethylene glycol oxide, Kynoar, polycaprolactone, polystyrene, polymethyl
One of sour methyl esters is a variety of.
3. a kind of preparation method of graphene paper as described in claim 1, which is characterized in that the collection of the step (1)
Bottom plate is the metal plate with pierced pattern.
4. a kind of preparation method of graphene paper as claimed in claim 3, which is characterized in that the step (2) is by oxygen
Graphite alkene dispersion liquid is placed in the liquid storage mechanism of electrostatic atomizer, and the collecting mechanism of the electrostatic atomizer is computer
The two-dimensional movement platform of control, the collection bottom plate by step (1) nano fibrous membrane substrate together with its bottom are placed in two-dimentional shifting
On moving platform, using electrostatic spraying processes on nano fibrous membrane substrate direct spraying combined oxidation graphene film, the step
Suddenly during the electrostatic spray of (2), the vertical distance of spray head and nano fibrous membrane substrate is 1.5~4cm, spray voltage 7~
The propulsion of 10KV, liquid storage mechanism pump 20~40 μ L/min of fltting speed.
5. a kind of preparation method of graphene paper as described in claim 1, which is characterized in that oxidation stone described in step (2)
The solvent of black alkene dispersion liquid is n,N-Dimethylformamide, and contained graphene oxide concentration is 11.7mg/g.
6. a kind of preparation method of graphene paper as described in claim 1, which is characterized in that the step (3) is that will walk
Suddenly (2) resulting composite film material is dipped in the solvent of the high molecular polymer of dissolvable step (1), is impregnated until nanofiber
Film substrate takes out sample after being completely dissolved, and graphene oxide film is obtained after being cleaned with deionized water.
7. a kind of preparation method of graphene paper as described in claim 1, which is characterized in that the step (3) is step
(2) resulting composite film material carries out high-temperature heat treatment under oxygen atmosphere, burn up take out after nano fibrous membrane substrate sample to get
Graphene oxide film.
8. a kind of preparation method of graphene paper as described in claim 1, which is characterized in that the step (4) is that will walk
Suddenly (3) resulting graphene oxide film, which is placed in reducing agent, carries out reduction reaction, after graphene oxide is reduced to graphene,
Cleaning, dry gained sample are up to graphene paper.
9. a kind of preparation method of graphene paper as claimed in claim 8, which is characterized in that the step (4) is that will walk
Suddenly (3) resulting graphene oxide film is dipped in the hydroiodic acid that concentration is 88wt%, is heated 100 DEG C and is restored 1 hour, aoxidizes stone
Black alkene is reduced, and with deionized water repeated flushing 3-4 times, gained sample is put into vacuum shelf dryer after air drying to obtain the final product
Graphene paper.
10. a kind of preparation method of graphene paper as described in claim 1, which is characterized in that the step (4) is that will walk
Suddenly (3) resulting graphene oxide film carries out high-temperature heat treatment under reducing atmosphere, until graphene oxide is reduced to get stone
Black alkene paper.
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| CN104409222A (en) * | 2014-11-21 | 2015-03-11 | 华东理工大学 | Preparation method for ternary composites of graphene/manganese dioxide nanosheet /polyaniline nanorod |
| CN105322146A (en) * | 2015-09-28 | 2016-02-10 | 复旦大学 | Molybdenum selenide/carbon nanofiber/graphene composite material and preparation method thereof |
| CN105883781A (en) * | 2016-03-09 | 2016-08-24 | 王祉豫 | Preparation method of large-area reduced graphene oxide membrane |
| CN106698405A (en) * | 2017-01-12 | 2017-05-24 | 东南大学 | Method for preparing large-area graphene paper by utilizing hydroiodic acid |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409222A (en) * | 2014-11-21 | 2015-03-11 | 华东理工大学 | Preparation method for ternary composites of graphene/manganese dioxide nanosheet /polyaniline nanorod |
| CN105322146A (en) * | 2015-09-28 | 2016-02-10 | 复旦大学 | Molybdenum selenide/carbon nanofiber/graphene composite material and preparation method thereof |
| CN105322146B (en) * | 2015-09-28 | 2017-07-28 | 复旦大学 | A kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof |
| CN105883781A (en) * | 2016-03-09 | 2016-08-24 | 王祉豫 | Preparation method of large-area reduced graphene oxide membrane |
| CN106698405A (en) * | 2017-01-12 | 2017-05-24 | 东南大学 | Method for preparing large-area graphene paper by utilizing hydroiodic acid |
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