CN106698407A - Flexible graphene film capable of being repeatedly folded, preparation method of flexible graphene film and flexible device comprising flexible graphene film - Google Patents
Flexible graphene film capable of being repeatedly folded, preparation method of flexible graphene film and flexible device comprising flexible graphene film Download PDFInfo
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- CN106698407A CN106698407A CN201710157761.1A CN201710157761A CN106698407A CN 106698407 A CN106698407 A CN 106698407A CN 201710157761 A CN201710157761 A CN 201710157761A CN 106698407 A CN106698407 A CN 106698407A
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Classifications
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
- C01P2006/90—Other properties not specified above
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention provides a flexible graphene film capable of being repeatedly folded, a preparation method of the flexible graphene film and a flexible device comprising the flexible graphene film. The graphene film is obtained by carrying out reduction treatment on a graphene oxide film; a porous structure is formed in the thickness direction of the graphene film; after the graphene film is folded, the graphene film can be recovered and folds are not formed; the thickness of the graphene oxide film is 0.01mu m to 500mu m; compared with the thickness of the graphene oxide film, the expanding multiple of the thickness of the graphene film is 2 to 30 times. The flexible graphene film provided by the invention has the advantages that the porous structure is formed in the thickness direction of the graphene film and the surface of the thin film is smooth and flat; the film has excellent flexible and foldable performance and can be rapidly recovered and has no folds after being folded singly or doubly for a plurality of times; after the film is treated at high temperature, the flexibility can still be kept. The preparation method provided by the invention is simple and convenient to operate and has the advantages of relatively low reduction temperature, small dosage of a reducing agent and small pollution to environment.
Description
Technical field
The flexibility assembled the present invention relates to a kind of Flexible graphene film and preparation method thereof and using the Flexible graphene film
Device, belongs to graphene film technical field.
Background technology
Graphene is to pass through sp by carbon atom2Hydridization close-packed arrays and the monolayer honeycomb shape lattice two dimensional crystal that is formed, it
Possess great specific surface area, excellent mechanical property, electric conductivity, heat conductivility, be a kind of material of very attractive.Stone
Black alkene film possesses the attributes such as stronger electric conductivity, thermal conductivity, flexibility as a kind of important morphological of Graphene so that it
The fields such as energy storage and transition material, electromagnetic shielding material, Heat Conduction Material, sensor material have a wide range of applications.
In order to adapt to demand of the modern life to flexible wearable electronic equipment, a kind of flexible, folding graphene film of exploitation and
Its preparation method tool is of great significance.
At present, the method for preparing graphene film can be largely classified into two kinds：One kind is direct using graphene nanometer sheet
Film forming, it is another kind of, it is by being obtained by further reduction treatment after graphene oxide film forming.For the former, although main
It is related to physical treatment method, but often causes that the mechanical property of resulting graphene film is poor.And the latter is by oxidation
The graphene film mechanical property carried out obtained by chemical or thermal reduction to it after Graphene film forming is preferable.Therefore, the latter is also current
The method for preparing graphene film for generally using.Electronation plays great work in the method for redox graphene film
With the electronation reagent for generally using has hydrazine, reproducibility acid or phenol, metal hydride, active metal, biological reductant
Deng.Additionally, the preparation method of the graphene film also having been reported that includes composite method, electrochemical reducing, chemical vapor deposition
Area method (CVD), arc discharge method etc., but technique is typically complex.
However, though graphene film prepared at present has flexibility, bent, but the overwhelming majority can not roll over
It is folded, can be broken after folding.Only one report is foldable by the graphene film of finely regulating preparation at present, but in folding
Poststack can produce plastic deformation, with folding line (citation [1]).Meanwhile, graphene film is generally solid construction, be unfavorable for its
Application in terms of energy storage and conversion.Additionally, thickness swelling can be prepared using hydrazine hydrate steam reduction graphene oxide film
50 times of honeycomb hole construction recovery graphene oxide foam (reference document [2]), but the flexibility of this film is not good, especially exists
It is easily broken again during stress and deformation.
Citation：
[1]M.Zang,Y.L.Wang,L.Huang,Z.P.Xu,C.Li,and G.Q.Shi,Multifunctional
Pristine Chemically Modified Graphene Films as Strong as Stainless Steel,Adv
Mater.2015,27:6708-6713；
[2]Z.Q.Niu,J.Chen,H.H.Hug,J.Ma,and X.D.Chen,A Leavening Strategy to
Prepare Reduced Graphene Oxide Foams,Adv Mater.2012,24:4144-4150.
Therefore, it is just existing for the research of graphene film, further research is also needed for the pliability of film, especially
It is to Flexible graphene film can folding property realization or improvement can not be said to be sufficient.
The content of the invention
Problems to be solved by the invention
For the problem that prior art is present, present invention firstly provides a kind of Flexible graphene film that can be folding,
The Flexible graphene film has loose structure in a thickness direction, the fast quick-recovery of energy after substance or multiple folding, and is folding
Point does not produce plastic deformation, does not stay folding line, is kept at the flatness and non-collapsible of burst or with before folding generation
It is identical.Meanwhile, the Flexible graphene film also has preferable mechanical property.
And then, present invention provides a kind of method for preparing above-mentioned Flexible graphene film that can be folding.
Additionally, present invention provides a kind of flexible device based on above-mentioned Flexible graphene film that can be folding, especially
It is flexible super capacitor.
The scheme for solving problem
Present invention firstly provides a kind of Flexible graphene film that can be folding, the Flexible graphene film is by right
Graphene oxide membrane carries out reduction treatment and obtains, and has loose structure, institute in the Flexible graphene film thickness direction
Stating Flexible graphene film can be folded, and after being restored to the folding, not occur in the burst of the Flexible graphene film
Plastic deformation；
The thickness of the graphene oxide membrane is 0.01-500 μm, preferably 2-100 μm；
Relative to the thickness of the graphene oxide membrane, the expansion multiple of the thickness of the Flexible graphene film is 2-30
Times, preferably 10-20 times.
Flexible graphene film in accordance with the above, the substance that is folded into is folded or multiple folding, and folding angles are small
In or equal to 180 °.
Flexible graphene film in accordance with the above, the reduction treatment is to be reduced with hydrazine hydrate solution.
Flexible graphene film in accordance with the above, the graphene oxide membrane is by graphene oxide powder or oxidation stone
Ink powder body is dispersed through liquid and is obtained through into film process or by its pressed by powder film forming.
Further, present invention provides a kind of preparation method of Flexible graphene film that can be folding, methods described
Comprise the following steps：
Step 1：Liquid is dispersed through into film process or by its pressed by powder by graphene oxide powder or by graphite oxide powder
The step of film forming；
Step 2：The step of reduction treatment is carried out to graphene oxide membrane and Flexible graphene film is obtained,
The Flexible graphene film has loose structure in a thickness direction, and the Flexible graphene film can be folded, and
After being restored to the folding, there is no plastic deformation in the burst of the Flexible graphene film,
The thickness of the graphene oxide membrane is 0.01-500 μm, preferably 2-100 μm；Relative to the graphene oxide
The thickness of film, the expansion multiple of the thickness of the Flexible graphene film is 2-30 times, preferably 10-20 times.
According to the preparation method of above Flexible graphene film, the concentration of dispersion liquid described in step 1 is 0.01-100mg/
mL；The dispersion solvent used in the dispersion liquid is selected from one or more in water or organic solvent.
According to the preparation method of above Flexible graphene film, it is selected from into film process described in step 1：Vacuum filtration film forming,
One kind in solvent volatilization film forming, spin-coating film, spraying film forming and solution surface/interfacial assembly film forming.
According to the preparation method of above Flexible graphene film, reduction treatment described in step 2 comprises the following steps：In oxidation
Graphene membrane surface uncoated hydrous hydrazine solution infiltrates in hydrazine hydrate solution graphene oxide membrane, carries out reduction reaction, its
In, the concentration of the hydrazine hydrate solution is 1-80%, preferably 20-80%.
According to the preparation method of above Flexible graphene film, reduction treatment described in step 2 is to carry out in a heated condition,
Wherein, heating-up temperature is 40-200 DEG C, and the heat time is 1min-7d, it is preferable that heating-up temperature is 70-100 DEG C, heat time
It is 0.5-12h.
According to the preparation method of above Flexible graphene film, the substance that is folded into is folded or multiple folding, folding angles
It is less than or equal to 180 °.
According to the preparation method of above Flexible graphene film, the preparation method also includes post-processing step, the rear place
Reason step includes：The step of being made annealing treatment to Flexible graphene film in atmosphere of inert gases, preferably in argon atmosphere
In made annealing treatment under conditions of -3000 DEG C of room temperature.
Additionally, present invention also offers a kind of flexible device, the flexible device includes can roll over repeatedly according to more than
Folded Flexible graphene film or according to above-mentioned preparation method obtain can be folding Flexible graphene film.
According to above flexible device, it includes flexible energy storage and transfer electron, flexible sensor, flexible super electric capacity
Device, flexible electromagnetic shielding film, flexible conducting material or flexible Heat Conduction Material.
The effect of invention
The invention provides a kind of Flexible graphene film that can be folding, compared with existing grapheme material, with such as
Lower advantage：
A () Flexible graphene film of the invention has loose structure in a thickness direction, and film surface is smooth, smooth,
Thickness swelling multiple is controlled between 2-30 times,
B () Flexible graphene film of the invention has excellent pliability and excellent foldability energy, multiple substance
Or after double folding, the graphene film still can quick-recovery soon, and do not stay folding line in burst,
Even if c () is after through high-temperature post-treatment, its pliability remains to keep, so as to expand its use condition and side
Formula, can provide excellent, lasting performance under environmental condition widely.
D () preparation method of the present invention is simple, easy to operate, reduction temperature is relatively low, and reducing agent consumption is small, environmental pollution
It is small.
Therefore, Flexible graphene film that can be folding provided by the present invention, with and preparation method thereof gained flexibility
Graphene film product is in the field such as flexible electrode material, ultracapacitor or rechargeable battery, Heat Conduction Material, electromagnetic shielding material
All it is with a wide range of applications.
Brief description of the drawings
Fig. 1 shows the folding degree (θ angles) in the present invention；
Fig. 2 is the Flexible graphene film of preparation in embodiment 1 through the scanning electron microscope diagram piece after substance folding；
Fig. 3 is the Flexible graphene film of preparation in embodiment 1 through the scanning electron microscope diagram piece after double folding；
Fig. 4 is that the Flexible graphene film of preparation in embodiment 2 folds the optical imagery launched after pressing；
Fig. 5 is that the Flexible graphene film of preparation in embodiment 2 folds expansion, the front including folding point after pressing
(a), reverse side (b), section (c) scanning electron microscope diagram piece；
Fig. 6 is the optics launched after 1300 DEG C of Flexible graphene films folding pressings of post processing of preparation in embodiment 2
Image；
Fig. 7 be prepare in embodiment 2 fold pressing through 1300 DEG C of Flexible graphene films of post processing after launch, include
Fold front (a), reverse side (b), section (c) the scanning electron microscope diagram piece of point；
Fig. 8 is the image of the ultracapacitor that the graphene film obtained by the present invention is prepared into, including unfolded (a), through list
180 ° are weighed to fold (b), fold (c) through dual 180 °；
Specific embodiment
Hereinafter, various specific embodiments of the invention will be described in detail.
First embodiment
In first embodiment of the invention, there is provided a kind of Flexible graphene film that can be folding.
The Flexible graphene film is obtained, the Flexible graphene film by carrying out reduction treatment to graphene oxide membrane
Having loose structure, the Flexible graphene film in a thickness direction can rapidly recover after folding and not stay folding line.Specifically：
<Graphite oxide>
Graphene oxide membrane in the present invention, refers to that the dispersion liquid of graphene oxide powder or graphite oxide powder is carried out
Processed through press mold into film process or its powder and obtained.
The preparation method for preparing graphite oxide at present mainly has physical method and chemical method.Physical method is typically with honest and clean
The crystalline flake graphite or expanded graphite of valency are raw material, by without substrate gas phase synthesis method, thermal expansion stripping method, mechanical stripping method, liquid
Phase or the direct stripping method of gas phase etc. directly prepare the graphite of single or multiple lift, then obtain final product graphite oxide by a series of oxidation.
The advantage of Physical is that raw material is easy to get, and operates relatively easy, and the graphite purity of synthesis is high, but time-consuming, the shortcomings of low yield
Make them unsuitable for large-scale production.Chemical method is typically all oxidized by natural flake graphite or natural graphite powder and peels off system
It is standby, mainly have Brodie methods, Staudenmaier methods, Hummer methods etc. using more method for oxidation, Brodie methods and
Staudenmaier methods, degree of oxidation is easily controlled, but pernicious gas can be produced in course of reaction, and the reaction time is very long.
Staudemaier methods are more tight to graphite laminate structural damage using the concentrated sulfuric acid and the mixing acid treatment graphite of fuming nitric aicd
Weight.The Hummer method reaction time is short, is produced without toxic gas, and security is higher, thus is commonly used as graphite oxide is prepared
Method.
As long as the graphite oxide powder material in the present invention does not just have in the case where final effect of the invention is not influenceed
There is special limitation.For example, graphite oxide powder of the invention can be to peel off to obtain by the oxidation of graphite, the oxidation
Stripping means is Brodie methods, Staudemaier methods or Hummer methods.
Aoxidizing the principle of stripping method is：Processed with inorganic strong protonic acid (concentrated sulfuric acid and fuming nitric aicd or their mixture)
Raw material graphite, graphite layers are inserted by strong acid small molecule, then with strong oxidizer (KMnO4、KClO4Deng) it is aoxidized.By force
The concentration and oxidization time of oxidant have considerable influence to the size and thickness of graphite oxide, by controlling response parameter, can be with
Degree of oxidation graphite oxide powder higher is prepared, reaction efficiency is improved, is easy to next step to use reducing agent reduction-oxidation
Graphite composite powder synthesizing graphite alkene film.
In the present invention, for production facility and security angle for, preferably use and be prepared into through Hummer methods
The graphite oxide powder for arriving, especially present invention preferably uses the graphite oxide powder that improved Hummer methods are prepared.
For example, 5g natural flake graphites, 5g sodium nitrate, ice-water bath feelings are added in dry 500mL there-necked flasks
To 98% concentrated sulfuric acid that 150mL is slowly added in there-necked flask under condition, opening agitating paddle stirring is completely dissolved solid mixture.
Divide 5 times and be slowly added to 15g potassium permanganate, per minor tick 12min, control temperature is at 0-5 DEG C.There-necked flask is warming up to 35 DEG C,
And stirring reaction 6h at this temperature.Then be added slowly with stirring 200mL deionized waters, control temperature 95-100 DEG C it
Between continue react 15min.After the completion of reaction, liquid in there-necked flask is poured into the beaker of 2000mL, be added thereto to 700mL
Deionized water dilute reaction solution, adds 30% hydrogen peroxide 50mL, stirring, and now solution is in glassy yellow.With 15% salt acid elution
Solution, pours out supernatant liquid after stratification, same method carries out a pickling again.After being washed twice with deionized water, finally
The graphite oxide mud for obtaining pH value ≈ 7 is centrifuged with supercentrifuge, freeze-drying obtains graphite oxide powder after grinding, protects
Deposit standby.
<Graphene oxide membrane>
In the present invention, graphene oxide powder or above-mentioned resulting graphite oxide powder can be distributed in solvent and obtained
To graphene oxide dispersion, then dispersion liquid is carried out to dispersion liquid into film process to obtain the graphene oxide membrane；Can also
Graphene oxide powder or graphite oxide powder obtained above are carried out into pressing mold treatment to obtain the graphene oxide membrane.
For in the present invention graphene oxide dispersion into film process, there is no particular limitation, as long as will can aoxidize
Graphene dispersing solution is processed into the film of satisfactory smooth even, can be volatilized from vacuum filtration film forming, solvent
One kind in film forming, spin-coating film, spraying film forming and solution surface/interfacial assembly film forming, preferably spun on film forming.Spin-coating film
Method is attached the substrate on the flat board on spin coating instrument, while spin coating instrument is rotated with certain revolution, in the upper of its middle
Certain density graphene oxide solution is dripped with given pace in side, and the graphene oxide for dripping is more, the graphite oxide for obtaining
Alkene film is thicker.
In the present invention, there is no particular limitation for the thickness of above-mentioned graphene oxide membrane, is disperseed according to above-mentioned graphene oxide
The concentration and volume of liquid is adjusted, it is however generally that, its thickness between 0.01-500 μm, between preferably 2-100 μm.If on
The thickness of graphene oxide membrane is stated more than 500 μm, may cause that the graphene film that next step reduction treatment is obtained is also blocked up, may
The flexibility of graphene film, foldability is caused to be deteriorated；If coating thickness is too low, the uniformity coefficient of film forming may be influenceed (outstanding
It is the surface smoothness of film, smoothness) and subsequent film product mechanical property etc..
In the present invention, it is also possible to which graphene oxide powder or above-mentioned resulting graphite oxide powder are carried out into press mold shaping
Treatment, to obtain the graphene oxide membrane.
<Reduction treatment>
In the present invention, graphene oxide membrane obtained above is carried out reduction treatment to obtain graphene film.
For the reduction treatment of graphene oxide membrane, reduction treatment is carried out from reducing agent hydrazine hydrate solution in the present invention,
Because graphene oxide membrane can be expanded in a thickness direction during hydrazine hydrate solution is reduced, obtain cellular porous
The graphene film of structure.Specifically, can be in graphene oxide membrane surface uncoated hydrous hydrazine solution or by graphene oxide membrane
Infiltrate in hydrazine hydrate solution and take out, then typically can for example be clipped between two smooth sheets carries out reduction reaction, this hair
Bright discovery, even if the usage amount of less reducing agent, can also also improve the effective depth of reduction.Heretofore described hydrazine hydrate solution
The optional wider range of concentration, such as reductant solution concentration can select 1-80%, preferably 20-80%.For reduction treatment
Temperature, the present invention in reduction treatment carry out in a heated condition, preferably 40-200 DEG C, more preferably 70-100 DEG C, fire-bar
The speed of reduction reaction is favorably improved under part.
Additionally, for the time of reduction treatment, depending on different reductant concentrations, reduction temperature, required reducing degree without
Together, for example can be a few minutes to several days.In the present invention, the reduction treatment time is preferably -7 days 1 minute, preferably 0.5-12h.
During above-mentioned reduction treatment is carried out, relative to the thickness of above-mentioned graphene oxide membrane, the graphene film
Thickness expansion multiple be 2-30 times.Preferably, the expansion multiple of the thickness of the graphene film is 10-20 times.The present invention
It was found that, when the expansion multiple of Graphene is between 10-20 times, can more favorably be formed it is of the invention can be folding
Flexible graphene film.Under conditions of some are extreme, for example, limited by some restoring method, when the expansion of control Graphene
When multiple is less than 10 times, although will not finally lead to not realize effect of the invention, but extra supplementary means may be needed,
The complexity of equipment can be increased and controllability is reduced；When the expansion multiple of Graphene is more than 20 times, in some extreme feelings
Under condition, the final thickness of such as Graphene is thicker, although will not finally lead to not realize effect of the invention, but folding
Number of times have reduction relative to optimal effectiveness.
Although additionally, be also related to that graphene oxide membrane is carried out the record of hydrazine hydrate steam treatment in the prior art,
The expansion multiple of the graphene film obtained by it is higher, about 50 times or so, and thus, the thickness of resulting graphene film is thicker.
Therefore, plastic deformation can occur after folding, it is impossible to automatically reply back original state, folding line can be left.Even due on thickness direction
Expansion multiple it is too high and cause the flexibility of graphene film, degraded toughness, although disclosure satisfy that certain mechanical performance, but nothing
Method realizes that flexibility is used, and especially easily graphene film is directly broken in burst in the case of folding.And according to this
The viewpoint of invention, the loose structure that the graphene film in the present invention is formed in a thickness direction, because the control of its expansion multiple exists
Within present invention scope defined above, may cause that it has good mechanical property, also, obtaining flexible foldable
Can quickly be restored to the original state without leaving folding line again while property.
Loose structure of the invention comes from the gas produced by reduction reaction.Typically, loose structure of the invention can be with
So that showing the structure of layering inside Graphene.Each layer can continuously or discontinuously, rule or irregular.Loose structure
The hole of formation launches with along the direction of graphene film plane, can be that insertion can also be not insertion between this some holes
's.
Folding in the present invention, can be the folding of substance folding, double folding to graphene film or more weight.Fold
Degree can be less than or equal to 180 °, such as shown in Fig. 1, fold degree can be more than 10 °, more than 40 °, more than 90 °,
More than 120 ° or 160 ° with first-class.It should be further stated that, folding of the invention refers to folding the introversion of point
Situation of the rate radius close to zero.Fold point outer curvature radius be not particularly limited, for example can be thickness 1/2 with
On.Typically, represented in the form of accompanying drawing 1 and folded defined in the present invention.Now, the signified doubling of the present invention can refer to from folding
There is overlapped or parallel situation in two folding faces that the folding point of folded point side section sets out, that is, the degree for folding is (θ
Angle) 180 °.In addition, typically, folding point, the continuous linear or curve for folding are produced.Typically, folding
When, burst can apply pressure on twocouese.
Graphene film recovers rapidly in burst and does not leave folding line after folding of the present invention, refers to, feels in macroscopic view
There is no plastic deformation in official face, the burst of graphene film, thus, will not also occur in appearance relative to folding before folding
Place part or the difference of the part folded with other.Particularly be not in the smoothness of graphene membrane surface, put down
Difference on whole degree or other performances.From microcosmic, the burst of graphene film before being folded after microscopic appearance not yet
There is obvious change, such as from the test of tangent plane Electronic Speculum, pore size, distribution before and after burst folding etc. do not occur obvious
Change.Such performance is described in accompanying drawing 2- accompanying drawings 7.
Folding involved folding times of the invention are not limited, and can be the folding of 2 foldings or more time.
Typically, folding times of the invention can be more than 2000 times, the effect above before and after preferably more than 3000 times, and folding
Still keep.Fold occurred position also not limit, such as can refer in the folding of same position or not
With the folding of position.
Additionally, folding of the invention, pressure can be applied in burst, as shown in Figure 4 and Figure 6 as example.Apply
Pressure can be realized by applying thing, it is preferred that the quality for applying thing is unrestricted, for example, can be the film being folded
More than 10000 times of quality.
The graphene film obtained by reduction treatment, preferably through post processing.Such as through Overheating Treatment, especially at warm high
Reason, further to reduce and removes defect therein.Typically, the graphene film that will be obtained by reduction treatment is in inert gas
The high temperature anneal is carried out in atmosphere.Graphene film obtained by high annealing post processing can be caused further is reduced more
Thoroughly, and reduce defect therein, obtain quality graphene film higher, the graphene film that high-temperature post-treatment is obtained it is flexible
Property remain to keep.The inert gas can be argon gas or nitrogen, and they can play guarantor in annealing process to graphene film
The effect of shield, can be according to the purposes of film in room temperature to 3000 DEG C of heat treated below.
Two parts film is substantially overlapping after final graphene film doubling obtained by the present invention, gapless.Plane thermal conductivity
According to post-processing temperature difference between 50-1400W/mK.
Plane thermal conductivity detection method of the invention can be according to commonly using in the prior art method, specifically can be with
For：Laser shines method (LFA).
Second embodiment
Second embodiment of the present invention provides a kind of preparation method for preparing Flexible graphene film that can be folding.
Methods described comprises the following steps：
Step 1：The dispersion liquid of graphene oxide powder or graphite oxide powder is carried out into film process or enters its powder
The step of row press mold is processed and obtains graphene oxide membrane；
Step 2：The step of reduction treatment is carried out to graphene oxide membrane and graphene film is obtained,
Classical ground, preparation method of the invention can be carried out in accordance with the following steps：
Prepare the raw material for forming graphite oxide in advance, such as natural flake graphite is dissolved into strong protonic acid, it is described
Course of dissolution is formed preferably in the presence of shearing force, such as more typically can such as use magnetic force using conventional mixing plant
Mixing plant.Form preferably 0-4 DEG C of the temperature of above-mentioned solution.Being subsequently adding strong oxidizer carries out oxidation reaction, controls temperature
Between 10-15 DEG C, graphite oxide powder is obtained, collected standby.
Further, it is possible to the graphene oxide powder that above-mentioned graphite oxide powder or other approach are obtained is dissolved in suitably
In container, certain density solution is prepared into.The solution is formed preferably in the presence of vibrations or shearing force, can such as be made
With conventional mixing plant or vibrations equipment, more typically as used magnetic stirring equipment or ultrasonic disperse instrument.
For the specific concentration of solvent species that forms solution, there is no particular limitation, as long as disclosure satisfy that follow-up dispersion
Requirement of the liquid into film process.Typically, solvent can use water or organic solvent.The organic solvent is selected from ethanol, third
Alcohol, ethylene glycol, acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran, dimethylformamide, 1-METHYLPYRROLIDONE, ethyl acetate equal solvent
In one or more.
In addition, in the present invention, from from the point of view of forming uniform dispersion, the concentration that the above forms dispersion liquid is
0.01-100mg/mL, preferably 0.1-20mg/mL.
Then, film process is carried out into above-mentioned dispersion liquid, dispersion liquid film forming is selected from：Vacuum filtration film forming, solvent are evaporated into
One kind in film, spin-coating film, spraying film forming and solution surface/interfacial assembly film forming.Additionally, for these dispersion liquid film forming
There is no particular limitation for the specific equipment of mode, as long as the graphene oxide membrane of desired smooth even can be obtained.
Further, directly the graphene oxide powder that above-mentioned graphite oxide powder or other approach are obtained can also be carried out
Pressing mold processes to obtain the graphene oxide membrane.
The present invention carries out reduction treatment to the graphene oxide membrane after film forming, becomes the stone of the flexible foldable of conduction
Black alkene film.
Reduction treatment is carried out from reducing agent hydrazine hydrate solution in the present invention, because graphene oxide membrane is in hydrazine hydrate solution
During reduction, gas is discharged by hydrazine is oxidized, therefore can expanded in a thickness direction, obtain cellular many
The graphene film of pore structure.Specifically, can be in graphene oxide membrane surface uncoated hydrous hydrazine solution or by graphene oxide
Then film infiltration typically can be for example clipped between two smooth sheets to taking-up in hydrazine hydrate solution, carry out reduction reaction, can
To reduce the usage amount of reducing agent, while the effective depth of reduction can also be improved.Therefore, heretofore described hydrazine hydrate solution
Concentration selects 1-80%, preferably 20-80%.For the temperature of reduction treatment, in the present invention, reduction treatment is in a heated condition
Carry out, preferably 40-200 DEG C, more preferably 70-100 DEG C, the speed of reduction reaction is favorably improved under heating condition.
Further, it is preferable that above-mentioned graphene film may also pass through post processing, such as through Overheating Treatment, especially warm high
Treatment, further to reduce and removes defect therein.Typically, the graphene film that will be obtained by reduction treatment is in indifferent gas
The high temperature anneal is carried out in body atmosphere.Graphene film obtained by high annealing post processing can be caused further is reduced more
Plus thoroughly, and defect therein is reduced, it is favourable to improving electrical conductivity and thermal conductivity.The inert gas can be argon gas or nitrogen
Gas, they can play a part of protection in annealing process to graphene film, preferably carry out heat to less than 3000 DEG C in room temperature
Treatment.
For the heat treatment involved by above-mentioned post processing, it is a discovery of the invention that such last handling process can be further
Control graphene oxide reducing degree.That is, the use that the later stage passes through different heat treatment temperatures, reality that can be more controllable
The reducing degree of existing required graphene oxide, electrical conductivity and thermal conductivity, therefore, it can to obtain performance it is controllable can be folding
Flexible graphene film product.
3rd implementation method
It is in third embodiment of the present invention, there is provided a kind of flexible device, such as flexible energy storage and transfer electron, soft
Property sensor, flexible super capacitor, flexible electromagnetic shielding film, flexible conducting material or flexible Heat Conduction Material etc..The flexibility
Device includes or has used Flexible graphene film according to first embodiment wherein or according to the second embodiment party
What the preparation method of the Flexible graphene film described in formula was obtained can be folding Flexible graphene film, and through device assemble and obtain
Arrive.
Flexible device of the invention can be typically flexible super capacitor.
In such products formed, the presence of Flexible graphene film causes the ultracapacitor also category with flexible foldable
Property, folded by multiple substance or multiple folding, still can quickly restore to the original state and not leave folding line, it is wearable electronic
Equipment is provided may.
Embodiment
Hereinafter, the present invention will be explained in detail and will be enumerated by specific embodiment, it should be noted that the present invention
It is not limited in following implementation method, meanwhile, implementation method below is also not construed as to be made that the present invention
Extra limitation.It should be noted that in following each examples, folding radius of curvature and being outer curvature radius, described folding is included
Doubling.
Embodiment 1
(1) with natural flake graphite as raw material, using improved Hummer methods, obtain aoxidizing stone by graphite is fully oxidized
Ink, is washed with deionized water the graphite oxide aqueous solution that solid content 20mg/mL is prepared to neutrality, and ultrasonic vibration is uniformly dispersed into oxygen
Graphite alkene aqueous dispersions, spin-coating film, the thickness of the graphene oxide membrane of preparation is 45 μm.
(2) graphene oxide membrane of 3 × 4cm is cut, the hydrazine hydrate solution that fraction is 50% of improving quality is coated with filter paper, dried
70 DEG C of heating 10h, prepare the redox graphene film of the flexible honeycomb hole structure of excess of export in case, and film surface is very smooth, light
Sliding, film thickness expands 10 times, and thickness is changed into 450 μm, and it is 245 μm to fold radius of curvature, and plane thermal conductivity is 110W/mK.
(3) after redox graphene film being placed in into the lower 2200 DEG C for the treatment of 2h of argon atmosphere in tube furnace, thickness is substantially not
Become, remain in that honeycomb hole structure, film flexility is without prejudice, and fast quick-recovery is remained to after folding, and does not stay folding line.
Embodiment 2
(1) with natural flake graphite as raw material, using improved Hummer methods, obtain aoxidizing stone by graphite is fully oxidized
Ink, is washed with deionized water the graphite oxide aqueous solution that solid content 10mg/mL is prepared to neutrality, and ultrasonic vibration is uniformly dispersed to be formed
Graphene oxide aqueous dispersions, take 10mL and pour into plastic culture dish, at room temperature drying and forming-film, the graphene oxide membrane of preparation
Thickness is 19 μm.
(2) graphene oxide membrane of 3 × 4cm is cut, the hydrazine hydrate solution that fraction is 80% of improving quality is coated with swab stick, dried
90 DEG C of heating 2h, prepare the redox graphene film of the flexible honeycomb hole structure of excess of export in case, and film surface is very smooth, light
Sliding, film thickness expands 15 times, and thickness is changed into 210 μm, and it is 125 μm to fold radius of curvature, and plane thermal conductivity is 90W/mK.
(3) after redox graphene film being placed in into the lower 800 DEG C for the treatment of 1h of argon atmosphere in tube furnace, thickness is substantially not
Become, remain in that honeycomb hole structure, film flexility is without prejudice, and fast quick-recovery is remained to after folding, and does not stay folding line.
Embodiment 3
(1) with natural flake graphite as raw material, using improved Hummer methods, obtain aoxidizing stone by graphite is fully oxidized
Ink, is washed with deionized water to neutrality, is configured to the graphite oxide aqueous solution of solid content 2mg/mL, and ultrasonic vibration is uniformly dispersed into oxygen
Graphite alkene aqueous dispersions, with the anodic alumina films (AAO films) in 0.02 μm of aperture for suction filtration film, prepared by vacuum filtration film forming
Graphene oxide membrane thickness be 8 μm.
(2) graphene oxide membrane of 3 × 4cm is cut, the hydrazine hydrate solution that fraction is 50% of improving quality is coated with filter paper, dried
80 DEG C of heating 5h, prepare the redox graphene film of the flexible honeycomb hole structure of excess of export in case, and film surface is very smooth, light
Sliding, film thickness expands 16.2 times, and thickness is changed into 130 μm, and it is 90 μm to fold radius of curvature, and plane thermal conductivity is 70W/mK.
(3) after redox graphene film being placed in into the lower 1300 DEG C for the treatment of 2h of argon atmosphere in tube furnace, thickness is substantially not
Become, remain in that honeycomb hole structure, film flexility is without prejudice, and fast quick-recovery is remained to after folding, and does not stay folding line.
Comparative example 1
(1) with natural flake graphite as raw material, using improved Hummer methods, obtain aoxidizing stone by graphite is fully oxidized
Ink, is washed with deionized water the graphite oxide aqueous solution that solid content 2mg/mL is prepared to neutrality, and ultrasonic vibration is uniformly dispersed into oxidation
Graphene aqueous dispersions, with the anodic alumina films (AAO films) in 0.02 μm of aperture for suction filtration film, vacuum filtration film forming, preparation
The thickness of graphene oxide membrane is 8 μm.
(2) graphene oxide membrane of 3 × 4cm is cut, is vacantly put into the sealed glass container for being equipped with hydrazine hydrate solution, dried
95 DEG C of heating 5h in case, prepare the redox graphene film of honeycomb hole structure, and film surface occurs many not of uniform size
Bubbling, film thickness expands 47 times, and thickness is changed into 375 μm, and film is broken in folding process.
(3) after redox graphene film being placed in into the lower 1300 DEG C for the treatment of 2h of argon atmosphere in tube furnace, thickness is substantially not
Become, remain in that honeycomb hole structure, film is broken in folding process.
Comparative example 2
(1) with natural flake graphite as raw material, using improved Hummer methods, obtain aoxidizing stone by graphite is fully oxidized
Ink, is washed with deionized water the graphite oxide aqueous solution that solid content 2mg/mL is prepared to neutrality, and ultrasonic vibration is uniformly dispersed into oxidation
Graphene aqueous dispersions, with the anodic alumina films (AAO films) in 0.02 μm of aperture for suction filtration film, vacuum filtration film forming, preparation
The thickness of graphene oxide membrane is 8 μm.
(2) graphene oxide membrane of 3 × 4cm is cut, graphene oxide membrane is soaked in the appearance for filling aqueous solution of hydrogen iodide
In device, it is placed in 100 DEG C of vacuum drying oven and heats 1h, the thickness of the redox graphene film prepared is changed into 6 μm, after folding
Film not resilient, the surface of film leaves folding line.
Industrial applicibility
Flexible graphene film of the invention and preparation method thereof can be produced industrially, also, of the invention soft
Property graphene film can be assembled as flexible super capacitor and use by device.
Claims (13)
1. a kind of Flexible graphene film that can be folding, it is characterised in that the Flexible graphene film is by oxidation stone
Black alkene film carries out reduction treatment and obtains, and has loose structure, the flexibility in the Flexible graphene film thickness direction
Graphene film can be folded, and after being restored to the folding, in the burst of the Flexible graphene film plasticity shape not occur
Become；
The thickness of the graphene oxide membrane is 0.01-500 μm, preferably 2-100 μm；
Relative to the thickness of the graphene oxide membrane, the expansion multiple of the thickness of the Flexible graphene film is 2-30 times, excellent
Elect 10-20 times as.
2. Flexible graphene film according to claim 1, it is characterised in that the substance that is folded into is folded or multiple folding
Folded, folding angles are less than or equal to 180 °.
3. Flexible graphene film according to claim 1 and 2, it is characterised in that the reduction treatment is molten with hydrazine hydrate
Liquid is reduced.
4. the Flexible graphene film according to claim any one of 1-3, it is characterised in that the graphene oxide membrane be by
Graphene oxide powder or graphite oxide powder are dispersed through liquid and are obtained into film process or by its pressed by powder film forming.
5. a kind of preparation method of Flexible graphene film that can be folding, it is characterised in that methods described comprises the following steps：
Step 1：Liquid is dispersed through into film process or by its pressed by powder film forming by graphene oxide powder or by graphite oxide powder
The step of；
Step 2：The step of reduction treatment is carried out to graphene oxide membrane and Flexible graphene film is obtained,
The Flexible graphene film has loose structure in a thickness direction, and the Flexible graphene film can be folded, and right
After the folding is restored, there is no plastic deformation in the burst of the Flexible graphene film,
The thickness of the graphene oxide membrane is 0.01-500 μm, preferably 2-100 μm；Relative to the graphene oxide membrane
Thickness, the expansion multiple of the thickness of the Flexible graphene film is 2-30 times, preferably 10-20 times.
6. the preparation method of Flexible graphene film according to claim 5, it is characterised in that dispersion liquid described in step 1
Concentration be 0.01-100mg/mL；The dispersion solvent used in the dispersion liquid is selected from the one kind or many in water or organic solvent
Kind.
7. the preparation method of the Flexible graphene film according to claim 5 or 6, it is characterised in that film forming described in step 1
Treatment is selected from：Vacuum filtration film forming, solvent volatilization film forming, spin-coating film, spraying film forming and solution surface/interfacial assembly film forming
In one kind.
8. the preparation method of the Flexible graphene film according to claim any one of 5-7, it is characterised in that institute in step 2
Reduction treatment is stated to comprise the following steps：On graphene oxide membrane surface uncoated hydrous hydrazine solution or by graphene oxide membrane infiltration arrive
In hydrazine hydrate solution, reduction reaction is carried out, the concentration of the hydrazine hydrate solution is 1-80%, preferably 20-80%.
9. the preparation method of the Flexible graphene film according to claim any one of 5-8, it is characterised in that institute in step 2
State reduction treatment is carried out in a heated condition, and heating-up temperature is 40-200 DEG C, and the heat time is 1min-7d, it is preferable that heating temperature
It is 70-100 DEG C to spend, and the heat time is 0.5-12h.
10. the preparation method of the Flexible graphene film according to claim any one of 5-9, it is characterised in that the folding
For substance is folded or multiple folding, folding angles are less than or equal to 180 °.
The preparation method of the 11. Flexible graphene film according to claim any one of 5-10, it is characterised in that the preparation
Method also includes post-processing step, and the post-processing step is annealed in being included in atmosphere of inert gases to Flexible graphene film
The step for the treatment of, made annealing treatment under conditions of -3000 DEG C of room temperature preferably in the argon atmosphere.
12. a kind of flexible devices, it is characterised in that the flexible device is included according to claim any one of 1-4
The flexibility that the preparation method of Flexible graphene film or the Flexible graphene film according to claim any one of 5-11 is obtained
Graphene film.
13. flexible devices according to claim 12, it is characterised in that the flexible device include flexible energy storage with
Transfer electron, flexible sensor, flexible super capacitor, flexible electromagnetic shielding film, flexible conducting material or flexible Heat Conduction Material.
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| CN107651670A (en) * | 2017-10-13 | 2018-02-02 | 杭州高烯科技有限公司 | A kind of preparation method of no folding line elastic graphite alkene film |
| CN108011180A (en) * | 2017-11-24 | 2018-05-08 | 武汉理工大学 | A kind of preparation method of graphene antenna for mobile phone |
| CN108172414A (en) * | 2017-12-25 | 2018-06-15 | 浙江华正新材料股份有限公司 | A kind of preparation method and applications of the graphene film of Polyaniline-modified |
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