CN107500271A - Flexible graphene film and Flexible graphene based composites film and preparation method thereof - Google Patents
Flexible graphene film and Flexible graphene based composites film and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012528 membrane Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- 239000010439 graphite Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 229910052961 molybdenite Inorganic materials 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- -1 graphite Alkene Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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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
- C01B2204/04—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
- C01B2204/32—Size or surface area
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- C—CHEMISTRY; METALLURGY
- 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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Abstract
The present invention relates to Flexible graphene film and Flexible graphene based composites film and preparation method thereof, respectively by carrying out being heat-treated expansion to graphene oxide membrane and graphene oxide composite membrane to obtain, heat treatment process media thickness expansion multiple is controlled between 2 20 times, the graphene film and its composite membrane have loose structure in a thickness direction, the graphene film and its composite membrane have excellent flexible foldability energy, original shape is promptly restored to after folding and does not stay folding line, the similar folding resilience behavior of flexible body, and preparation method is simple, it is easy to operate.
Description
Technical field
The invention belongs to graphene film and its preparing technical field, and in particular to Flexible graphene film and soft graphite alkenyl
Composite material film and preparation method thereof.
Background technology
Graphene is to pass through sp by carbon atom2Hydridization close-packed arrays and the monolayer honeycomb shape lattice two dimensional crystal formed, it
Possess great specific surface area, excellent mechanical property, electric conductivity, heat conductivility, be a kind of material of very attractive.Stone
A kind of important morphological of the black alkene film as graphene, possesses the attributes such as stronger electric conductivity, thermal conductivity, flexibility so that graphite
Alkene film and its composite membrane have in energy storage and the fields such as transition material, electromagnetic shielding material, Heat Conduction Material, sensor material
It is widely applied prospect.In order to adapt to demand of the modern life to flexible electronic devices, a kind of flexible, folding graphite of exploitation
The preparation method of alkene film and its flexible compound film tool is of great significance.
At present, the method for preparing graphene film can be largely classified into two kinds：One kind be using graphene nanometer sheet directly into
Film, it is another kind of, it is by being obtained after graphene oxide film forming by further reduction treatment.
However, though graphene film prepared at present has flexibility, bent, but the overwhelming majority can not roll over
It is folded, it can be broken after folding.Although having been reported that the graphene film prepared by finely regulating is foldable, after folding can
Plastic deformation is produced, there is folding line, the performance of graphene film can be influenceed after repeatedly folding.
Therefore, for the existing research for graphene film, also need further to study 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
Invention will solve the problems, such as exist for prior art, and present invention firstly provides a kind of flexibility that can be folding
Graphene film, the Flexible graphene film have a loose structure in thickness orientation, the fast quick-recovery of energy after substance or multiple folding,
And do not produce plastic deformation folding point, do not stay folding line, the flatness at folding at non-collapsible or with folding with occurring
Keep before identical.Meanwhile the Flexible graphene also has preferable mechanical property.
And then present invention provides a kind of preparation method of above-mentioned Flexible graphene film that can be folding.
In addition, present invention provides a kind of preparation method of Flexible graphene group compound film that can be folding.
The solution used to solve the problem：Present invention firstly provides a kind of Flexible graphene film, the graphene film passes through
Thermal reduction processing is carried out to graphene oxide membrane and is obtained, and there is loose structure in graphene film thickness orientation, institute
Stating graphene film can be folded, and after being restored to the folding, plastic deformation does not occur at the folding of the graphene film；
The thickness of the graphene oxide membrane is 0.5-100 μm, and the expansion multiple of the thickness of the graphene film is 2-20.
In embodiments of the present invention, described to be folded into substance folding or multiple folding, folding angles are to be less than or wait
In 180 °.
In embodiments of the present invention, the graphene oxide membrane is that graphene oxide powder is suppressed into film forming or oxidation
Graphite composite powder is dispersed through liquid film process and obtained.
Further, present invention provides a kind of preparation method of Flexible graphene film, comprise the following steps：
Step 1：The step of graphene oxide powder is suppressed film forming or graphite oxide powder is dispersed through into liquid film process；
Step 2：The step of reduction treatment is carried out to graphene oxide membrane and obtains graphene film；
The graphene film has loose structure in thickness orientation, and the graphene film can be folded, and to the folding
After recovery, plastic deformation does not occur at the folding of the graphene film.
In embodiments of the present invention, the thickness of the graphene oxide membrane is 0.5-100 μm；Relative to the oxygen
The thickness of graphite alkene film, the expansion multiple of the thickness of the graphene film is 2-20 times.
In embodiments of the present invention, the concentration of dispersion liquid described in step 1 is 0.01-100mg/mL；It is described scattered
One or more of the dispersion solvent used in liquid in water or organic solvent.
In embodiments of the present invention, film process are selected from described in step 1：Vacuum filtration film forming, solvent evaporate into
One kind in film, spin-coating film, spraying film forming and solution surface/interfacial assembly film forming.
In embodiments of the present invention, reduction treatment comprises the following steps described in step 2：Graphene oxide membrane is lazy
Property atmosphere in heat, heat-treated, heating-up temperature be 300-3000 DEG C, heat time 1min-4h；Preferably, add
Hot temperature is 500-2000 DEG C, heat time 2-3h.
In embodiments of the present invention, described to be folded into substance folding or multiple folding, folding angles are to be less than or wait
In 180 °.
In addition, present invention also offers a kind of preparation method of Flexible graphene based composites film, comprise the following steps：
Step 1：Other materials are mixed to compacting film forming with graphene oxide powder, or other materials and graphite oxide powder are mixed
Conjunction is dispersed through liquid film process, or in-situ preparation other materials forerunner after other materials presoma is mixed with graphite oxide powder
The step of body is dispersed through liquid film process or mixed powder compacting film forming with graphene oxide mixed powder；
Step 2：Thermal reduction processing is carried out to graphene oxide based composites film and obtains the step of graphene-based composite material film
Suddenly；
The graphene-based composite material film has loose structure in thickness orientation, and the graphene-based composite material film can quilt
Fold, and after being restored to the folding, plastic deformation does not occur at the folding of the graphene-based composite material film.
In embodiments of the present invention, the thickness of the graphene oxide based composites film is 0.5-100 μm；Relatively
In the thickness of the graphene oxide based composites film, the expansion multiple of the thickness of the graphene-based composite material film is 2-
20。
In embodiments of the present invention, described other materials is inorganic nano material, including metal（Gold, silver etc.）、
Metal oxide and sulfide（TiO2, ZnO2, Al2O3、MoS2Deng）, carbide（SiC etc.）, nitride（BN, Si3N4, AlN etc.）
Or other ceramic materials（SiO2Deng）In one or more, other materials is with the shape of nano particle, nanofiber or nanometer sheet
Formula is compound with graphene, and other materials accounting is less than 50wt%.
In embodiments of the present invention, the concentration of dispersion liquid described in step 1 is 0.01-100mg/mL；It is described scattered
One or more of the dispersion solvent used in liquid in water or organic solvent.
In embodiments of the present invention, film process are selected from described in step 1：Vacuum filtration film forming, solvent evaporate into
One kind in film, spin-coating film, spraying film forming and solution surface/interfacial assembly film forming.
In embodiments of the present invention, reduction treatment comprises the following steps described in step 2：Graphite oxide alkenyl is compound
Material membrane heats in atmosphere of inert gases, is heat-treated, and heating-up temperature is 300-3000 DEG C, heat time 1min-4h；
Preferably, heating-up temperature is 500-1500 DEG C, heat time 2-3h.
In embodiments of the present invention, described to be folded into substance folding or multiple folding, folding angles are to be less than or wait
In 180 °.
The effect of invention：
The invention provides Flexible graphene film that can be folding and Flexible graphene based composites film and preparation method thereof,
Compared with existing grapheme material, have the following advantages that：
（a）The Flexible graphene film and Flexible graphene based composites film of the present invention has loose structure in thickness orientation,
And film surface is smooth, smooth, thickness swelling multiple is controlled between 2-20 times；
（b）The Flexible graphene film and Flexible graphene based composites film of the present invention has excellent pliability and excellent
Foldability energy, after multiple substance or double folding, the graphene film and its composite membrane still can fast quick-recovery, and
Folding line is not stayed at folding；
（c）The Flexible graphene film and Flexible graphene based composites film of the present invention possesses pliability after high-temperature process,
So as to expand its use condition and mode, excellent, lasting performance can be provided under very extensive environmental condition；
（d）Preparation method of the present invention is simple, easy to operate, environmentally safe.
Therefore, Flexible graphene film that can be folding and Flexible graphene based composites film provided by the present invention,
In wearable device, flexible electrode material, flexible super capacitor or rechargeable battery, flexible Heat Conduction Material, flexible electromagnetic screen
The fields such as material are covered all to be with a wide range of applications.
Brief description of the drawings
The present invention is described further below in conjunction with the accompanying drawings：
Fig. 1 shows the exemplary folding degree of the present invention（θ angles）；
Fig. 2 is the scanning electron microscope diagram piece of the upper loose structure of graphene film thickness orientation in embodiment 1；
Fig. 3 is the optical imagery after graphene oxide membrane folding in comparative example 1；
Fig. 4 is the optical imagery that graphene oxide membrane is deployed after folding in comparative example 1；
Fig. 5 is the optical imagery after graphene film folding in embodiment 1；
Fig. 6 is the optical imagery that graphene film deploys after folding in embodiment 1；
Fig. 7 is optical imagery of the graphene film after double folding in embodiment 1；
Fig. 8 is the optical imagery that graphene film deploys after double folding in embodiment 1；
Fig. 9 is the optical imagery after graphene-based composite material film folding in embodiment 2；
It is the optical imagery deployed after graphene-based composite material film folds in Figure 10 embodiments 2；
It is that the optical imagery replied during pressing thing is unclamped after graphene-based composite material film folds in Figure 11 embodiments 2.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, without structure
Into limitation of the present invention.
Embodiment 1
（1）Using natural flake graphite as raw material, using improved Hummer methods, graphite oxide is obtained by graphite is fully oxidized,
The graphite oxide aqueous solution that solid content 3mg/mL is prepared to neutrality is washed with deionized water, ultrasonic vibration is uniformly dispersed into oxidation stone
Black alkene aqueous dispersions, the thickness for being filtered by vacuum the graphene oxide membrane of preparation are 10 μm.
（2）Graphene oxide membrane is put into the lower 1500 DEG C of processing 2h of argon atmosphere in tube furnace, prepares that excess of export is flexible has
The redox graphene film of honeycomb hole structure, film surfacing, smooth, film thickness expands 2.8 times, and thickness is changed into 28 μm.
（3）By the fast quick-recovery of energy after redox graphene film single fold or double folding, and do not stay folding line.
Embodiment 2
（1）Using natural flake graphite as raw material, using improved Hummer methods, graphite oxide is obtained by graphite is fully oxidized,
The graphite oxide aqueous solution that solid content 5mg/mL is prepared to neutrality is washed with deionized water, adds Nano-meter SiO_22Particle ultrasonic vibration
It is uniformly dispersed into SiO2/ graphene oxide aqueous dispersions, SiO prepared by solvent volatilization2The thickness of/graphene oxide membrane is 8 μm.
（2）By SiO2/ graphene oxide membrane is put into the lower 1600 DEG C of processing 3h of argon atmosphere in tube furnace, and it is flexible to prepare excess of export
The SiO of honeycomb hole structure2/ redox graphene film, film surfacing, smooth, film thickness expands 4 times, and thickness is changed into 32 μ
m。
（3）By SiO2The fast quick-recovery of energy after/redox graphene film single fold or double folding, and folding is not stayed
Trace.
Embodiment 3
（1）Using natural flake graphite as raw material, using improved Hummer methods, graphite oxide is obtained by graphite is fully oxidized,
The graphite oxide aqueous solution that solid content 5mg/mL is prepared to neutrality is washed with deionized water, adds acetylacetone,2,4-pentanedione ferrous solution, ultrasound shake
Swing the in-situ preparation Fe that is uniformly dispersed2O3/ graphene oxide aqueous dispersions, Fe prepared by solvent volatilization2O3/ graphene oxide membrane
Thickness is 8 μm.
（2）By Fe2O3/ graphene oxide membrane is put into the lower 600 DEG C of processing 3h of argon atmosphere in tube furnace, and it is flexible to prepare excess of export
The Fe of honeycomb hole structure2O3/ redox graphene film, film surfacing, smooth, film thickness expands 4 times, and thickness is changed into 32 μ
m。
（3）By Fe2O3The fast quick-recovery of energy after/redox graphene film single fold or double folding, and folding is not stayed
Trace.
Comparative example 1
（1）Using natural flake graphite as raw material, graphite oxide is obtained by graphite is fully oxidized using improved Hummer methods, used
Deionized water is washed till neutrality, prepares the solid content 3mg/mL graphite oxide aqueous solution, and ultrasonic vibration is uniformly dispersed into graphite oxide
Alkene aqueous dispersions, the thickness for being filtered by vacuum the graphene oxide membrane of preparation are 10 μm.
（2）Occur obvious folding line, and easy fracture after graphene oxide membrane is folded.
Comparative example 2
（1）Using natural flake graphite as raw material, using improved Hummer methods, graphite oxide is obtained by graphite is fully oxidized,
The graphite oxide aqueous solution that solid content 8mg/mL is prepared to neutrality is washed with deionized water, ultrasonic vibration is uniformly dispersed, solvent volatilization
The thickness of the graphene oxide membrane of preparation is 15 μm.
（2）Graphene oxide membrane is put into 90 DEG C of processing 1h, the redox graphene film prepared in HI solution.
（3）Redox graphene film has compact texture, is broken after film bending.
Above embodiment describes the general principle and principal character of the present invention.The technical staff of the industry should
Understand, protection scope of the present invention is not restricted to the described embodiments, any change expected without creative work or
Replace, should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with claims institute
The protection domain of restriction is defined.
Industrial applicibility
The Flexible graphene film and Flexible graphene based composites film of the present invention can be produced industrially, also, this
It is super that the Flexible graphene film and its composite material film of invention can be widely applied to wearable device, flexible electrode material, flexibility
Level capacitor or rechargeable battery, flexible Heat Conduction Material, flexible electromagnetic shielding material etc. field.
Claims (10)
1. a kind of Flexible graphene film, it is characterised in that the graphene film to graphene oxide membrane by carrying out at thermal reduction
To manage and obtain, and there is loose structure in graphene film thickness orientation, the graphene film can be folded, and to institute
After stating folding recovery, plastic deformation does not occur at the folding of the graphene film；The thickness of the Flexible graphene film is 1-
500μm。
2. Flexible graphene film according to claim 1, it is characterised in that the graphene oxide membrane is by graphite oxide
Alkene pressed by powder film forming or graphite oxide powder are dispersed through liquid film process and obtained；The thickness of the graphene oxide membrane is
0.5-100μm；The reduction treatment is handled for thermal reduction；Relative to the thickness of the graphene oxide membrane, the soft graphite
The expansion multiple of the thickness of alkene film is 2-20 times；Described to be folded into substance folding or multiple folding, folding angles are to be less than or wait
In 180 °.
3. a kind of preparation method of Flexible graphene film, it is characterised in that comprise the following steps：
Step 1：Graphene oxide powder is suppressed into film forming or graphite oxide powder is dispersed through liquid film process；
Step 2：The step of thermal reduction processing is carried out to graphene oxide membrane and obtains graphene film,
The graphene film has loose structure in thickness orientation, and the graphene film can be folded, and to the folding
After recovery, plastic deformation does not occur at the folding of the graphene film；
The thickness of the Flexible graphene film is 1-500 μm；Relative to the thickness of the graphene oxide membrane, the soft graphite
The expansion multiple of the thickness of alkene film is 2-20 times.
4. the preparation method of Flexible graphene film according to claim 3, it is characterised in that the graphene oxide membrane
Thickness is 0.5-100 μm；Described to be folded into substance folding or multiple folding, folding angles are less than or equal to 180 °.
5. the preparation method of Flexible graphene film according to claim 3, it is characterised in that dispersion liquid described in step 1
Concentration be 0.01-100mg/mL；The one kind or more of the dispersion solvent used in the dispersion liquid in water or organic solvent
Kind；Film process are selected from described in step 1：It is filtered by vacuum film forming, solvent volatilization film forming, spin-coating film, spraying film forming and molten
One kind in liquid surface/interface assembling film forming.
6. the preparation method of the Flexible graphene film according to any one of claim 3, it is characterised in that institute in step 2
Reduction treatment is stated to comprise the following steps：Graphene oxide membrane heats in atmosphere of inert gases, is heat-treated, and heating-up temperature is
300-3000 DEG C, heat time 1min-4h；Preferably, heating-up temperature is 500-2000 DEG C, heat time 2-3h.
7. a kind of preparation method of Flexible graphene based composites film, it is characterised in that comprise the following steps：
Step 1：Other materials are mixed to compacting film forming with graphene oxide powder, or other materials and graphite oxide powder are mixed
Conjunction is dispersed through liquid film process, or in-situ preparation other materials forerunner after other materials presoma is mixed with graphite oxide powder
The step of body is dispersed through liquid film process or mixed powder compacting film forming with graphene oxide mixed powder；
Step 2：The step of being heat-treated to graphene oxide group compound film and obtaining graphene-based composite material film；
The graphene-based composite material film has loose structure in thickness orientation, and the graphene-based composite material film can quilt
Fold, and after being restored to the folding, plastic deformation does not occur at the folding of the graphene-based composite material film；
The thickness of the graphene oxide based composites film is 1-500 μm；Relative to the graphene oxide based composites
The thickness of film, the expansion multiple of the thickness of the graphene-based composite material film is 2-20 times.
8. the preparation method of Flexible graphene based composites film according to claim 7, it is characterised in that the oxidation
The thickness of graphene-based composite material film is 0.5-100 μm；Described to be folded into substance folding or multiple folding, folding angles are small
In or equal to 180 °；Other materials is inorganic nano material in the Flexible graphene based composites, including metal, metal oxygen
Compound and sulfide, carbide, the one or more of nitride or other ceramic materials；Other materials is with nano particle, nanometer
The form of fiber or nanometer sheet is compound with graphene；The metal is selected from the one or more of gold, silver etc., the metal oxide
And sulfide is selected from TiO2、ZnO2, Al2O3、MoS2One or more in, the carbide are selected from SiC etc., the nitride
Selected from BN, Si3N4, the one or more in AlN etc., other described ceramic materials also include SiO2Deng；Other materials in composite membrane
Accounting be less than 50wt%.
9. the preparation method of Flexible graphene based composites film according to claim 7, it is characterised in that in step 1
The concentration of the dispersion liquid is 0.01-100mg/mL；The dispersion solvent used in the dispersion liquid is in water or organic solvent
One or more；Film process are selected from described in step 1：It is filtered by vacuum film forming, solvent volatilization film forming, spin-coating film, spraying
One kind in film forming and solution surface/interfacial assembly film forming.
10. the preparation method of the Flexible graphene based composites film according to any one of claim 7, its feature exist
In reduction treatment described in step 2 comprises the following steps：Graphene oxide based composites film adds in atmosphere of inert gases
Heat, heat-treated, heating-up temperature is 300-3000 DEG C, heat time 1min-4h；Preferably, heating-up temperature 500-
1500 DEG C, heat time 2-3h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108724867A (en) * | 2018-06-06 | 2018-11-02 | 合肥工业大学 | A kind of porous graphene driver of double stimulus response, preparation method and application |
| CN109775697A (en) * | 2019-03-17 | 2019-05-21 | 杭州高烯科技有限公司 | Highly conductive foldable graphene film of one kind and the preparation method and application thereof |
| CN110002438A (en) * | 2019-05-23 | 2019-07-12 | 科炭(厦门)新材料有限公司 | A kind of flexible, porous graphene film and its preparation method and application |
| CN112512287A (en) * | 2021-01-06 | 2021-03-16 | 泰兴挚富显示技术有限公司 | High-thermal-conductivity flexible graphene composite heat dissipation film and preparation method thereof |
| CN113526495A (en) * | 2021-08-16 | 2021-10-22 | 内蒙古元瓷新材料科技有限公司 | Preparation method of magnetic graphene film with high electromagnetic wave absorption efficiency |
| CN114014305A (en) * | 2020-04-03 | 2022-02-08 | 常州富烯科技股份有限公司 | Preparation method of graphene heat-conducting film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346024A (en) * | 2013-06-18 | 2013-10-09 | 常州大学 | Method for preparing high-conductivity flexible graphene membrane electrode |
| CN106365159A (en) * | 2016-09-08 | 2017-02-01 | 江苏师范大学 | Silver nanoparticle-carbon nanotube embedded graphene oxide composite film, and preparation method and application thereof |
| CN106698407A (en) * | 2017-03-16 | 2017-05-24 | 北京化工大学 | Flexible graphene film capable of being repeatedly folded, preparation method of flexible graphene film and flexible device comprising flexible graphene film |
| CN106893128A (en) * | 2017-02-28 | 2017-06-27 | 上海大学 | Graphene composite heat-conducting film of transparent insulation and preparation method thereof |
| CN107089656A (en) * | 2017-05-24 | 2017-08-25 | 华中科技大学 | A kind of method for preparing large-area graphene nanometer sieve film |
-
2017
- 2017-08-31 CN CN201710771570.4A patent/CN107500271A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346024A (en) * | 2013-06-18 | 2013-10-09 | 常州大学 | Method for preparing high-conductivity flexible graphene membrane electrode |
| CN106365159A (en) * | 2016-09-08 | 2017-02-01 | 江苏师范大学 | Silver nanoparticle-carbon nanotube embedded graphene oxide composite film, and preparation method and application thereof |
| CN106893128A (en) * | 2017-02-28 | 2017-06-27 | 上海大学 | Graphene composite heat-conducting film of transparent insulation and preparation method thereof |
| CN106698407A (en) * | 2017-03-16 | 2017-05-24 | 北京化工大学 | Flexible graphene film capable of being repeatedly folded, preparation method of flexible graphene film and flexible device comprising flexible graphene film |
| CN107089656A (en) * | 2017-05-24 | 2017-08-25 | 华中科技大学 | A kind of method for preparing large-area graphene nanometer sieve film |
Non-Patent Citations (2)
| Title |
|---|
| BIN SHEN ET AL.: "Ultrathin Flexible Graphene Film: An Excellent Thermal Conducting Material with Efficient EMI Shielding", 《ADV. FUNCT. MATER.》 * |
| LI PENG ET AL.: "Ultrahigh Thermal Conductive yet Superflexible Graphene Films", 《ADV. MATER.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108724867A (en) * | 2018-06-06 | 2018-11-02 | 合肥工业大学 | A kind of porous graphene driver of double stimulus response, preparation method and application |
| CN108724867B (en) * | 2018-06-06 | 2020-05-19 | 合肥工业大学 | Porous graphene driver with double stimulus sources responding, preparation method and application |
| CN109775697A (en) * | 2019-03-17 | 2019-05-21 | 杭州高烯科技有限公司 | Highly conductive foldable graphene film of one kind and the preparation method and application thereof |
| CN109775697B (en) * | 2019-03-17 | 2020-08-18 | 杭州高烯科技有限公司 | High-conductivity foldable graphene film and preparation method and application thereof |
| CN110002438A (en) * | 2019-05-23 | 2019-07-12 | 科炭(厦门)新材料有限公司 | A kind of flexible, porous graphene film and its preparation method and application |
| CN114014305A (en) * | 2020-04-03 | 2022-02-08 | 常州富烯科技股份有限公司 | Preparation method of graphene heat-conducting film |
| CN112512287A (en) * | 2021-01-06 | 2021-03-16 | 泰兴挚富显示技术有限公司 | High-thermal-conductivity flexible graphene composite heat dissipation film and preparation method thereof |
| CN113526495A (en) * | 2021-08-16 | 2021-10-22 | 内蒙古元瓷新材料科技有限公司 | Preparation method of magnetic graphene film with high electromagnetic wave absorption efficiency |
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