CN106185905B - A kind of pure graphene composite electromagnetic screen film and preparation method thereof - Google Patents
A kind of pure graphene composite electromagnetic screen film and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 29
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- 238000010792 warming Methods 0.000 claims description 25
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- 239000011261 inert gas Substances 0.000 claims description 18
- -1 graphite alkene Chemical class 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
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- 238000000643 oven drying Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005087 graphitization Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
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- 239000007864 aqueous solution Substances 0.000 claims description 2
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- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims 1
- 229930003268 Vitamin C Natural products 0.000 claims 1
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- 235000019154 vitamin C Nutrition 0.000 claims 1
- 239000011718 vitamin C Substances 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 3
- 241000446313 Lamella Species 0.000 abstract 1
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- 239000011668 ascorbic acid Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 239000004964 aerogel Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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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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- C—CHEMISTRY; METALLURGY
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2006/10—Solid density
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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
- C01P2006/12—Surface area
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Abstract
The present invention obtains pure graphene composite electromagnetic screen film by assembling graphene solid microsphere, hollow microsphere and lamella graphene oxide.By high-temperature annealing process, graphene defect is repaired, perfect big conjugated structure is formed, ensure that the unimpeded of graphene conductive access.High-temperature annealing process so that functional group comes off to form gas on graphene oxide simultaneously, and graphene sheet layer is removed under the synergistic effect of graphene microballoon, forms multistage cavernous structure.Highly conductive graphene-based bottom adds multistage cavernous structure so that graphene film of the invention has extremely strong capability of electromagnetic shielding.
Description
Technical field
The present invention relates to field of composite material preparation more particularly to a kind of pure graphene composite electromagnetic screen film and its preparations
Method.
Background technology
The fast development of electronics industry makes that the integrated level of electronic device is higher and higher, electromagnetic radiation power of electronic device
Higher and higher, electronic device size becomes less and less.The electromagnetic wave of electronic equipment transmitting not only influences equipment of itself and its
The normal operation of his equipment, it is also possible to have an adverse effect to human body and natural environment.Metal is as traditional high shielding properties
The shortcomings of material due to its density height, easily corrodes, difficult processing so that the exploitation of Combined Electromagnetic Shielding Materials obtains academia
With the extensive concern of industrial quarters.Electromagnetic shielding material with efficient and light weight is one of the hot research direction in this field.
Graphene has a good capability of electromagnetic shielding as high-specific surface area and the carbon material of high conductivity, but mesh
Preceding prepared macroscopical graphene film material is all with CVD method, based on composite material or high-density graphite alkene film.Electromagnetic screen
Cover performance all than relatively low, in 60dB hereinafter, and its density it is all very high, more than 0.2g/cm3.For this purpose, scientific research personnel is in graphite
Stomata is introduced in alkene film, on the one hand increases reflection of the electromagnetic wave in material internal；On the other hand the density of film is reduced.It is however same
In the case of sample density, unit thickness shield effectiveness still has the space of promotion.
For this purpose, we, by introducing graphene microballoon, after gradually high temperature handling return, further improve porous graphite
The porosity of alkene film reduces the stacking of graphene film interlayer, finally so that its electromagnetic shielding efficiency improves 20%.This method
Difference lies in the introducing of graphene microballoon hinders the overlapping between graphene layer, further increases with conventional porous graphene film
Graphene porosity is added.The ultralight film of graphene prepared by this method realizes the excellent of high-efficiency shielding performance and low-density
Characteristic provides good material for application of the ultralight film of graphene in futurity industry, military project and aerospace field.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of pure graphene composite electromagnetic screen film and its system
Preparation Method.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of pure graphene composite electromagnetic screen film, it is described
The density of electromagnetic shielding film is 0.001-0.1g/cm3, carbon content 100%, the electromagnetic shielding film by multiple graphene layers with
And the graphene microballoon composition between graphene layer, graphene microsphere diameter are 1~5um；The graphene layer is by plane
The graphene film of orientation is formed by the pi-conjugated effects of π mutually overlap joint；Adjacent graphene layer under the support of graphene microballoon,
Channel is formed, the sectional area of channel accounts for the 10~60% of total sectional area.
A kind of preparation method of pure graphene composite electromagnetic screen film, includes the following steps：
(1) graphene oxide of the average-size of 100 parts by weight more than 100 μm is configured to a concentration of 0.1-100mg/ml
Graphene oxide water solution adds in the graphene microballoon of 0.1-10 parts by weight in the solution, after ultrasonic disperse, passes through film build method
Graphene oxide membrane is prepared into, is then restored with reducing agents such as hydrazine hydrates.
(2) obtained graphene film is first warming up to 800 DEG C under atmosphere of inert gases with the rate of 0.3 DEG C/min,
Keep the temperature 0.5-2h；
(3) 1300 DEG C are warming up to the rate of 2 DEG C/min under atmosphere of inert gases, keep the temperature 0.5-2h；
(4) 3000 DEG C are warming up to the rate of 10 DEG C/min under atmosphere of inert gases, keep the temperature 0.5-2h；After Temperature fall
It can obtain efficient and light weight electromagnetic shielding graphene film.
Further, the film build method used includes pouring molding oven drying method, knifing oven drying method, phase inversion, spray coating method
Etc. membrane formation process.
Further, graphene oxide membrane is restored using hydrazine hydrate, amine, ascorbic acid, hydrogen iodide etc., due to water
Closing hydrazine can cause membrane material to expand in reduction process, preferentially using hydrazine hydrate.
Further, in the step 1, the quality of graphene microballoon is the 4% of graphene oxide quality.Graphene microballoon
A diameter of 4-5um.
Further, the hollow graphite alkene microballoon ball wall is mutually overlapped by 1-6 layer graphenes piece by π-πconjugation
It forms, surface is covered with micro- fold；Microsphere diameter is 500nm-10 μm；Its inner hollow has great specific surface area 500-
2000m2/g；Microballoon is made of zero defect graphene, has perfect conjugated structure, ID/IG＜ 0.001.
Further, the hollow graphite alkene is micro- is prepared by the following method to obtain：
(1) graphene oxide weak solution is obtained into graphene oxide microballoon, dried oxygen by the method for atomization drying
It is 5-20wt% that graphite alkene microballoon, which contains free water,..
(2) the graphene oxide microballoon for obtaining step (1), quick (15-20 DEG C/min) are warming up to 800-1300 DEG C, it
3000 DEG C of progress graphitization processings are warming up to 1~5 DEG C/min again afterwards.
Further, a concentration of 0.1-10mg/mL of weak solution described in step (1)；The solvent be water, DMF,
DMAc, methanol, ethyl alcohol, isopropanol, tetrahydrofuran, methyl ethyl ketone isopolarity dispersant.
Further, the atomization drying temperature described in step (1) is 80-150 DEG C.
The polymorphic composite film material capability of electromagnetic shielding of pure graphene that present invention process is simple, prepares is excellent, suitable
Large-scale production can be applied to the equipment such as the aerospace of high-efficiency electromagnetic shielding, flexible device, space structure material.
By the present invention in that formed a film with super large piece graphene oxide, and allow under the mode that it anneals at high temperature, perfection is repaiied
Multiple graphene defect, and edge defect is preferably minimized, perfect big conjugated structure is formed, conjugation size even extends to
The graphene of full wafer, ensure that the unimpeded of graphene thermal conducting path；In addition, the introducing of graphene microballoon, greatly hinders
The overlapping of graphene sheet layer so that graphene film porosity greatly increases, and benefits electromagnet shield effect.Graphene microballoon assists
Multistage cavernous structure and highly conductive graphene-based bottom so that graphene film of the invention have extremely strong electromagnetic wave shielding
Energy.
Description of the drawings
Fig. 1 is the structure chart of pure graphene film；
Fig. 2 is the structure chart of graphene hollow ball；
Fig. 3 is the structure chart of composite membrane graphene film；
Fig. 4 is the structure diagram of composite electromagnetic screen film of the present invention.
Fig. 5 is the scanning electron microscope (SEM) photograph of the more fold hollow graphite alkene microballoons of high-specific surface area.
Fig. 6 is the transmission plot of the more fold hollow graphite alkene microballoons of high-specific surface area.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and embodiments.The present embodiment be served only for being the present invention into
The explanation of one step, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according in foregoing invention
Appearance makes some nonessential changes and adjustment, all belongs to the scope of protection of the present invention.
Embodiment 1：
(1) that a concentration of 4mg/mL graphene oxide water solutions are obtained graphene oxide by the method for atomization drying is micro-
Ball.Atomization drying temperature is 120 DEG C
(2) the graphene oxide microballoon for obtaining step (1), is rapidly heated with 20 DEG C/min to 800 DEG C, and maintain
10min is warming up to 3000 DEG C of progress graphitization processings again with 5 DEG C/min later.
Through above step, the obtained more fold hollow graphite alkene microsphere diameters of high-specific surface area are 3 μm, as shown in Figure 5.Its
Specific surface area is 600m2/ g, graphene ball wall are made of four layer graphenes, as shown in Figure 6.
(3) that average-size is configured to a concentration of 0.1mg/ml graphene oxides more than 100 μm of graphene oxide is water-soluble
Liquid adds in 0.1% graphene microballoon of graphene oxide quality in the solution；After ultrasonic disperse, dried by pouring molding
Method is prepared into graphene oxide membrane, is then restored with hydrazine hydrate reduction agent.
(4) obtained graphene film is first warming up to 800 DEG C under atmosphere of inert gases with the rate of 0.3 DEG C/min,
Keep the temperature 0.5h；
(5) 1300 DEG C are warming up to the rate of 2 DEG C/min under atmosphere of inert gases, keep the temperature 0.5h；
(6) 3000 DEG C are warming up to the rate of 10 DEG C/min under atmosphere of inert gases, keep the temperature 0.5h, be after Temperature fall
It can obtain efficient and light weight electromagnetic shielding graphene film.
Final prepared graphene composite film density is 0.1g/cm3, the sectional area of channel accounts for being averaged for total sectional area
It is 10% to be worth, and electromagnet shield effect is 100dB (0.8mm).
Embodiment 2：
(1) the graphene oxide DMF solution of a concentration of 1mg/mL is obtained into graphene oxide by the method for atomization drying
Microballoon.Atomization drying temperature is 100 DEG C.
(2) the graphene oxide microballoon for obtaining step (1), is rapidly heated with 15 DEG C/min to 1000 DEG C, and maintain
10min is warming up to 3000 DEG C of progress graphitization processings again with 3 DEG C/min later.
Through above step, the obtained more fold hollow graphite alkene microsphere diameters of high-specific surface area are 5 μm.Its specific surface area is
1100m2/g。
(3) graphene oxide of the average-size more than 100 μm is configured to a concentration of 1mg/ml graphene oxide water solutions,
1% graphene microballoon of graphene oxide quality is added in the solution；After ultrasonic disperse, oxygen is prepared by knifing oven drying method
Graphite alkene film, is then restored with ascorbic acid.
(4) obtained graphene film is first warming up to 800 DEG C under atmosphere of inert gases with the rate of 0.3 DEG C/min,
Keep the temperature 1h；
(5) 1300 DEG C are warming up to the rate of 2 DEG C/min under atmosphere of inert gases, keep the temperature 1h；
(6) 3000 DEG C are warming up to the rate of 10 DEG C/min under atmosphere of inert gases, keep the temperature 1h, after Temperature fall
Obtain efficient and light weight electromagnetic shielding graphene film.
Final prepared graphene composite film density is 0.04g/cm3, the sectional area of channel accounts for the flat of total sectional area
Mean value is 40%, and electromagnet shield effect is 110dB (0.8mm)
Embodiment 3：
(1) the graphene oxide methanol solution of a concentration of 10mg/mL is obtained into graphite oxide by the method for atomization drying
Alkene microballoon.Atomization drying temperature is 150 DEG C
(2) the graphene oxide microballoon for obtaining step (1), is rapidly heated with 18 DEG C/min to 1300 DEG C, and maintain
10min is warming up to 3000 DEG C of progress graphitization processings again with 5 DEG C/min later.
Through above step, the obtained more fold hollow graphite alkene microsphere diameters of high-specific surface area are 4 μm.Its specific surface area is
1500m2/g。
(3) that average-size is configured to a concentration of 10mg/ml graphene oxides more than 100 μm of graphene oxide is water-soluble
Liquid adds in 4% graphene microballoon of graphene oxide quality in the solution；After ultrasonic disperse, it is prepared by phase inversion
Then graphene oxide membrane is restored with hydrogen iodide.
(4) obtained graphene film is first warming up to 800 DEG C under atmosphere of inert gases with the rate of 0.3 DEG C/min,
Keep the temperature 1h；
(5) 1300 DEG C are warming up to the rate of 2 DEG C/min under atmosphere of inert gases, keep the temperature 1h；
(6) 3000 DEG C are warming up to the rate of 10 DEG C/min under atmosphere of inert gases, keep the temperature 1h, after Temperature fall
Obtain efficient and light weight electromagnetic shielding graphene film.
As shown in Figure 1, arranging denser between pure graphene aerogel film graphene layer, it is hollow micro- to add in graphene
After ball (Fig. 2), the electromagnetic shielding film (Fig. 3) being prepared is by multiple graphene layers and the graphite between graphene layer
Alkene microballoon forms, and wherein graphene layer is formed by the graphene film of planar orientation by the pi-conjugated effects of π mutually overlap joint；Adjacent
Graphene layer forms channel under the support of graphene microballoon, and the average value that the sectional area of channel accounts for total sectional area is 50%, stone
The black compound film density of alkene is 0.02g/cm3, electromagnet shield effect 115dB.
Embodiment 4：Graphene oxide of the average-size more than 100 μm is configured to a concentration of 100mg/ml graphene oxides
Aqueous solution adds in 10% graphene microballoon of graphene oxide quality in the solution；After ultrasonic disperse, pass through knifing oven drying method
Graphene oxide membrane is prepared into, is then restored with hydrazine hydrate.
(2) obtained graphene film is first warming up to 800 DEG C under atmosphere of inert gases with the rate of 0.3 DEG C/min,
Keep the temperature 2h；
(3) 1300 DEG C are warming up to the rate of 2 DEG C/min under atmosphere of inert gases, keep the temperature 2h；
(4) 3000 DEG C are warming up to the rate of 10 DEG C/min under atmosphere of inert gases, keep the temperature 2h, after Temperature fall
Obtain efficient and light weight electromagnetic shielding graphene film.
Final prepared graphene composite film density is 0.01g/cm3, the sectional area of channel accounts for the flat of total sectional area
Mean value is 60%, electromagnet shield effect 120dB.
Comparative example：
Using 4 the method for embodiment, graphene microballoon is not added, finally by density domination in 0.01g/cm3, it is measured
Electromagnet shield effect there was only 97dB.
As can be seen from the above embodiments, the ruler of the mass ratio and graphene microballoon of graphene microballoon and graphene oxide sheet
It is very little that properties of product are had a major impact, with the addition of graphene microballoon, graphene sheet layer is hindered in high-temperature annealing process
In overlapping so that while graphene film porosity greatly increases, increase effective graphite that electromagnetic wave reflects wherein
The alkene number of plies or path, benefit electromagnet shield effect.
Claims (9)
1. a kind of pure graphene composite electromagnetic screen film, it is characterised in that：The density of the electromagnetic shielding film is 0.001-0.1g/
cm3, carbon content 100%, hollow graphite alkene of the electromagnetic shielding film by multiple graphene layers and between graphene layer
Microballoon forms, and hollow graphite alkene microsphere diameter is 1 ~ 5um；The graphene layer is pi-conjugated by π by the graphene film of planar orientation
Effect mutually overlap joint is formed；Adjacent graphene layer forms channel, the sectional area of channel under the support of hollow graphite alkene microballoon
Account for the 10 ~ 60% of total sectional area.
2. a kind of preparation method of pure graphene composite electromagnetic screen film, which is characterized in that include the following steps：
（1）Graphene oxide of the average-size of 100 parts by weight more than 100 μm is configured to a concentration of 0.1-100mg/ml oxidations
Graphene aqueous solution adds in the hollow graphite alkene microballoon of 0.1-10 parts by weight in the solution, after ultrasonic disperse, passes through film build method
Graphene oxide membrane is prepared into, is then restored with hydrazine hydrate；
（2）By obtained graphene film first with 0.3 under atmosphere of inert gasesoThe rate of C/min is warming up to 800oC, heat preservation
0.5-2h；
（3）With 2 under atmosphere of inert gasesoThe rate of C/min is warming up to 1300oC keeps the temperature 0.5-2h；
（4）With 10 under atmosphere of inert gasesoThe rate of C/min is warming up to 3000oC keeps the temperature 0.5-2h；After Temperature fall
Obtain composite electromagnetic screen film.
3. preparation method as claimed in claim 2, it is characterised in that：The film build method used include pouring molding oven drying method,
Knifing oven drying method, phase inversion, spray coating method.
4. preparation method as claimed in claim 2, it is characterised in that：Graphene oxide membrane is using hydrazine hydrate, amine, Vitamin C
Acid, hydrogen iodide are restored.
5. preparation method according to claim 2, which is characterized in that the step（1）In, the matter of hollow graphite alkene microballoon
Measure 4% for graphene oxide quality；A diameter of 4-5um of graphene microballoon.
6. preparation method according to claim 2, which is characterized in that the hollow graphite alkene microballoon ball wall is by 1-6 layers of stone
Black alkene piece is mutually overlapped by π-πconjugation, and surface is covered with micro- fold；Microsphere diameter is 500nm-10 μm；Inside it
It is hollow, there is great specific surface area 500-2000 m2/g；Microballoon is made of zero defect graphene, and there is perfect conjugation to tie
Structure, ID/IG＜ 0.001.
7. preparation method according to claim 6, which is characterized in that the hollow graphite alkene is micro- to be prepared by the following method
It obtains：
（1）Graphene oxide weak solution is obtained into graphene oxide microballoon, dried oxidation stone by the method for atomization drying
It is 5-20wt% that black alkene microballoon, which contains free water,；
（2）By step（1）Obtained graphene oxide microballoon, 15-20 DEG C/min are warming up to 800-1300 DEG C, later again with 1 ~
5 DEG C/min is warming up to 3000 DEG C of progress graphitization processings.
8. the method according to the description of claim 7 is characterized in that step（1）Described in a concentration of 0.1-10 of weak solution
mg/mL；Solvent is water, DMF, DMAc, methanol, ethyl alcohol, isopropanol, tetrahydrofuran, methyl ethyl ketone.
9. the method according to the description of claim 7 is characterized in that step（1）Described in atomization drying temperature be 80-150oC。
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| CN201610565804.5A CN106185905B (en) | 2016-07-15 | 2016-07-15 | A kind of pure graphene composite electromagnetic screen film and preparation method thereof |
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| CN106185905B true CN106185905B (en) | 2018-06-15 |
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| CN106966383B (en) * | 2017-04-28 | 2019-08-09 | 杭州高烯科技有限公司 | A kind of spitball shape graphene microballoon and preparation method thereof |
| CN109082123B (en) * | 2018-06-28 | 2021-06-04 | 上海电缆研究所有限公司 | Graphene modified electromagnetic shielding silicon rubber material and preparation method thereof |
| CN109336099B (en) * | 2018-09-28 | 2020-05-22 | 西安交通大学 | Method for repairing structural defects of graphene nanosheets and splicing graphene nanosheets |
| CN110040724B (en) * | 2019-05-23 | 2021-08-24 | 科炭(厦门)新材料有限公司 | Preparation method of folded graphene and electromagnetic shielding material thereof |
| CN110395716A (en) * | 2019-07-26 | 2019-11-01 | 中国电子科技集团公司第三十三研究所 | A kind of preparation method of the microwave defense material based on graphene |
| CN111362256B (en) * | 2020-03-12 | 2021-11-02 | 杭州高烯科技有限公司 | Preparation method of graphene electromagnetic shielding material |
| CN113825375B (en) * | 2021-08-11 | 2022-09-20 | 清华大学 | Vertical layered graphene electromagnetic shielding material and preparation method and application thereof |
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| CN105731434A (en) * | 2016-01-25 | 2016-07-06 | 浙江伟星新型建材股份有限公司 | Graphene film for light efficient electromagnetic shielding and preparation method thereof |
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