CN108003364A - A kind of Flexible graphene group compound film and preparation method thereof and the application as electromagnetic shielding material - Google Patents
A kind of Flexible graphene group compound film and preparation method thereof and the application as electromagnetic shielding material Download PDFInfo
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Abstract
Application the invention discloses a kind of Flexible graphene group compound film and preparation method thereof and as electromagnetic shielding material, its preparation method is to handle graphene oxide by cell disruptor with solvent, add silver/carbon nano-fiber composite material and magnetic ferroferric oxide, handled using cell disruptor, it is eventually adding sodium alginate soln, handled using cell disruptor, obtain dispersion liquid；Dispersion liquid obtains complex thin film structure by vacuum filtration method；Membrane structure is placed in the closed kettle equipped with low boiling point liquid reducing agent, reduced by fumigating system, up to uniform component distribution, there is loose structure, the preferable Flexible graphene group compound film of pliability, its good electromagnet shield effect, and preparation method operating procedure is simple, efficient, it is easy to accomplish industrialization production and application.
Description
Technical field
The present invention relates to a kind of electromagnetic shielding material, more particularly to a kind of Flexible graphene group compound film and preparation method thereof
And application, belong to electromagnetic shielding material preparation field.
Background technology
Ferroso-ferric oxide (Fe3O4) main component as magnetic iron ore, it is a kind of traditional magnetic material.As application most
Early nonmetal magnetic material, ferroso-ferric oxide have the excellent physicochemical property of many, therefore, are ground in the application of magnetic material
Study carefully field, ferroso-ferric oxide-directly favored be subject to researcher.At present, magnetic composite has been widely used in each neck
Domain, such as electro-magnetic wave absorption, lithium ion battery, the targeted delivery of medicine, magnetic resonance imaging, efficient circulation oil absorption material and heavy metal
Ionic adsorption.Ferroso-ferric oxide functionalization composite material is a main trend of magnetic material research field.
Grapheme material is due to special two-dimensional structure, big specific surface area and the excellent properties such as density is low, and one
Directly paid attention to be subject to investigation of materials person.The graphene of two-dimensional layered structure possesses big specific surface area, can using graphene as
Base-material, is loaded with the nano-particle of specific function to its functionalization.Correlative study shows, the two-dimensional sheet knot that graphene possesses
Structure is relative to conventional nano spherical particle, it will has more excellent absorbing property.Ferroso-ferric oxide inhales ripple material as tradition
Material, Fe is prepared into by graphene and ferroso-ferric oxide by certain experimental method3O4/ graphene composite material, can integrate two
The advantage of person, very wide application prospect is also had in absorbing material field.At present, investigation of materials person all over the world has used
Graphene with magnetic ferroferric oxide is compound prepares nano wave-absorbing material, and achieve certain achievement.Such as Chinese patent
(CN106358429A) ferroferric oxide wave absorbing material that a kind of graphene is modified is disclosed, it is from top to bottom by impedance matching
Layer, depletion layer and reflecting layer composition, impedance matching layer are distributed to shape in neoprene by graphene powder/ferroso-ferric oxide powder
Into depletion layer is distributed in neoprene for hydroxy iron powder and is formed, and reflecting layer is formed by graphite dispersion into neoprene, described
Impedance matching layer contains graphene powder/ferroso-ferric oxide powder of 2-5%.When the absorbing material thickness is 0.2mm, it is maximum
Absorption exceedes -9.46dB, excellent performance.Chinese patent (CN106118594A) discloses a kind of graphene oxide/tetra- and aoxidizes three
The preparation method of iron composite material, under conditions of only with heating and ultrasound, by specific heating and ultrasonic step, is being not required to
In the case of wanting any reducing agent, graphene oxide/ferriferrous oxide composite material has been obtained；And the present invention prepare it is compound
Material ferroferric oxide nano granules close-packed arrays but it is dispersed, form class " file surface " structure, it is also effective to solve
Scattering problem between graphene sheet layer, realizes dispersed and stone of the ferroferric oxide nano granules in graphene surface
It is dispersed between black alkene lamella.It is to have preferable absorption in the range of 2~18GHz in frequency, such as reaches most in 10.28GHz
Greatly, absorption maximum is -34.95dB, and ripple is inhaled in 5.72~7.88GHz frequency ranges and reaches below -10dB, effectively absorbs width and is
2.1GHz.Graphene/ferriferrous oxide composite material prepared by these methods is mainly compact texture, and is non-compliant structure,
Electric conductivity is poor.
The content of the invention
For ferroso-ferric oxide/graphene composite material of the prior art as absorbing material there are the defects of, this hair
Bright purpose be to provide the soft graphite alkenyl that a kind of lightweight, flexibility, applicable band are wide, effectiveness is good it is compound
Film, the Flexible graphene group compound film meet electromagnetic shielding material " thin, light, wide, strong " application requirement.
Another object of the present invention is to be to provide a kind of easy to operate, inexpensive to prepare the soft graphite alkenyl
The method of composite membrane.
Third object of the present invention is to provide the Flexible graphene group compound film as electromagnetic shielding material
Using the Flexible graphene group compound film has the characteristics that lightweight, flexibility, applicable band are wide, effectiveness is good, meets electricity
Magnetic shielding material " thin, light, wide, strong " application requirement.
In order to realize above-mentioned technical purpose, the present invention provides a kind of preparation method of Flexible graphene group compound film, its
Comprise the following steps：
1) graphene oxide is mixed with solvent and is handled by cell disruptor, obtain dispersion liquid A；
2) silver/carbon nano-fiber composite material and magnetic ferroferric oxide are added in dispersion liquid A, using cell disruptor
Processing, obtains dispersion liquid B；
3) sodium alginate soln is added in dispersion liquid B, is handled using cell disruptor, obtain dispersion liquid C；
4) dispersion liquid C is obtained into complex thin film structure by vacuum filtration method；
5) complex thin film structure is placed in the closed kettle equipped with low boiling point liquid reducing agent, is reduced by fumigating system, i.e.,
.
Preferable scheme, the time that cell disruptor is handled in step 1) is 10~30min.
Preferable scheme, the time that cell disruptor is handled in step 2) is 10~30min.
Preferable scheme, the time that cell disruptor is handled in step 3) is 10~30min.
Preferable scheme, the additive amount of silver/carbon nano-fiber composite material is graphene oxide, silver/carbon nano-fiber is multiple
The 18~43% of condensation material and magnetic ferroferric oxide three's gross mass.
Preferable scheme, the additive amount of magnetic ferroferric oxide is graphene oxide, silver/carbon nano-fiber composite material and
The 12~30% of magnetic ferroferric oxide three's gross mass.
More preferably scheme, the magnetic ferroferric oxide are obtained by chemical coprecipitation.
More preferably scheme, the silver/carbon nano-fiber composite material are obtained by chemical deposition.
More preferably scheme, graphene oxide are obtained using Hummer methods.
Preferable scheme, the concentration of the sodium alginate soln is 0.5~1.25mg/mL；Sodium alginate quality is oxidation
0.5~1.5 times of graphene quality.
Preferable scheme, the low boiling point liquid reducing agent are hydrazine hydrate.
Preferable scheme, the condition of the fumigating system reduction：Temperature is 90~120 DEG C, and the time is 8~10h.
Present invention also offers a kind of Flexible graphene group compound film, it is prepared by the above method.
Preferable scheme, Flexible graphene group compound film have loose structure, and graphite in Flexible graphene group compound film
Alkene, silver/carbon nano-fiber composite material and magnetic ferroferric oxide uniform component distribution.
Present invention also offers a kind of application of Flexible graphene group compound film, as electromagnetic shielding material application.
The preparation method of the Flexible graphene group compound film of the present invention includes step in detail below：
(1) weigh 30~52wt% by mass fraction and weigh graphene oxide (with graphene oxide, silver/carbon nano-fiber
Composite material and magnetic ferroferric oxide three gross mass are 100% metering), it is added in beaker, adds appropriate absolute ethyl alcohol,
Work 10~30min under cell disruptor, obtains uniform dispersion；The carbon nanometer of load silver is separately added into by mass fraction again
18~46wt% of fiber and magnetic ferroferric oxide 10~35wt% of powder, continues with cell disruptor and disperses the mixed liquor；
(2) sodium alginate powder is evenly spread in distilled water, obtains the alginic acid that concentration is 0.5~1.25mg/mL
Sodium solution (sodium alginate quality is 0.5~1.5 times of graphene oxide quality), and mixed with the dispersion liquid of step (1), then
Work 10~30min under cell disruptor；
(3) method by the mixed liquor that step (2) obtains using vacuum filtration, filtering use organic system miillpore filter, ruler
Very little 50mm*0.22 μm, obtain laminated film, and 8~12h of standing and drying at normal temperatures and pressures；
(4) film that step (3) obtains is taken off, seals and insert the teflon lined that appropriate hydrazine hydrate has been added dropwise not
Become rusty in steel autoclave, be heated to 90~120 DEG C, 8~10h of reduction reaction time, is cooled to room temperature, and taking-up obtains Flexible graphene
Group compound film.
The Flexible graphene group compound film of technical scheme aoxidizes three using graphene as matrix with magnetism four
Iron particle and silver/carbon nano-fiber composite material by sodium alginate molding bonded between a variety of materials, are obtained as dopant material
Flexible, uniform component distribution, and the membrane material with loose structure are obtained, it has electromagnetic shielding effect well after tested
Can, suitable for production application.Relatively existing graphene/ferriferrous oxide composite material, Flexible graphene group compound film maximum
Feature is that have preferable flexibility, and is mixed with the carbon nano-fiber of load silver, due to the carbon nano-fiber electrical conductivity of load silver
Height, during exclusive use, does not possess microwave absorbing property, but be filled with the ferroso-ferric oxide in magnetic loss and the stone of dielectric loss
Between black alkene, dielectric polarization is produced, the mutual supplement with each other's advantages of three kinds of components, obtains efficient electromagnetic shielding material.In addition, using seaweed
For sour sodium as binding agent, there is substantial amounts of-COO in it-With-OH-Group, can form complex, therefore with polyvalent metal ion
Metal ion in sodium alginate matrix content increase to a certain extent when, interionic combination power enhancing, it is sufficient to overcome ion
Between electrostatic repulsion effect and it is connected with each other, form conductive particle subchain, improve the electromagnetic shielding of fabric and antistatic
Ability, therefore using sodium alginate as the viscous of graphene, magnetic ferroferric oxide particle and silver/carbon nano-fiber composite material
Knot agent can obtain electromagnetic shielding flexible fabric.
The Flexible graphene group compound film of the present invention has loose structure, the solid graphite alkenyl prepared compared to other methods
The effectiveness of laminated film will be got well, and reason is micro- mainly due to being obtained by Multiple Scattering and reflection from loose structure
Ripple absorbs.With microcellular structure, it is more that to be absorbed without be anti-from foam that can make electromagnetic wave for hydrazine hydrate steam reduction
It is emitted back towards and, is more preferable wave-absorber.Total effectiveness of nearly 24dB is shown under 120 μm of low thickness, can stop to
Few 99% electromagenetic wave radiation.
Compared with prior art, the solution have the advantages that：
(a) graphene oxide is reduced into redox graphene by the present invention by the way of hydrazine hydrate steam reduction, and
The carbon nano-fiber of load silver is added, its electric conductivity is raised to 52~56S/m from 1.7~2.1S/m, and the appropriate of electric conductivity improves
Contribute to the enhancing of effectiveness.
(b) by the way of hydrazine hydrate steam reduction, composite membrane is softened the present invention, becomes porous from close state
State, loose structure can be by Multiple Scatterings and reflection enhancement microwave absorption, so that the electromagnet shield effect with higher.
(c) present invention is using sodium alginate as binding agent, it is not only to increasing effectiveness, and effectively
Improve the pliability and formability of composite membrane.
(d) graphene powder material produced by the present invention possesses that wave absorbtion ability is strong, small, thickness of inhaling wave frequency bandwidth, density
The advantages of small and performance is stablized.Section Example shows that the absorbing material is in X-band, and total electromagnet shield effect is up to 20dB
More than, can stop 99% electromagenetic wave radiation.Finished product uniformity is good, and size is controllable, simple process and low cost, meets industrialization
Production requirement.
Brief description of the drawings
【Fig. 1】For microscopic cross contrast schematic diagram before and after the composite membrane reduction of the embodiment of the present invention 1.
【Fig. 2】For microscopic cross contrast schematic diagram before and after the composite membrane reduction of the embodiment of the present invention 2.
【Fig. 3】For microscopic cross contrast schematic diagram before and after the composite membrane reduction of the embodiment of the present invention 3.
【Fig. 4】For the electromagnet shield effect figure of application examples 1 of the present invention.
【Fig. 5】For the electromagnet shield effect figure of application examples 2 of the present invention.
【Fig. 6】For the surface microscopic schematic diagram of the graphene-based composite membrane of the present invention.
【Fig. 7】For the contrast schematic diagram of electrical conductivity before and after the graphene-based composite membrane reduction of the present invention.
【Fig. 8】For the graphene-based composite membrane macro morphology schematic diagram of the present invention.
Embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, the common skill in this area
Art personnel all other embodiments obtained without making creative work, belong to the model that the present invention protects
Enclose.
It is the section Example of inventor in test below：
Embodiment 1
(1) 30mg graphene oxides are weighed, are added in beaker, add 160ml absolute ethyl alcohols, the work under cell disruptor
Make 15min, obtain uniform dispersion.Again the carbon nano-fiber 33wt% of load silver and magnetic four oxygen are separately added into by mass fraction
Change three iron powder 17wt%, continue with cell disruptor and disperse the mixed liquor.
(2) 30mg sodium alginate powders are evenly spread in 40ml distilled water, and are mixed with the dispersion liquid of step (1),
Work 15min under cell disruptor again.
(3) method by the mixed liquor that step (2) obtains using vacuum filtration, obtains laminated film, and in normal temperature and pressure
Lower standing and drying 12h.
(4) film that step (3) obtains is taken off, seals and insert the teflon lined that 4 drop hydrazine hydrates have been added dropwise not
Become rusty in steel autoclave, be heated to constant temperature at 100 DEG C and keep 9h, be cooled to room temperature, taking-up obtains Flexible graphene group compound film.
Fig. 1 is microscopic cross contrast schematic diagram before and after composite membrane reduction, and section becomes loose structure, thickness by compact texture
110.67~129.33 μm are increased to by 66.52~70.50 μm.It is due to the effect of hydrazine hydrate reduction, makes graphene base body piece
Layer struts.
Embodiment 2
(1) 30mg graphene oxides are weighed, are added in beaker, add 160ml absolute ethyl alcohols, the work under cell disruptor
Make 15min, obtain uniform dispersion.Again the carbon nano-fiber 43wt% of load silver and magnetic four oxygen are separately added into by mass fraction
Change three iron powder 14wt%, continue with cell disruptor and disperse the mixed liquor.
(2) 30mg sodium alginate powders are evenly spread in 40ml distilled water, and are mixed with the dispersion liquid of step (1),
Work 15min under cell disruptor again.
(3) method by the mixed liquor that step (2) obtains using vacuum filtration, obtains laminated film, and in normal temperature and pressure
Lower standing and drying 12h.
(4) film that step (3) obtains is taken off, seals and insert the teflon lined that 4 drop hydrazine hydrates have been added dropwise not
Become rusty in steel autoclave, be heated to constant temperature at 110 DEG C and keep 9h, be cooled to room temperature, taking-up obtains Flexible graphene group compound film.
Fig. 2 is microscopic cross contrast schematic diagram before and after composite membrane reduction, and section becomes loose structure, thickness by compact texture
112.00~135.20 μm are increased to by 70.67~86.67 μm.It is due to the effect of hydrazine hydrate reduction, makes graphene base body piece
Layer struts.
Embodiment 3
(1) 30mg graphene oxides are weighed, are added in beaker, add 160ml absolute ethyl alcohols, the work under cell disruptor
Make 15min, obtain uniform dispersion.Again the carbon nano-fiber 33wt% of load silver and magnetic four oxygen are separately added into by mass fraction
Change three iron powder 33wt%, continue with cell disruptor and disperse the mixed liquor.
(2) 30mg sodium alginate powders are evenly spread in 40ml distilled water, and are mixed with the dispersion liquid of step (1),
Work 15min under cell disruptor again.
(3) method by the mixed liquor that step (2) obtains using vacuum filtration, obtains laminated film, and in normal temperature and pressure
Lower standing and drying 12h.
(4) film that step (3) obtains is taken off, seals and insert the teflon lined that 4 drop hydrazine hydrates have been added dropwise not
Become rusty in steel autoclave, be heated to constant temperature at 120 DEG C and keep 9h, be cooled to room temperature, taking-up obtains Flexible graphene group compound film.
Fig. 3 is microscopic cross contrast schematic diagram before and after composite membrane reduction, and section becomes loose structure, thickness by compact texture
119.20~124.00 μm are increased to by 72.67~98.01 μm.It is due to the effect of hydrazine hydrate reduction, makes graphene base body piece
Layer struts.
Application examples 1
In order to measure capability of electromagnetic shielding, the method by using rectangular waveguide at room temperature, electromagnetism is have studied in X-band
Shielding properties, the S parameter (S of sample11And S21) measured by vector network analyzer (N5230C).By the flexible stone of the gained of embodiment 2
Mertenyl composite membrane cuts into suitably sized (being consistent with X-band waveguide chip size, 22.86*10.16mm), is adhered to paraffin
On substrate and it is placed on stent.(because paraffin mass is a kind of electromagnetic wave transparent material, matrix effect is only served in the measurements, so can
The electromagnetic parameter for thinking to measure is entirely due to film).
SE is determined according to the S parameter of measurementTAnd SEAAnd SERIt is as follows：
R=| S11|2, T=| S21|2.
A=1-R-T
SER(dB)=- 10log (1-R)
SEA(dB)=- 10log (T/ (1-R))
SET(dB)=SER+SEA
Wherein R is reflectance factor, and T is transmission coefficient, and A is absorption coefficient.
Final gained electromagnet shield effect as shown in figure 4, total electromagnet shield effect close to 20dB.
Application examples 2
In order to measure capability of electromagnetic shielding, the method by using rectangular waveguide at room temperature, electromagnetism is have studied in X-band
Shielding properties, the S parameter (S of sample11And S21) measured by vector network analyzer (N5230C).By the flexible stone of the gained of embodiment 3
Mertenyl composite membrane cuts into suitably sized (being consistent with X-band waveguide chip size, 22.86*10.16mm), is adhered to paraffin
On substrate and it is placed on stent.(because paraffin mass is a kind of electromagnetic wave transparent material, matrix effect is only served in the measurements, so can
The electromagnetic parameter for thinking to measure is entirely due to film).
SE is determined according to the S parameter of measurementTAnd SEAAnd SERIt is as follows：
R=| S11|2, T=| S21|2.
A=1-R-T
SER(dB)=- 10log (1-R)
SEA(dB)=- 10log (T/ (1-R))
SET(dB)=SER+SEA
Wherein R is reflectance factor, and T is transmission coefficient, and A is absorption coefficient
Final gained electromagnet shield effect as shown in figure 5, total electromagnet shield effect close to 24dB, better performances and should
Use-case 1 compares the increase for being primarily due to ferroso-ferric oxide mass fraction.
Claims (10)
- A kind of 1. preparation method of Flexible graphene group compound film, it is characterised in that：Comprise the following steps：1) graphene oxide is mixed with solvent and is handled by cell disruptor, obtain dispersion liquid A；2) silver/carbon nano-fiber composite material and magnetic ferroferric oxide are added in dispersion liquid A, at cell disruptor Reason, obtains dispersion liquid B；3) sodium alginate soln is added in dispersion liquid B, is handled using cell disruptor, obtain dispersion liquid C；4) dispersion liquid C is obtained into complex thin film structure by vacuum filtration method；5) complex thin film structure is placed in the closed kettle equipped with low boiling point liquid reducing agent, is reduced by fumigating system, to obtain the final product.
- A kind of 2. preparation method of Flexible graphene group compound film according to claim 1, it is characterised in that：The time that cell disruptor is handled in step 1) is 10~30min；The time that cell disruptor is handled in step 2) is 10~30min；The time that cell disruptor is handled in step 3) is 10~30min.
- A kind of 3. preparation method of Flexible graphene group compound film according to claim 1, it is characterised in that：Silver/carbon is received The additive amount of rice fibrous composite is graphene oxide, silver/carbon nano-fiber composite material and magnetic ferroferric oxide three The 18~43% of gross mass, the additive amount of magnetic ferroferric oxide is graphene oxide, silver/carbon nano-fiber composite material and magnetic The 12~30% of property ferroso-ferric oxide three's gross mass.
- A kind of 4. preparation method of Flexible graphene group compound film according to claim 3, it is characterised in that：The magnetism Ferroso-ferric oxide is obtained by chemical coprecipitation；Silver/the carbon nano-fiber composite material is obtained by chemical deposition.
- A kind of 5. preparation method of Flexible graphene group compound film according to claim 1, it is characterised in that：The seaweed The concentration of acid sodium solution is 0.5~1.25mg/mL；Sodium alginate quality is 0.5~1.5 times of graphene oxide quality.
- A kind of 6. preparation method of Flexible graphene group compound film according to claim 1, it is characterised in that：The low boiling Point liquid reducing agent is hydrazine hydrate.
- 7. according to a kind of preparation method of Flexible graphene group compound film of claim 1~6 any one of them, its feature exists In：The condition of the fumigating system reduction：Temperature is 90~120 DEG C, and the time is 8~10h.
- A kind of 8. Flexible graphene group compound film, it is characterised in that：It is prepared by any one of claim 1~7 method.
- A kind of 9. Flexible graphene group compound film according to claim 8, it is characterised in that：Flexible graphene group compound film With loose structure, and graphene, silver/carbon nano-fiber composite material and the oxidation of magnetism four three in Flexible graphene group compound film Iron uniform component distribution.
- A kind of 10. application of Flexible graphene group compound film described in claim 8 or 9, it is characterised in that：As electromagnetic shielding Materials application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711193707.9A CN108003364B (en) | 2017-11-24 | 2017-11-24 | Flexible graphene-based composite membrane, preparation method thereof and application of flexible graphene-based composite membrane as electromagnetic shielding material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711193707.9A CN108003364B (en) | 2017-11-24 | 2017-11-24 | Flexible graphene-based composite membrane, preparation method thereof and application of flexible graphene-based composite membrane as electromagnetic shielding material |
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| Publication Number | Publication Date |
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| CN108003364A true CN108003364A (en) | 2018-05-08 |
| CN108003364B CN108003364B (en) | 2020-10-16 |
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| CN113831599A (en) * | 2021-09-26 | 2021-12-24 | 北京理工大学 | Magnetoelectric coupling type electromagnetic shielding film and preparation method and application thereof |
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| CN109548394A (en) * | 2018-11-27 | 2019-03-29 | 湖南国盛石墨科技有限公司 | A kind of flexibility PU graphene electromagnetic shielding material and preparation method thereof |
| CN109750493A (en) * | 2019-01-18 | 2019-05-14 | 中国航发北京航空材料研究院 | A kind of preparation method of graphene electromagnetic shielding composite material |
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| CN111935965A (en) * | 2020-07-14 | 2020-11-13 | 西安工程大学 | Preparation method of silver/biomass porous carbon electromagnetic wave absorption composite material |
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| CN113629405A (en) * | 2021-08-16 | 2021-11-09 | 南京信息工程大学 | Light flexible wave-absorbing film and preparation method thereof |
| CN113629405B (en) * | 2021-08-16 | 2023-05-12 | 南京信息工程大学 | Preparation method of light flexible wave-absorbing film |
| CN113831599A (en) * | 2021-09-26 | 2021-12-24 | 北京理工大学 | Magnetoelectric coupling type electromagnetic shielding film and preparation method and application thereof |
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