CN105744817B - A kind of preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film - Google Patents
A kind of preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film Download PDFInfo
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- CN105744817B CN105744817B CN201610048384.3A CN201610048384A CN105744817B CN 105744817 B CN105744817 B CN 105744817B CN 201610048384 A CN201610048384 A CN 201610048384A CN 105744817 B CN105744817 B CN 105744817B
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- 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
- H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses a kind of preparation methods of graphene metal composite electromagnetic shielding film.This method prepares graphene oxide gel film by graphene oxide of the super large piece without fragment, after freezing, is sent into high temperature furnace and carries out 3000 DEG C of high-temperature heat treatments, obtains the graphene aerogel film of the highly conductive ultralight orientation of high heat conduction；Then graphene film layer surface in metal deposit to graphene aerogel film is obtained using graphene film as substrate by electroless plating, the electromagnetic shielding film that graphene and metal layer stack；Graphene aerogel metal composite film high pressure is suppressed, obtains graphene metal composite film.Graphene metal composite film thickness prepared by the present invention, size can be adjusted, micro-structure is regular, have that high electric conductivity, absorption band are wide, be with a wide range of applications being electromagnetically shielded and inhaling wave field.
Description
Technical field
Preparation method more particularly to a kind of highly oriented graphene metal layer assembling electricity the present invention relates to electromagnetic shielding film
The preparation method of magnetic shield film.
Background technology
Electronic component is to extraneous interference, referred to as EMI (Electromagnetic Interference).With information and
The development of communication apparatus, electronic and electrical equipment tend to multi-functional and miniaturization, and accompanied electronic product quantity increases sharply, in environment
Contamination of Electromagnetic Wave also getting worse, not only causes various instrumental function failures and system mistake, also easily human body is had an impact.
Traditional battery shielding material is based on metal, has the shortcomings that density of material is high, perishable, absorption band is narrow.Therefore, it is right
Electromagnetic shielding material also proposed lightweight, high shielding properties, widescreen cover the requirements such as frequency band.2010, Manchester, England was big
Two professor Andre Geim and the Konstantin Novoselov learned are obtained because being successfully separated out stable graphene for the first time
Nobel Prize in physics is obtained, has started the upsurge that graphene is studied in the whole world.Graphene (Graphene) is a kind of unimolecule
Layer two dimensional crystal, have the highest intensity of known materials (Science, 2008,321,385-388) and excellent electric conductivity and
Thermal conductivity is current optimal two-dimension nano materials.Based on its excellent electric conductivity, thermal conductivity, mechanical performance and low-density,
Graphene can be as carbon-based electromagnetic shielding material.
The document report delivered recently capability of electromagnetic shielding of the thin graphene piece at 100 DEG C has reached 38dB
(Advanced materials2014,26,3357.)；In another document, the graphene film of 0.3 mm of thickness is in room temperature table
Reveal the capability of electromagnetic shielding (J.Mater.Chem.C2014,2,5057.) of 46.3dB；It is newest that be published in advanced function material miscellaneous
One article of will is prepared for the graphene film of large area by the method for evaporation of the solvent self assembly, in 2000 degree of high-temperature process
Afterwards, thickness only have the capability of electromagnetic shielding of the graphene film of 0.0084mm reached 20dB (Adv.Funct.Mater.2014,
24,4542.).Although these graphene films all have certain capability of electromagnetic shielding, from actual requirement also have it is certain away from
From.It, just can be by graphene high heat conduction, high-ductility if can be prepared by graphene and metal composite graphene-metallic composite
Property, low-density the advantages of combined with the high capability of electromagnetic shielding of metal, prepare thin light weight, thickness, good toughness, shielding bandwidth
New material.
But existing preparation method has the following problems：First, said graphene film is not real stone
Black alkene assembling film, but graphite film greatly reduce the effectiveness of graphene；Second, current graphene metal composite film is also not
Perfect assembling can be reached, one layer of metal of coating is only carried out on surface, due composite effect is not achieved；Third, it connects
Continuous extensive preparation or a very big challenge.
Invention content
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of highly oriented graphene metal layer assembling electromagnetism
The preparation method of screened film.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of highly oriented graphene metal layer assembling electromagnetism
The preparation method of screened film, its step are as follows：
(1) by the average-size of a concentration of 4-20mg/mL>The graphene oxide water solution of 100um goes out from linear type
After continuously and smoothly squeezes out in the preparation facilities of mouth, stopped 10-100 seconds in solidification liquid or liquid nitrogen, be frozen into graphene oxide and coagulate
Graphene oxide gel film is put into -4~-20 DEG C of refrigerator in frost 1-12h or liquid nitrogen and is rapidly frozen by glued membrane.
(2) it by graphite oxide aerogel film after step 1 freezing processing, is sent into high temperature furnace and carries out high-temperature heat treatment,
Processing mode is：400 DEG C first are warming up to 0.1-4 DEG C/min under atmosphere of inert gases, 0.5-1h is kept the temperature, then in indifferent gas
1300 DEG C are warming up to 2-4 DEG C/min under body atmosphere, keeps the temperature 1-4h, is then heated up under atmosphere of inert gases with 2-4 DEG C/min
To 3000 DEG C, 1-2h is kept the temperature, you can obtain the pure graphene aerogel film of continuous ultralight rule orientating.
(3) the pure graphene aerogel film obtained using step 2 passes through electroless plating deposited metal nanoparticle as substrate
Son so that metal nanoparticle is deposited on graphene film, obtains graphene aerogel metal composite electromagnetic shielding film；
Further, the rate of extrusion is between 4-20m/min.
Further, the temperature of the solidification liquid is 30-60 DEG C, by methanol, ethyl alcohol, ethyl acetate, n-butanol, second two
In alcohol, cyclohexanone, glycerine, butyl acetate, propylene glycol, n-propyl acetate, acetic acid, glycerine, isobutanol, methyl acetate etc.
It is one or more to be formed according to arbitrary ratio.
Further, graphene oxide of the average-size more than 100um obtains by the following method in the step 1：
(1) oxidized graphite flake for obtaining Modified-Hummer methods reaction solution dilution after, in 140 mesh mesh screen into
Row filtering, obtains filtration product；
(2) by the filtration product that step 1 obtains in ice water according to volume ratio 1：10 after mixing, stands 2h, adds dropwise
Enter hydrogen peroxide (H2O2Mass fraction for 30%), until the color of mixed liquor no longer changes, (potassium permanganate i.e. in mixed liquor is
Removal completely)；
(3) concentrated hydrochloric acid (a concentration of 12mol/L) is added dropwise into step 2 treated mixed liquor, until cotton-shaped oxygen
Graphite disappears, then goes out graphite oxide chip with the screen filtration of 140 mesh；
(4) the graphite oxide chip that step 3 obtains is placed in shaking table, 20~80 turns/min, concussion washing so that oxidation
Graphite wafer is removed, and obtains the graphene oxide of no fragment super large piece, and average-size is more than 100um, and breadth coefficient is in 0.2-0.5
Between.
Further, the Modified-Hummer methods in the step 1 are specially：At -10 DEG C, potassium permanganate is filled
Point be dissolved in the concentrated sulfuric acid that mass fraction is 98%, add in graphite, stop stirring after 60 revs/min of stirring 2h, low temperature (-
10~20 DEG C) under react 6-48h, obtain the oxidized graphite flake reaction solution of wide distribution；Graphite, potassium permanganate and the concentrated sulfuric acid
Mass volume ratio is：1g：2-4g：30-40ml, the granularity of graphite are more than 150 μm.
Further, the mesh screen is the acidproof mesh screens such as titanium alloy.
Further, in the step 1, the reaction solution of oxidized graphite flake is diluted by diluents such as the concentrated sulfuric acids, dilute
The volume for releasing agent is 1-10 times of reaction solution volume.
Further, the metal nanoparticle mainly by gold, silver, aluminium, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, iridium,
Rhodium, ruthenium, titanium, vanadium, magnesium, indium, lanthanum, indium, the one or more of antimony nano-particle form according to arbitrary ratio.
The present invention has the advantage that compared with prior art：It is prepared into graphene metal composite electromagnetic shielding film alkene film
Middle graphene is assembled by few layer graphene, and the presence of few layer graphene structure has truly played the effect of graphene
The efficiency of energy rather than pure graphite-structure；Graphene metal composite electromagnetic shielding film alkene film is prepared by graphene and metal
Layer assembly forms, and has played the performance of composite material to greatest extent；Pass through metallic atom or nano-particle between two components
Deposition absorption, substantially increases absorption and the conductive performance of energy, can be used for high-power electromagnetic wave radiation field；Electromagnetic shielding film
Thickness for 10-10000 μm, conductivity 100-10000S/cm, thermal conductivity 100-1000W/mK, capability of electromagnetic shielding is
110-160dB.This composite membrane effectiveness is good, shields bandwidth, can be used for different application fields.
Description of the drawings
Fig. 1 be filtering before graphite oxide crystal (left side), the graphite oxide crystal (right side) after filtering.
Fig. 2 be filtering before graphene oxide (left side), the graphene oxide (right side) after filtering.
Fig. 3 is graphene oxide obtained by the reaction under 50 degree.
Fig. 4 is graphene oxide Size Distribution (left side) obtained by the reaction under 50 degree, graphite oxide obtained by the reaction under 20 degree
Alkene Size Distribution (right side).
Specific embodiment
By the present invention in that being formed a film with super large piece graphene oxide, wherein the average-size of planar orientation is more than 100 μm
Graphene film important role during graphene film of the present invention is formed, the present invention wash it in graphite oxide crystal
Before, using the method for mesh screen separation, fragment is isolated.And 10 times are used to be diluted with the ice water of upper volume so that it is brilliant
Piece will not be destroyed due to the heat of solution of sulfuric acid.Further using shaking table concussion washing so that graphene oxide layer is being shelled
From when avoid the broken of mechanical force.Further, the present invention also prepares graphene film by cryogenic conditions, in low temperature
Under, potassium permanganate oxidation is weaker, and the rate that selfdecomposition generates oxygen is slow, therefore gas is to graphite oxide crystal
Fragmentation is just very weak so that the graphene oxide of big lamella is preserved.And do not have in reaction process and cleaning process
Violent stirring and ultrasonic procedure, thus lamella there is no it is broken.In summary some, we have obtained the nothing of super large piece
The graphene oxide of fragment, average-size are more than 87um, and for breadth coefficient between 0.2-0.5, shive content is less than 1%.
Preparation facilities used in the present invention with linear type outlet is the prior art, is rectangular parallelepiped structure, intermediate
Linear type die orifice is provided with, the linear type die orifice is a runner become narrow gradually.The runner become narrow gradually can be effectively increased
Flow field is conducive to the formation of the regular orientation texture of graphene dispersion system to the active force of graphene film.
The present invention is described specifically with reference to embodiment, the present embodiment is served only for doing further the present invention
It is bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment, all belong to the scope of protection of the present invention.
Embodiment 1：The preparation of graphene oxide without fragment super large piece
Embodiment 1-1
(1) potassium permanganate is slowly added into the concentrated sulfuric acid quickly stirred at -10 DEG C, after abundant dissolving, added in
Graphite, 60 revs/min are slowly stirred stopping stirring after 2h, react 6h respectively at 20 DEG C, 50 DEG C, respectively obtain the oxygen of wide distribution
Graphite crystal；As shown in Figure 1, there are more fragments in the graphite oxide chip obtained at a temperature of two kinds, this causes it
Corresponding graphene oxide equally has many fragments (Fig. 2).
(2) (extension rate can be arbitrary multiple to the reaction solution diluting concentrated sulfuric acid obtained step 1, and the present embodiment is dilute
Release 10 times or so), and graphite oxide crystal is filtered out into (reaction solution time with the titanium alloy mesh screen of 150um apertures (140 mesh)
Receive), and be poured slowly into the ice water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, is slowly added to H2O2, with
Except potassium permanganate extra in dereaction, suitable hydrochloric acid is added in until cotton-shaped graphite oxide disappears, then with titanium alloy mesh screen
(140 mesh) filters out graphite oxide chip；Shaking table slowly shakes washing, and the graphene oxide for obtaining no fragment super large piece is (average
Size is 87um, breadth coefficient 0.5).Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1g：2g：40ml, graphite
Granularity is 200um.
As shown in figure 3, the oxidation stone washed after the graphite oxide chip separation isolated after the lower reaction of 50 degree of high temperature
Black alkene equally has many fragments；From fig. 4, it can be seen that large stretch of graphene oxide size under low temperature after (20 DEG C) Reaction Separation
It is few to be distributed more uniform concentration, shive content.
Embodiment 1-2
Potassium permanganate is slowly added at -10 DEG C in the concentrated sulfuric acid quickly stirred, after abundant dissolving, adds in stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 48h under low temperature (0 DEG C), obtain reaction solution；Reaction solution is distinguished
It is diluted with the concentrated sulfuric acid of more than 98% mass fraction, the dilute sulfuric acid that mass fraction is 10%, then with the titanium in 150um apertures
Graphite oxide crystal is filtered out (reaction solution recycling) by alloy mesh screen, and be poured slowly into quickly stir relative to filtration product
In the ice water of 10 times of volumes, 2h is stood, is slowly added to H2O2, to remove potassium permanganate extra in dereaction, add in suitable hydrochloric acid
Until cotton-shaped graphite oxide disappears, then be sieved through with titanium alloy reticulated and filter out graphite oxide chip；Shaking table slowly shakes washing, obtains anti-
Answer product.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：4g：30ml；The granularity of graphite is 500um.
Using diluting concentrated sulfuric acid, graphene oxide (average-size 98um, the distribution of no fragment super large piece obtained by the reaction
Coefficient is diluted with dilute sulfuric acid 0.4), and containing a large amount of fragments in obtained product, Size Distribution coefficient is more than 100%.This is
It is highly exothermic due in dilute sulfuric acid dilution, destroy graphite oxide crystal.
Embodiment 1-3
Potassium permanganate is slowly added at -10 DEG C in the concentrated sulfuric acid quickly stirred, after abundant dissolving, adds in stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, react 28h under low temperature (20 DEG C), the graphite oxide for obtaining wide distribution is brilliant
Body；Graphite oxide crystal is filtered out into (reaction solution by reaction solution diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um apertures
Recycling), and be poured slowly into respectively quickly stir relative to 5 times of volumes of filtration product, 8 times of volumes, 10 times of volumes ice water in,
2h is stood, is slowly added to H2O2, to remove potassium permanganate extra in dereaction, suitable hydrochloric acid is added in until cotton-shaped graphite oxide
It disappears, then is sieved through with titanium alloy reticulated and filters out graphite oxide chip；Shaking table slowly shakes washing, obtains reaction product；Graphite, Gao Meng
Sour potassium is with concentrated sulfuric acid mass volume ratio：1：5g：34ml, the granularity of graphite is 2mm.
Experimental result shows, the ice water of 5 times of volumes and 8 times of volumes cannot obtain the graphene film of size uniformity,
The graphene oxide of no fragment super large piece can be just obtained under 10 times of volumes, and (average-size 92um, breadth coefficient is 0.2).Thus
It is found that the amount of ice water is too low, the heat of mixing will be caused to concentrate release, destroy crystal structure.
Embodiment 2：Highly oriented graphene is prepared using the graphene oxide without fragment super large piece that embodiment 1 is prepared
Metal layer assembles electromagnetic shielding film.
By the average-size of a concentration of 15-20mg/mL or so>The graphene oxide water solution of 100um is from linear type
After continuously and smoothly (20m/min) squeezes out in the preparation facilities of outlet, stopped 10 seconds in liquid nitrogen, be frozen into graphene oxide gel
Graphene oxide gel film is put into -20 DEG C of refrigerator and freezes 12h by film.
Graphite oxide aerogel film step 1 freezing processing after is sent into high temperature furnace according to shown in 1~table of table 3
Mode carries out high-temperature heat treatment, obtains the pure graphene aerogel film of continuous ultralight rule orientating.
The pure graphene aerogel film obtained using step 2 deposits copper nano-particle as substrate by electroless plating so that
Copper nano-particle is deposited on graphene film, obtains graphene aerogel copper nano-particle composite electromagnetic screen film；Sedimentary condition
For：Voltage 12V, electrolyte copper sulphate, concentration 1mol/L, metallic copper are anode, and graphene aerogel film is cathode.
Electromagnetic shielding film is placed under high pressure and is suppressed, pressure 50MP obtains highly oriented graphene metal layer assembling electricity
Magnetic shield film.The performance of battery screened film that Different Heat Treatment Conditions obtain is as shown in table 1~3.
Table 1
Table 2
Table 3
From 1~table of table 3 as can be seen that being determined in terms of the performance of this material mainly has three, one material internal graphite oxide
Alkene chip architecture repair situation, i.e., functional group come off and high temperature under carbon conjugated structure reparation.Second, material internal three-dimensional takes
To the continuity of structure, i.e., the connectivity of internal lamellar structure.Third, the formation of micro- air bag just can guarantee material flexibility and
The presence of graphene sheet layer structure.Three's collective effect is to increase the performance of graphene film.
In table 1, by comparing A1 B1 C1 D1, A1 and B1 temperature it is too low, be not enough to remove most of degradable official
It can roll into a ball, gas in second step pyroprocess is caused largely quickly to generate, tears lamellar structure at high temperature；D1 temperature is excessively high, production
Angry body is too fast, can largely tear material internal structure, both can cause deterioration in material properties.It has only at a temperature of C, function
It rolls into a ball meeting slowly and thoroughly removes, to ensure material property.By comparing C1 E1 F1 G1 H1, E1 heating rates are too low, gas
Release is excessively slow, it is impossible to so that material internal forms through-hole, be unfavorable for the formation of micro- air bag in next temperature-rise period.
Have only just can not only ensure the formation of micro- air bag, but also can guarantee the complete of channel under CFGH heating rates.By comparing C1 I1
J1 K1 L1, I1 temperature-rise periods are too fast, and gas release is too fast, tear material internal structure, are unfavorable for being formed transmission channel I1 guarantors
The warm time is too short, it is impossible to ensure the degradation of most of functional group；J1, soaking time is too short, is unfavorable for graphited progress；Heat preservation
Process is long, and M1 insulating processes are long, can absorb the tar inside stove, is unfavorable for the promotion of performance.K1 and L1 are just avoided
Both of the above.
In table 2, by comparing A2 B2 C2 D2 E2, A2 heating rates are too low to be not enough to form small gap structure,
Prevent film seriously affects capability of electromagnetic shielding from forming micro- air bag.E2 heating rates are excessively high, can tear and tie between graphene layer
Structure so that graphene film link property is deteriorated, and heat conduction capability of electromagnetic shielding is all deteriorated.It has only under the heating rate of B2, C2, D2,
It capable can not only ensure micro- airbag structure but also ensure the continuity inside graphene film.By comparing C2 F2 G2 H2, F2 temperature
It is too low so that stable functional group cannot be sufficiently disengaged from, and in follow-up graphited transition release gas easy in the process, destroy micro-
Stablizing for air bag is formed；H2 temperature is excessively high, has reached graphitization temperature, and under conditions of gas release at this time, temperature is also not
It is enough to maintain the formation of micro- air bag, the micro- airbag structure formed at this time is imperfect；By comparing C2 I2 J2 K2 L2 M2, I2
Soaking time is too short, and stable functional group cannot fully come off；M2 overlong times, the easy tar adsorption of graphene film, are unfavorable for
The promotion of film properties；And fully coming off for stabilising functional group can be not only ensured under the conditions of C2, J2, K2, M2, but also be avoided that tar
Puzzlement.
In table 3, by comparing A3 B3 C3 D3 E3, E3 heating rates are too low, and most stabilising functional group comes off excessively slow, shape
Into the formation for being not enough to support micro- air bag during micro- air bag；A3 outlet temperatures are too low so that and graphitization process is not perfect,
B3, D3 outlet temperature are excessively high so that graphite part vaporizes；E3 temperature-rise periods are too fast, and gas release and high-temperature expansion are too fast, hold
The formation of the micro- air bag of destructible.In the case of only C, formation that micro- air bag could be stablized, the structure on graphene could be slowly
Reparation.By comparing C3 F3 G3 H3 I3, I3 outlet temperatures are excessively high, and graphene can be vaporized；The temperature of C3, F3, G3, H3
Degree is lower could not only to ensure the reparation of graphene-structured, but also will not be vaporized.By comparing C3 J3 K3 L3 M3, J3 keep the temperature when
Between it is too low, graphene-structured cannot be repaired fully, and M3 soaking times are long, can also cause adsorb furnace body in tar, influence film
Performance.
Embodiment 3：Highly oriented graphene is prepared using the graphene oxide without fragment super large piece that embodiment 1 is prepared
Metal layer assembles electromagnetic shielding film.
By the average-size of a concentration of 4mg/mL>The graphene oxide water solution of 100um is from the system exported with linear type
After continuously and smoothly squeezes out in standby device, 10 seconds (4m/min) is stopped in methanol (30 DEG C), is frozen into graphene oxide gel film,
Graphene oxide gel film is put into -4 DEG C of refrigerator and freezes 1h.
It by graphite oxide aerogel film after step 1 freezing processing, is sent into high temperature furnace and carries out high-temperature heat treatment, handle
Mode is：400 DEG C first are warming up to 0.1 DEG C/min under atmosphere of inert gases, 0.5h is kept the temperature, then under atmosphere of inert gases
1300 DEG C are warming up to 2 DEG C/min, keeps the temperature 1h, is then warming up to 3000 DEG C under atmosphere of inert gases with 2 DEG C/min, heat preservation
1h, you can obtain the pure graphene aerogel film of continuous ultralight rule orientating.
The pure graphene aerogel film obtained using step 2 passes through electroless plating deposited metal silver so that silver is heavy as substrate
Product obtains graphene aerogel metal composite electromagnetic shielding film on graphene film；Sedimentary condition is：Voltage 6V is electrolysed molten sulfur
Sour silver, concentration 0.5mol/L, metallic silver are anode, and graphene aerogel film is cathode.
The conductivity of prepared electromagnetic shielding film is 3000S/cm, shield effectiveness 120dB.
Embodiment 4：Highly oriented graphene is prepared using the graphene oxide without fragment super large piece that embodiment 1 is prepared
Metal layer assembles electromagnetic shielding film.
By the average-size of a concentration of 20mg/mL>The graphene oxide water solution of 100um is from the system exported with linear type
After continuously and smoothly squeezes out in standby device, 100 seconds (20m/min) is stopped in acetic acid (60 DEG C), is frozen into graphene oxide gel
Graphene oxide gel film is put into -20 DEG C of refrigerator and freezes 12h by film.
It by graphite oxide aerogel film after step 1 freezing processing, is sent into high temperature furnace and carries out high-temperature heat treatment, handle
Mode is：400 DEG C first are warming up to 4 DEG C/min under atmosphere of inert gases, 1h is kept the temperature, then with 4 under atmosphere of inert gases
DEG C/min is warming up to 1300 DEG C, 4h is kept the temperature, is then warming up to 3000 DEG C under atmosphere of inert gases with 4 DEG C/min, keeps the temperature 2h, i.e.,
The pure graphene aerogel film of continuous ultralight rule orientating can be obtained.
The pure graphene aerogel film obtained using step 2 deposits zinc so that zinc is deposited on as substrate by electroless plating
On graphene film, graphene aerogel metal composite electromagnetic shielding film is obtained；Sedimentary condition is：Voltage 10V, electrolyte sulfuric acid
Zinc, concentration 0.1mol/L, metallic zinc are anode, and graphene aerogel film is cathode.
The conductivity of prepared electromagnetic shielding film is 10000S/cm, shield effectiveness 130dB.
Embodiment 5：Highly oriented graphene is prepared using the graphene oxide without fragment super large piece that embodiment 1 is prepared
Metal layer assembles electromagnetic shielding film.By the average-size of a concentration of 14mg/mL>The graphene oxide water solution of 100um is from tool
Have in the preparation facilities of linear type outlet after continuously and smoothly's extrusion, the stop 50 seconds (12m/min) in propylene glycol (40 DEG C), solidification
Into graphene oxide gel film, graphene oxide gel film is put into -12 DEG C of refrigerator and freezes 2h.
It by graphite oxide aerogel film after step 1 freezing processing, is sent into high temperature furnace and carries out high-temperature heat treatment, handle
Mode is：First be warming up to 400 DEG C with 1 DEG C/min under atmosphere of inert gases, keep the temperature 0.6h, then under atmosphere of inert gases with
3 DEG C/min is warming up to 1300 DEG C, keeps the temperature 2h, is then warming up to 3000 DEG C under atmosphere of inert gases with 3 DEG C/min, heat preservation
1.5h, you can obtain the pure graphene aerogel film of continuous ultralight rule orientating.
The pure graphene aerogel film obtained using step 2 deposits magnesium so that magnesium is deposited on as substrate by electroless plating
On graphene film, graphene aerogel metal composite electromagnetic shielding film is obtained；Sedimentary condition is：Voltage 9V, electrolyte magnesium sulfate,
Concentration 0.8mol/L, metallic copper are magnesium pole, and graphene aerogel film is cathode.
The conductivity of prepared electromagnetic shielding film is 1000S/cm, shield effectiveness 110dB.
Embodiment 6：Highly oriented graphene is prepared using the graphene oxide without fragment super large piece that embodiment 1 is prepared
Metal layer assembles electromagnetic shielding film.By the average-size of a concentration of 14mg/mL>The graphene oxide water solution of 100um is from tool
Have in the preparation facilities of linear type outlet after continuously and smoothly's extrusion, in the mixed liquor of ethyl acetate and ethyl alcohol (volume ratio 1:Isosorbide-5-Nitrae 0
DEG C) in stop 50 seconds (12m/min), be frozen into graphene oxide gel film, graphene oxide gel film be put into -12 DEG C of ice
2h is freezed in case.
It by graphite oxide aerogel film after step 1 freezing processing, is sent into high temperature furnace and carries out high-temperature heat treatment, handle
Mode is：First be warming up to 400 DEG C with 1 DEG C/min under atmosphere of inert gases, keep the temperature 0.6h, then under atmosphere of inert gases with
3 DEG C/min is warming up to 1300 DEG C, keeps the temperature 2h, is then warming up to 3000 DEG C under atmosphere of inert gases with 3 DEG C/min, heat preservation
1.5h, you can obtain the pure graphene aerogel film of continuous ultralight rule orientating.
The pure graphene aerogel film obtained using step 2 passes through electroless plating deposition of aluminum so that al deposition exists as substrate
On graphene film, graphene aerogel metal composite electromagnetic shielding film is obtained；Sedimentary condition is：Voltage 20V, electrolyte sulfuric acid
Aluminium, concentration 3mol/L, metallic copper are aluminium pole, and graphene aerogel film is cathode.
Prepared electromagnetic shielding membrane conductivity is 100S/cm, shield effectiveness 110dB.
Claims (8)
1. a kind of preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film, which is characterized in that its step are as follows：
（1）By the average-size of a concentration of 4-20mg/mL>The graphene oxide water solution of 100um with linear type from exporting
After continuously and smoothly squeezes out in preparation facilities, stopped 10-100 seconds in solidification liquid or liquid nitrogen, be frozen into graphene oxide gel film,
Graphene oxide gel film is put into freeze in 1-12h or liquid nitrogen in -4~-20 DEG C of refrigerator and is rapidly frozen；
（2）It by graphite oxide aerogel film after step 1 freezing processing, is sent into high temperature furnace and carries out high-temperature heat treatment, handle
Mode is：First with 0.1-4 under atmosphere of inert gasesoC/min is warming up to 400oC keeps the temperature 0.5-1h, then in inert gas atmosphere
With 2-4 under enclosingoC/min is warming up to 1300oC keeps the temperature 1-4h, then with 2-4 under atmosphere of inert gasesoC/min is warming up to
3000oC keeps the temperature 1-2h, you can obtains the pure graphene aerogel film of continuous ultralight rule orientating；
（3）The pure graphene aerogel film obtained using step 2, by electroless plating deposited metal nano-particle, makes as substrate
It obtains metal nanoparticle to be deposited on graphene film, obtains graphene aerogel metal composite electromagnetic shielding film.
2. the preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film as described in claim 1, feature exist
In the rate of extrusion is between 4-20m/min.
3. the preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film as described in claim 1, feature exist
In the temperature of the solidification liquid is 30-60oC, by methanol, ethyl alcohol, ethyl acetate, n-butanol, ethylene glycol, cyclohexanone, acetic acid
It is one or more according to arbitrarily comparing group in butyl ester, propylene glycol, n-propyl acetate, acetic acid, glycerine, isobutanol, methyl acetate
Into.
4. the preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film as described in claim 1, feature exist
In graphene oxide of the average-size more than 100 um obtains by the following method in the step 1：
（1）After the reaction solution dilution for the oxidized graphite flake that Modified-Hummer methods are obtained, carried out in the mesh screen of 140 mesh
Filter, obtains filtration product；
（2）The filtration product that step 1 is obtained is with ice water according to volume ratio 1：10 after mixing, stands 2h, is added dropwise double
Oxygen water, H2O2Mass fraction for 30%, until the color of mixed liquor no longer changes, i.e., the potassium permanganate in mixed liquor is gone completely
It removes；
（3）The concentrated hydrochloric acid of a concentration of 12mol/L is added dropwise into step 2 treated mixed liquor, until cotton-shaped oxidation stone
Ink disappears, then goes out graphite oxide chip with the screen filtration of 140 mesh；
（4）The graphite oxide chip that step 3 obtains is placed in shaking table, 20 ~ 80 turns/min, concussion washing so that graphite oxide
Chip is removed, and obtains the graphene oxide of no fragment super large piece, and average-size is more than 100um, breadth coefficient 0.2-0.5 it
Between.
5. the preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film according to claim 4, feature
It is, the Modified-Hummer methods in the step 1 are specially：- 10oUnder C, potassium permanganate is completely dissolved in quality
Score is in 98% concentrated sulfuric acid, adds in graphite, stops stirring after 60 revs/min of stirring 2h, in -10-20oIt is reacted in a low temperature of C
6-48h obtains the oxidized graphite flake reaction solution of wide distribution；Graphite, potassium permanganate and the concentrated sulfuric acid mass volume ratio be：1
g：2-4g：30-40ml, the granularity of graphite are more than 150 μm.
6. the preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film according to claim 4, feature
It is, the mesh screen is the acidproof mesh screen of titanium alloy.
7. the preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film according to claim 4, feature
It is, in the step 1, the reaction solution of oxidized graphite flake is diluted by diluting concentrated sulfuric acid agent, and the volume of diluent is anti-
Answer 1-10 times that liquid accumulates.
8. the preparation method of highly oriented graphene metal layer assembling electromagnetic shielding film as described in claim 1, feature exist
In, the metal nanoparticle mainly by gold, silver, aluminium, copper, iron, zinc, chromium, nickel, cobalt, platinum, palladium, iridium, rhodium, ruthenium, titanium, vanadium,
Magnesium, indium, lanthanum, the one or more of antimony nano-particle form according to arbitrary ratio.
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