CN105744817A - Preparation method for highly-oriented electromagnetic shielding membrane by assembling graphene and metal layer by layer - Google Patents
Preparation method for highly-oriented electromagnetic shielding membrane by assembling graphene and metal layer by layer Download PDFInfo
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- CN105744817A CN105744817A CN201610048384.3A CN201610048384A CN105744817A CN 105744817 A CN105744817 A CN 105744817A CN 201610048384 A CN201610048384 A CN 201610048384A CN 105744817 A CN105744817 A CN 105744817A
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- H05K9/0073—Shielding materials
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Abstract
The invention discloses a preparation method for a highly-oriented electromagnetic shielding membrane by assembling graphene and metal layer by layer. The method comprises the following steps of preparing a graphene oxide gel membrane from oversized fragment-free graphene oxide, freezing the graphene oxide gel membrane, and introducing the frozen graphene oxide gel membrane into a high-temperature furnace for high-temperature thermal treatment at 3,000 DEG C, thus acquiring an oriented graphene aerogel membrane with high heat conduction, electrical conduction and ultralight weight; depositing metal on the surface of a graphene sheet layer in the graphene aerogel membrane by chemical electroplating to obtain the electromagnetic shielding membrane taking a graphene membrane as a substrate and formed by stacking the grapheme and metal layer by layer; and pressing the graphene aerogel and metal composite membrane with high pressure to obtain the graphene and metal composite membrane. The graphene and metal composite membrane prepared according to the method has the advantages of high conductivity and wide absorption bandwidth, the thickness and the size both can be adjusted, a microstructure is regular, and the graphene and metal composite membrane has wide application prospect in the field of electromagnetic shielding and wave absorption.
Description
Technical field
The preparation method that the present invention relates to electromagnetic shielding film, particularly relates to the preparation method that a kind of highly oriented Graphene metal layer assembles electromagnetic shielding film.
Background technology
Electronic component interference to external world, is called EMI (ElectromagneticInterference).Development along with information and communication apparatus, electronic and electrical equipment tends to multi-functional and miniaturization, and accompanied electronic product quantity increases sharply, and in environment, Contamination of Electromagnetic Wave is also day by day serious, not only cause various instrumental function fault and system mistake, also easily human body is produced impact.Traditional battery shielding material is based on metal, has the shortcomings such as density of material is high, perishable, absorption band is narrow.Therefore, electromagnetic shielding material it is also proposed lightweight, high shielding properties, widescreen cover the requirements such as frequency band.2010, two professor AndreGeim and KonstantinNovoselov of Univ Manchester UK obtained Nobel Prize in physics because being successfully separated out stable Graphene first, have started the upsurge that Graphene is studied by the whole world.Graphene (Graphene) is a kind of monolayer two dimensional crystal, has electric conductivity and the heat conductivity of the highest intensity of known materials (Science, 2008,321,385-388) and excellence, is current optimal two-dimension nano materials.Based on the electric conductivity of its excellence, thermal conductivity, mechanical performance and low-density, Graphene can as the electromagnetic shielding material of carbon back.
The one section of bibliographical information delivered the recently thin graphene sheet capability of electromagnetic shielding when 100 DEG C has reached 38dB (Advancedmaterials2014,26,3357.)；In another section of document, the graphene film of 0.3 mm of thickness shows the capability of electromagnetic shielding of 46.3dB (J.Mater.Chem.C2014,2,5057.) at room temperature；The method that the up-to-date one section of article being published in advanced function material magazine evaporates self assembly by solvent is prepared for large-area graphene film, after 2000 degree of high-temperature process, thickness only has the capability of electromagnetic shielding of the graphene film of 0.0084mm to reach 20dB (Adv.Funct.Mater.2014,24,4542.).Although these graphene films all possess certain capability of electromagnetic shielding, but also have certain distance from actual requirement.If can by Graphene and metal composite, prepare Graphene-metallic composite, just Graphene height heat conduction, high tenacity, low-density advantage can be combined with metal height capability of electromagnetic shielding, prepare that light weight, thickness is thin, the new material of good toughness, shielding bandwidth.
But, existing preparation method there is problems in that one, said graphene film are not real Graphene assembling film, but graphite film, greatly reduce the effectiveness of Graphene；Its two, current Graphene metal composite film can't reach perfect assembling, be only be coated layer of metal on surface, do not reach due composite effect；Its three, it is extensive preparation or a very big challenge continuously.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that the preparation method that a kind of highly oriented Graphene metal layer assembles electromagnetic shielding film.
It is an object of the invention to be achieved through the following technical solutions: the preparation method that a kind of highly oriented Graphene metal layer assembles electromagnetic shielding film, its step is as follows:
(1) it being the average-size of 4-20mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, solidification liquid or liquid nitrogen stop the 10-100 second, it is frozen into graphene oxide gel film, graphene oxide gel film is put into the refrigerator of-4～-20 DEG C freezes quick freezing in 1-12h or liquid nitrogen.
(2) by step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 0.1-4 DEG C/min under atmosphere of inert gases, insulation 0.5-1h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 2-4 DEG C/min, is incubated 1-4h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 2-4 DEG C/min, insulation 1-2h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating.
(3) with the pure graphene aerogel thin film of step 2 acquisition for substrate, deposit metal nanoparticle by electroless plating so that metal nanoparticle is deposited on graphene film, obtain graphene aerogel metal composite electromagnetic shielding film；
Further, described rate of extrusion is between 4-20m/min.
Further, the temperature of described solidification liquid is 30-60 DEG C, is made up of according to arbitrarily ratio one or more in methanol, ethanol, ethyl acetate, n-butyl alcohol, ethylene glycol, Ketohexamethylene, glycerol, butyl acetate, propylene glycol, n-propyl acetate, acetic acid, glycerol, isobutanol, methyl acetate etc..
Further, in described step 1, the average-size graphene oxide more than 100um obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 orders is filtered, and obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, is added dropwise over hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes (namely the potassium permanganate in mixed liquor is removed completely)；
(3) mixed liquor after processing to step 2 is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped graphite oxide disappears, then goes out graphite oxide wafer with the screen filtration of 140 orders；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20～80 turns/min, concussion washing so that graphite oxide wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, and average-size is more than 100um, and breadth coefficient is between 0.2-0.5.
Further, Modified-Hummer method in described step 1 is particularly as follows: at-10 DEG C, potassium permanganate is completely dissolved in the concentrated sulphuric acid that mass fraction is 98%, add graphite, stirring is stopped after 60 revs/min of stirring 2h, under low temperature (-10～20 DEG C), react 6-48h, obtain the oxidized graphite flake reactant liquor of wide distribution；Described graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1g:2-4g:30-40ml, the granularity of graphite is more than 150 μm.
Further, described mesh screen is the acidproof mesh screens such as titanium alloy.
Further, in described step 1, the reactant liquor of oxidized graphite flake is diluted by diluent such as concentrated sulphuric acids, and the volume of diluent is 1-10 times of reactant liquor volume.
Further, described metal nanoparticle mainly by gold, silver, aluminum, copper, ferrum, zinc, chromium, nickel, cobalt, platinum, palladium, iridium, rhodium, ruthenium, titanium, vanadium, magnesium, indium, lanthanum, indium, antimony nanoparticle one or more form according to arbitrarily ratio.
The present invention compared with prior art has the advantages that being prepared in Graphene metal composite electromagnetic shielding film alkene film Graphene is assembled by few layer graphene, the existence of few layer graphene structure has truly played the usefulness of Graphene rather than the usefulness of pure graphite-structure；It is prepared into Graphene metal composite electromagnetic shielding film alkene film to be assembled by Graphene and metal layer, plays the performance of composite to greatest extent；By metallic atom or nanoparticle deposition absorption between two components, substantially increase absorption and the conductive performance of energy, it is possible to for high-power electromagnetic wave radiation field；The thickness of electromagnetic shielding film is 10-10000 μm, and conductivity is 100-10000S/cm, and thermal conductivity is 100-1000W/mK, and capability of electromagnetic shielding is 110-160dB.This composite membrane effectiveness is good, shields bandwidth, it is possible to for different applications.
Accompanying drawing explanation
Fig. 1 is the graphite oxide crystal (left side) before filtering, the graphite oxide crystal (right side) after filtration.
Fig. 2 is the graphene oxide (left side) before filtering, the graphene oxide (right side) after filtration.
Fig. 3 is the graphene oxide being obtained by reacting under 50 degree.
Fig. 4 is the graphene oxide distribution of sizes (left side) being obtained by reacting under 50 degree, the graphene oxide distribution of sizes (right side) being obtained by reacting under 20 degree.
Detailed description of the invention
By the present invention in that by super large sheet graphene oxide film forming, the wherein average-size of the planar orientation graphene film more than 100 μm important role in the process constituting graphene film of the present invention, the present invention, before graphite oxide crystal is washed, adopts the way of mesh screen separation, chip separation is gone out.And adopting 10 times to be diluted with the frozen water of upper volume so that its wafer will not be destroyed because of the heat of solution of sulphuric acid.Adopt shaking table concussion washing further so that graphene oxide lamella avoids the broken of mechanical force when peeling off.Further, the present invention prepares graphene film also by cryogenic conditions, at low temperatures, potassium permanganate oxidation is more weak, the speed that its selfdecomposition produces oxygen is slow, and therefore gas is just very weak to the fragmentation of graphite oxide crystal so that the graphene oxide of big lamella is preserved.And course of reaction and cleaning process do not have violent stirring and ultrasonic procedure, therefore lamella there is no broken.Comprehensive above some, we obtain the graphene oxide without fragment of super large sheet, and average-size is more than 87um, and breadth coefficient is between 0.2-0.5, and shive content is lower than 1%.
The preparation facilities with in-line outlet used in the present invention is prior art, and it is rectangular structure, and centre has in-line die orifice, and described in-line die orifice is a runner become narrow gradually.The runner become narrow gradually can be effectively increased the flow field active force to graphene film, is conducive to the formation of the regular orientation texture of graphene dispersion system.
Below in conjunction with embodiment, the present invention is described specifically; the present embodiment is served only for that the present invention is described further; it is not intended that limiting the scope of the invention; those skilled in the art makes some nonessential change and adjustment according to the content of foregoing invention, belongs to protection scope of the present invention.
Embodiment 1: without the preparation of the graphene oxide of fragment super large sheet
Embodiment 1-1
(1) potassium permanganate is slowly added in the concentrated sulphuric acid of quickly stirring at-10 DEG C, after fully dissolving, add graphite, 60 revs/min be slowly stirred 2h after stop stirring, at 20 DEG C, 50 DEG C, react 6h respectively, respectively obtain the graphite oxide crystal of wide distribution；As it is shown in figure 1, all there is more fragment in the graphite oxide wafer obtained at two kinds of temperature, this makes the graphene oxide of its correspondence have a lot of fragments (Fig. 2) equally.
(2) (extension rate can be any multiple to reactant liquor diluting concentrated sulfuric acid step 1 obtained, the present embodiment dilutes about 10 times), and with the titanium alloy mesh screen of 150um aperture (140 order), graphite oxide crystal is filtered out (reactant liquor recovery), and it is poured slowly in the frozen water relative to 10 times of volumes of filtration product of quickly stirring, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then filter out graphite oxide wafer with titanium alloy mesh screen (140 order)；Shaking table slowly shakes washing, obtains the graphene oxide without fragment super large sheet (average-size is 87um, and breadth coefficient is 0.5).Graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1g:2g:40ml, the granularity of graphite is 200um.
As it is shown on figure 3, wash, after the separation of isolated graphite oxide wafer, the graphene oxide obtained after the lower reaction of high temperature 50 degree have a lot of fragments equally；From fig. 4, it can be seen that large stretch of graphene oxide distribution of sizes uniform concentration more after (20 DEG C) Reaction Separation under low temperature, shive content is few.
Embodiment 1-2
Potassium permanganate is slowly added in the concentrated sulphuric acid of quickly stirring at-10 DEG C, after fully dissolving, adds graphite, 60 revs/min be slowly stirred 2h after stop stirring, under low temperature (0 DEG C), react 48h, obtain reactant liquor；Reactant liquor is diluted with the dilute sulfuric acid that the concentrated sulphuric acid of mass fraction more than 98%, mass fraction are 10% respectively, then with the titanium alloy mesh screen in 150um aperture, graphite oxide crystal is filtered out (reactant liquor recovery), and it is poured slowly in the frozen water relative to 10 times of volumes of filtration product of quickly stirring, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then leach graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains product.Graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1:4g:30ml；The granularity of graphite is 500um.
Adopt diluting concentrated sulfuric acid, the graphene oxide of the super large without fragment being obtained by reacting sheet (average-size is 98um, breadth coefficient 0.4), and dilute with dilute sulfuric acid, the product obtained contains a large amount of fragments, distribution of sizes coefficient is more than 100%.This is due in dilute sulfuric acid dilution, highly exothermic, destroys graphite oxide crystal.
Embodiment 1-3
Potassium permanganate is slowly added in the concentrated sulphuric acid of quickly stirring at-10 DEG C, after fully dissolving, adds graphite, 60 revs/min be slowly stirred 2h after stop stirring, under low temperature (20 DEG C), react 28h, obtain the graphite oxide crystal of wide distribution；By reactant liquor diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um aperture, graphite oxide crystal is filtered out (reactant liquor recovery), and be poured slowly into respectively quickly stirring relative to 5 times of volumes of filtration product, 8 times of volumes, 10 times of volumes frozen water in, stand 2h, be slowly added to H2O2, to remove potassium permanganate unnecessary in reaction, add appropriate hydrochloric acid until cotton-shaped graphite oxide disappears, then leach graphite oxide wafer with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains product；Graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1:5g:34ml, the granularity of graphite is 2mm.
Experimental result shows, the frozen water of 5 times of volumes and 8 times of volumes all can not the graphene film obtaining size uniformity, under 10 times of volumes, just can obtain graphene oxide without fragment super large sheet (average-size is 92um, breadth coefficient 0.2).It follows that the amount of frozen water is too low, the heat of mixing will be made to concentrate release, destroy crystal structure.
Embodiment 2: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares is prepared highly oriented Graphene metal layer and assembled electromagnetic shielding film.
It being the average-size of about 15-20mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly (20m/min) extrusion, liquid nitrogen stops 10 seconds, it is frozen into graphene oxide gel film, graphene oxide gel film is put into frost 12h in the refrigerator of-20 DEG C.
By step 1 freezing processing rear oxidation graphene aerogel thin film, in feeding high temperature furnace, the mode shown in table 1～table 3 carries out high-temperature heat treatment, it is thus achieved that the pure graphene aerogel thin film of continuous ultralight rule orientating.
With the pure graphene aerogel thin film of step 2 acquisition for substrate, deposit copper nano-particle by electroless plating so that copper nano-particle is deposited on graphene film, obtain graphene aerogel copper nano-particle composite electromagnetic screen film；Sedimentary condition is: voltage 12V, electrolyte copper sulfate, concentration 1mol/L, and metallic copper is anode, and graphene aerogel film is negative electrode.
Being put by electromagnetic shielding film and under high pressure suppress, pressure is 50MP, obtains highly oriented Graphene metal layer and assembles electromagnetic shielding film.The performance of the battery screened film that Different Heat Treatment Conditions obtains is such as shown in table 1～3.
Table 1
Table 2
Table 3
From table 1～table 3 it can be seen that the performance of this material mainly has three aspects to determine, one material internal graphene oxide sheet structure repair situation, i.e. the coming off and the reparation of carbon conjugated structure under high temperature of functional group.Its two, the seriality of material internal 3 D tropism structure, the i.e. connectivity of internal sheets Rotating fields.Its three, the existence forming the flexibility of guarantee material and graphene film Rotating fields of micro-air bag.Three's combined effect is to increase the performance of graphene film.
In table 1, by compare A1 B1 C1 the temperature of D1, A1 and B1 too low, be not enough to remove the functional group that major part is degradable, cause that in second step pyroprocess, gas quickly produces in a large number, at high temperature tearing sheet Rotating fields；D1 temperature is too high, produces gas too fast, can tear material internal structure in a large number, both can make deterioration in material properties.Having only at C temperature, functional group can slowly and thoroughly remove, to ensure material property.By compare C1 E1 F1 G1 H1, E1 heating rate too low, gas release excessively slow, it is impossible to make material internal formed through hole, ensuing temperature-rise period is unfavorable for the formation of micro-air bag.Have the formation that just can both ensure micro-air bag under CFGH heating rate only, can guarantee that again the complete of passage.By compare C1 I1 J1 K1 L1, I1 temperature-rise period too fast, gas release too fast, tear material internal structure, be unfavorable for formed transmission channel I1 temperature retention time too short, it is impossible to ensure major part functional group degraded；J1, temperature retention time is too short, is unfavorable for graphited carrying out；Insulating process is long, and M1 insulating process is long, can absorb the tar inside stove, is unfavorable for the lifting of performance.K1 and L1 just avoids both.
In table 2, by compare A2 B2 C2 D2 too low being not enough to of E2, A2 heating rate form small gap structure so that film can not form micro-air bag, has a strong impact on capability of electromagnetic shielding.E2 programming rate is too high, can tear Graphene interlayer structure so that graphene film link property is deteriorated, and heat conduction capability of electromagnetic shielding is all deteriorated.Have only under the programming rate of B2, C2, D2, just capable not only can ensure micro-airbag structure but also ensure the seriality within graphene film.By compare C2 F2 G2 H2, F2 temperature too low so that stable functional group can not be sufficiently disengaged from, in follow-up graphited process easy transition release gas, destroy the stable formation of micro-air bag；H2 temperature is too high, has reached graphitization temperature, and when now gas release, its temperature is also not enough to maintain the formation of micro-air bag, and the micro-airbag structure now formed is imperfect；By compare C2 I2 J2 K2 L2 M2, I2 temperature retention time too short, stable functional group can not fully come off；M2 overlong time, the easy tar adsorption of graphene film, it is unfavorable for the lifting of film properties；And when C2, J2, K2, M2, both can ensure that fully coming off of stabilising functional group, it is avoided that again the puzzlement of tar.
In table 3, by compare A3 B3 C3 D3 E3, E3 heating rate too low, it is excessively slow that most stabilising functional group comes off, and forms the formation being not enough to support micro-air bag in the process of micro-air bag；A3 outlet temperature is too low so that graphitization process imperfection, and B3, D3 outlet temperature is too high so that graphite part is vaporized；E3 temperature-rise period is too fast, and gas release and high-temperature expansion are too fast, it is easy to destroy the formation of micro-air bag.Only when C, the formation that micro-air bag could be stable, the structure on Graphene could be repaired slowly.By compare C3 F3 G3 H3 I3, I3 outlet temperature too high, Graphene can be vaporized；Could both ensure the reparation of graphene-structured at the temperature of C3, F3, G3, H3, will not be vaporized again.By compare C3 J3 K3 L3 M3, J3 temperature retention time too low, graphene-structured can not fully be repaired, and M3 temperature retention time is long, also can make absorption body of heater in tar, affect the performance of film.
Embodiment 3: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares is prepared highly oriented Graphene metal layer and assembled electromagnetic shielding film.
It being the average-size of 4mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, methanol (30 DEG C) stops 10 seconds (4m/min), it is frozen into graphene oxide gel film, graphene oxide gel film is put into frost 1h in the refrigerator of-4 DEG C.
By step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 0.1 DEG C/min under atmosphere of inert gases, insulation 0.5h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 2 DEG C/min, is incubated 1h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 2 DEG C/min, insulation 1h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating.
With the pure graphene aerogel thin film of step 2 acquisition for substrate, deposit argent by electroless plating so that deposition of silver, on graphene film, obtains graphene aerogel metal composite electromagnetic shielding film；Sedimentary condition is: voltage 6V, electrolyte silver sulfate, concentration 0.5mol/L, and argent is anode, and graphene aerogel film is negative electrode.
The electrical conductivity of prepared electromagnetic shielding film is 3000S/cm, and shield effectiveness is 120dB.
Embodiment 4: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares is prepared highly oriented Graphene metal layer and assembled electromagnetic shielding film.
It being the average-size of 20mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, acetic acid (60 DEG C) stops 100 seconds (20m/min), it is frozen into graphene oxide gel film, graphene oxide gel film is put into frost 12h in the refrigerator of-20 DEG C.
By step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 4 DEG C/min under atmosphere of inert gases, insulation 1h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 4 DEG C/min, is incubated 4h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 4 DEG C/min, insulation 2h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating.
With the pure graphene aerogel thin film of step 2 acquisition for substrate, deposit zinc by electroless plating so that zinc is deposited on graphene film, obtain graphene aerogel metal composite electromagnetic shielding film；Sedimentary condition is: voltage 10V, electrolyte zinc sulfate, concentration 0.1mol/L, and metallic zinc is anode, and graphene aerogel film is negative electrode.
The electrical conductivity of prepared electromagnetic shielding film is 10000S/cm, and shield effectiveness is 130dB.
Embodiment 5: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares is prepared highly oriented Graphene metal layer and assembled electromagnetic shielding film.It being the average-size of 14mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, propylene glycol (40 DEG C) stops 50 seconds (12m/min), it is frozen into graphene oxide gel film, graphene oxide gel film is put into frost 2h in the refrigerator of-12 DEG C.
By step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 1 DEG C/min under atmosphere of inert gases, insulation 0.6h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 3 DEG C/min, is incubated 2h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 3 DEG C/min, insulation 1.5h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating.
With the pure graphene aerogel thin film of step 2 acquisition for substrate, deposit magnesium by electroless plating so that magnesium is deposited on graphene film, obtain graphene aerogel metal composite electromagnetic shielding film；Sedimentary condition is: voltage 9V, electrolyte magnesium sulfate, concentration 0.8mol/L, and metallic copper is magnesium pole, and graphene aerogel film is negative electrode.
The electrical conductivity of prepared electromagnetic shielding film is 1000S/cm, and shield effectiveness is 110dB.
Embodiment 6: the graphene oxide of the sheet of super large without fragment that employing embodiment 1 prepares is prepared highly oriented Graphene metal layer and assembled electromagnetic shielding film.It being the average-size of 14mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, mixed liquor (volume ratio 1:1 at ethyl acetate and ethanol, 40 DEG C) 50 seconds (12m/min) of middle stop, it is frozen into graphene oxide gel film, graphene oxide gel film is put into frost 2h in the refrigerator of-12 DEG C.
By step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 1 DEG C/min under atmosphere of inert gases, insulation 0.6h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 3 DEG C/min, is incubated 2h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 3 DEG C/min, insulation 1.5h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating.
With the pure graphene aerogel thin film of step 2 acquisition for substrate, by electroless plating deposition of aluminum so that al deposition, on graphene film, obtains graphene aerogel metal composite electromagnetic shielding film；Sedimentary condition is: voltage 20V, electrolyte aluminum sulfate, concentration 3mol/L, and metallic copper is aluminum pole, and graphene aerogel film is negative electrode.
Prepared electromagnetic shielding membrane conductivity is 100S/cm, and shield effectiveness is 110dB.
Claims (8)
1. the preparation method that a highly oriented Graphene metal layer assembles electromagnetic shielding film, it is characterised in that its step is as follows:
(1) it being the average-size of 4-20mg/mL by concentration > graphene oxide water solution of 100um is from the preparation facilities with in-line outlet after continuously and smoothly's extrusion, solidification liquid or liquid nitrogen stop the 10-100 second, it is frozen into graphene oxide gel film, graphene oxide gel film is put into the refrigerator of-4～-20 DEG C freezes quick freezing in 1-12h or liquid nitrogen.
(2) by step 1 freezing processing rear oxidation graphene aerogel thin film, send in high temperature furnace and carry out high-temperature heat treatment, processing mode is: be first warmed up to 400 DEG C with 0.1-4 DEG C/min under atmosphere of inert gases, insulation 0.5-1h, then under atmosphere of inert gases, it is warmed up to 1300 DEG C with 2-4 DEG C/min, is incubated 1-4h, then under atmosphere of inert gases, is warmed up to 3000 DEG C with 2-4 DEG C/min, insulation 1-2h, can obtain the pure graphene aerogel thin film of continuous ultralight rule orientating.
(3) with the pure graphene aerogel thin film of step 2 acquisition for substrate, deposit metal nanoparticle by electroless plating so that metal nanoparticle is deposited on graphene film, obtain graphene aerogel metal composite electromagnetic shielding film.
2. the method for claim 1, it is characterised in that described rate of extrusion is between 4-20m/min.
3. the method for claim 1, it is characterized in that, the temperature of described solidification liquid is 30-60 DEG C, is made up of according to arbitrarily ratio one or more in methanol, ethanol, ethyl acetate, n-butyl alcohol, ethylene glycol, Ketohexamethylene, glycerol, butyl acetate, propylene glycol, n-propyl acetate, acetic acid, glycerol, isobutanol, methyl acetate etc..
4. the preparation method of the high thermal conductivity graphene thin film of a kind of super flexibility as claimed in claim 1, it is characterised in that in described step 1, the average-size graphene oxide more than 100um obtains by the following method:
(1), after the reactant liquor dilution of oxidized graphite flake Modified-Hummer method obtained, the mesh screen in 140 orders is filtered, and obtains filtration product；
(2) filtration product step 1 obtained is after frozen water is according to volume ratio 1:10 mix homogeneously, stands 2h, is added dropwise over hydrogen peroxide (H2O2Mass fraction be 30%), until the color of mixed liquor no longer changes (namely the potassium permanganate in mixed liquor is removed completely)；
(3) mixed liquor after processing to step 2 is added dropwise over concentrated hydrochloric acid (concentration is 12mol/L), until cotton-shaped graphite oxide disappears, then goes out graphite oxide wafer with the screen filtration of 140 orders；
(4) graphite oxide wafer step 3 obtained is placed in shaking table, 20～80 turns/min, concussion washing so that graphite oxide wafer is peeled off, and obtains the graphene oxide without fragment super large sheet, and average-size is more than 100um, and breadth coefficient is between 0.2-0.5.
5. method according to claim 4, it is characterized in that, Modified-Hummer method in described step 1 is particularly as follows: at-10 DEG C, potassium permanganate is completely dissolved in the concentrated sulphuric acid that mass fraction is 98%, add graphite, stop stirring after 60 revs/min of stirring 2h, under low temperature (-10-20 DEG C), react 6-48h, obtain the oxidized graphite flake reactant liquor of wide distribution；Described graphite, potassium permanganate and concentrated sulphuric acid mass volume ratio be: 1g:2-4g:30-40ml, the granularity of graphite is more than 150 μm.
6. method according to claim 4, it is characterised in that described mesh screen is the acidproof mesh screens such as titanium alloy.
7. method according to claim 4, it is characterised in that in described step 1, the reactant liquor of oxidized graphite flake is diluted by diluent such as concentrated sulphuric acids, and the volume of diluent is 1-10 times of reactant liquor volume.
8. the method for claim 1, it is characterized in that, described metal nanoparticle mainly by gold, silver, aluminum, copper, ferrum, zinc, chromium, nickel, cobalt, platinum, palladium, iridium, rhodium, ruthenium, titanium, vanadium, magnesium, indium, lanthanum, indium, antimony nanoparticle one or more form according to arbitrarily ratio.
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