CN107041113B - A method of it carries out compound preparing highly conductive high electromagnetic shielding flexible composite using graphene sponge and dimethyl silicone polymer - Google Patents
A method of it carries out compound preparing highly conductive high electromagnetic shielding flexible composite using graphene sponge and dimethyl silicone polymer Download PDFInfo
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Abstract
A method of it carries out compound preparing highly conductive high electromagnetic shielding flexible composite using graphene sponge and dimethyl silicone polymer；Belong to the technical field of highly conductive flexible composite.The invention solves existing graphene sponge product, there are sizes by equipment limit, flexible difference problem.Method: one, graphene oxide sponge is prepared；Two, graphene oxide sponge is restored with hydrazine hydrate steam；Three, it compresses；Four, it is heat-treated；Five, PDMS solution is perfused；Six, vacuum solidification to get arrive PDMS/ graphene sponge composite material.The PDMS/ graphene sponge composite material that the present invention obtains has flexible and electromagnetic shielding performance well, electromagnetic shielding performance can achieve 59dB (2mm), and its conductivity is 1.03S/cm, is had in electromagnetic shielding field application potential；Preparation method of the invention can be widely used in industrial production.
Description
Technical field
The invention belongs to the technical fields of highly conductive flexible composite；More particularly to a kind of using graphene sponge and poly-
Dimethyl siloxane carries out the compound method for preparing highly conductive high electromagnetic shielding flexible composite.
Background technique
Graphene only has one layer of carbon atom, and tightly packed at bi-dimensional cellular shape lattice structure, each carbon atom and phase
Three adjacent carbon atoms form covalent bond.Each carbon atom has a s track and three p tracks in graphene, wherein s track
Three carbon atoms adjacent with surrounding with two p tracks form chemical bond, do not contribute the conductivity of graphene, and remaining
The one mutual hydridization of p track forms valence band and conduction band, affects the electric property of graphene.This unique two-dimensional structure makes
Graphene has excellent mechanics, electricity and heat performance.Transmission of the free electron on graphene is not susceptible to scatter, electronics
Mobility can achieve 2 × 105cm/Vs, be more than 100 times of electron mobility in silicon；Its conductivity is up to 106S/m, is
Excellent conductive material at room temperature.Graphene elasticity modulus is up to 1TPa, breaking strength 125GPa, and room temperature thermal conductivity is 5.3
× 103W/mK, specific surface area 2630m2/g.Graphene also has excellent optical property, the visible light of single-layer graphene
Absorptivity is only 2.3%.This two-dimensional graphene film is also shown excellent other than with high conductivity and transmitance
Chemical stability and thermal stability, can be used as the substitute of solar energy transparent electrode.Graphene is in composite material, catalysis material
The fields such as material, energy storage material, high function nanometer electronic device, gas sensor have sizable application value, also attract numerous
Graphene is deeply systematically studied in scholar's expansion.
In order to apply these excellent properties, extensive synthesizing graphite alkene is needed, and single-layer graphene is assembled into macro
See structure.The method for preparing graphene at present includes simple mechanical stripping graphite crystal, metal surface epitaxial growth, chemistry stripping
Powdered graphite is removed from graphene oxide or liquid phase ultrasound.Wherein, the method for chemical stripping graphene oxide is because of process letter
It is single, it is easy large-scale production, is widely used in assembling graphene macrostructure.Graphene uniform is dispersed in matrix material
Material is a kind of important research direction for playing graphene excellent properties in metal, macromolecule, inorganic material.However, because
Graphene big L/D ratio, the presence of strong π-π, graphene are difficult to be uniformly dispersed in polymeric matrix material between each other.
Shenyang metal institute Zongping Chen etc. is using the method for chemical vapor deposition using nickel as template growth graphene sea
Silk floss backfills PDMS under vacuum condition again later, etches away nickel template using hydrochloric acid, prepares GF/PDMS composite material, graphite
When alkene content is as low as 0.8wt%, only the electromagnetic shielding performance of the composite material of 1mm can reach 20dB, have very big
Application value, these contents are published on " Advanced Materials ".
Graphene and polymethyl methacrylate are mixed into methylene chloride by Hao-Bin Zhang etc., are carried out later
Hot pressing carries out carbon dioxide critical freeze-drying after obtaining material, porous PMMA/ graphene sponge is obtained, when graphene
When volume fraction reaches 1.8vol%, conductivity can achieve 3.11S/m, electromagnetic shielding performance when material with a thickness of
It is 13~19dB when 2.4mm, related content is published on " AcsApplied Materials&Interfaces ".
Mohammed H.Al-Saleh etc. is prepared for polypropylene multi-walled carbon nanotube pipe composite material and has studied its electromagnetic screen
Property is covered, when the content of multi-walled carbon nanotube is 7.5vol%, electromagnetic shielding performance can achieve 34.8dB, related content
It is published in " Journal oftheAmerican Chemical Society ".
Currently, directly in the polymer by graphene nanometer sheet dispersion, there is dispersibility, poor connectivity etc., directly
Connect the performances such as the conductivity for affecting composite material, electromagnetic shielding；And graphene sea is prepared using the method for chemical vapor deposition
Silk floss, complicated, at high cost, graphene sponge size that there are preparation process are increased system by experimental facilities restriction problem in this way
The cost and difficulty of standby graphene composite material, influence the stability of composite material；The survey found that with a thickness of
2mm, graphene content are lower than under the conditions of 3wt%, and the electromagnetic shielding performance of graphene composite material is not higher than 40dB.
Currently, previous big size graphene sponge prepares the status restricted by experimental facilities；Graphene and polymer are compound
When graphene dispersion problem；The electromagnetic shielding performance of existing graphene sponge is not higher than 35dB.
Summary of the invention
The invention solves existing graphene sponge product, there are sizes by equipment limit, flexible difference problem；There is provided one
Kind carries out the compound side for preparing highly conductive high electromagnetic shielding flexible composite using graphene sponge and dimethyl silicone polymer
Method.
It is a kind of in the present invention to carry out compound preparing highly conductive high electromagnetic screen using graphene sponge and dimethyl silicone polymer
The method for covering flexible composite carries out in the steps below:
Step 1: graphene oxide dispersion to be freezed to 10h~for 24 hours under the conditions of -50 DEG C~-20 DEG C, it is freeze-dried 72h
~100h obtains graphene oxide sponge (brown color).
Step 2: being restored with hydrazine reducing agent steam to graphene oxide sponge, graphene oxide sponge is after reduction
(Dark grey, density are 6~22mg/cm to Dark grey3)；
Step 3: being then compressed into 0.1~10mm (0.01~0.08g/cm of density under the conditions of 1~100Kpa3)；
Step 4: being again protection gas with inert gas, heat treatment 1h~5h is carried out under the conditions of 750 DEG C~1000 DEG C；
Step 5: being then placed in poly dimethyl dilution, vacuumized by several times at 10Mpa~30Mpa, between each time
It is divided into 5min~30min, is perfusion completely when sponge sinks to backsight in diluted PDMS completely, pulls out and be placed on shelf, put
Set 40min~150min；
Step 6: being subsequently placed in vacuum tank, solidify 10min~300min under the conditions of 30 DEG C~200 DEG C to get arriving
PDMS/ graphene sponge composite material；
Wherein, poly dimethyl dilution described in step 5 the preparation method is as follows: by PDMS matrix resin and solidified resin
It is mixed according to mass ratio 10:1, is put into and vacuumizes 10~40min (gas in removing solution in vacuum tank at 10Mpa~30Mpa
Bubble), acetone is then added, magnetic agitation 10min~40min is placed into vacuum tank, is taken out under the conditions of 5Mpa~20Mpa true
Empty 5min~30min (removing the bubble in dilution), obtains the poly dimethyl that acetone quality content is 5%~30% and dilutes
Liquid.
Graphene oxide described in step 1 is prepared as follows: natural flake graphite is added in nitration mixture,
20min~60min is stirred with 200r/min~700r/min revolving speed, divides later 5~8 times and height is added every 20min equivalent
Potassium manganate strong oxidizer, then adjusting whipping temp and rate is 35 DEG C~80 DEG C, 200r/min~800r/min, and is placed in water
Constant temperature stirs 5h~18h in bath, is then added in ice water, and the hydrogen peroxide that mass fraction is 30% is added into ice water,
Suspension is obtained, is filtered, centrifuge washing obtains graphene oxide；
Wherein, the mass ratio of the volume of the nitration mixture and natural flake graphite is (10mL~300mL): 1g；Described
The quality of potassium permanganate and the volume ratio of nitration mixture are (8g~100g): 1L；The quality and hydrogen peroxide of the natural flake graphite
Volume ratio be 1g:(2mL~8mL)；
The phosphoric acid that nitration mixture is the sulfuric acid that mass fraction is 20%~98% and mass fraction is 20%~80% according to (3~
10): 1 volume ratio mixes.
Graphene oxide dispersion is by graphene oxide deionized water by (0.3mg~24mg): 1mL in step 1
Made of proportion mixes.
It is specifically that 80wt% hydrazine reducing agent aqueous solution and graphene oxide sponge are placed in closed reaction in step 2
In container, interlayer is placed, following to place hydrazine reducing agent solution, and top places graphene oxide sponge, is heated to 50 DEG C~100
DEG C using hydrazine reducing agent steam to graphene oxide sponge reductase 12 h~5h, obtain the graphene sponge of Dark grey.
Hydrazine reducing agent described in step 2 is hydrazine, hydrazine hydrate, dimethylhydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine.This hair
Bright method and process is simply low in cost, and high production efficiency, controllability are good, and can prepare large scale sample, can satisfy not
With the needs of engineering, solves previous big size graphene sponge and prepare the status restricted by experimental facilities；
The present invention has the characteristics that satisfactory electrical conductivity using graphene, prepares graphene sponge by Freeze Drying Technique,
By the concentration for adjusting graphene, thus it is possible to vary the density and thickness of graphene coating, thus mechanics, electricity to graphene sponge
It learns and the performances such as calorifics is adjusted；
The present invention can solve the dispersion problem of graphene and polymer compound tense graphene；
The PDMS/ graphene sponge composite material that the present invention obtains has flexible and electromagnetic shielding performance well, electricity
Magnetic shield performance can achieve 59dB (2mm), and its conductivity is 1.03S/cm, has and answers in electromagnetic shielding field
Use potentiality；
Preparation method of the invention can be widely used in industrial production.
Detailed description of the invention
Fig. 1 is the graphene sponge material photo of one step 2 of embodiment preparation；
Fig. 2 is the compressed graphite alkene sponge that one step 4 of embodiment obtains；
Fig. 3 is the PDMS/ graphene sponge composite material that one step 8 of embodiment obtains；
Fig. 4 is the picture when PDMS/ graphene sponge composite material that one step 8 of embodiment obtains bends；
Fig. 5 is the picture when PDMS/ graphene sponge composite material that one step 8 of embodiment obtains twists.
Specific embodiment
Embodiment one:
This example is related to existing graphene sponge product there are sizes by equipment limit, and flexible difference problem provides a kind of benefit
The compound method for preparing highly conductive high electromagnetic shielding flexible composite is carried out with graphene sponge and dimethyl silicone polymer:
One, it prepares graphene oxide: 20g natural flake graphite being added in sulfuric acid and phosphoric acid, mixture is made, stirring,
Condition is 500r/min, 40min.Divide 7 addition potassium permanganate (time interval 20min) later, adjusts whipping temp and speed
Rate is 35 DEG C, 500r/min, and is placed in constant temperature in water-bath and stirs 5h, and stirring mixture is added in ice water later, and
Into ice water be added mass fraction be 30% hydrogen peroxide, obtain graphene suspension, finally by graphene oxide suspension into
Row filters, and centrifuge washing is obtained graphene oxide, is finally diluted using deionized water, concentration 12mg/mL.
The quality and sulfuric acid of the potassium permanganate and the volume ratio of phosphoric acid mixing acid are 6g:1L；The natural scale stone
The volume ratio for the hydrogen peroxide that the quality and mass fraction of ink are 30% is 1g:2mL；
Sulfuric acid and phosphoric acid mixing acid are the mixture of the phosphoric acid of mass fraction 50% and the sulfuric acid of mass fraction 50%；Described
The volume ratio of the phosphoric acid of the sulfuric acid and mass fraction 50% of mass fraction 50% is 3:1；
Centrifuge washing processing carries out according to the following steps: using centrifugal separator, and deionized water centrifugal rinsing 5 is added
It is secondary, hydrochloric acid solution centrifugal rinsing 5 times of 0.2mol/L are then added, are eventually adding ethyl alcohol centrifugal rinsing 5 times；
Two, it prepares graphene oxide sponge: obtained graphene oxide dispersion is poured into mold, it is cold at -20 DEG C
Freeze for 24 hours, the graphene dispersing solution freeze-drying 100h of freezing is obtained into graphene oxide sponge.
The color of the obtained graphene oxide sponge is brown color.
Three, redox graphene sponge: 80wt% hydrazine hydrate aqueous solution redox graphene sponge is utilized, by two kinds
Reactant is placed in closed reaction vessel, and interlayer is placed, and places hydrazine hydrate solution below, and graphene oxide sea is placed in top
Silk floss is placed in baking oven, is heated to 90 DEG C and is carried out reduction 3h to graphene oxide sponge using hydrazine hydrate steam, the oxidation after reduction
Graphene sponge is Dark grey, obtains graphene sponge (see Fig. 1).
It is described restored after graphene oxide sponge density be 12mg/cm3.The thickness of the obtained graphene sponge
Degree is 8mm.
Four, compressed graphite alkene sponge: the graphene sponge of preparation is placed in a mold, is compressed under the conditions of 10Kpa
2mm (see Fig. 2).
Five, heat-treated graphite alkene sponge: graphene sponge prepared by step 2 is put into tube furnace, and in N2It protects
Gas is heat-treated 1.5h under the conditions of 900 DEG C.
Six, dimethyl silicone polymer (PDMS) dilution is prepared: by PDMS matrix resin and solidified resin according to mass ratio
The ratio of 10:1 is configured to resin solution, is put into the bubble vacuumized at 30Mpa in 40min removing solution in vacuum tank.It
9% acetone is added afterwards, magnetic agitation 40min obtains poly dimethyl dilution, is reentered into vacuum tank in 20Mpa condition
Under vacuumize 30min remove dilution in bubble, obtain diluted poly dimethyl dilution.
Seven, vacuum auxiliary pouring graphene sponge: the heat-treated graphite alkene sponge that step 2 obtains is put into step 4 and is matched
It in the dilution of system, will be vacuumized by several times at 30Mpa in container dislocation vacuum tank, each time interval is 20min, has been obtained
The graphene sponge being perfused entirely.Obtained graphene sponge is pulled out from solution, is placed on pre-prepd shelf, is relied on
Self gravity flows out PDMS dilution from sponge, places 40min.
Eight, solidify PDMS/ graphene sponge composite material: graphene sponge/PDMS that step 5 is obtained is placed in vacuum
In case, at 60 DEG C, precuring 30min, while removing diluent acetone and obtaining PDMS/ graphene sponge composite material (Fig. 3).
The obtained thickness of composite material is 2mm.
It is 12mg/cm that the present embodiment, which obtains original graphite alkene sponge material density by the quality and volume of test sample,3,
It shows good compression performance with 3 D stereo network structure, under conditions of compression ratio is 80%, still is able to completely
It restores to the original state；The density of graphene sponge is 31mg/cm after compression heat treatment3, while the method for the present invention preparation based on graphite
Alkene sponge composite material has very high conductivity, is 1.03S/cm by the conductivity that conductivity testing experiment obtains, average
Electromagnetic shielding performance can achieve 54.26dB.
The PDMS/ graphene sponge composite material manufactured in the present embodiment known to Figure 4 and 5 has flexible well.
Embodiment two:
This example is related to existing graphene sponge product there are sizes by equipment limit, and flexible difference problem provides a kind of benefit
The compound method for preparing highly conductive high electromagnetic shielding flexible composite is carried out with graphene sponge and dimethyl silicone polymer:
One, it prepares graphene oxide: 200g natural flake graphite being added in sulfuric acid and phosphoric acid, mixture is made, stirred
It mixes, condition 500r/min, 60min.Divide 8 addition potassium permanganate (time interval 20min) later, adjustment whipping temp and
Rate is 50 DEG C, 800r/min, and is placed in constant temperature in water-bath and stirs 18h, and stirring mixture is added in ice water later, and
And the hydrogen peroxide that mass fraction is 30% is added into ice water, graphene suspension is obtained, finally by graphene oxide suspension
It is filtered, centrifuge washing, obtains graphene oxide, be finally diluted using deionized water, concentration 12mg/mL.
The volume of the sulfuric acid and phosphoric acid mixing acid and the mass ratio of natural flake graphite are 100mL:1g；The Gao Meng
The quality and sulfuric acid of sour potassium and the volume ratio of phosphoric acid mixing acid are 80g:1L；The quality and mass fraction of the natural flake graphite
Volume ratio for 30% hydrogen peroxide is 1g:6mL；
Two, it prepares graphene oxide sponge: obtained graphene oxide dispersion is poured into mold, it is cold at -50 DEG C
Freeze for 24 hours, the graphene dispersing solution freeze-drying 90h of freezing is obtained into graphene oxide sponge.
The color of the obtained graphene oxide sponge is brown color.
Three, redox graphene sponge: 80wt% hydrazine hydrate aqueous solution redox graphene sponge is utilized, by two kinds
Reactant is placed in closed reaction vessel, and interlayer is placed, and places hydrazine hydrate solution below, and graphene oxide sea is placed in top
Silk floss is placed in baking oven, is heated to 90 DEG C and is carried out reduction 3h to graphene oxide sponge using hydrazine hydrate steam, the oxidation after reduction
Graphene sponge is Dark grey, obtains graphene sponge.
It is described restored after graphene oxide sponge density be 12mg/cm3.The thickness of the obtained graphene sponge
Degree is 4mm.
Four, compressed graphite alkene sponge: the graphene sponge of preparation is placed in a mold, is compressed under the conditions of 10Kpa
2mm。
Five, heat-treated graphite alkene sponge: graphene sponge prepared by step 2 is put into tube furnace, and is protected in N2
Gas is heat-treated 1.5h under the conditions of 900 DEG C.
Six, dimethyl silicone polymer (PDMS) dilution is prepared: by PDMS matrix resin and solidified resin according to mass ratio
The ratio of 10:1 is configured to resin solution, is put into the bubble vacuumized at 30Mpa in 40min removing solution in vacuum tank.It
9% acetone is added afterwards, magnetic agitation 40min obtains poly dimethyl dilution, is reentered into vacuum tank in 20Mpa condition
Under vacuumize 30min remove dilution in bubble, obtain diluted poly dimethyl dilution.
Seven, vacuum auxiliary pouring graphene sponge: the heat-treated graphite alkene sponge that step 2 obtains is put into step 4 and is matched
It in the dilution of system, will be vacuumized by several times at 30Mpa in container dislocation vacuum tank, each time interval is 20min, has been obtained
The graphene sponge being perfused entirely.Obtained graphene sponge is pulled out from solution, is placed on pre-prepd shelf, is relied on
Self gravity flows out PDMS dilution from sponge, places 40min.
Eight, solidify PDMS/ graphene sponge composite material: graphene sponge/PDMS that step 5 is obtained is placed in vacuum
In case, at 60 DEG C, solidify 30min, while removing diluent acetone and obtaining PDMS/ graphene sponge composite material.
The obtained thickness of composite material is 2mm.
It is 22mg/cm that the present embodiment, which obtains graphene sponge density of material by the quality and volume of test sample,3, tool
There is 3 D stereo network structure, show good compression performance, under conditions of compression ratio is 80%, still is able to restore completely
Original state；Density after compression heat treatment sponge is 17mg/cm3, while the method for the present invention preparation is compound based on graphene sponge
Material has very high conductivity, is 0.39S/cm by the conductivity that conductivity testing experiment obtains, average electromagnetic wave shielding
39.06dB can be can achieve.
Claims (10)
1. a kind of prepare highly conductive high electromagnetic shielding flexible compound using graphene sponge and dimethyl silicone polymer progress are compound
The method of material, it is characterised in that this method carries out in the steps below:
Step 1: graphene oxide dispersion is freezed to 10h~for 24 hours under the conditions of -50 DEG C~-20 DEG C, freeze-drying 72h~
100h obtains graphene oxide sponge；
Step 2: being restored with hydrazine reducing agent steam to graphene oxide sponge；
Step 3: being then compressed into 0.1~10mm thickness under the conditions of 1~100Kpa；
Step 4: being again protection gas with inert gas, heat treatment 1h~5h is carried out under the conditions of 750 DEG C~1000 DEG C；
Step 5: being then placed in poly dimethyl dilution, vacuumized by several times at 10Mpa~30Mpa, each time interval is
5min~30min is pulled out and is placed on shelf, places 40min~150min；
Step 6: being subsequently placed in vacuum tank, solidifying under the conditions of 30 DEG C~200 DEG C, curing time is 10min~300min,
Obtain PDMS/ graphene sponge composite material；
Wherein, poly dimethyl dilution described in step 5 the preparation method is as follows: by PDMS matrix resin and solidified resin according to
Mass ratio 10:1 mixing, is put into vacuum tank and vacuumizes 10~40min at 10Mpa~30Mpa, acetone, magnetic force is then added
10min~40min is stirred, is placed into vacuum tank, is vacuumized 5min~30min under the conditions of 5Mpa~20Mpa, obtain acetone
The poly dimethyl dilution that mass content is 5%~30%.
2. preparation method according to claim 1, it is characterised in that graphene oxide described in step 1 is by following sides
Method preparation: natural flake graphite is added in nitration mixture, 20min~60min is stirred with 200r/min~700r/min revolving speed,
Divide later 5~8 times and potassium permanganate is added every 20min equivalent, then adjusting whipping temp and rate is 35 DEG C~80 DEG C, 200r/
Min~800r/min, and be placed in constant temperature in water-bath and stir 5h~18h, it is then added in ice water, and be added into ice water
The hydrogen peroxide that mass fraction is 30%, obtains suspension, filters, centrifuge washing obtains graphene oxide；
Wherein, the mass ratio of the volume of the nitration mixture and natural flake graphite is (10mL~300mL): 1g；The Gao Meng
The quality of sour potassium and the volume ratio of nitration mixture are (8g~100g): 1L；The quality of the natural flake graphite and the body of hydrogen peroxide
Product is than being 1g:(2mL~8mL)；
The phosphoric acid that nitration mixture is the sulfuric acid that mass fraction is 20%~98% and mass fraction is 20%~80% is according to (3~10): 1
Volume ratio mix.
3. preparation method according to claim 1, it is characterised in that graphene oxide dispersion is will to aoxidize in step 1
Made of graphene and deionized water are mixed by the proportion of (0.3mg~24mg): 1mL.
4. preparation method according to claim 1, it is characterised in that be specifically by 80wt% hydrazine reducing agent in step 2
Aqueous solution and graphene oxide sponge are placed in closed drier, following to place hydrazine reducing agent solution, and oxidation is placed in top
Graphene sponge is heated to 50 DEG C~100 DEG C using hydrazine reducing agent steam to graphene oxide sponge reductase 12 h~5h, obtains
The graphene sponge of Dark grey.
5. preparation method according to claim 1, it is characterised in that hydrazine reducing agent described in step 2 is hydrazine, hydration
Hydrazine, dimethylhydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine.
6. preparation method according to claim 1, it is characterised in that step 4 is heat-treated under the conditions of 900 DEG C
1.5h。
7. preparation method according to claim 1, it is characterised in that the inert gas of step 4 is nitrogen or argon gas.
8. preparation method according to claim 1, it is characterised in that vacuumized by several times at 30Mpa in step 5, every time
Time interval is 20min.
9. preparation method according to claim 1, it is characterised in that step 6 solidifies 30min under the conditions of 60 DEG C.
10. preparation method according to claim 1, it is characterised in that solidified resin described in step 5 is poly dimethyl silicon
Oxygen alkane (PDMS).
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| WO2019109726A1 (en) * | 2017-12-08 | 2019-06-13 | 中车青岛四方机车车辆股份有限公司 | Electromagnetic shielding filler, electromagnetic shielding coating comprising same, preparation method and application thereof |
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| CN103819890A (en) * | 2014-01-23 | 2014-05-28 | 哈尔滨工业大学 | Method for preparing graphene sponge based on traditional sponge serving as template |
| CN105067160A (en) * | 2015-07-23 | 2015-11-18 | 东南大学 | Oxidized graphene sponge-based flexible pressure sensor and manufacturing method thereof |
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