CN106082202B - A kind of preparation method and application of graphene aerogel - Google Patents
A kind of preparation method and application of graphene aerogel Download PDFInfo
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- CN106082202B CN106082202B CN201610486741.4A CN201610486741A CN106082202B CN 106082202 B CN106082202 B CN 106082202B CN 201610486741 A CN201610486741 A CN 201610486741A CN 106082202 B CN106082202 B CN 106082202B
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a kind of preparation method and applications of graphene aerogel, are related to grapheme material technical field.The preparation method comprises the following steps：Graphene oxide dispersion is uniformly mixed with amine curing agent to obtain graphene oxide liquid mixture；The amine curing agent is one or more in diaminodiphenyl-methane, diaminodiphenylsulfone, diethylenetriamines, trien, diethylaminopropylamine, m-phenylene diamine (MPD)；By the graphene oxide liquid mixture heated sealed, graphene hydrogel is obtained；Freeze-drying, obtains graphene aerogel, and graphene aerogel obtained can obtain having high conduction performance and graphene aerogel/epoxy resin composite material of excellent mechanical performance for epoxy resin.It is uniform macroporous structure inside graphene aerogel produced by the present invention, porosity is high, and amine curing agent is used in preparation process, the interface cohesion with epoxy resin is improved, to promote the conduction and mechanical property of epoxy resin.
Description
Technical field
The invention belongs to graphene aerogel technical fields, and in particular to a kind of preparation method of graphene aerogel and answer
With.
Background technology
Graphene is both most thin material, and most tough material, fracture strength are 200 times higher than steel.While it
There are good elasticity, stretch range that can reach the 20% of own dimensions again.Graphene most potential application at present is as silicon
Substitute manufactures ultra micro transistor npn npn, for producing following supercomputer.Replace silicon, computer processor with graphene
The speed of service will improve hundreds times.
Graphene is the new carbon for having bi-dimensional cellular shape structure, has very high mechanical strength, elasticity, heat conduction
Property, electric conductivity and quantum hall effect etc. cause the extensive concern of academia and industrial quarters in recent years.Graphene conduct
A kind of nano-particle reinforced epoxy composite material has been research hotspot, but graphene nano particle is in epoxy resin-base
Middle bad dispersibility is easily reunited, and the performance of composite material after resin modified is caused not rise anti-drop in some aspects.
Aeroge is a kind of solid matter form, the solid of world's upper density minimum.Density can reach 3kg/m3.It is general normal
The aeroge seen is silica aerogel, is made earliest in 1931 by the Kistler in the U.S..There are many type of aeroge, there is silicon
System, carbon system, sulphur system, metal oxide system, metal system etc..Any substance aeroge, and can after drying and removing internal solvent
Substantially its shape invariance is kept, and product has high porosity, low-density.
Aeroge includes a large amount of hole, and hole ratio is a kind of porous material with nanostructure 80% or more,
The aspects such as mechanics, acoustics, calorifics, optics show its peculiar property.They differ markedly from pore space structure in micron and milli
The porous material of rice magnitude, very thin nanostructure make the thermal conductivity of material extremely low, have great specific surface area airsettings
Glue is more much smaller than traditional porous material to the scattering of light, sound, these unique properties not only make the material in base
It is intriguing in plinth research, and contain the foreground of being widely applied in many fields.
Graphene aerogel inherits graphene and aeroge high-specific surface area, high porosity, high conductivity and good
Thermal conductivity and mechanical strength the advantages that.It breaches the application limitation of traditional zero dimension, a peacekeeping two-dimensional graphene, Yi Qifeng
Rich hole and continuous three-dimensional structure may be directly applied to battery electrode, sorbing material, catalyst carrier, resin composite materials
Equal fields, and composite property can be improved, so that it is caused the very big concern and research of researcher in sphere of learning.Stone
There are many kinds of the production methods of black alkene aeroge, but traditional method cost of manufacture is higher, and the technology of making is more demanding, no
It is easy to control, the manufacture difficulty of graphene aerogel is improved, so being needed for the production method of graphene aerogel further
Research improves.
Invention content
In view of the above-mentioned problems, the present invention proposes a kind of preparation method and application of graphene aerogel, graphene is reduced
The cost of manufacture of aeroge, and epoxy resin composite material is used it for, it is dispersed in resin matrix to overcome graphene
Problem improves the conductive and mechanical properties of epoxy resin composite material.
The present invention is to solve above-mentioned technical problem by the following technical programs：
A kind of preparation method of graphene aerogel, is as follows：
A. using stripping graphite oxide method prepare graphene oxide dispersion, and by the graphene oxide dispersion with
Amine curing agent is uniformly mixed and obtains graphene oxide liquid mixture；
Wherein, the amine curing agent is diaminodiphenyl-methane, diaminodiphenylsulfone, diethylenetriamines, three
It is one or more in ethylene tetra, diethylaminopropylamine, m-phenylene diamine (MPD)；
B. graphene oxide liquid mixture sealing is placed in 90 ~ 120 DEG C of environment and is heated, amine curing agent is made to restore
The graphene oxide obtains graphene hydrogel；
C. by step（b）The graphene hydrogel of gained uses acetone and water washing successively, and is freeze-dried, and obtains graphite
Alkene aeroge.
Further, the graphene oxide dispersion specific make step is：
1. crystalline flake graphite, sodium nitrate are mixed with the concentrated sulfuric acid under the conditions of 0~5 DEG C, potassium permanganate reaction is added；
2. by step 1. made of under the conditions of mixed liquor is placed in 30~40 DEG C, further oxidation reaction adds hydrogen peroxide,
After supersound process, dialysis 7~14 days are stood, finally use centrifuge extraction upper liquid up to graphene oxide dispersion,
Wherein, the rotating speed of the centrifuge is 2000~5000rpm.
Further, step（a）In, a concentration of 1~10mg/mL of the graphene oxide dispersion.
Further, step（a）In, the mass ratio of graphene oxide and amine curing agent in the graphene oxide liquid mixture
It is 1:10~1:100.
Further：Step（c）In, the temperature of the freeze-drying is -65 ~ -50 DEG C, and the time is 20~45h.
The density of the graphene aerogel obtained by the preparation method of above-mentioned graphene aerogel is 3~15mg/cm3, hole
Diameter is distributed between 20~100um.
The graphene aerogel that the present invention obtains can be used for being mixed with out epoxy resin composite material with epoxy resin,
The conduction and mechanical property of epoxy resin can be improved.
Further, the specific make step of the graphene aerogel and epoxy resin composite material is：
A is first added epoxy resin and curing agent, stirs evenly, obtain mixture I；
Mixture I is poured into and is placed in the mold of graphene aerogel by B, is placed in 50 ~ 70 DEG C, -5 ~ -40KPa vacuum rings
In border, so that epoxy resin is fully infiltrated graphene aerogel, be then heating and curing, finally obtain with high conduction performance and mechanics
Graphene aerogel/epoxy resin composite material of performance.
Further, the epoxy resin is bisphenol-A, aliphatic category epoxy resin.
Detailed, the curing agent is amine curing agent, including diaminodiphenyl-methane, diaminodiphenylsulfone, two Asias
Ethyl triamine, trien, diethylaminopropylamine, m-phenylene diamine (MPD).
Beneficial effects of the present invention are：
（1）The present invention with tradition prepare graphene aerogel difference lies in：Three-dimensional grapheme aeroge is prepared first, profit
With amine curing agent come redox graphene, and be self-assembled into graphene hydrogel, after prepared by Freeze Drying Technique
Graphene aerogel effectively prevents the stacking of graphene sheet layer, the structure for the graphene aerogel prepared and traditional stone
Black alkene aeroge is dramatically different, and concrete structure is seen figure 1 and figure 2.
（2）Graphene aerogel and epoxy resin prepared by the present invention is compound, as a result shows the graphene gas of the present invention
Gel can significantly increase epoxy resin electric conductivity and mechanical property.
（3）It uses amine curing agent as reducing agent in the manufacturing process of graphene aerogel in the present invention, stone can be improved
The interface cohesion of black alkene aeroge and epoxy resin-base, improves the conductive and mechanical properties of composite material.
（4）Preparation process of the present invention is simple, easy to control, and raw material sources are wide, greatly reduces production cost.
Description of the drawings
Fig. 1：The macroscopical graphene aerogel photo obtained in the embodiment of the present invention 1；
Fig. 2：The graphene aerogel electron scanning micrograph obtained in the embodiment of the present invention 1.
Specific implementation mode
Below in conjunction with specific embodiment, present invention is further described in detail.
In following case study on implementation, graphite used is provided by Nanjing Xian Feng nanometers of Co., Ltd, and graphite used is high-purity scale
Graphite, average grain diameter 500um, remaining raw material are the commercially available pure grade chemical reagent of analysis.
Embodiment 1：
A kind of preparation method of graphene aerogel, the specific steps are：
The first step：Prepare graphene oxide dispersion：Using stripping graphite oxide method, specially：First by the natural squamas of 5g
Piece graphite, 3g sodium nitrate are mixed with the 120mL concentrated sulfuric acids under conditions of 5 DEG C, are slowly added to that 15g potassium permanganate is added, 35 DEG C are stirred
6h is mixed, the hydrogen peroxide of 15mL30% is added after adding 500mL deionized waters to dilute, ultrasonic 0.5h outwells supernatant, thoroughly after standing 1 day
Analysis 7 days, 2000rpm centrifuging and taking upper liquids obtain finely dispersed graphene oxide dispersion；
Second step prepares graphene oxide liquid mixture：Diaminodiphenyl-methane is evenly spread into graphene oxide point
In dispersion liquid, graphene oxide liquid mixture is obtained, the wherein mass ratio of graphene oxide and diaminodiphenyl-methane is 1:10, institute
Obtain a concentration of 2mg/mL of graphene oxide in mixed liquor；
Third walks, and graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 95 DEG C of baking ovens, reacts 10h, obtains
To graphene hydrogel；
4th step, acetone, milli-Q water are used by graphene hydrogel successively, are freezed under conditions of being placed in -60 DEG C dry
Dry 30h, obtains graphene aerogel.
Fig. 1 is the macroscopical graphene aerogel photo obtained in the embodiment of the present invention 1, is that the present embodiment obtains as shown in Figure 1
The macro morphology picture of the graphene aerogel arrived, it can be seen that the structure is continuous cylinder block structure, microstructure
Be illustrated in figure 2 graphene aerogel hole be macroporous structure, aperture be 20~100um, more uniformly, graphene aerogel it is close
Spend 4.5mg/cm3.After preparing this graphene aerogel, using its macroporous structure, make in epoxy resin infiltration to hole, warp
Graphene aerogel reinforced epoxy functional composite material can be prepared after de-bubbled, heat cure.
Composite material is made applied to epoxy resin in graphene aerogel：The bisphenol A type epoxy resin E51 for weighing 20g, sets
Diaminodiphenyl-methane is added after heating 0.5h in 60 DEG C of oil bath pans, and stirring 0.2h makes it be uniformly mixed, it then will be upper
The graphene aerogel for stating preparation is put into liquid resin and is placed in 60 DEG C of vacuum drying ovens and is evacuated 2h, keeps liquid resin abundant
In the hole for infiltrating graphene aerogel, then takes out the good graphene aerogel of resin infiltration and be placed in sample in silica gel mould
Product cure, and finally obtain graphene aerogel/epoxy resin composite material, the wherein mass fraction shared by graphene aerogel is
0.3wt%, conductivity 0.26S/m, compressive strength 118MPa, and it is not added with the electricity of the epoxy resin of graphene aerogel
Conductance is 1.02 × 10-14S/m, compressive strength 110MPa.It can be seen that graphene aerogel can significantly improve epoxy resin
The electric conductivity and mechanical property of composite material.
Embodiment 2：
A kind of preparation method of graphene aerogel, the specific steps are：
First, configure graphene oxide dispersion：Using stripping graphite oxide method, first by 5g natural flake graphites, 3g
Sodium nitrate is mixed with the 120mL concentrated sulfuric acids at 4 DEG C, and 15g potassium permanganate is added, is slowly added to, and 40 DEG C of stirring 6h add 500mL to go
The hydrogen peroxide of 15mL30% is added after ionized water dilution, ultrasonic 0.5h outwells supernatant after standing 1 day, dialyse 9 days, 3000rpm
Centrifuging and taking supernatant liquid obtains finely dispersed graphene oxide dispersion；
Second, configure graphene oxide liquid mixture：Diaminodiphenyl-methane is evenly spread into graphene oxide dispersion
In liquid, wherein the mass ratio of graphene oxide and diaminodiphenyl-methane is 1:40, graphene oxide is dense in gained mixed liquor
Degree is 4mg/mL；
Graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 100 DEG C of baking ovens by third, reacts shape after 8h
At graphene hydrogel；
4th, graphene hydrogel is used into acetone, milli-Q water successively, is freeze-dried under conditions of being placed in -65 DEG C
25h obtains graphene aerogel.
Manufactured graphene aerogel hole is macroporous structure, and aperture is 20~100um, more uniformly, graphene aerogel
Density 6.3mg/cm3.After preparing this graphene aerogel, using its macroporous structure, make epoxy resin infiltration to hole
In, it can prepare graphene aerogel reinforced epoxy functional composite material after degassed bubble, heat cure.
Composite material is made applied to epoxy resin in manufactured graphene aerogel：Weigh the bisphenol A type epoxy tree of 40g
Fat E44, being placed in 60 DEG C of oil bath pans that curing agent diaminodiphenyl-methane is added after heating 1h and stirs 0.4h makes it uniformly, so
The graphene aerogel of above-mentioned preparation is put into liquid resin afterwards and is placed in 60 DEG C, in the vacuum drying oven of -20KPa and is evacuated
3h makes liquid resin fully infiltrate in the hole of graphene aerogel, then takes out the good graphene aerogel of resin infiltration
It is placed in its in silica gel mould to cure, finally obtains graphene aerogel/epoxy resin composite material, wherein graphene aerogel institute
The mass fraction accounted for is 0.51wt%, conductivity 0.42S/m, compressive strength 123MPa, and is not added with graphene aerogel
Epoxy resin conductivity be 1.02 × 10-14S/m, compressive strength 110MPa, it can be seen that graphene aerogel can be shown
Writing improves the electric conductivity and mechanical property of epoxy resin composite material.
Embodiment 3：
A kind of preparation method of graphene aerogel, the specific steps are：
First, configure graphene oxide dispersion：Using stripping graphite oxide method, first by 5g natural flake graphites, 3g
Sodium nitrate is mixed with the 120mL concentrated sulfuric acids at 3 DEG C, and 15g potassium permanganate is added, is slowly added to, and 35 DEG C of stirring 6h add 500mL to go
The hydrogen peroxide of 15mL30% is added after ionized water dilution, ultrasonic 0.5h outwells supernatant after standing 1 day, dialyse 10 days, 4000rpm
Centrifuging and taking upper liquid obtains finely dispersed graphene oxide dispersion；
Second, configure graphene oxide liquid mixture：Diaminodiphenyl-methane is evenly spread into graphene oxide dispersion
In liquid, wherein the mass ratio of graphene oxide and diaminodiphenyl-methane is 1:60, graphene oxide is dense in gained mixed liquor
Degree is 6mg/mL；
Graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 120 DEG C of baking ovens by third, reacts shape after 6h
At graphene hydrogel；
4th, graphene hydrogel is used into acetone, milli-Q water successively, is freeze-dried under conditions of being placed in -50 DEG C
36h obtains graphene aerogel.
Its hole of manufactured graphene aerogel is macroporous structure, and aperture is 20~100um, more uniformly, graphene airsetting
The density 8.7mg/cm of glue3.After preparing this graphene aerogel, using its macroporous structure, make epoxy resin infiltration to hole
In gap, graphene aerogel/epoxy resin composite material can be prepared after degassed bubble, heat cure.
Composite material is made applied to epoxy resin in manufactured graphene aerogel：Weigh the bisphenol A type epoxy tree of 60g
Fat E55, being placed in 60 DEG C of oil bath pans that curing agent diaminodiphenyl-methane is added after heating 1.5h and stirs 0.6h makes it uniformly,
Then the graphene aerogel of above-mentioned preparation is put into liquid resin and is placed in 55 DEG C, in the vacuum drying oven of -40KPa and be evacuated
4h makes liquid resin fully infiltrate in the hole of graphene aerogel, then takes out the good graphene aerogel of resin infiltration
It is placed in silica gel mould and cures sample, finally obtain graphene aerogel/epoxy resin composite material, wherein graphene airsetting
Mass fraction shared by glue is 0.75wt%, and conductivity 0.48S/m, compressive strength is 127MPa；And it is not added with graphene
The conductivity of the epoxy resin of aeroge is 1.02 × 10-14S/m, compressive strength 110MPa, it can be seen that graphene aerogel
The electric conductivity and mechanical property of epoxy resin composite material can be significantly improved.
Embodiment 4：
A kind of preparation method of graphene aerogel, the specific steps are：
First, configure graphene oxide dispersion：Using stripping graphite oxide method, first by 5g natural flake graphites, 3g
Sodium nitrate is mixed with the 120mL concentrated sulfuric acids at 2 DEG C, and 15g potassium permanganate is added, is slowly added to, and 30 DEG C of stirring 6h add 500mL to go
The hydrogen peroxide of 15mL30% is added after ionized water dilution, ultrasonic 0.5h outwells supernatant after standing 1 day, dialyse 12 days, 5000rpm
Centrifuging and taking upper liquid obtains finely dispersed graphene oxide dispersion；
Second, configure graphene oxide liquid mixture：Diaminodiphenyl-methane is evenly spread into graphene oxide dispersion
In liquid, wherein the mass ratio of graphene oxide and diaminodiphenyl-methane is 1:80, graphene oxide is dense in gained mixed liquor
Degree is 8mg/mL；
Graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 100 DEG C of baking ovens by third, reacts shape after 8h
At graphene hydrogel；
4th, graphene hydrogel is used into acetone, milli-Q water successively, is freeze-dried under conditions of being placed in -55 DEG C
35h obtains graphene aerogel.
Its hole of manufactured graphene aerogel is macroporous structure, and aperture is 20~100um, more uniformly, graphene airsetting
The density 12.4mg/cm of glue3.After preparing this graphene aerogel, using its macroporous structure, make epoxy resin infiltration to hole
In gap, graphene aerogel/epoxy resin composite material can be prepared after degassed bubble, heat cure.
Composite material is made applied to epoxy resin in manufactured graphene aerogel：Weigh the bisphenol A type epoxy tree of 80g
Fat, being placed in 60 DEG C of oil bath pans that curing agent diaminodiphenyl-methane is added after heating 2h and stirs 0.8h makes it uniformly, then
The graphene aerogel of above-mentioned preparation is put into liquid resin and is placed in 65 DEG C, in the vacuum drying oven of -5KPa and 5h is evacuated, makes
Liquid resin fully infiltrates in the hole of graphene aerogel, then takes out the good graphene aerogel of resin infiltration and is placed in silicon
Sample is cured in sealing rubber die, graphene aerogel/epoxy resin composite material is finally obtained, wherein shared by graphene aerogel
Mass fraction be 0.93wt%, conductivity 0.56S/m, compressive strength 134MPa；And it is not added with graphene aerogel
The conductivity of epoxy resin is 1.02 × 10-14S/m, compressive strength 110MPa, it can be seen that graphene aerogel can be notable
Improve the electric conductivity and mechanical property of epoxy resin composite material.
Embodiment 5：
A kind of preparation method of graphene aerogel, the specific steps are：
First, configure graphene oxide dispersion：Using stripping graphite oxide method, first by 5g natural flake graphites, 3g
Sodium nitrate is mixed with the 120mL concentrated sulfuric acids at 0 DEG C, and 15g potassium permanganate is added, is slowly added to, and 30 DEG C of stirring 6h add 500mL to go
The hydrogen peroxide of 15mL30% is added after ionized water dilution, ultrasonic 0.5h outwells supernatant after standing 1 day, dialyse 14 days, 3000rpm
Centrifuging and taking upper liquid obtains finely dispersed graphene oxide dispersion；
Second, configure graphene oxide liquid mixture：Diaminodiphenylsulfone is evenly spread in graphene oxide dispersion,
Wherein the mass ratio of graphene oxide and diaminodiphenylsulfone is 1：40, a concentration of 4mg/ of graphene oxide in gained mixed liquor
mL；
Graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 100 DEG C of baking ovens by third, reacts shape after 9h
At graphene hydrogel；
4th, graphene hydrogel is used into acetone, milli-Q water successively, is freeze-dried under conditions of being placed in -60 DEG C
40h obtains graphene aerogel.
Manufactured graphene aerogel hole is macroporous structure, and aperture is 20~100um, more uniformly, graphene aerogel
Density 5.6mg/cm3.After preparing this graphene aerogel, using its macroporous structure, make epoxy resin infiltration to hole
In, it can prepare graphene aerogel reinforced epoxy functional composite material after degassed bubble, heat cure.
Composite material is made applied to epoxy resin in manufactured graphene aerogel：Weigh the aliphatic category epoxy of 40g
Resin TDE85, being placed in 60 DEG C of oil bath pans that curing agent diaminodiphenylsulfone is added after heating 1h and stirs 0.4h makes it uniformly, so
The graphene aerogel of above-mentioned preparation is put into liquid resin afterwards and is placed in 70 DEG C, in -30KPa vacuum drying ovens and is evacuated 3h,
So that liquid resin is fully infiltrated in the hole of graphene aerogel, then takes out the good graphene aerogel of resin infiltration and be placed in
Sample is cured in silica gel mould, finally obtains graphene aerogel/epoxy resin composite material, wherein graphene aerogel institute
The mass fraction accounted for be 0.49wt%, conductivity 0.39S/m, compressive strength 203.6MPa,；And untreated ring
The conductivity of oxygen resin is 3.1 × 10-13S/m, compressive strength 184.3MPa, it can be seen that graphene aerogel can be notable
Improve the electric conductivity and mechanical property of epoxy resin composite material.
Embodiment 6:
A kind of preparation method of graphene aerogel, the specific steps are：
First, configure graphene oxide dispersion：Using stripping graphite oxide method, first by 5g natural flake graphites, 3g
Sodium nitrate mixes at 5 DEG C with the 120mL concentrated sulfuric acids, and 15g potassium permanganate is added, is slowly added to, and 35 DEG C of stirring 6h add 500mL to go
The hydrogen peroxide of 15mL 30% is added after ionized water dilution, ultrasonic 0.5h outwells supernatant after standing 1 day, dialyse 14 days,
3000rpm centrifuging and taking upper liquids obtain finely dispersed graphene oxide dispersion；
Second, configure graphene oxide liquid mixture：Trien is evenly spread in graphene oxide dispersion,
Wherein the mass ratio of graphene oxide and trien is 1:40, a concentration of 4mg/ of graphene oxide in gained mixed liquor
mL；
Graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 100 DEG C of baking ovens by third, reacts shape after 8h
At graphene hydrogel；
4th, graphene hydrogel is used into acetone, milli-Q water successively, is freeze-dried under conditions of being placed in -60 DEG C
30h obtains graphene aerogel.
Manufactured graphene aerogel hole is macroporous structure, and aperture is 20~100um, more uniformly, graphene aerogel
Density 5.2mg/cm3.After preparing this graphene aerogel, using its macroporous structure, make epoxy resin infiltration to hole
In, it can prepare graphene aerogel reinforced epoxy functional composite material after degassed bubble, heat cure.
Composite material is made applied to epoxy resin in manufactured graphene aerogel：Weigh the bisphenol A type epoxy tree of 40g
Fat E51, being placed in 60 DEG C of oil bath pans that curing agent diaminodiphenylsulfone is added after heating 1h and stirs 0.4h makes it uniformly, then will
The graphene aerogel of above-mentioned preparation, which is put into liquid resin, is placed in 65 DEG C, in -40KPa vacuum drying ovens and is evacuated 3h, makes liquid
Body resin fully infiltrates in the hole of graphene aerogel, then takes out the good graphene aerogel of resin infiltration and is placed in silica gel
Sample is cured in mold, graphene aerogel/epoxy resin composite material is finally obtained, wherein shared by graphene aerogel
Mass fraction is 0.55wt%, conductivity 0.36S/m, compressive strength 104MPa；And it is not added with the ring of graphene aerogel
The conductivity of oxygen resin is 3.14 × 10-14S/m, compressive strength 86MPa, it can be seen that graphene aerogel can significantly change
The electric conductivity and mechanical property of kind epoxy resin composite material.
Embodiment 7：
A kind of preparation method of graphene aerogel, the specific steps are：
First, configure graphene oxide dispersion：Using stripping graphite oxide method, first by 5g natural flake graphites, 3g
Sodium nitrate mixes at 5 DEG C with the 120mL concentrated sulfuric acids, and 15g potassium permanganate is added, is slowly added to, and 35 DEG C of stirring 6h add 500mL to go
The hydrogen peroxide of 15mL30% is added after ionized water dilution, ultrasonic 0.5h outwells supernatant after standing 1 day, dialyse 10 days, 3000rpm
Centrifuging and taking upper liquid obtains finely dispersed graphene oxide dispersion；
Second, configure graphene oxide liquid mixture：Diethylaminopropylamine is evenly spread in graphene oxide dispersion,
Wherein the mass ratio of graphene oxide and diethylaminopropylamine is 1:100, a concentration of 4mg/ of graphene oxide in gained mixed liquor
mL；
Graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 90 DEG C of baking ovens by third, is formed after reacting 8h
Graphene hydrogel；
4th, after graphene hydrogel is used acetone, milli-Q water successively, freezed using liquid nitrogen rapid freezing method, it is cold
It is freeze-dried 40h after jelly, obtains graphene aerogel.
Manufactured graphene aerogel hole is macroporous structure, and aperture is 20~100um, more uniformly, graphene aerogel
Density 4.8mg/cm3.After preparing this graphene aerogel, using its macroporous structure, make epoxy resin infiltration to hole
In, it can prepare graphene aerogel/epoxy resin composite material after degassed bubble, heat cure.
Composite material is made applied to epoxy resin in manufactured graphene aerogel：Weigh the bisphenol A type epoxy tree of 40g
Fat E55, being placed in 60 DEG C of oil bath pans that curing agent diethylaminopropylamine is added after heating 1h and stirs 0.4h makes it uniformly, then will
The graphene aerogel of above-mentioned preparation, which is put into liquid resin, is placed in 55 DEG C, in -10KPa vacuum drying ovens and is evacuated 3h, makes liquid
Body resin fully infiltrates in the hole of graphene aerogel, then takes out the good graphene aerogel of resin infiltration and is placed in silica gel
Sample is cured in mold, graphene aerogel/epoxy resin composite material is finally obtained, wherein shared by graphene aerogel
Mass fraction is 0.46wt%, conductivity 0.33S/m, compressive strength 98MPa；And untreated epoxy resin
Conductivity is 2.3 × 10-14S/m, compressive strength 81MPa, it can be seen that graphene aerogel can significantly improve epoxy resin
The electric conductivity and mechanical property of composite material.
Embodiment 8：
A kind of preparation method of graphene aerogel, the specific steps are：
First, configure graphene oxide dispersion：Using stripping graphite oxide method, first by 5g natural flake graphites, 3g
Sodium nitrate mixes at 5 DEG C with the 120mL concentrated sulfuric acids, and 15g potassium permanganate is added, is slowly added to, and 35 DEG C of stirring 6h add 500mL to go
The hydrogen peroxide of 15mL30% is added after ionized water dilution, ultrasonic 0.5h outwells supernatant after standing 1 day, dialyse 7 days, 3000rpm
Centrifuging and taking upper liquid obtains finely dispersed graphene oxide dispersion；
Second, configure graphene oxide liquid mixture：M-phenylene diamine (MPD) is evenly spread in graphene oxide dispersion, wherein
The mass ratio of graphene oxide and m-phenylene diamine (MPD) is 1：50, a concentration of 4mg/mL of graphene oxide in gained mixed liquor；
Graphene oxide liquid mixture is injected in sample bottle, is sealed and is placed in 100 DEG C of baking ovens by third, reacts shape after 8h
At graphene hydrogel；
4th, after graphene hydrogel is used acetone, milli-Q water successively, it is freeze-dried 40h, obtains graphene airsetting
Glue.
Its hole of manufactured graphene aerogel is macroporous structure, and aperture is 20~100um, more uniformly, graphene airsetting
The density 5.1mg/cm of glue3.After preparing this graphene aerogel, using its macroporous structure, make epoxy resin infiltration to hole
In gap, graphene aerogel reinforced epoxy functional composite material can be prepared after degassed bubble, heat cure.
Composite material is made applied to epoxy resin in manufactured graphene aerogel：Weigh the aliphatic category epoxy of 40g
Resin TDE85, being placed in 60 DEG C of oil bath pans that curing agent diaminodiphenylmethane is added after heating 1h and stirs 0.4h makes it uniformly,
Then the graphene aerogel of above-mentioned preparation is put into liquid resin and is placed in 50 DEG C, in -25KPa vacuum drying ovens and be evacuated
3h makes liquid resin fully infiltrate in the hole of graphene aerogel, then takes out the good graphene aerogel of resin infiltration
It is placed in silica gel mould and cures sample, finally obtain graphene aerogel/asphalt mixtures modified by epoxy resin composite material, wherein graphene aerogel
Shared mass fraction is 0.53wt%, conductivity 0.34S/m, compressive strength 224MPa；And it is not added with graphene airsetting
The conductivity of the epoxy resin of glue is 2.5 × 10-13S/m, compressive strength 201.4MPa, it can be seen that graphene aerogel can
To significantly improve the electric conductivity and mechanical property of epoxy resin composite material.
Claims (5)
1. a kind of preparation method of graphene aerogel, which is characterized in that the step of preparation method is as follows successively：1. by squama
Piece graphite, sodium nitrate are mixed with the concentrated sulfuric acid under the conditions of 0~5 DEG C, and potassium permanganate reaction is added；
2. by step 1. made of under the conditions of mixed liquor is placed in 30~40 DEG C, further oxidation reaction adds hydrogen peroxide, ultrasound
After processing, dialysis 7~14 days are stood, centrifuge is finally used to extract upper liquid up to graphene oxide dispersion；
3. the graphene oxide dispersion and amine curing agent are uniformly mixed to get graphene oxide liquid mixture；
It is heated 4. graphene oxide liquid mixture sealing is placed in 90 ~ 120 DEG C of environment, makes amine curing agent reduction-oxidation
Graphene obtains graphene hydrogel；
5. the graphene hydrogel of step 4. gained is used acetone and water washing successively, and it is freeze-dried, obtains graphene gas
Gel；
Wherein, the amine curing agent is diaminodiphenyl-methane, diaminodiphenylsulfone, trien, diethylamino
It is one or more in base propylamine.
2. a kind of preparation method of graphene aerogel according to claim 1, it is characterised in that：The centrifuge turns
Speed is 2000~5000rpm.
3. a kind of preparation method of graphene aerogel according to claim 1, it is characterised in that：Step 2. in, it is described
A concentration of 1~10mg/mL of graphene oxide dispersion.
4. a kind of preparation method of graphene aerogel according to claim 1, it is characterised in that：Step 3. in, it is described
The mass ratio of graphene oxide and amine curing agent is 1 in graphene oxide liquid mixture:10~1:100.
5. a kind of preparation method of graphene aerogel according to claim 1, it is characterised in that：Step 5. in, it is described
The temperature of freeze-drying is -65 ~ -50 DEG C, and the time is 20~45h.
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