CN104403275B - A kind of modified graphene/thermoset ting resin composite and preparation method thereof - Google Patents
A kind of modified graphene/thermoset ting resin composite and preparation method thereof Download PDFInfo
- Publication number
- CN104403275B CN104403275B CN201410732443.XA CN201410732443A CN104403275B CN 104403275 B CN104403275 B CN 104403275B CN 201410732443 A CN201410732443 A CN 201410732443A CN 104403275 B CN104403275 B CN 104403275B
- Authority
- CN
- China
- Prior art keywords
- graphene
- modified
- cnt
- resin composite
- modified graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of modified graphene/thermoset ting resin composite and preparation method thereof.The CNT of doped hydrochloride Polyaniline-modified is added in graphene oxide aqueous dispersions, reactant obtains modified graphene through filtering, washing after drying, uniformly mixed with the heat-setting resin of molten state again, it is cured to can obtain a kind of modified graphene/thermoset ting resin composite.The modified graphene that the present invention is provided has micro- capacitance structure, the CNT of doped hydrochloride Polyaniline-modified is by the pi-conjugated used loads of π on the surface of graphene, maintain the excellent electric property of graphene, and hinder contacting with each other for graphene sheet layer, modified graphene/thermoset ting resin composite for preparing has the advantages that high-k, low-dielectric loss, low percolation threshold, and the control to composite dielectric properties can be realized by adjusting the change that graphenic surface coats the content of carbon nanotubes of doped hydrochloride Polyaniline-modified.
Description
Technical field
The present invention relates to a kind of composite and preparation method thereof, more particularly to a kind of modified graphene/thermosetting resin
Composite and preparation method thereof.
Background technology
High-k, low-dielectric loss composite are functional materials important at present, in electronics, Aero-Space, life
The fields such as thing medical science have huge application value.There is huge electron mobility as the graphene of two-dimensional structure, it is larger
Specific surface area, and frequently as the reinforcement of high performance polymer base composite material.Graphene/polymer matrix composite is system
The important kind of standby high dielectric constant material, domestic and foreign scholars were a large amount of to graphene/polymer matrix composite expansion in recent years
Research, as a result shows, the agglomeration traits of graphene are the key factors for influenceing composite dielectric constant to improve, and graphene is entered
Row modification can efficiently solve its agglomeration traits, improve the dielectric properties of composite.
Before the present invention makes, document（Jiwu Shang, Yihe Zhang, Li Yu, Xinglong Luan,
Bo Shen, Zhilei Zhang, Fengzhu Lva and Paul K. Chu. J. Mater. Chem. A 2013;
1; 884–890.）Report and polyvinylidene fluoride-based composite is prepared with polyaniline-coated graphene, research shows polyaniline bag
Overlay on the surface of graphene, improve the dispersiveness of graphene, the presence of clad reduces the dielectric loss of material.But
The dielectric constant of the material is not high（Dielectric constant is 11）, because polyaniline is coated on the surface of graphene completely,
The delocalization of electronics on graphene planes can be hindered so that graphene electric property cannot be played.Document（Dongrui Wang,
Yaru Bao, Junwei Zha, Jun Zhao, Zhimin Dang, Guohua Hu. ACS Appl. Mater.
Interfaces 2012; 4; 6273−6279.）Polyvinyl alcohol is coated on graphene by chemical graft process and is prepared for gathering
Pvdf resin composite, polyvinyl alcohol is covered in the percolation threshold increase for causing composite on graphene, wants to obtain
High-k is obtained, generally requires to add the functive of high content（By volume, the percolation threshold of graphene/Kynoar
For 0.61%, and the percolation threshold of graphene/Kynoar of polyvinyl alcohol cladding is 2.24%, and the latter is the former 3.67
Times）, this will deteriorate other performances such as the manufacturability of composite, or even mechanical property.Similar example also occurs in polyaniline
On enveloped carbon nanometer tube/polyvinylidene fluoride composite material（Referring to document：Tao Zhou, Jun-Wei Zha, Yi Hou,
Dongrui Wang, Jun Zhao and ZhiMin Dang. ACS Appl. Mater. Interfaces 2011; 3
(12); 4557–4560.）.Although polyaniline is covered on the surface of carbon nanotubes, dielectric constant and the reduction of material are improved
Dielectric loss, but when the volume fraction of the CNT of polyaniline-coated is 8%, high-k could be obtained and low
Dielectric loss, the CNT of the polyaniline-coated of high content can cause the processing characteristics of composite to decline.
Therefore, graphene/polymer matrix composite wood of the research and development with high-k, low-dielectric loss and low percolation threshold
Material is a problem that there is major application to be worth.
The content of the invention
The present invention is directed to the not enough of polymer matrix composite presence in the prior art has high dielectric normal there is provided one kind
Modified graphene/thermoset ting resin composite of number, low-dielectric loss and low percolation threshold and preparation method thereof.
Realize that the technical scheme of the object of the invention is to provide a kind of preparation of modified graphene/thermoset ting resin composite
Method, step is as follows：
1st, by mass, the CNT of 0.005~1 part of doped hydrochloride Polyaniline-modified is added to 1 part of graphite oxide
In alkene aqueous dispersions, after 12~24h of reaction under conditions of temperature is 60~70 DEG C, 10 parts of L-AAs are added, in temperature
Spend to react 24~48h under conditions of 80~100 DEG C；
2nd, after reaction terminates, 1~2h is soaked in 500~700 parts of concentration is 1mol/L ammoniacal liquor, through suction filtration, washing, is done
It is dry, obtain the compound that a kind of CNT by graphene and doped hydrochloride Polyaniline-modified is constituted, as modified graphene；
3rd, the thermal curable resin of 100 parts of molten states is uniformly mixed with 0.757~2.25 part of modified graphene, it is cured
A kind of modified graphene/thermoset ting resin composite is obtained after processing.
In technical solution of the present invention, in the CNT of described doped hydrochloride Polyaniline-modified, doped hydrochloride polyaniline
Mass ratio with CNT is 0.4:1；CNT is single-walled carbon nanotube, multi-walled carbon nanotube or its combination.Described
Heat-setting resin is itself heat-setting resin, including BMI and its modified resin, cyanate ester resin and
One kind in its modified resin；Or the resin system being made up of the resin for itself being unable to heat cure with curing agent, including asphalt mixtures modified by epoxy resin
Fat etc..
Technical solution of the present invention also includes being prepared as described above modified graphene/thermosetting resin composite wood that method is obtained
Material.
Compared with prior art, the beneficial effects of the invention are as follows：
1. modified graphene prepared by the present invention is that the CNT of doped hydrochloride Polyaniline-modified is passed through into π-pi-conjugated work
With being supported on the surface of graphene, the conjugate planes structure of graphene is not destroyed, maintains the excellent electric property of graphene,
Be conducive to obtaining high-k and low percolation threshold.With this simultaneously, the CNT of doped hydrochloride Polyaniline-modified is interspersed in
The piece interlayer of graphene, hinders contacting with each other for graphene sheet layer, reduces the conductance caused by the interconnection of conductor and is lost,
Ensure that composite has low-dielectric loss.On the other hand, the CNT of doped hydrochloride Polyaniline-modified is that carbon is received
The nucleocapsid structure that mitron is core, doped hydrochloride polyaniline is shell, wherein CNT and graphene can be and middle as electrode
Doped hydrochloride polyaniline insulating barrier be dielectric, therefore, modified graphene constitutes micro- capacitance structure.By modified graphene with
Thermosetting resin compound tense, can increase substantially the dielectric constant of material.
2. by the regulation of load capacity of the CNT to doped hydrochloride Polyaniline-modified on graphenic surface, realize
The control of the dielectric properties of control and its composite to graphene dispersion.
3. the preparation method for modified graphene/thermoset ting resin composite that the present invention is provided has, technique is simple, ring
Protect, the characteristics of the cycle is short.
Brief description of the drawings
Fig. 1 is the CNT, graphene, modified graphene of doped hydrochloride Polyaniline-modified in the embodiment of the present invention 1
Infrared spectrum.
Fig. 2 is the CNT, graphene, modified graphene of doped hydrochloride Polyaniline-modified in the embodiment of the present invention 1
Raman spectrogram.
Fig. 3 is that the CNT, graphene and embodiment 1~3 of the doped hydrochloride Polyaniline-modified that embodiment 1 is provided are made
The X-ray diffractogram of standby modified graphene.
Fig. 4 is that the CNT, graphene and embodiment 1~3 of the doped hydrochloride Polyaniline-modified that embodiment 1 is provided are made
The scanning electron microscope (SEM) photograph of standby modified graphene.
Fig. 5 is CNT, graphene and the embodiment for the doped hydrochloride Polyaniline-modified that the embodiment of the present invention 1 is provided
Electrical conductivity block diagram of 1~3 modified graphene prepared in the case where frequency is 1Hz.
Fig. 6 is modification prepared by graphene/epoxy resin composite material that comparative example 1 of the present invention is provided and embodiment 1~3
The electrical conductivity of graphene/epoxy resin composite material is with frequency variation diagram.
Fig. 7 is modification prepared by graphene/epoxy resin composite material that comparative example 1 of the present invention is provided and embodiment 1~3
The electric capacity of graphene/epoxy resin composite material is with frequency variation diagram.
Fig. 8 is modification prepared by graphene/epoxy resin composite material that comparative example 1 of the present invention is provided and embodiment 1~3
The dielectric constant of graphene/epoxy resin composite material is with frequency variation diagram.
Fig. 9 is modification prepared by graphene/epoxy resin composite material that comparative example 1 of the present invention is provided and embodiment 1~3
The dielectric loss of graphene/epoxy resin composite material is with frequency variation diagram.
Figure 10 is the modified graphene/epoxy resin composite material of the preparation of the embodiment of the present invention 1~8 under frequency 1Hz
Electrical conductivity is with modified graphene changes of contents figure.
Embodiment
Below in conjunction with the accompanying drawings, embodiment and comparative example, technical solution of the present invention will be further described.
Embodiment 1
1st, the preparation of the CNT of doped hydrochloride Polyaniline-modified
In N2Under protection, under the conditions of 0~5 DEG C, 1g multi-walled carbon nanotubes are distributed in 500mL deionized water, plus
Enter and mix 0.5h under 0.99g lauryl sodium sulfate, stirring condition；Then 0.4g aniline is added, and adds 100mL hydrochloric acid solutions
（0.043mol/L）, 1h is sufficiently mixed under stirring condition；100mL ammonium persulfate solutions are slowly added dropwise（0.043mol/L）, it is added dropwise
After finishing, react 6h, after reaction terminates, through suction filtration, washing, dry Polyaniline-modified CNT.Prepared hydrochloric acid
Electricity under the infrared spectrum of CNT of doped polyaniline modification, Raman spectrogram, X-ray diffractogram, scanning electron microscope (SEM) photograph, 1Hz
Conductance is shown in accompanying drawing 1,2,3,4 and 5 respectively.
2nd, the preparation of graphite oxide
Take 2g graphite, 1g sodium nitrate and the mixing of the concentrated sulfuric acids of 46mL 98% to be placed in 0~4 DEG C of ice-water bath and stir 30min, take
6g potassium permanganate is slowly added in above-mentioned mixed liquor, and temperature control is at 10~15 DEG C and stirs 2h, is then transferred to flask
In 35 DEG C of water-baths, and insulated and stirred 30min.After reaction terminates, 92mL deionized waters are slowly added dropwise, and temperature is risen to 95
DEG C, 15min is incubated, then adds after 15mL 30% hydrogen peroxide, stirring 20min, adds 140mL deionized waters, products therefrom
It is 7 to be washed through centrifugation, 5% salt acid elution, deionized water to pH, is dried to obtain graphite oxide.
3rd, the preparation of graphene
The above-mentioned graphite oxides of 1g are scattered in 500mL deionized water, ultrasound and stir obtain yellowish-brown settled solution,
It is that graphene oxide is reduced into graphene by reducing agent to add 10g L-AAs, 24h is reacted at 80 DEG C, after reaction terminates
It is washed with deionized, suction filtration, 12h is dried in 60 DEG C of vacuum tanks, grinding obtains graphene.The INFRARED SPECTRUM of prepared graphene
Electrical conductivity under figure, Raman spectrogram, X-ray diffractogram, 1Hz is shown in accompanying drawing 1,2,3 and 5 respectively.
4th, the preparation of modified graphene
Weigh the above-mentioned graphite oxides of 1g to be scattered in 500mL deionized waters, stir and aoxidized after ultrasonically treated 1h
Graphene dispersing solution, adds the CNT of 0.25g doped hydrochloride Polyaniline-modifieds into graphene oxide dispersion, ultrasound is stirred
Mix, 12h is reacted at 60 DEG C, then add 10g L-AAs, reacting liquid temperature is risen to after 80 DEG C of reaction 24h,
1h is soaked in 500mL 1mol/L ammoniacal liquor, through suction filtration, washing after drying, obtains modified graphene, wherein doped hydrochloride gathers
The carbon nano-tube modified quality of aniline is 0.5 times of graphene quality.Infrared spectrum, the Raman spectrum of prepared modified graphene
Electrical conductivity under figure, X-ray diffractogram, scanning electron microscope (SEM) photograph, 1Hz is shown in accompanying drawing 1,2,3,4 and 5 respectively.
5th, the preparation of modified graphene/epoxy resin composite material
By 1.125g modified graphenes and 100g bisphenol A type epoxy resins（Trade mark E-51）It is added in flask, at 60 DEG C
Lower stirring is simultaneously after ultrasound 1h, and vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, obtains
Even mixture；Mixture is poured into mould, vacuum defoamation 30min, according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and
140 DEG C/4h techniques are solidified and are heat-treated, that is, obtain modified graphene/epoxy resin composite material.Its electrical conductivity is with frequency
Variation diagram, electric capacity with frequency variation diagram, dielectric constant with frequency variation diagram, dielectric loss with frequency variation diagram see respectively accompanying drawing 6,
7th, 8 and 9.
Referring to accompanying drawing 1, it is the CNT, graphene, modification for the doped hydrochloride Polyaniline-modified that the present embodiment is provided
The infrared spectrum of graphene, is 1290cm in wave number for the spectral line of the CNT of doped hydrochloride Polyaniline-modified-1The spy at place
The C-N keys that peak belongs in polyaniline are levied, doped hydrochloride polyaniline is indicated and has successfully coated on the surface of carbon nanotubes.
In the spectrogram of modified graphene, quinone ring C=C stretching vibrations of polyaniline are occurred in that（1569 cm-1）, C=C vibrations of phenyl ring（1492
cm-1）Vibrated with the N-H of secondary amine（1124 cm-1）Characteristic peak, show that the CNT of doped hydrochloride Polyaniline-modified has been wrapped
Overlay on graphene.
Referring to accompanying drawing 2, it is the CNT, graphene, modification for the doped hydrochloride Polyaniline-modified that the present embodiment is provided
G bands peak is occurred in that in the Raman spectrogram of graphene, the spectral line of graphene（1576cm-1）With D bands peak (1315 cm-1).G bands are represented
The SP of graphenic surface2The carbon atom of hybrid structure, and D bands are represented in graphene due to sp3Caused by hydridization it is unordered and
The strength ratio of defect sturcture, G bands and D bands, represents the change of graphenic surface chemical environment.Compared with the spectrogram of graphene,
Raman shifts of the G with peak of the Raman spectrogram of modified graphene increases to 1586 cm-1, absworption peak there occurs blue shift, and its reason is
Caused by electron cloud interaction between the CNT and graphene of doped hydrochloride Polyaniline-modified, show graphene and salt
There are strong π-π active forces between the CNT of acid doped polyaniline modification.With the strength ratio of G bands and D with peak of graphene
（0.84）Compare, and the strength ratio of the G bands of modified graphene and D bands brings up to 0.98, shows the graphene in modified graphene
Sp2Hybrid structure increase.Its reason is that the CNT of doped hydrochloride Polyaniline-modified is covered on graphene, on polyaniline
Conjugated structure and graphenic surface on conjugated structure form π-π active forces.Due to not chemically reacted with graphene,
Fail to increase the sp on graphenic surface3Structure, so not causing the disordered structure of modified graphene（D bands）Increase.
Embodiment 2
1st, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 500mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.50g doped hydrochloride Polyaniline-modifieds is added（Embodiment 1 is provided）To oxidation
In graphene dispersing solution, ultrasonic agitation reacts 12h at 60 DEG C, 10g L-AAs is then added, by reacting liquid temperature liter
To 80 DEG C of reaction 24h, 1h is soaked in 500mL 1mol/L ammoniacal liquor, through suction filtration, washing, after drying, obtain graphene-
The carbon mano-tube composite of doped hydrochloride Polyaniline-modified, the quality of the wherein CNT of doped hydrochloride Polyaniline-modified is stone
1 times of black alkene quality.Electrical conductivity under the X-ray diffractogram of prepared graphene modified graphene, scanning electron microscope (SEM) photograph, 1Hz
Accompanying drawing 3,4 and 5 is seen respectively.
2nd, the preparation of modified graphene/epoxy resin composite material
By 1.5g modified graphenes and 100g epoxy resin（Trade mark E-51）It is added in flask, stirs and surpass at 60 DEG C
After sound 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, obtains uniform mixture；
Mixture is poured into mould, vacuum defoamation 20min, according to+100 DEG C/2h of 80 DEG C/2h+120 DEG C/2h and 140
DEG C/the progress heat cure of 4h techniques, that is, obtain modified graphene/epoxy resin composite material.Its electrical conductivity is with frequency variation diagram, electricity
Appearance is shown in accompanying drawing 6,7,8 and 9 respectively with frequency variation diagram, dielectric loss with frequency variation diagram, dielectric constant with frequency variation diagram.
Embodiment 3
1st, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 500mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 1.0g doped hydrochloride Polyaniline-modifieds is added（Embodiment 1）To graphite oxide
In alkene dispersion liquid, ultrasonic agitation reacts 12h at 60 DEG C, then adds 10g L-AAs, reacting liquid temperature is risen into 80
After DEG C reaction 24h, 1h is soaked in 500mL 1mol/L ammoniacal liquor, through suction filtration, washing after drying, obtains modified graphene,
The quality of the wherein CNT of doped hydrochloride Polyaniline-modified is 2 times of graphene quality.The X of prepared modified graphene
Electrical conductivity under x ray diffration pattern x, scanning electron microscope (SEM) photograph, 1Hz is shown in accompanying drawing 3,4 and 5 respectively.
2nd, the preparation of modified graphene/epoxy resin composite material
By 2.25g modified graphenes and 100g epoxy resin（Trade mark E-51）It is added in flask, is stirred simultaneously at 60 DEG C
After ultrasonic 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, is uniformly mixed
Thing；Mixture is poured into mould, vacuum defoamation 20min, according to+120 DEG C/2h of+100 DEG C/2h of 80 DEG C/2h and
140 DEG C/4h techniques carry out heat cure, that is, obtain modified graphene/epoxy resin composite material.Its electrical conductivity changes with frequency
Figure, electric capacity are with frequency variation diagram, dielectric constant with frequency variation diagram, dielectric loss with the conductance under frequency variation diagram, frequency 1Hz
Rate is shown in accompanying drawing 6,7,8,9 and 10 respectively.
Referring to accompanying drawing 3, it is CNT, graphene and the implementation for the Polyaniline-modified that the embodiment of the present invention 1 is provided
The X-ray diffractogram of modified graphene prepared by example 1~3.For the CNT spectrogram of doped hydrochloride Polyaniline-modified, spreading out
Firing angle correspond to the complete graphite-structure of CNT for the peak at 25.8 °, and the peak at 19.5 ° is the diffraction of polyaniline
Peak.Graphene shows wider diffraction maximum at 24.5 °, because graphene is made by chemistry redox method,
Reduce the conjugated structure on its surface.And modified graphene shows narrower diffraction maximum at 24.5 ° in embodiment 1~3, show
The conjugated degree increase of graphene, makees because the CNT of doped hydrochloride Polyaniline-modified passes through π-π with graphene
With being coated on its surface.
Referring to accompanying drawing 4, it is CNT, the graphene for the doped hydrochloride Polyaniline-modified that the embodiment of the present invention 1 is provided
And the scanning electron microscope (SEM) photograph of the modification of the preparation of embodiment 1~3.As can be seen that for the carbon nanometer of doped hydrochloride Polyaniline-modified
Pipe, doped hydrochloride polyaniline particles are coated on the surface of CNT.The lamella of graphene is by doped hydrochloride Polyaniline-modified
CNT is separated, and hinders contacting with each other for piece interlayer, has reached the agglomeration traits for solving graphene.
Referring to accompanying drawing 5, it is CNT, the graphene for the doped hydrochloride Polyaniline-modified that the embodiment of the present invention 1 is provided
And electrical conductivity block diagram of the modified graphene of the preparation of embodiment 1~3 in the case where frequency is 1Hz.It can be seen that, doped hydrochloride gathers
The electrical conductivity of the CNT of aniline modification is suitable with the electrical conductivity of graphene, with the carbon nanometer of doped hydrochloride Polyaniline-modified
When pipe covering amount increases on graphene, the electrical conductivity increase of its modified graphene.Indicate doped hydrochloride Polyaniline-modified
It is carbon nanotube loaded on graphenic surface, not reduce graphene electric property.
The performance evaluation of comprehensive accompanying drawing 1,2,3,4 and 5, modified graphene prepared by the present invention has doped hydrochloride polyaniline
The characteristics of covering amount of the CNT of modification is controllable, by controlling the content of CNT of doped hydrochloride Polyaniline-modified to make
The surface for obtaining graphene is not completely covered, reaches the uncrossed purpose of pi-electron delocalization of graphenic surface；And doped hydrochloride
The CNT of Polyaniline-modified is interspersed in the piece interlayer of graphene, solves the agglomeration traits of graphene.In addition, doped hydrochloride
The CNT of Polyaniline-modified has excellent electric property, is supported on by π-πconjugation on graphene, maintains stone
The excellent electric property of black alkene itself.
The preparation of 1 graphene of comparative example/epoxy resin composite material
By 0.75g graphenes（Embodiment 1）With 100g epoxy resin（Trade mark E-51）It is added in flask, is stirred at 60 DEG C
Mix and after ultrasound 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continue to stir 10min, obtain uniform
Mixture；Mixture is poured into mould, vacuum defoamation 30min, according to+100 DEG C/2h+120 DEG C/2h of 80 DEG C/2h and
140 DEG C/4h techniques are solidified and are heat-treated, that is, obtain graphene/epoxy resin composite material.Its electrical conductivity changes with frequency
Figure, electric capacity are shown in accompanying drawing 6,7,8 respectively with frequency variation diagram, dielectric loss with frequency variation diagram, dielectric constant with frequency variation diagram
With 9.
Referring to accompanying drawing 6, it is the graphene/epoxy resin composite material and embodiment 1~3 that comparative example 1 of the present invention is provided
The electrical conductivity of the modified graphene/epoxy resin composite material of offer is with frequency variation curve.As seen from the figure, modified graphene/
The electrical conductivity of epoxy resin composite material is less than the electrical conductivity of graphene/epoxy resin composite material, because graphene quilt
The polyaniline of insulation is separated, it was demonstrated that doped hydrochloride Polyaniline-modified it is carbon nanotube loaded neighbouring in being reduced on graphene
Tunnel electric current between graphene, so that modified graphene/epoxy resin has relatively low electrical conductivity.On the other hand, with
Modified graphene/epoxy resin in the increase of the content of carbon nanotubes of doped hydrochloride Polyaniline-modified, embodiment 1~3 to be combined
Incremental trend is presented in material electric conductivity.The conductance and graphite of the CNT of doped hydrochloride Polyaniline-modified are learnt by accompanying drawing 5
The electrical conductivity of alkene powder is suitable, so, with the increase of the content of carbon nanotubes of doped hydrochloride Polyaniline-modified, modified graphite
The electrical conductivity of alkene/epoxy resin composite material can also increase therewith, it was demonstrated that can be gathered by changing doped hydrochloride on graphene
The content of the CNT of aniline modification controls the performance of modified graphene/epoxy resin composite material.
Referring to accompanying drawing 7, it is the graphene/epoxy resin composite material and embodiment 1~3 that comparative example 1 of the present invention is provided
The electric capacity of the modified graphene/epoxy resin composite material of offer is with frequency variation curve.As seen from the figure, modified graphene/ring
The electric capacity of epoxy resin composite material is higher than the electric capacity of graphene/epoxy resin composite material.Because graphenic surface is loaded
The CNT of doped hydrochloride Polyaniline-modified, the CNT of wherein doped hydrochloride Polyaniline-modified be by using CNT as
Core, in its Surface coating doped hydrochloride polyaniline formation nucleocapsid structure, therefore is a kind of nucleocapsid knot with conductor@insulating barriers
Structure.By this conductor loading for being coated with insulator, obtained modified graphene constitutes micro- capacitance structure on graphene, its
Middle CNT is electrode with graphene, and middle doped hydrochloride polyaniline insulating barrier is dielectric.Modified graphene/asphalt mixtures modified by epoxy resin
Micro- electric capacity number in resin composite material is more, also more favourable for obtaining high-k.
Referring to accompanying drawing 8, it is the graphene/epoxy resin composite material and embodiment 1~3 that comparative example 1 of the present invention is provided
The dielectric constant of the modified graphene/epoxy resin composite material of offer with frequency change curve.As seen from the figure, modified graphite
Alkene compound/dielectric constant of the epoxy resin composite material in whole frequency range is higher than graphene/epoxy resin composite wood
Material, such as embodiment 2 is under 100Hz, and its dielectric constant is up to 210, and its value is graphene/epoxy resin（68）3 times, this be because
To have substantial amounts of micro- capacitance structure in modified graphene/epoxy resin composite material, the increase of its dielectric constant, table are promoted
The graphene of the bright carbon nano-tube modification with doped hydrochloride Polyaniline-modified has notable in terms of high dielectric constant material is prepared
Application prospect.
Referring to accompanying drawing 9, it is the graphene/epoxy resin composite material and embodiment 1~3 that comparative example 1 of the present invention is provided
The dielectric loss of the modified graphene/epoxy resin composite material of offer is with frequency variation curve.Graphite prepared by comparative example 1
Alkene/epoxy resin composite material has the dielectric loss of graphene/composite under very high dielectric loss, such as 100Hz high
Up to 9.2.And the dielectric loss of modified graphene/epoxy resin composite material prepared by embodiment 1~3 is substantially reduced.This be because
CNT for doped hydrochloride Polyaniline-modified is interspersed between graphene sheet layer, due to doped hydrochloride polyaniline insulating barrier every
Contacting with each other between graphene sheet layer, hinders electronics running through between conductor graphite alkene, so as to cause to be modified stone absolutely
The reduction of the dielectric loss of black alkene/epoxy resin composite material, shows the carbon nano-tube modification of doped hydrochloride Polyaniline-modified
Graphene has prominent advantage in terms of low-dielectric loss composite is prepared.
The data analysis of comprehensive accompanying drawing 6,7,8 and 9, by the graphene of the carbon nano-tube modification of doped hydrochloride Polyaniline-modified
The dielectric constant of composite can be improved by being added in resin, and reduce its dielectric loss, prepare high-k and low
There is significant advantage in terms of dielectric loss composite.
Embodiment 4
1st, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 500mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.005g doped hydrochloride Polyaniline-modifieds is added（Embodiment 1 is provided）To oxygen
In graphite alkene dispersion liquid, ultrasonic agitation reacts 12h at 60 DEG C, 10g L-AAs is then added, by reacting liquid temperature
Rise to after 80 DEG C of reaction 24h, through suction filtration, washing after drying, obtains modified graphene.
2nd, the preparation of modified graphene/epoxy resin composite material
By 0.757g modified graphenes and 100g epoxy resin（Trade mark E-51）It is added in flask, is stirred simultaneously at 60 DEG C
After ultrasonic 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, is uniformly mixed
Thing；Mixture is poured into mould, vacuum defoamation 20min, according to+120 DEG C/2h of+100 DEG C/2h of 80 DEG C/2h and
140 DEG C/4h techniques carry out heat cure, that is, obtain modified graphene/epoxy resin composite material.Electrical conductivity under its frequency 1Hz
See accompanying drawing 10.
Embodiment 5
1st, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 500mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.025g doped hydrochloride Polyaniline-modifieds is added（Embodiment 1 is provided）To oxygen
In graphite alkene dispersion liquid, ultrasonic agitation reacts 12h at 60 DEG C, 10g L-AAs is then added, by reacting liquid temperature
Rise to after 80 DEG C of reaction 24h, 1h is soaked in 500mL 1mol/L ammoniacal liquor, through suction filtration, washing after drying, obtains being modified stone
Black alkene.
2nd, the preparation of modified graphene/epoxy resin composite material
By 0.787g modified graphenes and 100g epoxy resin（Trade mark E-51）It is added in flask, is stirred simultaneously at 60 DEG C
After ultrasonic 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, is uniformly mixed
Thing；Mixture is poured into mould, vacuum defoamation 20min, according to+120 DEG C/2h of+100 DEG C/2h of 80 DEG C/2h and
140 DEG C/4h techniques carry out heat cure, that is, obtain modified graphene/epoxy resin composite material.Electrical conductivity under its frequency 1Hz
See accompanying drawing 10.
Embodiment 6
1st, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 500mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.05g doped hydrochloride Polyaniline-modifieds is added（Embodiment 1 is provided）To oxidation
In graphene dispersing solution, ultrasonic agitation reacts 12h at 60 DEG C, 10g L-AAs is then added, by reacting liquid temperature liter
To 80 DEG C of reaction 24h, 1h is soaked in 500mL 1mol/L ammoniacal liquor, through suction filtration, washing after drying, obtains modified graphite
Alkene.
2nd, the preparation of modified graphene/epoxy resin composite material
By 0.825g modified graphenes and 100g epoxy resin（Trade mark E-51）It is added in flask, is stirred simultaneously at 60 DEG C
After ultrasonic 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, is uniformly mixed
Thing；Mixture is poured into mould, vacuum defoamation 20min, according to+120 DEG C/2h of+100 DEG C/2h of 80 DEG C/2h and
140 DEG C/4h techniques carry out heat cure, that is, obtain modified graphene/epoxy resin composite material.Electrical conductivity under its frequency 1Hz
See accompanying drawing 10.
Embodiment 7
1st, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 500mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.10g doped hydrochloride Polyaniline-modifieds is added（Embodiment 1 is provided）To oxidation
In graphene dispersing solution, ultrasonic agitation reacts 12h at 60 DEG C, 10g L-AAs is then added, by reacting liquid temperature liter
To 80 DEG C of reaction 24h, 1h is soaked in 500mL 1mol/L ammoniacal liquor, through suction filtration, washing after drying, obtains modified graphite
Alkene.
2nd, the preparation of modified graphene/epoxy resin composite material
By 1.30g modified graphenes and 100g epoxy resin（Trade mark E-51）It is added in flask, is stirred simultaneously at 60 DEG C
After ultrasonic 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, is uniformly mixed
Thing；Mixture is poured into mould, vacuum defoamation 20min, according to+120 DEG C/2h of+100 DEG C/2h of 80 DEG C/2h and
140 DEG C/4h techniques carry out heat cure, that is, obtain modified graphene/epoxy resin composite material.Electrical conductivity under its frequency 1Hz
See accompanying drawing 10.
Embodiment 8
1st, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 500mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.20g doped hydrochloride Polyaniline-modifieds is added（Embodiment 1 is provided）To oxidation
In graphene dispersing solution, ultrasonic agitation reacts 12h at 60 DEG C, 10g L-AAs is then added, by reacting liquid temperature liter
To 80 DEG C of reaction 24h, 1h is soaked in 500mL 1mol/L ammoniacal liquor, through suction filtration, washing after drying, obtains modified graphite
Alkene.
2nd, the preparation of modified graphene/epoxy resin composite material
By 1.05g modified graphenes and 100g epoxy resin（Trade mark E-51）It is added in flask, is stirred simultaneously at 60 DEG C
After ultrasonic 1h, vacuum defoamation 30min adds 4g 2-ethyl-4-methylimidazoles, continues to stir 10min, is uniformly mixed
Thing；Mixture is poured into mould, vacuum defoamation 20min, according to+120 DEG C/2h of+100 DEG C/2h of 80 DEG C/2h and
140 DEG C/4h techniques carry out heat cure, that is, obtain modified graphene/epoxy resin composite material.Electrical conductivity under its frequency 1Hz
See accompanying drawing 10.
Referring to accompanying drawing 10, it be in the present embodiment 1-8 modified graphene/epoxy resin composite material under frequency 1Hz
Electrical conductivity seeks the percolation threshold calculated with modified graphene content curve map（f c）It is plotted in illustration.It can be seen that, modified graphite
The percolation threshold of alkene/epoxy resin composite materialf cOnly the 1.10% of resin quality, it was demonstrated that modified graphene is filled out as function
During material, the composite of high-k, low-dielectric loss can be just prepared in low content.
Embodiment 9
1st, the preparation of doped hydrochloride Polyaniline-modified CNT
In N2Under protection, at 0~5 DEG C, 1g single-walled carbon nanotubes are distributed in 600mL deionized water, added
40min is mixed under 0.99g lauryl sodium sulfate, stirring condition；Then 0.4g aniline is added, and adds 50mL hydrochloric acid solutions
（0.086 mol/L）, 1h is sufficiently mixed under stirring condition；50mL ammonium persulfate solutions are slowly added dropwise（0.086mol/L）, it is added dropwise
After finishing, react 6h, after reaction terminates, through suction filtration, washing, dry doped hydrochloride Polyaniline-modified CNT.
2nd, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 550mL deionized waters, stirs and after ultrasonically treated 1h
Obtain graphene oxide dispersion；The CNT of 0.15g doped hydrochloride Polyaniline-modifieds prepared by the present embodiment step 1 adds
Enter into graphene oxide dispersion, ultrasonic agitation, 15h is reacted at 65 DEG C, then add 10g L-AAs, will react
Liquid temperature degree is risen to after 80 DEG C of reaction 48h, and 1h is soaked in 500mL 1mol/L ammoniacal liquor, and through suction filtration, washing after drying, is obtained
Modified graphene.
3rd, the preparation of modified graphene/cyanate composite material
0.975g modified graphenes and 100g bisphenol A cyanate esters are added in flask, stirred at 150 DEG C after 2h,
Obtain uniform mixture；Mixture is poured into mould in vacuumizing 0.5h at 140 DEG C, according to+180 DEG C of 160 DEG C/2h/
+ 200 DEG C of 2h/2h and 240 DEG C/6h techniques carry out heat cure, that is, obtain modified graphene/cyanate ester resin composite material.
Embodiment 10
1st, the preparation of doped hydrochloride Polyaniline-modified CNT
In N2Under protection, at 0~5 DEG C, the composition of 1g single-walled carbon nanotubes and multi-walled carbon nanotube is distributed to
In 700mL deionized water, add under 0.99g lauryl sodium sulfate, stirring condition and mix 50min；Then 0.4g benzene is added
Amine, and add 50mL hydrochloric acid solutions（0.086 mol/L）, 1h is sufficiently mixed under stirring condition；50mL ammonium persulfates are slowly added dropwise
Solution（0.086mol/L）, after completion of dropping, 8h is reacted, after reaction terminates, through suction filtration, washing, dry doped hydrochloride polyphenyl
Amine-modified CNT.
2nd, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 600mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.40g doped hydrochloride Polyaniline-modifieds prepared by the present embodiment step 1 is added
Into graphene oxide dispersion, ultrasonic agitation reacts 20h at 70 DEG C, 10g L-AAs is then added, by reaction solution
Temperature is risen to after 90 DEG C of reaction 30h, and 2h is soaked in 600mL 1mol/L ammoniacal liquor, and through suction filtration, washing after drying, is changed
Property graphene.
3rd, the preparation of modified graphene/ethylene rhodanate/epoxide resin composite
1.35g modified graphenes, 90g bisphenol A cyanate esters, 10g epoxy resin are added in flask, at 150 DEG C
Stir after 2h, obtain uniform mixture；Mixture is poured into mould in vacuumizing 0.5h at 140 DEG C, according to 160 DEG C/2h
+ 200 DEG C of+180 DEG C/2h/2h and 240 DEG C/4h techniques carry out heat cure, that is, obtain modified graphene/cyanate/epoxy
Resin composite materials.
Embodiment 11
1st, the preparation of doped hydrochloride Polyaniline-modified CNT
In N2Under protection, under 0~5 DEG C of temperature conditionss, 1g single-walled carbon nanotubes are distributed to 800mL deionization
In water, add under 0.99g lauryl sodium sulfate, stirring condition and mix 1h；Then 0.4g aniline is added, and adds 50mL hydrochloric acid
Solution（0.086 mol/L）, 2h is sufficiently mixed under stirring condition；50mL ammonium persulfate solutions are slowly added dropwise（0.086mol/L）,
After completion of dropping, react 10h, after reaction terminates, through suction filtration, washing, dry doped hydrochloride Polyaniline-modified CNT.
2nd, the preparation of modified graphene
Weigh 1g graphite oxides（Embodiment 1 is provided）It is scattered in 600mL deionized waters, stirs and after ultrasonically treated 1h
Graphene oxide dispersion is obtained, the CNT of 0.70g doped hydrochloride Polyaniline-modifieds prepared by the present embodiment step 1 is added
Into graphene oxide dispersion, ultrasonic agitation reacts 24h at 70 DEG C, 10g L-AAs is then added, by reaction solution
Temperature is risen to after 95 DEG C of reaction 24h, and 2h is soaked in 650mL 1mol/L ammoniacal liquor, and through suction filtration, washing after drying, is changed
Property graphene.
3rd, the preparation of modified graphene/Bismaleimide-Cyanate Ester Resin composite
By 1.80g modified graphenes, 54g N, N-4,4 '-diphenyl methane dimaleimide, 10g bisphenol A cyanate esters
With 36g 0,0 '-diallyl bisphenol is added in flask, and stirring and ultrasound 40min, that is, obtain modified graphite at 140 DEG C
Alkene/Bismaleimide-Cyanate Ester Resin mixture.Mixture is poured into mould in vacuumizing 0.5h at 140 DEG C, according to 150 DEG C/
+ 180 DEG C of 2h /+200 DEG C of 2h/2h and 220 DEG C/8h techniques carry out heat cure, that is, obtain modified graphene/span and carry out acyl
Imines/cyanate composite material.
Embodiment 12
1st, the preparation of doped hydrochloride Polyaniline-modified CNT
In N2Under protection, under 0~5 DEG C of temperature conditionss, 1g multi-walled carbon nanotubes are distributed to 800mL deionization
In water, add under 0.99g lauryl sodium sulfate, stirring condition and mix 0.5h；Then 0.4g aniline is added, and adds 50mL salt
Acid solution（0.086 mol/L）, 2h is sufficiently mixed under stirring condition；100mL ammonium persulfate solutions are slowly added dropwise（0.043mol/
L）, after completion of dropping, react 12h, after reaction terminates, through suction filtration, washing, dry doped hydrochloride Polyaniline-modified carbon nanometer
Pipe.
2nd, the preparation of modified graphene
Weigh 1g graphite oxides to be scattered in 600mL deionized waters, stir and obtain graphite oxide after ultrasonically treated 1h
Alkene dispersion liquid, adds the CNTs of 0.90g doped hydrochloride Polyaniline-modifieds prepared by the present embodiment step 1 to graphene oxide
In dispersion liquid, ultrasonic agitation reacts 24h at 70 DEG C, then adds 10g L-AAs, reacting liquid temperature is risen into 100
After DEG C reaction 24h, 2h is soaked in 700mL 1mol/L ammoniacal liquor, through suction filtration, washing after drying, obtains modified graphene.
3rd, the preparation of modified graphene/bismaleimide resin composite material
By 2.1g modified graphenes, 70g N, N-4,4 '-diphenyl methane dimaleimide, 30g 0,0 '-diallyl
Bisphenol-A is added in flask, and 45min is stirred at 130 DEG C, that is, obtains modified graphene/bimaleimide resin mixture.
Mixture is poured into mould in vacuumizing 0.5h at 130 DEG C, according to+200 DEG C/2h of+180 DEG C/2h of 150 DEG C/2h and
220 DEG C/8h techniques carry out heat cure, that is, obtain modified graphene/bismaleimide resin composite material.
Claims (6)
1. a kind of preparation method of modified graphene/thermoset ting resin composite, it is characterised in that comprise the following steps：
（1）By mass, the CNT of 0.005~1 part of doped hydrochloride Polyaniline-modified is added to 1 part of graphene oxide water
In dispersion liquid, 12~24h is reacted under conditions of temperature is 60~70 DEG C, 10 parts of L-AAs are added, be 80 in temperature
24~48h is reacted under conditions of~100 DEG C；
（2）After reaction terminates, 1~2h is soaked in 500~700 parts of concentration is 1mol/L ammoniacal liquor, through suction filtration, washing, is dried,
Obtain the compound that a kind of CNT by graphene and doped hydrochloride Polyaniline-modified is constituted, as modified graphene；
（3）The thermal curable resin of 100 parts of molten states is uniformly mixed with 0.757~2.25 part of modified graphene, cured place
A kind of modified graphene/thermoset ting resin composite is obtained after reason.
2. a kind of preparation method of modified graphene/thermoset ting resin composite according to claim 1, its feature exists
In：In the CNT of described doped hydrochloride Polyaniline-modified, the mass ratio of doped hydrochloride polyaniline and CNT is
0.4:1。
3. a kind of preparation method of modified graphene/thermoset ting resin composite according to claim 1 or 2, it is special
Levy and be：Described CNT is single-walled carbon nanotube, multi-walled carbon nanotube or its combination.
4. a kind of preparation method of modified graphene/thermoset ting resin composite according to claim 1, its feature exists
In：Described heat-setting resin is itself heat-setting resin；Or by itself being unable to the resin and curing agent of heat cure
The resin system of composition.
5. a kind of preparation method of modified graphene/thermoset ting resin composite according to claim 4, its feature exists
In：Itself described heat-setting resin includes BMI and its modified resin, cyanate ester resin and its modified tree
One kind in fat, or their any combination.
6. a kind of preparation method of modified graphene/thermoset ting resin composite according to claim 4, its feature exists
In：The described resin by itself being unable to heat cure includes epoxy resin with the resin system that curing agent is constituted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410732443.XA CN104403275B (en) | 2014-12-06 | 2014-12-06 | A kind of modified graphene/thermoset ting resin composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410732443.XA CN104403275B (en) | 2014-12-06 | 2014-12-06 | A kind of modified graphene/thermoset ting resin composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104403275A CN104403275A (en) | 2015-03-11 |
| CN104403275B true CN104403275B (en) | 2017-08-11 |
Family
ID=52640949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410732443.XA Active CN104403275B (en) | 2014-12-06 | 2014-12-06 | A kind of modified graphene/thermoset ting resin composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104403275B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804159A (en) * | 2015-05-04 | 2015-07-29 | 芜湖市宝艺游乐科技设备有限公司 | Graphene oxide melamine resin and preparation method thereof |
| CN104845009B (en) * | 2015-05-19 | 2018-03-23 | 中国科学院化学研究所 | Fluororesin/graphene composite material with isolation structure and preparation method and application |
| CN105062070B (en) * | 2015-09-07 | 2017-08-01 | 苏州大学 | A kind of graphene/thermoset ting resin composite of poly ion liquid modification and preparation method thereof |
| CN105330857A (en) * | 2015-11-19 | 2016-02-17 | 浙江大学 | Preparation method of PANI (polyaniline)-GO (graphene oxide)-CNTs (carbon nanotubes) composited electromagnetic shielding material |
| CN106810818B (en) * | 2015-11-30 | 2019-09-13 | 航天特种材料及工艺技术研究所 | A kind of graphene modified epoxy and preparation method thereof |
| CN105912759B (en) * | 2016-04-06 | 2019-07-23 | 清华大学 | Determine the calculation method of the percolation threshold of pressure-sensitive microballoon in non-linear dielectric materials |
| CN106098400B (en) * | 2016-06-30 | 2018-05-18 | 合肥工业大学 | A kind of aminooimidazole Ionic Liquid Modified graphene nanometer sheet/composite polyethylene material and preparation method thereof |
| CN108219368B (en) * | 2016-12-21 | 2019-11-12 | 南京中赢纳米新材料有限公司 | A method of modification nano-carbon material is to strengthen epoxy resin-base composite material |
| CN107057006B (en) * | 2017-05-25 | 2019-10-08 | 成都新柯力化工科技有限公司 | A kind of thermosetting phenolic resin special graphite alkene mother liquor and preparation method |
| CN107573645B (en) * | 2017-09-06 | 2020-07-24 | 深圳市峰泳科技有限公司 | Built-in high-dielectric-constant flexible resin composite material and preparation method and application thereof |
| CN110079087A (en) * | 2019-05-07 | 2019-08-02 | 中国电子科技集团公司第三十八研究所 | A kind of modified nano graphite/cyanate composite material, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937240A (en) * | 2014-04-21 | 2014-07-23 | 苏州大学 | Modified graphene/thermosetting resin composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680973A (en) * | 2012-09-14 | 2014-03-26 | 海洋王照明科技股份有限公司 | Polyaniline/graphene/carbon nanotube composite and preparation method thereof, as well as electrode plate and capacitor |
| CN103772975B (en) * | 2012-10-25 | 2016-04-20 | 黑龙江鑫达企业集团有限公司 | Graphene/composite conducting polymer material |
-
2014
- 2014-12-06 CN CN201410732443.XA patent/CN104403275B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937240A (en) * | 2014-04-21 | 2014-07-23 | 苏州大学 | Modified graphene/thermosetting resin composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 聚苯胺基复合物的制备及其电化学性能研究;魏从杰;《中国优秀硕士学位论文全文数据库 工程科技II辑》;20140215(第2期);第42页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104403275A (en) | 2015-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104403275B (en) | A kind of modified graphene/thermoset ting resin composite and preparation method thereof | |
| Du et al. | Strategies to succeed in improving the lithium-ion storage properties of silicon nanomaterials | |
| CN106450181B (en) | A kind of molybdenum disulfide/nitrogen-doped carbon nano-fiber composite material and preparation method and application | |
| CN101781459B (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| CN109390561B (en) | Lead negative plate of graphene lead-carbon battery and preparation method thereof | |
| CN105185956B (en) | A kind of preparation method of spongy 3 SiC 2/graphite alkene and CNT composite negative pole material | |
| CN106784819B (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN105645403A (en) | Preparation method of high-performance nitrogen-doped three-dimensional graphene | |
| WO2016138802A1 (en) | Method for preparing biomass graphene by using cellulose as raw material | |
| CN104973595B (en) | A kind of three-dimensional porous grapheme material and preparation method and application | |
| CN107180706A (en) | The preparation method and application of dyefunctionalized grapheme/polyaniline composite material | |
| CN107665984A (en) | A kind of preparation method of the lithium sulfur battery anode material based on the graphene-supported phosphatization nickel material of phosphorus doping | |
| CN102649843B (en) | Polyaniline/active carbon composite material and preparation method thereof | |
| CN107959027B (en) | Silicon-based negative electrode binder of lithium ion battery and preparation method of negative plate containing binder | |
| CN105070514B (en) | Interface method prepares polyaniline/graphene/manganese dioxide composite material applied to ultracapacitor | |
| CN104064365A (en) | Graphene hard carbon composite material, preparation method thereof and application thereof | |
| CN108520827A (en) | Carbon fiber/NiCo2O4The preparation method of/graphene composite material | |
| WO2016086628A1 (en) | Graphene-polyaniline modified carbon nanotube composite and preparation method therefor | |
| CN108831757A (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN109003826A (en) | N and S codope graphene-graphene nanobelt aeroge preparation method | |
| CN106654217A (en) | Composite carbon negative-electrode active material for lead carbon power battery as well as preparation method and application of composite carbon negative-electrode active material | |
| CN107275124A (en) | A kind of preparation method of film-type electrode of super capacitor | |
| CN109103442A (en) | A kind of preparation method of graphene-coated lithium iron phosphate positive electrode | |
| CN107098341A (en) | Graphene oxide new type water thermal stencil agent and its preparation method of nano composite material | |
| CN102532890B (en) | Fluorinated and oxidized grapheme/polyaniline composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |