CN107180706A - The preparation method and application of dyefunctionalized grapheme/polyaniline composite material - Google Patents
The preparation method and application of dyefunctionalized grapheme/polyaniline composite material Download PDFInfo
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- CN107180706A CN107180706A CN201710445911.9A CN201710445911A CN107180706A CN 107180706 A CN107180706 A CN 107180706A CN 201710445911 A CN201710445911 A CN 201710445911A CN 107180706 A CN107180706 A CN 107180706A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention provides a kind of preparation method and application of dyefunctionalized grapheme/polyaniline composite material, belongs to the preparing technical field of composite.The preparation method of the dyefunctionalized grapheme/polyaniline composite material of the present invention is first to prepare the big graphene oxide of specific surface area, then takes a certain amount of dyestuff to be well mixed with graphene oxide, and aniline monomer is added in acid condition；It is incubated after stirring under selected temperature, add the acid solution of initiator, certain time is reacted under selected temperature, obtain dyefunctionalized graphene oxide/polyaniline composite material, reduction is obtained into dyefunctionalized grapheme/polyaniline composite material by compound in the presence of reducing agent again, prepared dyefunctionalized grapheme/polyaniline composite material can be used for electrode material for super capacitor.Preparation method of the present invention is simple and easy to do, composite specific capacitance is larger.This method provides new method for the application in terms of ultracapacitor of composite.
Description
Technical field
The invention belongs to the preparing technical field of composite, a kind of dyefunctionalized graphene/polyphenyl is more particularly to
The preparation method and application of amine composite.
Background technology
Polyaniline all enjoys people to pay close attention to, still all the time as one of larger conducting polymer of theoretical specific capacitance
Easily there is Study of Volume Expansion in actual charge and discharge process, causes it as the electrode material of ultracapacitor in polyaniline
Cyclical stability is poor, and which also limits application of the polyaniline in terms of ultracapacitor.Therefore found for polyaniline a kind of steady
Qualitative preferable framework material, makes it uniformly grow on framework material, improving its stability becomes key, studied at present
Be used for grow the framework material of polyaniline and have CNT（Wu T M, Lin Y W, Liao C S. Preparation
and characterization of polyaniline/multi-walled carbon nanotube composites.
Carbon, 2005, 43: 734-740.）, carbon nanohorn（Maiti S, Khatua B B. Polyaniline
integrated carbon nanohorn: A superior electrode materials for advanced
energy storage. Express Polymer Letters, 2014, 8:895-907.）, carbon cloth（Zhong M, Song
Y, Li Y, et al. Effect of reduced graphene oxide on the properties of an
activated carbon cloth/polyaniline flexible electrode for supercapacitor
application. Journal of Power Sources, 2012, 217: 6-12.）, graphene（Wu Q, Xu Y,
Yao Z, et al. Supercapacitors based on flexible graphene/polyaniline
nanofiber composite films. ACS nano, 2010, 4: 1963-1970.）Deng.Wherein, graphene is except tool
The advantages of specific surface area of the advantage of standby above-mentioned carbon material, the also thermal conductivity with superelevation, excellent mechanical performance and superelevation.So
And in actual applications, graphene is very easy to reunite, this greatly reduces the performance of the skeleton function of graphene, and due to
Graphenic surface causes its dispersiveness and dissolubility poor so that polyaniline can not uniformly be grown in graphene without functional group
On lamella, so as to limit the combination property of compound.Therefore graphene is modified to avoid it from reuniting, allows it fully to send out
The stability for waving skeleton just seems and is even more important.
Graphene functionalized is broadly divided into covalent functionalization graphene and non-covalent functionalization graphene, and covalent functionalization can
Include opening its energy gap, tuning its electric conductivity to improve the performance of graphene, improve its dissolubility and stability etc..Non-covalent bond
Functionalization graphene mainly uses the p-p* between aromatic molecules and graphene-based bottom surface to be conjugated, such as porphyrin or perylene
Deng.Because covalent functionalization graphene is easily destroyed the p conjugated conductives of graphene, the excellent properties of graphene are caused to decline
（Uddin M E, Layek R K, Kim H Y, et al. Preparation and enhanced mechanical
properties of non-covalently-functionalized graphene oxide/cellulose acetate
nanocomposites. Composites Part B Engineering, 2016, 90:223-231）, the non-co- of graphene
Valence link functionalization is then conducive to keeping the electronic structure of graphene.However, due to its relative inertness of graphene, disperseing in a solvent
Limited, the problem of still there is complex process, efficiency in its functionalization of property.
The present invention utilizes conjugated dye molecular function graphene oxide, then is combined with polyaniline, finally by also
Graphene oxide in compound is reduced into graphene by former agent, and not only solve that graphene easily reunites in the course of the polymerization process shows
As, and the structure of graphene is not destroyed, technique is simple, can contain negative electricity with substantial amounts of on the graphene oxide after functionalization
The functional group of lotus so that the polyaniline protonated in an acidic solution is due to electrostatic interaction, it is easier to which homoepitaxial is in graphene
On lamella.In preparation process, by controlling such as temperature of the condition in course of reaction, the amount of initiator, reaction time etc. regulates and controls
The pattern of polyaniline, by changing graphene, the ratio of dyestuff and polyaniline three utilize the ratio electricity of polyaniline to greatest extent
Hold the stability with functionalization graphene to improve the chemical property of composite, make it for outstanding super capacitor electrode
Pole material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of dyefunctionalized grapheme/polyaniline composite material and its
Using, solve graphene and easily reunite, the problems such as polyaniline cyclical stability is poor.Obtained dyefunctionalized graphene/polyphenyl
The features such as amine composite has specific capacitance height, good cycle.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of dyefunctionalized grapheme/polyaniline composite material, prepares oxidation stone with expanded graphite first
Black alkene；Then dye molecule and graphene oxide are subjected to ultrasonic disperse uniformly, then aniline is uniformly aggregated in oxidation stone
On black alkene piece, dyefunctionalized grapheme/polyaniline composite material is prepared finally by reducing agent reduction.
Specifically include following steps：
1）The preparation of graphene oxide：Stannic oxide/graphene nano piece is prepared using improved hummers methods, and step by step after centrifugation
It is scattered to obtain graphene oxide water solution in aqueous.
2）The preparation of dyefunctionalized graphene oxide/polyaniline composite material：Dyestuff is added into graphene oxide water-soluble
Ultrasonic disperse is uniform in liquid, the solution is added aniline monomer under acid state, stirs in this case after 2 h selected anti-
30 min are incubated at a temperature of answering, dyefunctionalized graphene oxide/aniline acid mixed solution is obtained.Initiator is separately taken to be dissolved in acid molten
In liquid, 30 min are incubated under selected temperature, initiator acid solution is obtained.After both are well mixed, under selected temperature
The h of 4 h ~ 96 is reacted, washing is dried to obtain dyefunctionalized graphene oxide/polyaniline composite material.
Step 2）In, dyestuff used is blue for bent sharp benzene, amino black, acid orange, amaranth, malachite green, tetraphenylporphyrin
The one or more of tetrasulfonic acid.
Step 2）In, in the dyefunctionalized graphene oxide/aniline acid mixed solution, the mass ratio of dyestuff and aniline
For 1:100~10:100, the mass ratio of graphene oxide and aniline is 1:100~20:100.
Step 2）In, the selected reaction temperature is：-5 ℃~50 ℃.
Step 2）In, the acid in the acid state and acid solution uses HCl, H2SO4、H3PO4Or HNO3In one kind；
Wherein sour concentration is：0.2~3.0 mol/L.
Step 2）In, initiator is chosen for ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, H2O2/FeCl2Or K2CrO4In
One or more.
Step 2）In, the mol ratio of initiator and aniline monomer is 4:1~1:4.
3）The preparation of dyefunctionalized grapheme/polyaniline composite material：By above-mentioned dyefunctionalized graphene oxide/poly-
Aniline composite is dispersed into the aqueous solution, adds reducing agent, and 12 h are reacted at 90 DEG C, are cooled to after room temperature, uses
Deionized water washing obtains dyefunctionalized grapheme/polyaniline composite material after drying.
Step 3）In, the one or more being chosen in sodium borohydride, hydrazine hydrate, sodium hypophosphite, ammoniacal liquor of reducing agent.
Dyefunctionalized grapheme/polyaniline composite material as described above is in electrode material for super capacitor is prepared
Using.
The beneficial effects of the present invention are：
1）The present invention is with aniline, and dyestuff, expanded graphite is raw material, using the conjugation of dye molecule and graphene oxide, prevents
Stop the reunion of graphene oxide, and polyaniline is easier uniform length in graphene oxide layer after graphene functionalized
On, graphene oxide is reduced into graphene finally by the reduction of reducing agent, obtain dyefunctionalized graphene/polyaniline and answer
Condensation material.
2）Dyefunctionalized grapheme/polyaniline composite material prepared by the present invention has excellent chemical property,
Improve graphene in use, easily reunite, the shortcomings of dispersed poor, improve stable in polyaniline charge and discharge process
Property shortcoming, and improve its specific capacitance, and make it that functionalization process is simple and easy to do, can as preferable super capacitor electricity
Pole material.
Brief description of the drawings
Fig. 1 is the SEM of the blue functionalization graphene/polyaniline composite material of the sharp benzene of song prepared by embodiments of the invention 1
Picture；
Fig. 2 is that the different electric currents of the blue functionalization graphene/polyaniline composite material of the sharp benzene of song prepared by embodiments of the invention 1 are close
Charging and discharging curve under degree；
Fig. 3 is tetraphenylporphyrin tetrasulfonic acid functionalization graphene/polyaniline composite material prepared by embodiments of the invention 2
SEM pictures；
Fig. 4 is tetraphenylporphyrin tetrasulfonic acid functionalization graphene/polyaniline composite material prepared by embodiments of the invention 2
Charging and discharging curve under 1 A/g；
Fig. 5 is that malachite green functionalization graphene/polyaniline composite material prepared by embodiments of the invention 5 fills through 2000
Stability curve after discharge cycles.
Fig. 6 is amino black functionalization graphene/polyaniline composite material prepared by embodiments of the invention 6 in 1 A/g
Charging and discharging curve under current density.
Embodiment
1）Stannic oxide/graphene nano piece is prepared using improved Hummers methods, and is dispersed in the aqueous solution after centrifugation step by step
In obtain graphene oxide water solution.
2）The preparation of dyefunctionalized graphene oxide/polyaniline composite material：Dyestuff is added into graphene oxide water-soluble
Ultrasonic disperse is uniform in liquid, the solution is added aniline monomer under acid state, stirs in this case after 2 h selected anti-
30 min are incubated at a temperature of answering, dyefunctionalized graphene oxide/aniline acid mixed solution is obtained.Separately initiator was taken to be dissolved in acid
Property solution in, 30 min are incubated under selected reaction temperature, initiator acid solution is obtained, by initiator acid solution and dyestuff
After functional graphene oxide/aniline acid mixed solution is well mixed, the h of 4 h ~ 96 is reacted under selected reaction temperature, washing is dry
It is dry to obtain dyefunctionalized graphene oxide/polyaniline composite material.
Above-mentioned dyestuff is Congo red, and bent profit benzene is blue, methylene blue, amino black, one kind of tetraphenylporphyrin tetrasulfonic acid or many
Kind.
In above-mentioned dyefunctionalized graphene oxide/aniline acid mixed solution, the mass ratio of dyestuff and aniline is 1:100~
10:100, preferably 4:100~5:100；The mass ratio of graphene oxide and aniline is 1:100~20:100, preferably 5:100~10:
100。
Above-mentioned selected reaction temperature is：- 5 DEG C ~ 50 DEG C, preferably 0 DEG C ~ 5 DEG C.
Acid in above-mentioned acid state and acid solution uses HCl, H2SO4、H3PO4Or HNO3In one kind.Wherein sour
Concentration is：The mol/L of 0.2 ~ 3.0 mol/L, preferably 1 mol/L ~ 2.
Above-mentioned initiator is chosen for ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, H2O2/FeCl2Or K2CrO4In one kind
Or it is several.
Above-mentioned initiator：The mol ratio of aniline is 4:1~1:4, preferably 1:1~1:2.
3）The preparation of dyefunctionalized grapheme/polyaniline composite material：By above-mentioned dyefunctionalized graphene oxide/poly-
Aniline composite is dispersed into the aqueous solution, adds reducing agent, and 12 h are reacted at 90 DEG C, are cooled to after room temperature, uses
Deionized water washing obtains dyefunctionalized grapheme/polyaniline composite material after drying.
The one or more being chosen in sodium borohydride, hydrazine hydrate, sodium hypophosphite, ammoniacal liquor of above-mentioned reducing agent.
（4）It is prepared by electrode：Electrode is prepared using pressed disc method, from stainless (steel) wire as collector, acetylene black is used as conduction
Agent, 5 wt.% polytetrafluoroethylene (PTFE) is binding agent, by composite, acetylene black, polytetrafluoroethylene (PTFE) according to 85:10:5 mass ratio
Example is mixed, ground, until grind flakiness, and thin slice is cut into the cm of 1 cm × 1 shape；Then by the thin slice cut
It is placed between two panels stainless (steel) wire, is placed under tablet press machine, under 10 MPa pressure, the min of pressurize 1 obtains working electrode；
（5）Electrochemical property test：The test system of electrode uses three-electrode system, and the electrode of sheet is considered as into working electrode,
Then test dye function graphite is carried out by electrochemical workstation with to electrode and reference electrode, being together placed in electrolyte
The chemical property of alkene/polyaniline composite material.
The purposes of the dyefunctionalized grapheme/polyaniline composite material of the present invention is the electrode for being used as ultracapacitor
Material.
The following is several specific embodiments of invention, the present invention is further illustrated, it is all according to scope of the present invention patent institute
The equivalent changes and modifications done, should all belong to the covering scope of the present invention.
Embodiment 1
（1）Using graphene oxide prepared by Hummers methods is improved, uniformly divided through centrifuging step by step, after ultrasonic disperse
Dispersion liquid, measures solid content for 3.17 mg/mL, takes 34mL (0.1081 g) graphene oxide dispersions in 50 mL beakers.
（2）The bent sharp benzene indigo plants of 0.04325 g are taken to add in the solution of above-mentioned graphene oxide, the h of ultrasonic disperse 1 adds 0.69
ML water and the 4.4 mL concentrated sulfuric acids, make the H in solution2SO4Concentration is 2 mol/L, adds 0.91 mL aniline monomer, stirring 2
H, is incubated 30 min at 5 DEG C.
（3）It is another to take 4.564 g ammonium persulfates to add in the mol/L of 10 mL 2 sulfuric acid, protected after dissolving completely at 0 DEG C
30 min of temperature.
（4）Will（3）Middle solution is slowly added to（2）In middle solution, 48 h are reacted at 0 DEG C after being well mixed.Use deionization
Water washing is dried to constant weight to pH=7 at 60 DEG C, obtains the bent blue functional graphene oxide/polyaniline composite material of sharp benzene.
Weigh 400 mg compounds to add in 200 mL water, the h of ultrasonic disperse 1 adds 0.8 mL hydrazine hydrates, 12 are reduced at 90 DEG C
H, is washed with deionized to pH=7, is dried at 60 DEG C to constant weight.Its SEM picture as shown in Figure 1, shows composite
Middle polyaniline is uniformly grown on graphene sheet layer, and agglomeration does not occur for graphene.The bent sharp blue functionalization of benzene of gained
The electrochemical property test result of grapheme/polyaniline composite material shows, the electrode material putting under 1 A/g current densities
Electric specific capacitance can reach 665 F/g.Its charging and discharging curve under different current densities is as shown in Figure 2.
Embodiment 2
（1）Using graphene oxide prepared by Hummers methods is improved, uniformly divided through centrifuging step by step, after ultrasonic disperse
Dispersion liquid, measures solid content for 3.17 mg/mL, takes 34 mL (0.1081 g) graphene oxide dispersions in 50 mL beakers.
（2）0.04325 g tetraphenylporphyrins tetrasulfonic acid is taken to add in the solution of above-mentioned graphene oxide, the h of ultrasonic disperse 1,
1.6 mL water and 3.4 mL hydrochloric acid are added, it is 1 mol/L to make the HCl concentration in solution, adds 0.91 mL aniline monomer,
Stir and be incubated 30 min at 2 h, 0 DEG C.
（3）It is another to take 2.282 g ammonium persulfates to add in the mol/L of 10 mL 1 watery hydrochloric acid, after dissolving completely at 0 DEG C
It is incubated 30 min.
（4）Will（3）Middle solution is slowly added to（2）In middle solution, 24 h are reacted at 0 DEG C after being well mixed.Use deionization
Water washing is dried to constant weight at 60 DEG C to pH=7, obtains tetraphenylporphyrin tetrasulfonic acid functional graphene oxide/polyaniline
Composite.Weigh 400 mg compounds to add in 200 mL water, the h of ultrasonic disperse 1 adds 0.8 mL hydrazine hydrates, at 90 DEG C
12 h of lower reduction, are washed with deionized to pH=7, are dried at 60 DEG C to constant weight.Its SEM picture as shown in Figure 3, can be with
Find out that graphene film is dispersed in composite, soilless sticking phenomenon, and polyaniline is uniformly grown in graphenic surface, nothing
The generation of homopolymer.The electrochemical property test of gained tetraphenylporphyrin tetrasulfonic acid functionalization graphene/polyaniline composite material
As a result show, electric discharge specific capacitance of the electrode material under 1 A/g current densities can reach 686 F/g（As shown in Figure 4）.
Embodiment 3
1）Using graphene oxide prepared by Hummers methods is improved, uniformly divided through centrifuging step by step, after ultrasonic disperse
Dispersion liquid, measures solid content for 3.17 mg/mL, takes 34.5 mL (0.1094 g) graphene oxide dispersions in 50 mL beakers
In.
（2）0.0547 g tetraphenylporphyrins tetrasulfonic acid is taken to add in the solution of above-mentioned graphene oxide, the h of ultrasonic disperse 1,
1.19 mL water and 3.4 mL hydrochloric acid are added, it is 1 mol/L to make the HCl concentration in solution, adds 0.91 mL aniline monomer,
Stir and be incubated 30 min at 2 h, 5 DEG C.
（3）It is another to take 2.282 g potassium peroxydisulfates to add in the mol/L of 10 mL 2 watery hydrochloric acid, after dissolving completely at 5 DEG C
It is incubated 30 min.
（4）Will（3）Middle solution is slowly added to（2）In middle solution, 12 h are reacted at 0 DEG C after being well mixed.Use deionization
Water washing is dried to constant weight at 60 DEG C to pH=7, obtains tetraphenylporphyrin tetrasulfonic acid functional graphene oxide/polyaniline
Composite.Weigh 400 mg compounds to add in 200 mL water, the h of ultrasonic disperse 1 adds 0.8 mL sodium borohydrides, 90
12 h are reduced at DEG C, are washed with deionized to pH=7, are dried at 60 DEG C to constant weight.Gained tetraphenylporphyrin tetrasulfonic acid work(
The electrochemical property test result of energy graphite alkene/polyaniline composite material shows that the electrode material is under 1 A/g current densities
Electric discharge specific capacitance can reach 580 F/g.
Embodiment 4
（1）Using graphene oxide prepared by Hummers methods is improved, uniformly divided through centrifuging step by step, after ultrasonic disperse
Dispersion liquid, measures solid content for 3.17 mg/mL, takes 35.7 mL (0.1134 g) graphene oxide dispersions in 50 mL beakers
In.
（2）0.0907 g amaranths are taken to add in the solution of above-mentioned graphene oxide, the h of ultrasonic disperse 1 adds 2.27 mL
Concentrated nitric acid, makes the HNO in solution3Concentration is 1 mol/L, adds 0.91 mL aniline monomer, stirs and is incubated at 2 h, 0 DEG C
30 min。
（3）It is another to take 2.381 g sodium peroxydisulfates to add in the mol/L of 10 mL 1 nitric acid, protected after dissolving completely at 0 DEG C
30 min of temperature.
（4）Will（3）Middle solution is slowly added to（2）In middle solution, 72 h are reacted at 0 DEG C after being well mixed.Use deionization
Water washing is being dried to constant weight at 60 DEG C to pH=7, is obtaining Congo red functional graphene oxide/polyaniline composite material.Claim
400 mg compounds are taken to add in 200 mL water, the h of ultrasonic disperse 1 adds 0.8 mL hydrazine hydrates, 12 h are reduced at 90 DEG C,
It is washed with deionized to pH=7, is dried at 60 DEG C to constant weight.Gained amaranth functionalization graphene/polyaniline composite wood
The electrochemical property test result of material shows that electric discharge specific capacitance of the electrode material under 1 A/g current densities can reach 630
F/g。
Embodiment 5
1）Using graphene oxide prepared by Hummers methods is improved, uniformly divided through centrifuging step by step, after ultrasonic disperse
Dispersion liquid, measures solid content for 3.17 mg/mL, takes 17.25 mL (0.0547 g) graphene oxide dispersions in 50 mL beakers
In.
（2）0.0547 g malachite greens are taken to add in the solution of above-mentioned graphene oxide, the h of ultrasonic disperse 1 adds 16.3
ML water and 5.54 mL concentrated nitric acids, make the HNO in solution3Concentration is 2 mol/L, adds 0.91 mL aniline monomer, stirring 2
H, is incubated 30 min at 0 DEG C.
（3）It is another to take 2.381 g sodium peroxydisulfates to add in the mol/L of 10 mL 1 nitric acid, protected after dissolving completely at 0 DEG C
30 min of temperature.
（4）Will（3）Middle solution is slowly added to（2）In middle solution, 24 h are reacted at 0 DEG C after being well mixed.Use deionization
Water washing is dried to constant weight at 60 DEG C to pH=7, obtains malachite green functional graphene oxide/polyaniline composite material.
Weigh 400 mg compounds to add in 200 mL water, the h of ultrasonic disperse 1 adds 0.8 mL ammoniacal liquor, 12 h are reduced at 90 DEG C,
It is washed with deionized to pH=7, is dried at 60 DEG C to constant weight.Gained malachite green functionalization graphene/polyaniline is combined
The electrochemical property test result of material shows that electric discharge specific capacitance of the electrode material under 1 A/g current densities can reach 544
F/g.It is after 2000 charge and discharge cycles, and its specific capacitance still has 100% conservation rate.As shown in Figure 5.
Embodiment 6
1）Using graphene oxide prepared by Hummers methods is improved, uniformly divided through centrifuging step by step, after ultrasonic disperse
Dispersion liquid, measures solid content for 3.17 mg/mL, takes 34.5 mL (0.1094 g) graphene oxide dispersions in 50 mL beakers
In.
（2）0.0547 g amino blacks are taken to add in the solution of above-mentioned graphene oxide, the h of ultrasonic disperse 1 adds 2.13 mL
Water and with 2.46 mL concentrated phosphoric acids, make the H in solution3PO4Concentration is 1 mol/L, adds 0.91 mL aniline monomer, stirring 2
H, is incubated 30 min at 0 DEG C.
（3）Separately take 1.942 g K2CrO4In the phosphoric acid for adding the mol/L of 10 mL 1, it is incubated after dissolving completely at 0 DEG C
30 min。
（4）Will（3）Middle solution is slowly added to（2）In middle solution, 48 h are reacted at 0 DEG C after being well mixed.Use deionization
Water washing is dried to constant weight at 60 DEG C to pH=7, obtains amino black functional graphene oxide/polyaniline composite material.Claim
400 mg compounds are taken to add in 200 mL water, the h of ultrasonic disperse 1 adds 0.8 mL sodium hypophosphites, 12 are reduced at 90 DEG C
H, is washed with deionized to pH=7, is dried at 60 DEG C to constant weight.Gained amino black functionalization graphene/polyaniline is combined
The electrochemical property test result of material shows that electric discharge specific capacitance of the electrode material under 1 A/g current densities can reach 589
F/g, as shown in Figure 6.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of preparation method of dyefunctionalized grapheme/polyaniline composite material, it is characterised in that comprise the following steps：
1）The preparation of graphene oxide：Stannic oxide/graphene nano piece is prepared using improved Hummers methods, deionization is dispersed to
Graphene oxide water solution is obtained in water；
2）The preparation of dyefunctionalized graphene oxide/polyaniline composite material：
1. dyestuff is added into ultrasonic disperse in graphene oxide water solution uniformly, makes solution add aniline list under acid state
Body, stirs be incubated 30 min under selected reaction temperature after 2 h in this case, obtain dyefunctionalized graphene oxide/aniline
Acid mixed solution；
2. weigh a certain amount of initiator to be dissolved in acid solution, be incubated 30 min under selected reaction temperature, obtain initiator
Acid solution；
3. after initiator acid solution is well mixed with dyefunctionalized graphene oxide/aniline acid mixed solution, selected
The h of 4 h ~ 96 is reacted under reaction temperature, after the completion of reaction, washing is dried to obtain dyefunctionalized graphene oxide/polyaniline and is combined
Material；
3）The preparation of dyefunctionalized grapheme/polyaniline composite material：By above-mentioned dyefunctionalized graphene oxide/polyaniline
Composite is dispersed into the aqueous solution, adds reducing agent, and 12 h are reacted at 90 DEG C, are cooled to after room temperature, spend from
Sub- water washing obtains dyefunctionalized grapheme/polyaniline composite material after drying.
2. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 1, it is characterised in that：Step
Rapid 2）In dyestuff used it is blue for bent sharp benzene, amino black, acid orange, amaranth, malachite green, one kind of tetraphenylporphyrin tetrasulfonic acid
Or it is a variety of.
3. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 1, it is characterised in that：Step
Rapid 2）In the dyefunctionalized graphene oxide/aniline acid mixed solution, the mass ratio of dyestuff and aniline is 1:100~10:
100, the mass ratio of graphene oxide and aniline is 1:100~20:100.
4. the preparation of dyefunctionalized graphene oxide/polyaniline composite material according to claim 1, its feature exists
In：The step 2）In, selected reaction temperature is：-5℃~50℃.
5. the preparation of dyefunctionalized graphene oxide/polyaniline composite material according to claim 1, its feature exists
In：The step 2）1. in acid state and 2. in acid solution in acid use HCl, H2SO4、H3PO4Or HNO3In
One kind；Acid concentration is：0.2~3.0 mol/L.
6. the preparation of dyefunctionalized graphene oxide/polyaniline composite material according to claim 1, its feature exists
In：Step 2）In, initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, H2O2/FeCl2Or K2CrO4。
7. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 2, it is characterised in that：Institute
State step 2）In, the mol ratio of initiator and aniline monomer is 4:1~1:4.
8. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 1, it is characterised in that：Institute
State step 3）In, reducing agent is sodium borohydride, hydrazine hydrate, sodium hypophosphite, the one or more in ammoniacal liquor.
9. a kind of dyefunctionalized grapheme/polyaniline composite material prepared such as claim 1 ~ 8 either method.
10. a kind of application of dyefunctionalized grapheme/polyaniline composite material as claimed in claim 9, it is characterised in that：
For preparing electrode material for super capacitor.
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