CN103966644B - A kind of preparation method of graphene/polymer emulsion composite film material - Google Patents
A kind of preparation method of graphene/polymer emulsion composite film material Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of graphene/polymer emulsion composite film material.The method uses electro-deposition method to prepare graphene/polymer emulsion composite film material on copper electrode surface, the laminated film thickness of preparation, size are controlled, Graphene uniformly, disperse continuously, has good mechanical property and electric conductivity in macromolecule matrix.Compared with prior art, the technological process that electrodeposition process prepares composite film material is simple, easily operates, low cost and environmental protection, is expected to be applied to large-scale industrial production.
Description
Technical field
The invention belongs to the preparation field of polymer nanocomposites, be specifically related to a kind of graphene/polymer emulsion
The preparation method of composite film material.
Background technology
Graphene is a kind of bi-dimensional cellular shape material with carbon element tightly packed by monolayer carbon atom.Graphene has tradition
(electrical conductivity is up to 10 to the incomparable electrical properties of conductive filler6S/cm), (thermal conductivity is 3000-5000J/ to thermal property
M K s), (light transmittance can reach for mechanical property (intensity be 110-130GPa, elastic modelling quantity be 1.0TPa) and optical property
97.7%)；Graphene both can optimize and improve the original character of polymer, can become again functional group in composite
Point, have become as grinding of the fields such as catalysis, high-strength material, electronics, energy conversion and storage, biotechnology, biochemical sensor
Study carefully focus, have broad application prospects.
Electrochemical deposition method is a kind of environmental protection, method easy and simple to handle, can be by the most at random
Or change intensity and the direction of electric field, the activation energy of regulation and control electrode reaction and response speed, and then regulation and control product characteristics continuously,
There is the prospect of wide industrial applications；But the method is applied to the research that graphene composite material synthesis field is carried out
Also it is nowhere near.Wang et al. uses electro-deposition polymerization to synthesize grapheme/polyaniline composite material, has good stretching
Performance and chemical property, this material be applicable to electrode of super capacitor (Wang D W, et al.ACS NANO, v3,2009,
1745-1752).Feng et al. further provides and the method to be widely used in composite field
Viewpoint, and use the method for an one-step electrochemistry deposition to be prepared for graphene-based polymer composite film material, this thin film on a large scale
There is high conductivity and good biocompatibility (Feng X M, et al.Adv.Funct.Mater.V21,2011,2989-
2996).Electronation graphene oxide and polyaniline nano fiber are combined stratification by the electrodeposition process that Gao et al. is also adopted by being similar to
Shape (layer-by-layer) composite (Gao Z, et al.Electrochiaica Acta, v91,2013,185-194).
Chen et al. uses two step continuous print electrochemical-deposition step to prepare the composite of 3D porous, and they are first
The first conducting matrix grain with the redox graphene of electrochemical reduction as composite, being filled in polymer uniform the most again
In this skeleton.This composite porous material presents the chemical property of excellence, is expected in ultracapacitor, lithium ion battery, combustion
The material field such as battery, electrochemical sensor is applied (Chen K W, et a1.Journal of Materials
Chemistry, v22,2012,20968-20976).
At present have been achieved for many important achievements in research preparing graphene/polymer nano composite material field.
It is low that Stankovich etc. use solution blended process to prepare conduction excess effusion value, and Graphene/styrene that electrical conductivity is high is nano combined
Material (Stankovich S, et al.Nature, 2006, v442,282～286).Zhang etc. utilize melt-blending process to prepare
Graphene/polyethylene terephthalate composite (Zhang H B, the et of satisfactory electrical conductivity are gone out to have
Al.Polymer, 2010, v51,1191-1196).Park et al. and is gathered the Graphene of phenyl functionalization by situ aggregation method
Acid imide be combined prepare have composite that fabulous heat stability, electric conductivity and impedance change with tension (Park O K,
Et al.Nano Letters, v12,2012,1789-1793).Although the above method can prepare better performances graphite
Alkene/polymer nanocomposites, but all there are disadvantages that.As solution blended process needs substantial amounts of solvent, cost is high, ring
Environment pollution is serious；In nano composite material prepared by melt-blending process, graphene dispersion is poor；Situ aggregation method operation is multiple
Miscellaneous, and the existence of Graphene can change kinetics of polymerization, and the molecular weight of polymer also can reduce.Therefore, utilization electrification is probed into
Learn that sedimentation preparation is green, low cost and the controlled graphene/polymer emulsion composite film material of reaction are one and extremely have
The research topic being worth.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of graphene/polymer is provided
The preparation method of emulsion composite film material.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of graphene/polymer emulsion composite film material, the method comprises the following steps:
Prepare the graphene oxide hydrosol: add graphene oxide in water, ultrasonic disperse 2～3 hours, prepare quality dense
Degree is the monolithic layer finely dispersed graphene oxide hydrosol of 0.1～1mg/ml；
Prepare the redox graphene hydrosol: surfactant is added graphene oxide prepared by step (1) water-soluble
In glue, surfactant is 1:(100～1000 with the mass ratio of the graphene oxide hydrosol), use magnetic agitation, rotating speed 100
Rev/min～500 revs/min, stir 10～30 minutes to mix homogeneously, ultrasonic disperse 1 hour；Add reducing agent, reduction
Agent is 1:(10～1000 with the volume ratio of the graphene oxide hydrosol), ultrasonic disperse 2～3 hours, prepare and there is stable dispersion
Property the black redox graphene hydrosol, wherein redox graphene exists with monolayer or which floor state；
Electrodeposition process prepares graphene/polymer emulsion composite film material: use one or multi-step electrodeposition process by oxygen
The functionalized graphene hydrosol or the redox graphene hydrosol deposit to be formed on copper electrode laminated film material with macromolecule emulsion
Material.
Described surfactant is the one in dodecylbenzene sodium sulfonate, sodium lauryl sulphate, sodium cholate or many
Kind.
Described reducing agent is the one in hydrazine, hydrazine hydrate, Dimethylhydrazine, sodium borohydride, ascorbic acid, gallic acid or many
Kind.
Described macromolecule emulsion is one or more in different model styrene-acrylic emulsion.
Described electrodeposition process specifically comprises the following steps that macromolecule emulsion and the graphene oxide hydrosol or oxygen reduction fossil
The ink alkene hydrosol is by volume for 1:(1～5) mix, magnetic agitation to mix homogeneously, it is prepared as complex emulsions；Will be through in advance
Cu electrode after process is placed in above-mentioned complex emulsions and carries out electrodeposit reaction, and voltage is 1～10 volt, the response time be 10～
30 minutes；After reaction terminates, taking out electrode and be dried at 80 DEG C, the electrode processing drying is sampled, juxtaposition
In hydrochloric acid and solution that hydrogen peroxide volume ratio is 1:1, it is heated to 50 DEG C and gets rid of the Copper Foil substrate as copper electrode, can make
Obtain graphene/polymer emulsion composite film material；
The rotating speed of described magnetic agitation is 100 revs/min～500 revs/min, and mixing time is 10～30 minutes；
Described electrodeposition process specifically comprises the following steps that and pretreated Cu electrode is placed in the graphene oxide hydrosol or goes back
Carrying out electrodeposit reaction in the former graphene oxide hydrosol, voltage is 1～10 volt, and the response time is 10s, electrode adsorption thickness
For 1mm；After reaction terminates, electrode is dried at 80 DEG C, repeats above-mentioned electrodeposition process 5～10 times；Then will
Gained dried Cu electrode immerses in macromolecule emulsion, makes macromolecule emulsion uniformly pave at electrode surface, after drying, from
Peel off on Cu electrode, can be prepared by graphene/polymer emulsion composite film material.
Described electrodeposition process specifically comprises the following steps that macromolecule emulsion and the graphene oxide hydrosol or oxygen reduction fossil
The ink alkene hydrosol is by volume for 1:(1～5) mix, magnetic agitation to mix homogeneously, it is prepared as complex emulsions；Will be through in advance
Cu electrode after process is placed in above-mentioned complex emulsions and carries out electrodeposit reaction, and voltage is 1～10 volt, and the deposition reaction time is
10～30 minutes；Reconnecting circuit, make former anelectrode become negative electrode, former negative electrode becomes anelectrode and carries out reduction reaction,
Voltage is 10 volts～30 volts, and the reduction reaction time is 120～240 minutes, after reaction terminates, is carried out by electrode at 80 DEG C
Being dried, sampling is placed in hydrochloric acid and solution that hydrogen peroxide volume ratio is 1:1, is heated to 50 DEG C and gets rid of the copper as copper electrode
Paper tinsel substrate, can be prepared by graphene/polymer emulsion composite film material.
The preprocess method of described Cu electrode is: using as the Copper Foil substrate of copper electrode carry out successively fine sandpaper polishing,
Ethanol/acetone oil removing epoxy-type impurity, washing, weak acid are washed, are washed, 10%HCl activating surface.
In electrodeposition process, it is not only due to the movement of free charge in solution and produces electric current, there is also oxidation also simultaneously
Former reaction；Based on electrophoresis during low-voltage (≤2.5 volts), based on redox reaction during high voltage (＞ 2.5 volts).
We have found that when voltage is less than 2.5 volts (comprising 2.5 volts) effect, bath resistance is apparently higher than bigger voltage
Resistance during effect.According to electrode reaction principle of dynamics it can be said that time under low-voltage effect, the mechanism process of adsorption reaction
May be different with during high voltage.Bubble is not the most produced, it is believed that be not occur oxidation also during low-voltage (2.5 volts) effect
, only there is electro-deposition effect in former reaction.Along with the raising of clamping voltage, unreacted on redox graphene/graphene oxide
Oxygen-containing functional group participate in reaction, be reduced further.CRGO solution is acid, and pH value is between 2～4, and electrode reaction equation is:
Negative electrode 2H++2e-=H2↑
Anode Graphene--2e-=[Graphene]
Analyzing from experimental phenomena, bubble produces at negative electrode, gradually spreads to anelectrode, also with above-mentioned analysis
It is consistent.
Owing to emulsion droplet surface exists sub-fraction carboxyl, hydroxyl or sulfonic group, it ionizes in water and makes emulsion droplet
Electronegative, when certain voltage, the coalescence of emulsion droplet is moment, and they closely adsorb at electrode surface.Face at this
Below boundary's voltage, its coalescence speed increases with voltage and increases steadily.According to Stern double electrode layer theory, electrode surface is remotely
Electromotive force distribution gradient in dispersion layer；Therefore macromolecule emulsion is adsorbed to a certain marginal value (has with electrode surface and clamping voltage
Close) time its thickness be not further added by.
Compared with prior art, the invention have the characteristics that:
1, the thickness of composite film material, the size prepared are controlled, and Graphene (graphene oxide) is in macromolecule matrix
Can uniformly, disperse continuously, the composite film material of preparation has good mechanical property and electric conductivity；
2, using electrodeposition process, its technological process is simple, easily operates, low cost and environmental protection, is expected to be applied to big
Technical scale metaplasia is produced.
Accompanying drawing explanation
Fig. 1 is a step electrodeposition process composition principle schematic diagram of graphene/polymer emulsion composite film material；
Description of symbols in figure: the 1 graphene oxide hydrosol, 2 redox graphenes, 3 styrene-acrylic emulsions
Fig. 2 is the multistep electrodeposition process composition principle schematic diagram of graphene/polymer emulsion composite film material；
Description of symbols in figure: 4 graphene films
Fig. 3 is the pictorial diagram of embodiment 1 gained graphene/polymer emulsion composite film material；
Fig. 4 is the SEM figure of embodiment 1 gained graphene/polymer emulsion composite film material；
Fig. 5 is the AFM figure of redox graphene in embodiment 1；
Fig. 6 is the pictorial diagram of embodiment 2 gained graphene/polymer emulsion composite film material；
Fig. 7 is the SEM figure of embodiment 2 gained graphene/polymer emulsion composite film material；
Fig. 8 is the pictorial diagram of embodiment 3 gained graphene/polymer emulsion composite film material；
Fig. 9 is the SEM figure of embodiment 3 gained graphene/polymer emulsion composite film material；
Figure 10 is the pictorial diagram of embodiment 4 gained graphene/polymer emulsion composite film material；
Figure 11 is the SEM figure of embodiment 4 gained graphene/polymer emulsion composite film material.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.With graphene film 4
Embodiment 1
As shown in Fig. 1 and Fig. 3～5, prepare graphite oxide solution 400ml of 1.0mg/ml with graphene film 4, ultrasonic 2 little
The graphene oxide hydrosol 1 is formed time after；Add and account for the detergent alkylate sulphur that graphene oxide colloid mass fraction is 0.1wt%
Acid sodium, magnetic agitation, rotating speed is 100 revs/min, and mixing time is 30 minutes, ultrasonic 1 hour；Add after adding 0.4ml hydrazine hydrate
Heat, to 80C, obtains redox graphene 2 in ultrasonic 3 hours.The hydrazine hydrate reduction graphene oxide hydrosol and styrene-acrylic emulsion 3 are pressed
It is 5:1 mix homogeneously according to volume ratio；In the complex emulsions adding apparatus that will mix, connection circuit, clamping voltage 1.0 volts,
Adsorption time 10 minutes.80 DEG C fully dried, and sampling is put in hydrochloric acid and solution that hydrogen peroxide volume ratio is 1:1, and heat is to 50
DEG C get rid of Copper Foil substrate.
As shown in Figure 4, the SEM figure of graphene/polymer emulsion laminated film, it can be seen that Graphene is in phenylpropyl alcohol matrix
Favorable dispersibility, part Graphene laps one another or spacing is less, illustrates that graphene/polymer emulsion laminated film is to pass through stone
Ink alkene is constituted conductive network in the base or is conducted electricity by quantum tunneling effect.
Being illustrated in figure 5 the AFM figure of gained redox graphene, as can be seen from the figure the splitting of Graphene is relatively
Good, surfactant is distributed in the surface of Graphene, and the lamella area of Graphene is from 1 μm2～6 μm2, but main still with 1
μm2It is main.After reduction, Graphene is almost without reunion, and thickness is 2nm, presents the state of 1～3 layer on the whole.
Embodiment 2
Prepare graphite oxide solution 400ml of 0.1mg/ml with graphene film, after ultrasonic 3 hours, form graphene oxide
The hydrosol 1；It is the dodecylbenzene sodium sulfonate of 1wt% that addition accounts for graphene oxide colloid mass fraction, and magnetic agitation, rotating speed is
500 revs/min, mixing time is 10 minutes, ultrasonic 1 hour；Addition 40ml hydrazine hydrate post-heating, to 80 DEG C, obtains for ultrasonic 2 hours
To redox graphene 2.The hydrazine hydrate reduction graphene oxide hydrosol and styrene-acrylic emulsion 3 are that 1:1 mixing is equal according to volume ratio
Even；In the complex emulsions adding apparatus that will mix, connect circuit, clamping voltage 10 volts, adsorption time 30 minutes.80 DEG C are filled
Point dried, sampling is put in hydrochloric acid and solution that hydrogen peroxide volume ratio is 1 two 1, and heat gets rid of Copper Foil substrate to 50 DEG C.
Embodiment 3
As shown in Fig. 1 and Fig. 6～7, prepare graphite oxide solution 400ml of 1.0mg/ml with graphene film 4, ultrasonic 2 little
The graphene oxide hydrosol 1 is formed time after；By the graphene oxide hydrosol 1 and styrene-acrylic emulsion 3 according to volume ratio be 3:1 mixing all
Even；In the complex emulsions adding apparatus that will mix, connect circuit, clamping voltage 1.0 volts, adsorption time 15 minutes.80℃
Fully dried, sampling is put in hydrochloric acid and solution that hydrogen peroxide volume ratio is 1:1, and heat gets rid of Copper Foil substrate to 50 DEG C.
As it is shown in fig. 7, the SEM figure of graphene oxide/macromolecule emulsion laminated film, it can be seen that graphene oxide is at benzene
Favorable dispersibility in propyl group body, graphene oxide sheet interlayer spacing is bigger.
Embodiment 4
As shown in Fig. 2 and Fig. 8～9, prepare graphite oxide solution 400ml of 1.0mg/ml with graphene film 4, ultrasonic 2 little
Time, it is the dodecylbenzene sodium sulfonate of 0.2wt% that addition accounts for graphene oxide colloid mass fraction, and magnetic agitation, rotating speed is 100
Rev/min, mixing time is 30 minutes, ultrasonic 1 hour；Addition 0.4ml hydrazine hydrate post-heating, to 80 DEG C, obtains for ultrasonic 3 hours
The redox graphene hydrosol；By in redox graphene hydrosol adding apparatus, connect circuit；Adsorption process voltage 5
Volt, the response time is 10s, and adsorption thickness is about 1mm, and 80 DEG C are fully dried, and this adsorption process is repeated 5 times；By dried
The Cu electrode that graphene film is modified is immersed in styrene-acrylic emulsion, and abundant dried product exhibited can directly be peeled off from Cu electrode.
As it is shown in figure 9, the SEM figure of graphene/polymer emulsion laminated film, Graphene prepared by electrochemical deposition method is multiple
Close Graphene in thin film still to exist with stratiform, explain its reason with satisfactory electrical conductivity.
Embodiment 5
Prepare graphite oxide solution 400ml of 0.1mg/ml with graphene film, ultrasonic 3 hours, add and account for graphene oxide
Colloid mass fraction is the dodecylbenzene sodium sulfonate of 0.1wt%, magnetic agitation, and rotating speed is 500 revs/min, and mixing time is
10 minutes, ultrasonic 1 hour；Addition 40ml hydrazine hydrate post-heating, to 80 DEG C, obtains redox graphene in ultrasonic 2 hours water-soluble
Glue；By in redox graphene hydrosol adding apparatus, connect circuit；Adsorption process voltage 10 volts, the response time is
10s, 80 DEG C are fully dried, and this adsorption process is repeated 10 times；The Cu electrode that dried graphene film is modified is immersed in benzene
Acrylic emulsion, abundant dried product exhibited can directly be peeled off from Cu electrode.
Embodiment 6
Graphene film prepares graphite oxide solution 400ml of 1.0mg/ml, ultrasonic 2 hours, adds and accounts for graphene oxide glue
Weight mark is the dodecylbenzene sodium sulfonate of 1wt%, magnetic agitation, and rotating speed is 500 revs/min, and mixing time is 10 points
Clock, ultrasonic 1 hour；Addition 40ml hydrazine hydrate post-heating, to 80 DEG C, obtains the redox graphene hydrosol in ultrasonic 3 hours；Will
In redox graphene hydrosol adding apparatus, connect circuit；Adsorption process voltage 5 volts, the response time is 10s, 80 DEG C
Fully being dried, this adsorption process is repeated 5 times；The Cu electrode that dried graphene film is modified is immersed in styrene-acrylic emulsion, fills
Dried product exhibited is divided directly to peel off from Cu electrode.
Embodiment 7
Prepare graphite oxide solution 400ml of 1.0mg/ml with graphene film, after ultrasonic 2 hours, form graphene oxide water
Colloidal sol, by prepared graphene oxide hydrosol adding apparatus, connects circuit；Adsorption process voltage 5 volts, the response time is
10s, 80 DEG C are fully dried, and this adsorption process is repeated 5 times；The Cu electrode that dried graphene film is modified is immersed in phenylpropyl alcohol
Emulsion, abundant dried product exhibited can directly be peeled off from Cu electrode.
Embodiment 8
Prepare graphite oxide solution 400ml of 0.1mg/ml with graphene film, after ultrasonic 3 hours, form graphene oxide water
Colloidal sol, by prepared graphene oxide hydrosol adding apparatus, connects circuit；Adsorption process voltage 10 volts, the response time
For 10s, 80 DEG C are fully dried, and this adsorption process is repeated 10 times；The Cu electrode that dried graphene film is modified is immersed in
Styrene-acrylic emulsion, abundant dried product exhibited can directly be peeled off from Cu electrode.
Embodiment 9
As shown in Fig. 1 and Figure 10～11, prepare graphite oxide solution 400ml of 1.0mg/ml with graphene film 4, ultrasonic 2
The graphene oxide hydrosol 1 is formed after hour；According to the ratio that the volume ratio of styrene-acrylic emulsion 3 and the graphene oxide hydrosol 1 is 1:1
Example mix homogeneously；In the reactant liquor adding apparatus that will mix, connecting circuit, adsorption process voltage 1.0 volts, the persistent period is
30 minutes；Reduction process voltage 10 volts, the recovery time is 120 minutes.80 DEG C the most dried, and hydrochloric acid and dioxygen are put in sampling
Water volume ratio is in the solution of 1:1, is heated to 50 DEG C and gets rid of Copper Foil substrate.
As shown in figure 11, the SEM figure of graphene/polymer emulsion laminated film, it can be seen that Graphene is at phenylpropyl alcohol matrix
Middle favorable dispersibility, graphene film interlamellar spacing is bigger.
Embodiment 10
Prepare graphite oxide solution 400ml of 0.1mg/ml with graphene film, after ultrasonic 3 hours, form graphene oxide water
Colloidal sol；The ratio mix homogeneously that volume ratio is 1:5 according to styrene-acrylic emulsion and the graphene oxide hydrosol；The reaction that will mix
In liquid adding apparatus, connecting circuit, adsorption process voltage 10 volts, the persistent period is 10 minutes；Reduction process voltage 30 volts,
Recovery time is 240 minutes.80 DEG C fully dried, and sampling is put in hydrochloric acid and solution that hydrogen peroxide volume ratio is 1:1, heating
Copper Foil substrate is got rid of to 50 DEG C.
Embodiment 11
Prepare graphite oxide solution 400ml of 1.0mg/ml with graphene film, after ultrasonic 2 hours, form graphene oxide water
Colloidal sol；It is the dodecylbenzene sodium sulfonate of 0.1wt% that addition accounts for graphene oxide colloid mass fraction, and magnetic agitation, rotating speed is
100 revs/min, mixing time is 30 minutes, ultrasonic 1 hour；Addition 0.4ml hydrazine hydrate post-heating, to 80 DEG C, obtains for ultrasonic 3 hours
To redox graphene 2.Mix according to the ratio that volume ratio is 1:1 of styrene-acrylic emulsion 3 and the redox graphene hydrosol
Uniformly；In the reactant liquor adding apparatus that will mix, connecting circuit, adsorption process voltage 1.0 volts, the persistent period is 30 points
Clock；Reduction process voltage 10 volts, the recovery time is 120 minutes.80 DEG C the most dried, and hydrochloric acid and dioxygen water body are put in sampling
Long-pending ratio, in the solution of 1:1, is heated to 50 DEG C and gets rid of Copper Foil substrate.
Embodiment 12
Prepare graphite oxide solution 400ml of 0.1mg/ml with graphene film, after ultrasonic 3 hours, form graphene oxide water
Colloidal sol 1；It is the dodecylbenzene sodium sulfonate of 1wt% that addition accounts for graphene oxide colloid mass fraction, and magnetic agitation, rotating speed is
500 revs/min, mixing time is 10 minutes, ultrasonic 1 hour；Addition 40ml hydrazine hydrate post-heating, to 80 DEG C, obtains for ultrasonic 2 hours
To redox graphene 2.Mix according to the ratio that volume ratio is 1:5 of styrene-acrylic emulsion 3 and the redox graphene hydrosol
Uniformly；In the reactant liquor adding apparatus that will mix, connecting circuit, adsorption process voltage 10 volts, the persistent period is 10 minutes；
Reduction process voltage 30 volts, the recovery time is 240 minutes.80 DEG C the most dried, and hydrochloric acid and hydrogen peroxide volume are put in sampling
Ratio, in the solution of 1:1, is heated to 50 DEG C and gets rid of Copper Foil substrate.
Claims (8)
1. the preparation method of a graphene/polymer emulsion composite film material, it is characterised in that the method includes following step
Rapid:
(1) the graphene oxide hydrosol is prepared: add graphene oxide in water, ultrasonic disperse 2～3 hours, prepare quality dense
Degree is the monolithic layer finely dispersed graphene oxide hydrosol of 0.1～1mg/ml；
(2) the redox graphene hydrosol is prepared: surfactant is added the graphene oxide hydrosol prepared by step (1)
In, surfactant is 1:(100～1000 with the mass ratio of the graphene oxide hydrosol), use magnetic agitation, rotating speed 100
Rev/min～500 revs/min, stir 10～30 minutes to mix homogeneously, ultrasonic disperse 1 hour；Add reducing agent, reduction
Agent is 1:(10～1000 with the volume ratio of the graphene oxide hydrosol), ultrasonic disperse 2～3 hours, prepare and there is stable dispersion
Property the black redox graphene hydrosol, wherein redox graphene exists with monolayer or which floor state；
(3) electrodeposition process prepares graphene/polymer emulsion composite film material: use one or multi-step electrodeposition process to aoxidize
The Graphene hydrosol or the redox graphene hydrosol deposit to be formed on copper electrode composite film material with macromolecule emulsion；
Wherein, the electrodeposition process described in step (3) specifically comprise the following steps that macromolecule emulsion and the graphene oxide hydrosol or
The redox graphene hydrosol is by volume for 1:(1～5) mix, magnetic agitation to mix homogeneously, it is prepared as being combined
Emulsion；Being placed in above-mentioned complex emulsions by Cu electrode after pretreatment and carry out electrodeposit reaction, voltage is 1～10 volt, instead
It is 10～30 minutes between Ying Shi；After reaction terminates, taking out electrode and be dried at 80 DEG C, the electrode processing drying enters
Row sampling, is placed in hydrochloric acid and solution that hydrogen peroxide volume ratio is 1:1, is heated to 50 DEG C and gets rid of the Copper Foil as copper electrode
Substrate, can be prepared by graphene/polymer emulsion composite film material.
The preparation method of a kind of graphene/polymer emulsion composite film material the most according to claim 1, its feature exists
In, described surfactant is one or more in dodecylbenzene sodium sulfonate, sodium lauryl sulphate, sodium cholate.
The preparation method of a kind of graphene/polymer emulsion composite film material the most according to claim 1, its feature exists
In, described reducing agent is one or more in hydrazine, hydrazine hydrate, Dimethylhydrazine, sodium borohydride, ascorbic acid, gallic acid.
The preparation method of a kind of graphene/polymer emulsion composite film material the most according to claim 1, its feature exists
In, described macromolecule emulsion is one or more in different model styrene-acrylic emulsion.
The preparation method of a kind of graphene/polymer emulsion composite film material the most according to claim 1, its feature exists
In, the rotating speed of described magnetic agitation is 100 revs/min～500 revs/min, and mixing time is 10～30 minutes.
The preparation method of a kind of graphene/polymer emulsion composite film material the most according to claim 1, its feature exists
In, described electrodeposition process specifically comprises the following steps that and pretreated Cu electrode is placed in the graphene oxide hydrosol or oxygen reduction
Carrying out electrodeposit reaction in the functionalized graphene hydrosol, voltage is 1～10 volt, and the response time is 10s, and electrode adsorption thickness is
1mm；After reaction terminates, electrode is dried at 80 DEG C, repeats above-mentioned electrodeposition process 5～10 times；Then by institute
Obtain dried Cu electrode to immerse in macromolecule emulsion, make macromolecule emulsion uniformly pave at electrode surface, after drying, from Cu
Peel off on electrode, can be prepared by graphene/polymer emulsion composite film material.
The preparation method of a kind of graphene/polymer emulsion composite film material the most according to claim 1, its feature exists
Specifically comprise the following steps that macromolecule emulsion and the graphene oxide hydrosol or redox graphene in, described electrodeposition process
The hydrosol is by volume for 1:(1～5) mix, magnetic agitation to mix homogeneously, it is prepared as complex emulsions；By preprocessed
After Cu electrode be placed in above-mentioned complex emulsions and carry out electrodeposit reaction, voltage is 1～10 volt, the deposition reaction time be 10～
30 minutes；Reconnecting circuit, make former anelectrode become negative electrode, former negative electrode carries out reduction reaction after becoming anelectrode, electricity
Pressure is 10 volts～30 volts, and the reduction reaction time is 120～240 minutes, after reaction terminates, is done by electrode at 80 DEG C
Dry, sampling is placed in hydrochloric acid and solution that hydrogen peroxide volume ratio is 1:1, is heated to 50 DEG C and gets rid of the Copper Foil as copper electrode
Substrate, can be prepared by graphene/polymer emulsion composite film material.
8. according to the preparation method of a kind of graphene/polymer emulsion composite film material described in claim 1 or 6 or 7, its
Being characterised by, the preprocess method of described Cu electrode is: using as the Copper Foil substrate of copper electrode carry out successively fine sandpaper polishing,
Ethanol/acetone oil removing epoxy-type impurity, washing, weak acid are washed, are washed, 10%HCl activating surface.
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