CN102930991B - Electrochemistry one-step method prepares the method for graphene/polyaniline conductive composite material - Google Patents
Electrochemistry one-step method prepares the method for graphene/polyaniline conductive composite material Download PDFInfo
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Abstract
Electrochemistry one-step method prepares a method for graphene/polyaniline conductive composite material, after the ultrasonic disperse that is added to the water by graphite oxide, adds the further ultrasonic disperse of aniline monomer and forms Homogeneous phase mixing liquid; This mixed liquor is coated in also natural drying on electrode, adopts above-mentioned electrode to form two terminal battery, between electrode, inject acid dielectric; Apply scan round voltage or the cycle step voltage of Symmetrical at two electrodes of this battery, tend towards stability to electric current, in water, split battery, namely obtain graphene/polyaniline complexes membrane.The inventive method synchronously carries out the reduction of graphene oxide and the polymerization of aniline, in the composite membrane obtained, polyaniline nanoparticles is evenly dispersed between Graphene substrate, obtain the self-supporting composite membrane with good pliability and higher conductivity, the capacitor adopting this composite membrane to assemble has higher ratio capacitance value and superior cycle performance.
Description
Technical field
This method relates to a kind of preparation method of graphene/polyaniline conductive composite material, be specifically related to a kind of using graphene oxide/aniline as raw material, adopt electrochemical cyclic voltammetry or cycle potentials step method one-step method to prepare the method for graphene/polyaniline conductive composite material.
Background technology
Ultracapacitor, also known as electrochemical capacitor, is a kind of Novel energy storage apparatus between conventional electrostatic capacitor and chemical power source.Its stable performance, specific capacity is higher than traditional capacitor tens of even hundreds of times, and charge/discharge rates is fast, power density can more than 1000W/kg, and has extended cycle life and (can be greater than 10
5secondary), security maintenance-free.In recent years, because it shows application prospect of crucial importance in fields such as electric motor car, heavy-duty machinery, solar energy equipment, Aero-Space, ultracapacitor is classified as state key development project by many developed countries all.Relative to fuel cell, storage battery, the unique weakness of ultracapacitor is that energy density is on the low side.
Traditional electrode material for super capacitor mainly adopts material with carbon element, comprises active carbon, carbon nano-tube etc.The feature of this type of capacitor is that charge/discharge rates is exceedingly fast, and power density is high, and pure physics energy storage mode makes its cycle life overlength.But due to electric charge in double electric layer capacitor be the surface being stored in electrode material all the time, and can not to be stored in material body, therefore the raising of its energy density is restricted.Relative to traditional material with carbon element, according to the electrode material of conducting polymer composite as ultracapacitor, because it can be surperficial in the body of electrode material by charge storage by redox reaction, therefore the energy density of capacitor can be greatly improved, be much higher than the double electric layer capacitor making electrode with material with carbon element.But because high molecular electrode material change in volume in charge and discharge process is comparatively large, the reduction of its cycle life can be caused, be usually less than 10000 times, be significantly less than the cycle life (10 of material with carbon element capacitor
5secondary); And its mechanical performance and charge/discharge rates are also not as material with carbon element capacitor.
Therefore, many researchers are by conducting polymer and material with carbon element (as active carbon, carbon nano-tube, the Graphene etc.) compound with high-ratio surface sum mechanical strength in recent years, and are applied to the electrode material of ultracapacitor.Wherein grapheme/polyaniline composite material due to theoretical ratio capacitance value high, with low cost, most actual application prospect.Graphene in the grapheme/polyaniline composite material of current report is normally obtained by reduced graphene oxide serving, and the reduction process of graphene oxide and the polymerization process of aniline are that substep realizes, and so just cause the part that Graphene inevitably occurs in the reduction process of graphene oxide again to be built up.If can manage to solve the again accumulation of graphene oxide in reduction process and the problem of the reunion of polyaniline nanoparticles in the course of the polymerization process, Graphene substrate and polyaniline nanoparticles can be disperseed fully mutually, and so the energy-storage property of grapheme/polyaniline composite material and charge and discharge cycles stability can be further enhanced.
Summary of the invention
A kind of easy one-step method is the object of the present invention is to provide to prepare the electrochemical preparation method of graphene/polyaniline conductive composite material, with graphite oxide/aniline for raw material, electrochemical cyclic voltammetry or cycle potentials step method is adopted synchronously to carry out the reduction of graphene oxide and the polymerization of aniline, solve graphene oxide building up again and the polyaniline nanoparticles problem of reuniting in the course of the polymerization process in reduction process preferably, obtain polyaniline nanoparticles and be evenly dispersed in graphene/polyaniline conductive composite membrane between Graphene substrate.
The technical solution used in the present invention is as follows:
A kind of electrochemistry one-step method prepares the method for graphene/polyaniline conductive composite material, comprise the steps: 1) graphene oxide-aniline coating liquid preparation: graphite oxide is joined dispersant for ultrasonic dispersion and form uniform graphene oxide dispersion, aniline monomer is added further ultrasonic disperse in this dispersion liquid, form mixed uniformly coating liquid; 2) two terminal battery assembling: the coating liquid that step 1) is obtained is coated in also natural drying on electrode, adopts above-mentioned electrode to form two terminal battery, injects acid dielectric between electrode; 3) the electrochemistry preparation of graphene/polyaniline conductive composite material: in step 2) in two electrodes of battery apply the scan round voltage of Symmetricals or cycle step voltage, the cycle-index of control voltage, till the electric current of scan round to two electrode tends towards stability; In water, split this two terminal battery, obtain graphene/polyaniline conductive complexes membrane.
In the step 1) of the inventive method, described dispersant can be selected from common solvent, as water, ethanol etc., and dispersant preferred water.Described graphite oxide and the mass ratio of aniline are 32:1 ~ 1:8.
The step 2 of the inventive method) in, the preferred FTO of described electrode, ITO, stainless steel or Pt electrode.
Described acid dielectric is preferably from sulfuric acid, perchloric acid or hydrochloric acid, and concentration is between 0.2 ~ 4molL
-1between.
The electrochemical method adopted in the step 3) of the inventive method is symmetrical cycle potentials scanning method or cycle potentials step method.When adopting cycle potentials scanning method, scanning turns to current potential to be ± 1.0 ~ ± 2.0V, and potential scanning speed is 5 ~ 500mV/s, and cycle-index is 100 ~ 5000 times; When adopting cycle potentials step method, step potential is ± 1.0 ~ ± 2.0V, and snap time is 1 ~ 120 second, and cycle-index is 100 ~ 5000 times.
In described method, scan round temperature is at 0 ~ 30 DEG C.
The present invention is compared with graphene/polyaniline compound preparation method in prior art, have the following advantages: this method adopts graphene oxide and aniline as raw material, adopt electrochemical cyclic voltammetry or cycle potentials step method graphene oxide is reduced into Graphene simultaneously and aniline is oxidative polymerization into polyaniline.Because the reduction of graphene oxide and the polymerization of aniline are synchronously carried out, the method solves the again accumulation of graphene oxide in reduction process and the problem of the reunion of the polyaniline nanoparticles in aniline polymerization process preferably, in the composite membrane obtained, polyaniline nanoparticles is evenly dispersed between Graphene substrate.The self-supporting composite membrane adopting said method to obtain has good pliability and higher conductivity, the capacitor adopting this composite membrane to assemble has higher ratio capacitance value and superior cycle performance, ratio capacitance value can reach 300F/g, through 20000 charge-discharge test, ratio capacitance value is not less than 80% of initial value.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph (SEM) of graphene/polyaniline conductive composite material prepared by Fig. 1 embodiment of the present invention 1.
The cyclic voltammogram of graphene/polyaniline conductive composite material electrochemistry preparation process in Fig. 2 embodiment of the present invention 2.
The cyclical stability result of the test of the capacitor that the graphene/polyaniline conductive composite material that Fig. 3 adopts the embodiment of the present invention 4 to prepare is assembled into.
Specific embodiments
Embodiment 1
Graphite oxide is added to ultrasonic disperse 0.5-2h in water and forms uniform graphene oxide dispersion, concentration is 3mg/mL, aniline monomer is added further ultrasonic disperse 0.1-0.5h in this dispersion liquid and form Homogeneous phase mixing liquid, wherein the mass ratio of graphene oxide and aniline monomer is 4:1.This mixed liquor to be coated on FTO electrode and natural drying obtains membrane electrode.Adopt above-mentioned electrode to form two terminal battery, between electrode, inject acid concentration 1-4molL
-1sulfuric acid.Two electrodes of this battery add the scan round voltage between-1.4V ~+1.4V, the cycle-index of control voltage, potential scanning speed is 100mV/s, and cycle-index is 100-300 time, to the electric current of two electrodes tends towards stability.In water, split this battery, obtain graphene/polyaniline conductive complexes membrane.The complexes membrane proportion formed is less than water, floats on the water surface, and has good pliability and higher conductivity.
Embodiment 2
Graphite oxide is added to ultrasonic disperse 0.5-2h in water and forms uniform graphene oxide dispersion, concentration is 3mg/mL, aniline monomer is added further ultrasonic disperse 0.1-0.5h in this dispersion liquid and form Homogeneous phase mixing liquid, wherein the mass ratio of graphene oxide and aniline monomer is 2:1.This mixed liquor to be coated on FTO electrode and natural drying obtains membrane electrode.Adopt above-mentioned electrode to form two terminal battery, between two electrodes, inject acid concentration 1 ~ 4molL
-1perchloric acid.Two electrodes of this battery add the scan round voltage between-1.4V ~+1.4V, the cycle-index of control voltage, potential scanning speed is 100mV/s, and cycle-index is 100-300 time, to the electric current of two electrodes tends towards stability.In water, split this two terminal battery, obtain graphene/polyaniline conductive complexes membrane.
Embodiment 3
Graphite oxide is added to ultrasonic disperse 0.5-2h in water and forms uniform graphene oxide dispersion, concentration is 10mg/mL, aniline monomer is added further ultrasonic disperse 0.1-0.5h in this dispersion liquid and form Homogeneous phase mixing liquid, wherein the mass ratio of graphene oxide and aniline monomer is 1:1.This mixed liquor to be coated in ITO electrode and natural drying obtains membrane electrode.Adopt above-mentioned electrode to form two terminal battery, between two electrodes, inject acid concentration 0.5 ~ 2molL
-1hydrochloric acid.Two electrodes of this battery add the scan round voltage of-1.5V ~+1.5V, the cycle-index of control voltage, potential scanning speed 100mV/s, cycle-index is 100-300 time, to the electric current of two electrodes tends towards stability.In water, split this two terminal battery, obtain graphene/polyaniline conductive complexes membrane.
Embodiment 4
Graphite oxide is added to ultrasonic disperse 0.5-2h in water and forms uniform graphene oxide dispersion, concentration is 3mg/mL, aniline monomer is added further ultrasonic disperse 0.1-0.5h in this dispersion liquid and form Homogeneous phase mixing liquid, wherein the mass ratio of graphene oxide and aniline monomer is 32:1.This mixed liquor to be coated on Pt electrode and natural drying obtains membrane electrode.Adopt above-mentioned electrode to form two terminal battery, between two electrodes, inject acid concentration 1 ~ 4molL
-1sulfuric acid.Two electrodes of this battery add the scan round voltage of-1.5V ~+1.5V, the cycle-index of control voltage, potential scanning speed is 100mV/s, and cycle-index is 300-600 time, to the electric current of two electrodes tends towards stability.In water, split this two terminal battery, obtain graphene/polyaniline conductive complexes membrane, adopt this composite membrane to assemble ultracapacitor.
The cyclical stability result of the test of the capacitor dressed up as shown in Figure 3.Result shows, the capacitor adopting this composite membrane to assemble has higher ratio capacitance value and superior cycle performance, and ratio capacitance value is about 300F/g, and through 20000 charge-discharge test, ratio capacitance value is not less than 80% of initial value.
Embodiment 5
Graphite oxide is added to ultrasonic disperse 0.5-2h in water and forms uniform graphene oxide dispersion, concentration is 3mg/mL, aniline monomer is added further ultrasonic disperse 0.1-0.5h in this dispersion liquid and form Homogeneous phase mixing liquid, wherein the mass ratio of graphene oxide and aniline monomer is 8:1.This mixed liquor to be coated on FTO electrode and natural drying obtains membrane electrode.Adopt above-mentioned electrode to form two terminal battery, between two electrodes, inject acid concentration 1-4molL
-1sulfuric acid.Two electrodes of this battery add the cycle step voltage of-1.4V and+1.4V, and snap time is 10 seconds, and control the cycle-index of step voltage, cycle-index is 200-400 time, to the electric current of two electrodes tends towards stability.In water, split this two terminal battery, obtain graphene/polyaniline conductive complexes membrane.
Embodiment 6
Graphite oxide is added to ultrasonic disperse 0.5-2h in water and forms uniform graphene oxide dispersion, concentration is 5mg/mL, aniline monomer is added further ultrasonic disperse 0.1-0.5h in this dispersion liquid and form Homogeneous phase mixing liquid, wherein the mass ratio of graphene oxide and aniline monomer is 4:1.This mixed liquor to be coated on FTO electrode and natural drying obtains membrane electrode.Adopt above-mentioned electrode to form two terminal battery, between two electrodes, inject acid concentration 1-4molL
-1sulfuric acid.Two electrodes of this battery add the cycle step voltage of-1.6V and+1.6V, and snap time is 3 seconds, and control the cycle-index of step voltage, cycle-index is 100-300 time, to the electric current of two electrodes tends towards stability.In water, split this two terminal battery, obtain graphene/polyaniline conductive complexes membrane.
Claims (6)
1. electrochemistry one-step method prepares a method for graphene/polyaniline conductive composite material, comprises the steps:
1) preparation of graphene oxide-aniline coating liquid: graphite oxide is added dispersant for ultrasonic dispersion and form uniform graphene oxide dispersion, adds further ultrasonic disperse in this dispersion liquid, forms mixed uniformly coating liquid by aniline monomer;
2) two terminal battery assembling: the coating liquid that step 1) is obtained is coated in also natural drying on electrode, adopts above-mentioned electrode to form two terminal battery, between electrode, injects acidic electrolyte bath;
3) the electrochemistry preparation of graphene/polyaniline conductive composite material: in step 2) in two electrodes of battery apply the scan round voltage of Symmetricals or cycle step voltage, the cycle-index of control voltage, till the electric current of scan round to two electrode tends towards stability; In water, split this two terminal battery, obtain graphene/polyaniline conductive complexes membrane;
When applying scan round voltage, scanning turns to current potential to be ± 1.0 ~ ± 2.0V, and potential scanning speed is 5 ~ 500mV/s, and cycle-index is 100 ~ 5000 times;
When applying cycle step voltage, step potential is ± 1.0 ~ ± 2.0V, and snap time is 1 ~ 120 second, and cycle-index is 100 ~ 5000 times.
2. the method preparing graphene/polyaniline conductive composite material according to claim 1, is characterized in that, described dispersant is water.
3. the method preparing graphene/polyaniline conductive composite material according to claim 1, is characterized in that, described graphite oxide and the mass ratio of aniline are 32:1 ~ 1:8.
4. the method preparing graphene/polyaniline conductive composite material according to claim 1, is characterized in that, described electrode is FTO, ITO, stainless steel or Pt electrode.
5. the method preparing graphene/polyaniline conductive composite material according to claim 1, is characterized in that, described acidic electrolyte bath is selected from sulfuric acid, perchloric acid or hydrochloric acid, and concentration is between 0.2 ~ 4molL
-1between.
6. the method preparing graphene/polyaniline conductive composite material according to claim 1, is characterized in that, in described method, scan round temperature is at 0-30 DEG C.
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| CN103487573B (en) * | 2013-09-27 | 2015-07-01 | 安徽大学 | Electrogenerated chemiluminescence immunosensor for detecting human interleukin 6 as well as preparation method and detection method of immunosensor |
| CN103487484B (en) * | 2013-10-10 | 2015-05-27 | 佳木斯大学 | Making method for hypersensitive graphene electrode |
| CN104674294B (en) * | 2014-12-18 | 2018-02-06 | 南京航空航天大学 | The preparation method and application of graphene-layer/polyaniline conductive compound |
| CN105788880B (en) * | 2016-04-15 | 2018-05-25 | 上海交通大学 | A kind of graphene-polyaniline nanoparticles composite film electrode and preparation method thereof |
| CN106024420A (en) * | 2016-05-03 | 2016-10-12 | 常州工程职业技术学院 | Preparation method of graphene-containing energy storage polymer electrode sheet |
| CN106395805B (en) * | 2016-11-30 | 2018-09-28 | 中国科学院深圳先进技术研究院 | A kind of preparation method of graphene |
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| CN102220597A (en) * | 2011-05-20 | 2011-10-19 | 湖南大学 | Preparation method of conducting polymer-graphene composition |
| CN102629684A (en) * | 2011-09-14 | 2012-08-08 | 京东方科技集团股份有限公司 | Polyaniline-graphene composite film and its preparation method, cells and e-books |
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| CN102629684A (en) * | 2011-09-14 | 2012-08-08 | 京东方科技集团股份有限公司 | Polyaniline-graphene composite film and its preparation method, cells and e-books |
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| One-step electrochemical synthesis of graphene/polyaniline composite film and its Applications;Xiao-Miao Feng等;《Advanced Functional Materials》;20110809;第21卷(第15期);第2995页 * |
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