CN104576080A - One-step electrochemical method for preparing graphene/polyaniline (PANI) flexible electrode - Google Patents
One-step electrochemical method for preparing graphene/polyaniline (PANI) flexible electrode Download PDFInfo
- Publication number
- CN104576080A CN104576080A CN201410195022.8A CN201410195022A CN104576080A CN 104576080 A CN104576080 A CN 104576080A CN 201410195022 A CN201410195022 A CN 201410195022A CN 104576080 A CN104576080 A CN 104576080A
- Authority
- CN
- China
- Prior art keywords
- graphene
- electrode
- polyaniline
- flexible
- conductive substrate
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 invention discloses a one-step electrochemical method for preparing a graphene/polyaniline (PANI) flexible electrode. The method comprises the following steps: firstly, adding graphene nanosheets into a dispersing agent for ultrasonic dispersion and then adding aniline monomer and an acid solution for further ultrasonic dispersion to form a uniform mixture solution; secondly, using a flexible conductive substrate as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, and placing the electrodes into the prepared mixture solution containing graphene, aniline and acid liquid; performing electrochemical polymerization during continuous magnetic stirring, washing the samples using absolute ethyl alcohol and deionized water in sequence after the reaction is ended, and carrying out vacuum drying to obtain the graphene/PANI flexible electrode prepared through the one-step electrochemical method. According to the invention, plastics such as flexible conductive PET plastics are used as the conductive substrate, therefore, the conductive substrate has good flexibility and portability, can curl easily, has the bending advantage, and is expected to be a substitute for a rigid substrate such as glass.
Description
Technical field
The present invention relates to an a kind of one-step electrochemistry preparation method of graphene/polyaniline flexible electrode, be specifically related to an a kind of one-step electrochemistry preparation method of the graphene/polyaniline flexible electrode using flexiplast as conductive substrate.
Background technology
The flexibility of electronic product has become the fashion of Current electronic consumption market.Along with miniaturization and the lighting development of electronic device, flexible optoelectronic part, as Organic Light Emitting Diode, flexible flat panel display device, light flexible ultracapacitor, flexible solar battery etc., has caused the concern of more and more researcher.
The large multiplex Conducting Glass of traditional electrode material or metal substrate, wherein glass basis has weight greatly, easily broken, the shortcomings such as transport inconvenience, and metal substrate exists density greatly equally, not easily bend and lighttight problem, limit its scope of application to a great extent.Therefore, the compliant conductive plastics of lightweight transparent are adopted to address these problems preferably.
The flexible electrode of current use is flexible platinum electrode, the platinum plating in compliant conductive ITO plastic mainly through magnetron sputtering vacuum plating method or vaccum gas phase sedimentation method, but the manufacturing cost of platinum electrode own is expensive, complex process equipment; Relative to electro-conductive glass matrix, the usual non-refractory of flexiplast matrix, must reduce the treatment temperature of platinum plating during making, causes the adhesion between platinum and plastic substrate poor.So greatly limit the fast development of flexible optoelectronic part technology in industrialization, be therefore badly in need of seeking some alternative novel flexible electrode materials.
Polyaniline is the good conductive conjugated polymer of a kind of environmental stability.There is low cost, high chemical stability and the advantage such as preparation technology is simple, be widely used in the fields such as ultracapacitor, lithium battery, On Orgnic Luminous Materials and organic thin film solar cell material.Through long-term a large amount of research work both at home and abroad, people develop many methods preparing polyaniline flexible electrode.Such as emulsion polymerisation-assorted state polyaniline solutions spin-coating film on flexible substrate of extraction preparation; Utilize chemical oxidation adsorpting polymerization method on flexible pet substrate, prepare the Polyaniline Thin Film-Coated Electrode with satisfactory electrical conductivity, this electrode replaces ito glass, is applied in electroluminescent device research.Start at present to be devoted to research by with nano-carbon material compound, play the advantage of composite material, improve the electro-chemical activity of unitary electrode.Graphene is the novel nano material with carbon element of a kind of carbon atom tightly packed one-tenth individual layer bi-dimensional cellular shape lattice structure, has fabulous crystallinity and chemical property, its resistivity only about 10
-6Ω cm, is applied to the electrical efficiency that can significantly improve electrode in electrode by the composite material of itself and polyaniline.Graphene and polyaniline all have conjugated structure simultaneously, both good conjugation and synergy can be embodied, therefore with Graphene doped polyaniline, compliant conductive substrate prepares graphene modified polyaniline electrode by an one-step electrochemistry, can further improve the conductivity of electrode, optimize the catalytic performance of flexible electrode, promote the process of novel flexible electrode material practical application.
Summary of the invention
The object of the invention is, the easily shortcoming such as a broken and transport inconvenience and a kind of one-step electrochemistry preparation method of graphene/polyaniline flexible electrode using flexiplast as conductive substrate be provided large for glass basis weight in conventional electrode materials.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
An one one-step electrochemistry preparation method of graphene/polyaniline flexible electrode, step is as follows:
(1) graphene nanometer sheet is added dispersant for ultrasonic dispersion 0.1 ~ 12h, formed dispersed, concentration is the graphene dispersing solution of 0.1 ~ 50g/L;
(2) aniline monomer and acid solution are added successively the graphene dispersing solution of step (1) gained, ultrasonic disperse 0.1 ~ 12h again, is mixed with uniform mixed electrolyte solutions;
(3) choose compliant conductive substrate and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, cleans three electrodes successively, dried for standby with absolute ethyl alcohol, deionized water;
(4) three electrodes are placed in the mixed electrolyte solutions of step (2) gained, continuing magnetic force stirs; Adopt three-electrode system, at working electrode surface by an one-step electrochemistry method electro-deposition polyaniline, graphene nanometer sheet mixes polyaniline rete simultaneously, form graphene/polyaniline laminated film, a described one-step electrochemistry method comprises potentiostatic method, arranging anode potential is 0.8 ~ 2.4 V, and polymerization time is 100 ~ 2000 s; Galvanostatic method, arranging anode current is 0.1 ~ 10mA/cm
2, polymerization time is 100 ~ 2000 s; Cyclic voltammetry, arranges controlling potential at-0.2 ~ 2.0 V, and sweep speed is 10 ~ 200 mV/s, and scan round number of times is 100 ~ 2000 times;
(5) work electrode is taken out, successively with absolute ethyl alcohol, deionized water washing, at 40 ~ 100 DEG C of vacuum drying treatment 10 ~ 100h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Wherein, the compliant conductive substrate in step (3) is electrically conducting transparent PET, conduction PBT plastic, conduction PEN plastics, conduction PC plastics, conduction PMMA plastics, conduction PI plastics.
In described step (1), dispersant is deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol or butanols.
In described step (2), the mass ratio of aniline monomer and Graphene is 100:1 ~ 1:10.
In described step (2), acid solution is sulfuric acid, hydrochloric acid or perchloric acid.
In described step (2), acid solution take electrolyte solution as the concentration of benchmark is 0.1 ~ 2mol/L.
Compliant conductive substrate square resistance≤200 Ω/ in described step (3).
The invention has the beneficial effects as follows: (1) realizes an one-step electrochemistry legal system for graphene/polyaniline combination electrode, compared with chemical method, one one-step electrochemistry method can make starting monomer directly at matrix surface polymerization film formation, there is controllability good, anaerobic agent, products pure, environmental friendliness and the advantage such as operating process is easy; (2) adopt the plastics such as compliant conductive PET as conductive substrate, possess good pliability, portability, can be arbitrarily curling, the advantage of bending.Be expected to the renewal product becoming the hard substrates such as glass, all kinds of Foldable cellular flexible optoelectronic part can be manufactured, as flexible flat panel display device, ultracapacitor or flexible solar battery etc.; (3) the graphene/polyaniline flexible electrode prepared of the present invention is compared with platinized electrode, cost of manufacture is cheap, manufacturing process is simple, with Graphene doped polyaniline, high conductivity and efficient electrochemical reaction speed can be obtained, become the optimal selection in flexible electrode material, have good application prospect and economic benefit in fields such as flexible electrode material.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the obtained graphene/polyaniline flexible electrode of different constant potential (a:1.4V, b:1.6V, c:1.8V, d:2.0V, e:2.2V).
Fig. 2 is the infrared spectrogram of the obtained graphene/polyaniline flexible electrode of different constant potential (a:1.4V, b:1.6V, c:1.8V, d:2.0V, e:2.2V).
Embodiment
Embodiment 1
First graphene nanometer sheet is added deionized water for ultrasonic dispersion 30min, configuration concentration is the homodisperse graphene dispersing solution of 1g/L; Then aniline monomer and sulfuric acid are added graphene dispersing solution and carry out ultrasonic disperse 30min, wherein the mass ratio of aniline monomer and Graphene is 28:1, and the concentration of sulfuric acid is 0.5mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose flexible ITO conducting PET plastic substrate and make work electrode, platinum plate electrode is done electrode, saturated calomel electrode makes reference electrode, three electrodes are placed in above-mentioned mixed electrolyte solutions, adopt potentiostatic method, under 1.4V voltage, electrochemical polymerization 500 seconds continuing magnetic force stir, and form graphene/polyaniline laminated film; Take out work electrode, successively with absolute ethyl alcohol, deionized water washing, at 60 DEG C of vacuumize 12h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Testing result: be polymerized the stereoscan photograph of 500s gained graphene/polyaniline material under 1.4V constant voltage as shown in accompanying drawing 1-a, infrared spectrogram is as shown in accompanying drawing 2-a.From stereoscan photograph (Fig. 1-a), when constant voltage is 1.4V, on compliant conductive matrix, a large amount of diameter of growth in situ is the polyaniline granule of 30 ~ 40nm, and is mutually piled into bulky grain and short and thick nanorod structure.Adsorb graphene nano lamella at polyaniline particles film surface, contribute to the surface impedance reducing polyaniline electrode.From infrared spectrogram (Fig. 2-a), the characteristic absorption peak of PANI lays respectively at 1537 and 1417 cm
-1place, corresponding to quinone ring C-C stretching vibration peak and phenyl ring C-C stretching vibration peak; At 1283,1229 cm
-1place corresponds to the stretching vibration peak of benzene formula structure C-N and C=N key, 922 cm
-1place corresponds to quinoid structure atom N stretching vibration peak.
Embodiment 2
First graphene nanometer sheet is added deionized water for ultrasonic dispersion 40min, configuration concentration is the homodisperse graphene dispersing solution of 1.0g/L; Then aniline monomer and sulfuric acid are added graphene dispersing solution and carry out ultrasonic disperse 40min, wherein the mass ratio of aniline monomer and Graphene is 28:1, and the concentration of sulfuric acid is 0.5mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose flexible ITO conducting PET plastic substrate and make work electrode, platinum plate electrode is done electrode, saturated calomel electrode makes reference electrode, three electrodes are placed in above-mentioned mixed electrolyte solutions, adopt potentiostatic method, under 1.6V voltage, electrochemical polymerization 500 seconds continuing magnetic force stir, and form graphene/polyaniline laminated film; Take out work electrode, successively with absolute ethyl alcohol, deionized water washing, at 60 DEG C of vacuumize 24h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Testing result: be polymerized the stereoscan photograph of 500s gained graphene/polyaniline material under 1.6V constant voltage as shown in accompanying drawing 1-b.When constant voltage is 1.6V, the elongated polyaniline nano fiber of growth in situ on compliant conductive PET.In polyaniline rete, be doped with graphene platelet simultaneously, contribute to the surface impedance reducing polyaniline electrode.Shown in infrared spectrogram (Fig. 2-b), there is the characteristic absorption peak of PANI, the existence of polyaniline in flexible electrode has been described.
Embodiment 3
First graphene nanometer sheet is added deionized water for ultrasonic dispersion 50min, configuration concentration is the homodisperse graphene dispersing solution of 1g/L; Then aniline monomer and sulfuric acid are added graphene dispersing solution and carry out ultrasonic disperse 50min, wherein the mass ratio of aniline monomer and Graphene is 28:1, and the concentration of sulfuric acid is 0.5mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose flexible ITO conducting PET plastic substrate and make work electrode, platinum plate electrode is done electrode, saturated calomel electrode makes reference electrode, three electrodes are placed in above-mentioned mixed electrolyte solutions, adopt potentiostatic method, under 1.8V voltage, electrochemical polymerization 500 seconds continuing magnetic force stir, and form graphene/polyaniline laminated film; Take out work electrode, successively with absolute ethyl alcohol, deionized water washing, at 60 DEG C of vacuumize 36h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Testing result: be polymerized the stereoscan photograph of 500s gained graphene/polyaniline material under 1.8V constant voltage as shown in accompanying drawing 1-c.When constant voltage is 1.8V, it is about 120nm that compliant conductive pet sheet face deposits many diameters, and length is at the polyaniline nano fiber of about 800 nm.Start a small amount of polyaniline particles of in-situ polymerization on the graphene platelet surface of doping simultaneously.This phenomenon illustrates the rising along with current potential, and conductive graphene lamella starts the growth having occurred polyaniline.Shown in infrared spectrogram (Fig. 2-c), there is obvious PANI characteristic absorption peak, the existence of polyaniline in flexible electrode has been described.
Embodiment 4
First graphene nanometer sheet is added deionized water for ultrasonic dispersion 60min, configuration concentration is the homodisperse graphene dispersing solution of 1g/L; Then aniline monomer and sulfuric acid are added graphene dispersing solution and carry out ultrasonic disperse 60min, wherein the mass ratio of aniline monomer and Graphene is 28:1, and the concentration of sulfuric acid is 0.5mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose flexible ITO conducting PET plastic substrate and make work electrode, platinum plate electrode is done electrode, saturated calomel electrode makes reference electrode, three electrodes are placed in above-mentioned mixed electrolyte solutions, adopt potentiostatic method, under 2.0V voltage, electrochemical polymerization 500 seconds continuing magnetic force stir, and form graphene/polyaniline laminated film; Take out work electrode, successively with absolute ethyl alcohol, deionized water washing, at 60 DEG C of vacuumize 48h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Testing result: from the stereoscan photograph (Fig. 1-d) of graphene/polyaniline, when constant voltage is 2.0 V, graphene film is entrained in polyaniline film, simultaneously on Graphene, a large amount of diameter of growth in situ is about 25nm polyaniline nanoparticles, illustrates that the high potential of 2.0V is conducive to generating polyaniline nanoparticles fast at graphenic surface.Known through examination of infrared spectrum (Fig. 2-d), really there is polyaniline in combination electrode.
Embodiment 5
First graphene nanometer sheet is added deionized water for ultrasonic dispersion 70min, configuration concentration is the homodisperse graphene dispersing solution of 1g/L; Then aniline monomer and sulfuric acid are added graphene dispersing solution and carry out ultrasonic disperse 70min, wherein the mass ratio of aniline monomer and Graphene is 28:1, and the concentration of sulfuric acid is 0.5mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose flexible ITO conducting PET plastic substrate and make work electrode, platinum plate electrode is done electrode, saturated calomel electrode makes reference electrode, three electrodes are placed in above-mentioned mixed electrolyte solutions, adopt potentiostatic method, under 2.2V voltage, electrochemical polymerization 500 seconds continuing magnetic force stir, and form graphene/polyaniline laminated film; Take out work electrode, successively with absolute ethyl alcohol, deionized water washing, at 60 DEG C of vacuumize 60h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Testing result: be polymerized the stereoscan photograph of 500s gained graphene/polyaniline material under 2.2V constant voltage as shown in accompanying drawing 1-e.From stereoscan photograph (Fig. 1-e), when constant voltage is 2.2V, because current potential is too high, having there is significant peroxidating in polyaniline, causes the degraded of polyaniline, and specific area and conductivity decline.Shown in infrared spectrogram (Fig. 2-e), at 1229 cm
-1place corresponds to C=N key stretching vibration peak remitted its fury, illustrates that obvious peroxidating state appears in polyaniline.
Embodiment 6
First graphene nanometer sheet is added deionized water for ultrasonic dispersion 0.1h, configuration concentration is the homodisperse graphene dispersing solution of 0.1g/L; Then aniline monomer and sulfuric acid are added graphene dispersing solution and carry out ultrasonic disperse 0.1h, wherein the mass ratio of aniline monomer and Graphene is 100:1, and the concentration of sulfuric acid is 0.1mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose flexible ITO conducting PET plastic substrate and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, and wherein flexible PET conductive substrate square resistance is 10 Ω/; Three electrodes are placed in above-mentioned mixed electrolyte solutions, adopt potentiostatic method, under 0.8V anode potential, be polymerized 100s continuing magnetic force stir, form graphene/polyaniline laminated film; Take out electrode, successively with absolute ethyl alcohol, deionized water washing, at 40 DEG C of vacuumize 10h, a kind of graphene/polyaniline flexible compound electrode of final acquisition.
Embodiment 7
First graphene nanometer sheet is added ultrasonic disperse 12h in absolute ethyl alcohol, configuration concentration is the homodisperse graphene dispersing solution of 50g/L; Then aniline monomer and sulfuric acid are added graphene dispersing solution and carry out ultrasonic disperse 12h, wherein the mass ratio of aniline monomer and Graphene is 1:10, and the concentration of sulfuric acid is 2mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose compliant conductive PBT plastic substrate and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, and wherein flexible PBT plastic conductive substrate square resistance is 200 Ω/; Three electrodes are placed in above-mentioned mixed electrolyte solutions, adopt galvanostatic method, at 0.1 mA/cm
2under anode current, electropolymerization 2000s continuing magnetic force stirs, and forms graphene/polyaniline laminated film; Take out work electrode, successively with absolute ethyl alcohol, deionized water washing, at 100 DEG C of vacuumize 100h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Embodiment 8
First graphene nanometer sheet is added ultrasonic disperse 1h in ethylene glycol, configuration concentration is the homodisperse graphene dispersing solution of 1g/L; Then aniline monomer and perchloric acid are added graphene dispersing solution and carry out ultrasonic disperse 1h, wherein the mass ratio of aniline monomer and Graphene is 50:1, and the concentration of perchloric acid is 1mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose compliant conductive PEN and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, and wherein flexible PEN Plastic conductive substrate square resistance is 100 Ω/; Three electrodes are placed in above-mentioned mixed electrolyte solutions, and adopt cyclic voltammetry while stirring continuously, controlling potential is at-0.2V ~ 1.0V, and sweep speed is 10 mV/s, and scan round number of times is 2000 times; Question response terminates rear taking-up print, successively with absolute ethyl alcohol, deionized water washing, at 50 DEG C of vacuumize 50h, and a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Embodiment 9
First graphene nanometer sheet is added ultrasonic disperse 6h in ethylene glycol, configuration concentration is the homodisperse graphene dispersing solution of 10g/L; Then aniline monomer and perchloric acid are added graphene dispersing solution and carry out ultrasonic disperse 6h, wherein the mass ratio of aniline monomer and Graphene is 10:1, and the concentration of perchloric acid is 1.5mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose compliant conductive PC substrate and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, and wherein flexible PC Plastic conductive substrate square resistance is 60 Ω/; Three electrodes are placed in above-mentioned mixed electrolyte solutions, and adopt cyclic voltammetry while stirring continuously, controlling potential is at-0.2V ~ 2.0V, and sweep speed is 200 mV/s, and scan round number of times is 100 times; Question response terminates rear taking-up print, successively with absolute ethyl alcohol, deionized water washing, at 80 DEG C of vacuumize 20h, and a kind of graphene/polyaniline flexible compound electrode of final acquisition.
Embodiment 10
First graphene nanometer sheet is added ultrasonic disperse 0.5h in isopropyl alcohol, configuration concentration is the homodisperse graphene dispersing solution of 0.5g/L; Then aniline monomer and hydrochloric acid are added graphene dispersing solution and carry out ultrasonic disperse 10h, wherein the mass ratio of aniline monomer and Graphene is 1:1, and the concentration of hydrochloric acid is 0.5mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose compliant conductive PMMA substrate and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, and wherein flexible PMMA Plastic conductive substrate square resistance is 100 Ω/; Three electrodes are placed in above-mentioned mixed electrolyte solutions, and adopt potentiostatic method while stirring continuously, arranging anode potential is 2.4V, and polymerization time is 100s; Question response terminates rear taking-up print, successively with absolute ethyl alcohol, deionized water washing, at 50 DEG C of vacuumize 40h, and a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Embodiment 11
First graphene nanometer sheet is added ultrasonic disperse 10h in butanols, configuration concentration is the homodisperse graphene dispersing solution of 25g/L; Then aniline monomer and hydrochloric acid are added graphene dispersing solution and carry out ultrasonic disperse 10h, wherein the mass ratio of aniline monomer and Graphene is 1:8, and the concentration of hydrochloric acid is 0.2mol/L, preparation graphite rare/aniline mixed electrolyte solutions; Choose compliant conductive PI substrate and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, and wherein flexible PI Plastic conductive substrate square resistance is 150 Ω/; Three electrodes are placed in above-mentioned mixed electrolyte solutions, and adopt galvanostatic method while stirring continuously, arranging anode current is 10mA/cm
2, polymerization time is 100s; Question response terminates rear taking-up print, successively with absolute ethyl alcohol, deionized water washing, at 70 DEG C of vacuumize 60h, and a kind of graphene/polyaniline flexible composite electrode material of final acquisition.
Claims (6)
1. an one-step electrochemistry preparation method of graphene/polyaniline flexible electrode, is characterized in that step is as follows:
(1) graphene nanometer sheet is added dispersant for ultrasonic dispersion 0.1 ~ 12h, formed dispersed, concentration is the graphene dispersing solution of 0.1 ~ 50g/L;
(2) aniline monomer and acid solution are added successively the graphene dispersing solution of step (1) gained, ultrasonic disperse 0.1 ~ 12h again, is mixed with uniform mixed electrolyte solutions;
(3) choose compliant conductive substrate and make work electrode, platinum plate electrode is done electrode, and saturated calomel electrode makes reference electrode, cleans three electrodes successively, dried for standby with absolute ethyl alcohol, deionized water;
(4) three electrodes are placed in the mixed electrolyte solutions of step (2) gained, continuing magnetic force stirs; Adopt three-electrode system, at working electrode surface by an one-step electrochemistry method electro-deposition polyaniline, graphene nanometer sheet mixes polyaniline rete simultaneously, forms graphene/polyaniline laminated film;
(5) work electrode is taken out, successively with absolute ethyl alcohol, deionized water washing, at 40 ~ 100 DEG C of vacuum drying treatment 10 ~ 100h, a kind of graphene/polyaniline flexible composite electrode material of final acquisition;
Wherein, the compliant conductive substrate in step (3) is electrically conducting transparent PET, conduction PBT plastic, conduction PEN plastics, conduction PC plastics, conduction PMMA plastics, conduction PI plastics.
2. an one-step electrochemistry preparation method of a kind of graphene/polyaniline flexible electrode according to claim 1, is characterized in that: in described step (1), dispersant is deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol or butanols.
3. an one-step electrochemistry preparation method of a kind of graphene/polyaniline flexible electrode according to claim 1, is characterized in that: in described step (2), the mass ratio of aniline monomer and Graphene is 100:1 ~ 1:10.
4. an one-step electrochemistry preparation method of a kind of graphene/polyaniline flexible electrode according to claim 1, is characterized in that: in described step (2), acid solution is sulfuric acid, hydrochloric acid or perchloric acid.
5. an one-step electrochemistry preparation method of a kind of graphene/polyaniline flexible electrode according to claim 1, is characterized in that: in described step (2), acid solution take electrolyte solution as the concentration of benchmark is 0.1 ~ 2mol/L.
6. an one-step electrochemistry preparation method of a kind of graphene/polyaniline flexible electrode according to claim 1, is characterized in that: the square resistance≤200 Ω/ of compliant conductive substrate in described step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195022.8A CN104576080B (en) | 2014-05-09 | 2014-05-09 | An a kind of one-step electrochemistry preparation method for graphene/polyaniline flexible electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195022.8A CN104576080B (en) | 2014-05-09 | 2014-05-09 | An a kind of one-step electrochemistry preparation method for graphene/polyaniline flexible electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104576080A true CN104576080A (en) | 2015-04-29 |
| CN104576080B CN104576080B (en) | 2018-03-16 |
Family
ID=53091895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410195022.8A Active CN104576080B (en) | 2014-05-09 | 2014-05-09 | An a kind of one-step electrochemistry preparation method for graphene/polyaniline flexible electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104576080B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070532A (en) * | 2015-08-20 | 2015-11-18 | 西安岳达植物科技有限公司 | Graphene-based super capacitor preparation method |
| CN105118681A (en) * | 2015-08-17 | 2015-12-02 | 电子科技大学 | A method for manufacturing a graphene -based ternary composite flexible electrode |
| CN106531291A (en) * | 2016-12-06 | 2017-03-22 | 周潇潇 | Transparent conductive film material used for circuit board |
| CN107680820A (en) * | 2017-10-18 | 2018-02-09 | 东莞市共和电子有限公司 | A kind of solid-state super capacitor |
| CN109449221A (en) * | 2018-12-28 | 2019-03-08 | 苏州腾晖光伏技术有限公司 | A kind of graphene crystal silicon solar battery and its manufacturing method |
| CN110467738A (en) * | 2019-08-02 | 2019-11-19 | 温州医科大学 | A kind of preparation method of flexible nano electrode and its promoting the application in the growth of eye trigeminal neuralgia cell |
| CN111128472A (en) * | 2019-12-17 | 2020-05-08 | 浙江大学 | Method for preparing conductive polymer film on graphene surface through electrodeposition |
| CN114121496A (en) * | 2021-10-28 | 2022-03-01 | 中国科学院深圳先进技术研究院 | Flexible composite electrode, preparation method thereof and flexible energy storage device |
| CN116130608A (en) * | 2023-04-04 | 2023-05-16 | 山东科技大学 | Method for preparing titanium oxide film flexible electrode by self-assembly technology |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346337B (en) * | 2018-10-24 | 2020-06-09 | 南通南京大学材料工程技术研究院 | Preparation method of composite electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740228A (en) * | 2009-12-23 | 2010-06-16 | 南京航空航天大学 | Method for preparing counter electrode based on electrochemical synthesized polyaniline on surface of stainless steel |
| 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 |
-
2014
- 2014-05-09 CN CN201410195022.8A patent/CN104576080B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740228A (en) * | 2009-12-23 | 2010-06-16 | 南京航空航天大学 | Method for preparing counter electrode based on electrochemical synthesized polyaniline on surface of stainless steel |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 伍纳: "石墨烯/聚苯胺复合材料的可控电化学制备", 《湖南大学硕士学位论文》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105118681A (en) * | 2015-08-17 | 2015-12-02 | 电子科技大学 | A method for manufacturing a graphene -based ternary composite flexible electrode |
| CN105070532A (en) * | 2015-08-20 | 2015-11-18 | 西安岳达植物科技有限公司 | Graphene-based super capacitor preparation method |
| CN106531291A (en) * | 2016-12-06 | 2017-03-22 | 周潇潇 | Transparent conductive film material used for circuit board |
| CN107680820A (en) * | 2017-10-18 | 2018-02-09 | 东莞市共和电子有限公司 | A kind of solid-state super capacitor |
| CN109449221A (en) * | 2018-12-28 | 2019-03-08 | 苏州腾晖光伏技术有限公司 | A kind of graphene crystal silicon solar battery and its manufacturing method |
| CN109449221B (en) * | 2018-12-28 | 2024-04-09 | 苏州腾晖光伏技术有限公司 | Graphene crystalline silicon solar cell and manufacturing method thereof |
| CN110467738A (en) * | 2019-08-02 | 2019-11-19 | 温州医科大学 | A kind of preparation method of flexible nano electrode and its promoting the application in the growth of eye trigeminal neuralgia cell |
| CN110467738B (en) * | 2019-08-02 | 2021-08-17 | 温州医科大学 | Preparation method of flexible nano electrode and application of flexible nano electrode in promoting growth of eye trigeminal nerve cells |
| CN111128472A (en) * | 2019-12-17 | 2020-05-08 | 浙江大学 | Method for preparing conductive polymer film on graphene surface through electrodeposition |
| CN114121496A (en) * | 2021-10-28 | 2022-03-01 | 中国科学院深圳先进技术研究院 | Flexible composite electrode, preparation method thereof and flexible energy storage device |
| WO2023070856A1 (en) * | 2021-10-28 | 2023-05-04 | 中国科学院深圳先进技术研究院 | Flexible composite electrode and preparation method therefor, and flexible energy storage device |
| CN116130608A (en) * | 2023-04-04 | 2023-05-16 | 山东科技大学 | Method for preparing titanium oxide film flexible electrode by self-assembly technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104576080B (en) | 2018-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104576080B (en) | An a kind of one-step electrochemistry preparation method for graphene/polyaniline flexible electrode | |
| Zhong et al. | Improved energy density of quasi-solid-state supercapacitors using sandwich-type redox-active gel polymer electrolytes | |
| Mitchell et al. | High performance supercapacitor based on multilayer of polyaniline and graphene oxide | |
| Kim et al. | Synthesis and enhanced electrochemical supercapacitor properties of Ag–MnO2–polyaniline nanocomposite electrodes | |
| Li et al. | Electrochemical synthesis of polyaniline nanobelts with predominant electrochemical performances | |
| CN102723209B (en) | Preparation method for graphene nanosheet/conducting polymer nanowire composite material | |
| CN103011150B (en) | Flexible graphene composite film and preparation method thereof | |
| CN102629684B (en) | Polyaniline-graphene composite film and its preparation method, cells and e-books | |
| Zhang et al. | Tunable electrode morphology used for high performance supercapacitor: polypyrrole nanomaterials as model materials | |
| CN101694814B (en) | Electrochemistry preparation method of dye sensibilization solar cell nanometer conductive polymer counter electrode | |
| Ehsani et al. | Lignin-derived carbon as a high efficient active material for enhancing pseudocapacitance performance of p-type conductive polymer | |
| CN103123870A (en) | Nanocomposite film electrode material for supercapacitor and producing method thereof | |
| CN107170589B (en) | A kind of MnO2It is the preparation method of tri compound electrode material for super capacitor | |
| CN101488400A (en) | Production method for conductive polymer modified active carbon electrode material of super capacitor | |
| CN106449146B (en) | Application of the graphene oxide-polyaniline composite material of three-dimensional structure in capacitor electrode material | |
| Yavuz et al. | Polypyrrole-coated tape electrode for flexible supercapacitor applications | |
| CN109192527A (en) | It is a kind of using nickel foam as the poly- 3,4- ethene dioxythiophene electrode material for super capacitor of substrate | |
| CN104332639A (en) | Preparation method of co-doped conductive polymer electrode material | |
| CN102930991B (en) | Electrochemistry one-step method prepares the method for graphene/polyaniline conductive composite material | |
| CN108490051A (en) | A kind of flexible miniature is from driving gas at normal temperature sensor and preparation method thereof | |
| CN102426925B (en) | Method for preparing cobalt and zinc doped nickel hydroxide composite electrode material through electrodeposition | |
| CN103198934A (en) | Manufacturing method of composite membrane electrode materials | |
| Ren et al. | REN et al. | |
| Yao et al. | Effect of graphene quantum dots on the capacitance performances of flexible PEDOT: PSS films | |
| CN104505267A (en) | Production method of planar flexible supercapacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Qin Qi Inventor after: He Fang Inventor after: Song Meng Inventor after: Zhang Wangxi Inventor after: Zhang Qian Inventor before: Qin Qi Inventor before: Zhang Wangxi Inventor before: Zhang Qian Inventor before: He Fang |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |