CN103337377B - A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline - Google Patents
A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline Download PDFInfo
- Publication number
- CN103337377B CN103337377B CN201310236525.0A CN201310236525A CN103337377B CN 103337377 B CN103337377 B CN 103337377B CN 201310236525 A CN201310236525 A CN 201310236525A CN 103337377 B CN103337377 B CN 103337377B
- Authority
- CN
- China
- Prior art keywords
- epitaxial growth
- high power
- solution
- power capacity
- modification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Based on a preparation method for the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline, it relates to a kind of preparation method of support film.The poor stability of graphene oxide/polyaniline composite material of the present invention in order to solve existing method and prepare, structure is the technical problem of disordered structure.This method is as follows: one, prepare graphene oxide; Two, the acidifying of aniline; Three, preparation has the powder of graphene/polyaniline micron order composite construction; Four, will there is the powder dissolution of graphene/polyaniline micron order composite construction in water, adopt electrodeposition process, vertical czochralski method, natural sediment method, suction filtration sedimentation or spin-deposit process, to obtain final product.The present invention adopts multiple craft of orientated deposition techniques film forming, makes film have stratiform ordered structure; The film macro manifestations of preparation has good self-supporting performance, and cyclic voltammetry test result shows its capacitance high (can reach 323F/g), good stability.The invention belongs to the preparation field of electrode material.
Description
Technical field
The present invention relates to a kind of preparation method of support film.
Background technology
Ultracapacitor is as a kind of novel energy storage device, have very wide application prospect with its Large Copacity, high power density, strong charging and discharging capabilities, long circulation life, serviceability temperature wide ranges, a lot of significant advantage such as pollution-free at multiple fields, the today facing immense pressure in energy and environment as a kind of novel energy-conserving, energy storage device is developed rapidly.
The exploitation of high performance electrode material is the key factor limiting ultracapacitor development at present, adopts conducting polymer to have important breakthrough as electrode material for the conductivity and capacitance improving ultracapacitor.As a kind of novel conductive material, Graphene has started a research boom with the performance of its excellence since appearance.Graphene is a kind of carbonaceous new material of carbon atom tightly packed one-tenth individual layer bi-dimensional cellular shape lattice structure, is construct zero dimension fullerene, one dimension carbon nano-tube, the elementary cell of said three-dimensional body phase graphite etc.Due to the structure of its uniqueness, Graphene has a lot of excellent characteristic: (theoretical value is 2630m to high-specific surface area
2/ g), excellent conductivity (demonstrating metallicity, is zero gap semiconductor), good thermal stability, high mechanical properties, electro catalytic activity etc.These characteristics make Graphene have extensive use in ultracapacitor, lithium ion battery, solar cell, sensor.
Polyaniline is as studying conducting polymer the most widely at present, with its good thermal stability, chemical stability and electrochemical reversibility, excellent microwave absorption performance, potential solution and melt-processable, the characteristics such as unique doping phenomenon are also had to be considered to have most at present the conducting polymer of application prospect.In addition, monomer whose raw material is easy to get, simple synthetic method, material based on it, developing many new technologies at present, such as ultracapacitor, APollution prevention technology for ships, solar cell, electromangnetic spectrum, antistatic technology, electrochromism, sensor element and catalysis material etc.
The patent application " graphene oxide/polyaniline super capacitor composite electrode material and preparation method thereof, purposes " of the publication number CN1015227202A that the people such as Hao Qingli applied on April 24th, 2009, simple in-situ polymerization is carried out by being added drop-wise in graphene solution by aniline, make to be combined by Van der Waals force between bi-material, thus the stability of obtained graphene oxide/polyaniline composite material cannot be guaranteed, and graphene oxide is not reduced, affect conductivity of composite material, make capacitance less; In the patent application " a kind of grapheme/polyaniline nanometer fibrous composite material and preparation method thereof and the application on ultracapacitor " of the publication number CN102558857A that the people such as Yu Mei applied on November 23rd, 2011, the super capacitance electrode material of preparation is fibrous composite, make polyaniline and Graphene contact area little, affect capacitive property.In addition, the standby structure of above-mentioned two sections of patent systems is disordered structure, due to isotropic impact, make material cannot play whole capacitive properties, and material is without self-supporting, is unfavorable for practical application.
Summary of the invention
The object of the invention is the poor stability in order to solve graphene oxide/polyaniline composite material prepared by existing method, structure is the technical problem of disordered structure, provides a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8being mixed and heated to 80 DEG C with 1g phosphorus pentoxide, to add dried graphite powder solution be black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under the 0-4 DEG C of condition stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 95-98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out centrifuge washing with the hydrochloric acid that concentration is 0.1mol/L and can not produce BaCl to washing lotion
2precipitation, be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, then powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.01-50mg/ml,
Two, be dissolved in acid by aniline, aniline is 1: 1-100 with the volume ratio of acid, obtains the aniline of acidifying;
Acid described in step 2 is the composition of one or more in sulfuric acid, nitric acid, hydrochloric acid and glacial acetic acid;
Three, be the ratio of 1: 1-3000 according to the volume ratio of aniline and graphene oxide solution, the speed that the aniline of acidifying drips with 1-100 per minute under the condition of 0-20 DEG C is joined in graphene oxide solution, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 6-8h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder of graphene/polyaniline micron order composite construction must be had,
Four, will there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 1-100mg/mL, adopt electrodeposition process, vertical czochralski method, natural sediment method, suction filtration sedimentation or spin-deposit process, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Described in step 4, electrodeposition process is as follows:
By Ni sheet thick for 0.2mm or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, dry, then with Ni sheet or ito glass for substrate is inserted in the solution that concentration is 1-100mg/mL, electrophoresis apparatus is adjusted to constant voltage mode, under 1-100V, constant voltage deposition 5-200min, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Described in step 4, vertical czochralski method is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification be substrate, under the condition of 40 DEG C, adopt the pull rate of 10-500um/s, be lift 10-50 time in the solution of 1-100mg/mL in concentration, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
The method of natural sediment described in step 4 is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate insert in the solution that concentration is 1-100mg/mL, under the condition of 45 DEG C, vertical deposition 72h, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
The sedimentation of suction filtration described in step 4 is as follows:
Employing aperture is the filter membrane of 0.22 micron, is that the solution of 1-100mg/mL carries out negative pressure leaching under vacuum pump effect, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline by concentration.
Described in step 4, spin-deposit process is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate utilizes high precision numerical control even glue spin coating instrument in nitrogen atmosphere, with the rotating speed of 200-3000r/s, the rotational time spin coating 30 times of 20s/ time, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
The present invention is by the control of the volume ratio ratio to aniline and graphene oxide solution, the Compound Degree of micron order compound structure film can be regulated and controled at microcosmic, such as 1: 1750 time, calculating and actual measurement show that Microscopic is one deck graphenic surface epitaxial growth one deck polyaniline, when 1: 825, are two surface each epitaxial growth one deck polyanilines of Graphene, in like manner, during other ratios, this epitaxially grown number of plies is different, and different number of plies performances is had any different.
The present invention adopts the standby orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline of hydration legal system, product good dispersion, and in water, dispersion produces without precipitation; Improve conductivity and the thermal stability of polyaniline, wherein thermal stability improves nearly 100 DEG C.
The present invention adopts multiple craft of orientated deposition techniques film forming, makes film have stratiform ordered structure; The size of film can control according to size of foundation base, and film thickness is controlled; The film macro manifestations of preparation has good self-supporting performance, and cyclic voltammetry test result shows its capacitance high (can reach 323F/g), good stability.
The inventive method advantage is:
1, prepare the method simple possible of the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline, raw material is cheaply easy to get, mild condition, and manufacturing cycle is short, and size and the thickness of film are controlled;
2, the orderly high power capacity self-supporting film of the graphenic surface epitaxial growth polyaniline of preparation has good water dispersible and stability;
3, improve the degree of order of graphene/polyaniline laminated film, degree of crystallinity, conductivity and thermal stability, there is the characteristic of self-supporting and high power capacity.
Accompanying drawing explanation
Fig. 1 is the electron microscope shape appearance figure of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline prepared by test one;
Fig. 2 is the XRD figure of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline prepared by test two;
Fig. 3 is the cyclic voltammetry curve under different scanning speed of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline prepared by test two, in figure, A represents the cyclic voltammetry curve based on the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline under 150mV/s sweep speed, B represents the cyclic voltammetry curve based on the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline under 100mV/s sweep speed, C represents the cyclic voltammetry curve based on the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline under 50mV/s sweep speed, D represents the cyclic voltammetry curve based on the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline under 20mV/s sweep speed, E represents the cyclic voltammetry curve based on the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline under 10mV/s sweep speed,
Fig. 4 is the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline prepared by test two, test two preparation based on the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline and the thermal stability analysis curve of polyaniline, in figure, A represents the thermal stability analysis curve of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline prepared by test two, B represents the thermal stability analysis curve of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline prepared by test three, C represents the thermal stability analysis curve of polyaniline,
Fig. 5 is the orderly high power capacity self-supporting film pictorial diagram based on graphenic surface epitaxial growth polyaniline prepared by test four.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the preparation method of a kind of orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline of present embodiment carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8being mixed and heated to 80 DEG C with 1g phosphorus pentoxide, to add dried graphite powder solution be black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under the 0-4 DEG C of condition stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 95-98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out centrifuge washing with the hydrochloric acid that concentration is 0.1mol/L and can not produce BaCl to washing lotion
2precipitation, be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, then powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.01-50mg/ml,
Two, be dissolved in acid by aniline, aniline is 1: 1-100 with the volume ratio of acid, obtains the aniline of acidifying;
Acid described in step 2 is the composition of one or more in sulfuric acid, nitric acid, hydrochloric acid and glacial acetic acid;
Three, be the ratio of 1: 1-3000 according to the volume ratio of aniline and graphene oxide solution, the speed that the aniline of acidifying drips with 1-100 per minute under the condition of 0-20 DEG C is joined in graphene oxide solution, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 6-8h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder (emerald green powder) of graphene/polyaniline micron order composite construction must be had,
Four, will there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 1-100mg/mL, adopt electrodeposition process, vertical czochralski method, natural sediment method, suction filtration sedimentation or spin-deposit process, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
When described in present embodiment, acid is composition, between each composition be arbitrarily than.
Embodiment two: present embodiment and embodiment one are 0.5mg/mL unlike the concentration of graphene oxide solution in step one.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two are as follows unlike electrodeposition process described in step 4:
By Ni sheet thick for 0.2mm or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, dry, then with Ni sheet or ito glass for substrate is inserted in the solution that concentration is 1-100mg/mL, electrophoresis apparatus is adjusted to constant voltage mode, under 1-100V, constant voltage deposition 5-200min, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.Other is not identical with one of embodiment one or two.
Embodiment four: one of present embodiment and embodiment one or two are as follows unlike electrodeposition process described in step 4:
By Ni sheet thick for 0.2mm or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, dry, then with Ni sheet or ito glass for substrate is inserted in the solution that concentration is 10mg/mL, electrophoresis apparatus is adjusted to constant voltage mode, under 30V, constant voltage deposition 30min, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.Other is not identical with one of embodiment one or two.
Embodiment five: present embodiment is as follows unlike czochralski method vertical described in step 4 with one of embodiment one or two:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification be substrate, under the condition of 40 DEG C, adopt the pull rate of 10-500um/s, be lift 10-50 time in the solution of 1-100mg/mL in concentration, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.Other is not identical with one of embodiment one or two.
Embodiment six: present embodiment is as follows unlike czochralski method vertical described in step 4 with one of embodiment one or two:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.1%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification be substrate, under the condition of 40 DEG C, adopt the pull rate of 50um/s, be lift 20 times in the solution of 10mg/mL in concentration, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.Other is not identical with one of embodiment one or two.
Embodiment seven: one of present embodiment and embodiment one or two are as follows unlike the method for natural sediment described in step 4:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate insert in the solution that concentration is 1-100mg/mL, under the condition of 45 DEG C, vertical deposition 72h, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.Other is not identical with one of embodiment one or two.
Embodiment eight: one of present embodiment and embodiment one or two are as follows unlike the sedimentation of suction filtration described in step 4:
Employing aperture is the filter membrane of 0.22 micron, is that the solution of 1-100mg/mL carries out negative pressure leaching under vacuum pump effect, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline by concentration.Other is not identical with one of embodiment one or two.
Embodiment nine: one of present embodiment and embodiment one or two are as follows unlike spin-deposit process described in step 4:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate utilizes high precision numerical control even glue spin coating instrument in nitrogen atmosphere, with the rotating speed of 200-3000r/s, the rotational time spin coating 30 times of 20s/ time, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.Other is not identical with one of embodiment one or two.
Embodiment ten: one of present embodiment and embodiment one or two are as follows unlike spin-deposit process described in step 4:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.1%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate utilizes high precision numerical control even glue spin coating instrument in nitrogen atmosphere, with the rotating speed of 1000r/s, the rotational time spin coating 30 times of 20s/ time, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.Other is not identical with one of embodiment one or two.
Adopt following verification experimental verification effect of the present invention:
Test one:
A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8being mixed and heated to 80 DEG C with 1g phosphorus pentoxide, to add dried graphite powder solution be black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under 1 DEG C of condition stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out centrifuge washing with the hydrochloric acid that concentration is 0.1mol/L and can not produce precipitate B aCl to washing lotion
2be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, then powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.5mg/ml,
Two, 1ml aniline is dissolved in 10ml hydrochloric acid, obtains the aniline of acidifying;
Three, be the ratio of 1: 300 according to the volume ratio of aniline and graphene oxide solution, the aniline of acidifying is joined in graphene oxide solution with the speed of 20 per minute under the condition of 2 DEG C, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 6-8h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder (emerald green powder) of graphene/polyaniline micron order composite construction must be had,
Four, will there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 10mg/mL, by Ni sheet thick for 0.2mm or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, dry, then with Ni sheet or ito glass for substrate is inserted in the solution that concentration is 10mg/mL, electrophoresis apparatus is adjusted to constant voltage mode, and under 30V, constant voltage deposition 30min, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Test two:
A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8being mixed and heated to 80 DEG C with 1g phosphorus pentoxide, to add dried graphite powder solution be black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under 2 DEG C of conditions stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out centrifuge washing with the hydrochloric acid that concentration is 0.1mol/L and can not produce precipitate B aCl to washing lotion
2be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, then powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.5mg/ml,
Two, 1ml aniline is dissolved in 10ml hydrochloric acid, obtains the aniline of acidifying;
Three, be the ratio of 1: 500 according to the volume ratio of aniline and graphene oxide solution, the aniline of acidifying is joined in graphene oxide solution with the speed of 10 per minute under the condition of 2 DEG C, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 8h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder (emerald green powder) of graphene/polyaniline micron order composite construction must be had,
Four, to there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 10mg/mL, by quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.1%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate, under the condition of 40 DEG C, adopt the pull rate of 50um/s, be lift 20 times in the solution of 10mg/mL in concentration, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Test three:
A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8being mixed and heated to 80 DEG C with 1g phosphorus pentoxide, to add dried graphite powder solution be black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under 4 DEG C of conditions stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out centrifuge washing with the hydrochloric acid that concentration is 0.1mol/L and can not produce precipitate B aCl to washing lotion
2be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, then powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.5mg/ml,
Two, 1ml aniline is dissolved in 10ml hydrochloric acid, obtains the aniline of acidifying;
Three, be the ratio of 1: 700 according to the volume ratio of aniline and graphene oxide solution, the aniline of acidifying is joined in graphene oxide solution with the speed of 60 per minute under the condition of 2 DEG C, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 8h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder (emerald green powder) of graphene/polyaniline micron order composite construction must be had,
Four, to there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 10mg/mL, by quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.1%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate is inserted in the solution that concentration is 10mg/mL, under the condition of 45 DEG C, vertical deposition 72h, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Test four:
A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8being mixed and heated to 80 DEG C with 1g phosphorus pentoxide, to add dried graphite powder solution be black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under 3 DEG C of conditions stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out centrifuge washing with the hydrochloric acid that concentration is 0.1mol/L and can not produce precipitate B aCl to washing lotion
2be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, then powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.5mg/ml,
Two, 1ml aniline is dissolved in 10ml hydrochloric acid, obtains the aniline of acidifying;
Three, be the ratio of 1: 300 according to the volume ratio of aniline and graphene oxide solution, the aniline of acidifying is joined in graphene oxide solution with the speed of 50 per minute under the condition of 2 DEG C, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 7h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder (emerald green powder) of graphene/polyaniline micron order composite construction must be had,
Four, will there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 10mg/mL, employing aperture is the filter membrane of 0.22 micron, be that the solution of 10mg/mL carries out negative pressure leaching under vacuum pump effect by concentration, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Test five:
A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8being mixed and heated to 80 DEG C with 1g phosphorus pentoxide, to add dried graphite powder solution be black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under 4 DEG C of conditions stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out centrifuge washing with the hydrochloric acid that concentration is 0.1mol/L and can not produce precipitate B aCl to washing lotion
2be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, then powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.5mg/ml,
Two, 1ml aniline is dissolved in 10ml hydrochloric acid, obtains the aniline of acidifying;
Three, be the ratio of 1: 300 according to the volume ratio of aniline and graphene oxide solution, the aniline of acidifying is joined in graphene oxide solution with the speed of 50 per minute under the condition of 2 DEG C, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 6h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder (emerald green powder) of graphene/polyaniline micron order composite construction must be had,
Four, to there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 10mg/mL, by quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.1%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate utilizes high precision numerical control even glue spin coating instrument in nitrogen atmosphere, with the rotating speed of 1000r/s, the rotational time spin coating of 20s/ time 30 times, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Claims (10)
1., based on a preparation method for the orderly high power capacity self-supporting film of graphenic surface epitaxial growth polyaniline, it is characterized in that a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline carries out according to following steps:
One, graphene oxide is prepared:
By 2g graphite 80 DEG C of dryings, obtain graphite powder, by the 3ml concentrated sulfuric acid, 1gK
2s
2o
8be mixed and heated to 80 DEG C with 1g phosphorus pentoxide and add dried graphite powder, solution is black, when solution colour becomes black-and-blue, insulation 6h, naturally cool to room temperature, dilution, suction filtration, washing is until washing lotion is neutral, natural drying under room temperature, the solution be made up of 1g sodium nitrate and 45ml sulfuric acid is added under the 0-4 DEG C of condition stirred, after stirring 30min, add 6g potassium permanganate, stir 90min, obtain mixed liquor, then mixed liquor is warming up to 35 DEG C, Keep agitation 30min, add deionized water 92ml, be warmed up to 95-98 DEG C again, continue to stir 15min, add 280ml deionized water, add 5ml hydrogen peroxide, stratification, carry out no longer including precipitation in centrifuge washing to washing lotion with the hydrochloric acid that concentration is 0.1mol/L, be 7 by ultra-pure water centrifuge washing to the pH value of washing lotion again, the ultrasonic machine that power is 20KW is put into after adding ultra-pure water, sonic oscillation 40min is to dissolution homogeneity, then centrifugal, and filter residue is dried into powder, again powder ultrasonic is disperseed, obtain graphene oxide solution, the concentration of graphene oxide solution is 0.01-50mg/ml,
Two, be dissolved in acid by aniline, aniline is 1 ﹕ 1-100 with the volume ratio of acid, obtains the aniline of acidifying;
Acid described in step 2 is the composition of one or more in sulfuric acid, nitric acid, hydrochloric acid and glacial acetic acid;
Three, according to the ratio that the volume ratio of aniline and graphene oxide solution is 1 ﹕ 1-3000, the speed that the aniline of acidifying drips with 1-100 per minute under the condition of 0-20 DEG C is joined in graphene oxide solution, constant temperature stirs 20min, ultrasonic 20min, dripping 20ml concentration is that the ammonium persulfate solution of 0.65mol/l is until solution colour becomes black, add 15ml hydrazine hydrate, after ultrasonic process 80min, adding 10ml concentration is 0.1mol/L ammonium persulfate solution, 6-8h is stirred under the condition of 0 DEG C, filter, filter residue is adopted successively distilled water and mass concentration be 1% salt acid elution, finally remove unreacted compound with methyl alcohol, again filter residue is dried in 60 DEG C of vacuum, the powder of graphene/polyaniline micron order composite construction must be had,
Four, will there is the powder dissolution of graphene/polyaniline micron order composite construction in water, obtain the solution that concentration is 1-100mg/mL, adopt electrodeposition process, vertical czochralski method, natural sediment method, suction filtration sedimentation or spin-deposit process, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
2. the preparation method of a kind of orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1, is characterized in that the concentration of graphene oxide solution in step one is 0.5mg/mL.
3. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that described in step 4, electrodeposition process is as follows:
By Ni sheet thick for 0.2mm or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, dry, then with Ni sheet or ito glass for substrate is inserted in the solution that concentration is 1-100mg/mL, electrophoresis apparatus is adjusted to constant voltage mode, under 1-100V, constant voltage deposition 5-200min, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
4. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that described in step 4, electrodeposition process is as follows:
By Ni sheet thick for 0.2mm or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, dry, then with Ni sheet or ito glass for substrate is inserted in the solution that concentration is 10mg/mL, electrophoresis apparatus is adjusted to constant voltage mode, under 30V, constant voltage deposition 30min, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
5. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that described in step 4, vertical czochralski method is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification be substrate, under the condition of 40 DEG C, adopt the pull rate of 10-500um/s, be lift 10-50 time in the solution of 1-100mg/mL in concentration, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
6. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that described in step 4, vertical czochralski method is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.1%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification be substrate, under the condition of 40 DEG C, adopt the pull rate of 50um/s, be lift 20 times in the solution of 10mg/mL in concentration, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
7. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that the method for natural sediment described in step 4 is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate insert in the solution that concentration is 1-100mg/mL, under the condition of 45 DEG C, vertical deposition 72h, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
8. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that the sedimentation of suction filtration described in step 4 is as follows:
Employing aperture is the filter membrane of 0.22 micron, is that the solution of 1-100mg/mL carries out negative pressure leaching under vacuum pump effect, obtains the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline by concentration.
9. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that described in step 4, spin-deposit process is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.01-10%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate utilizes high precision numerical control even glue spin coating instrument in nitrogen atmosphere, with the rotating speed of 200-3000r/s, the rotational time spin coating 30 times of 20s/ time, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
10. a kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline according to claim 1 or 2, is characterized in that described in step 4, spin-deposit process is as follows:
By quartz plate or ito glass acetone, methyl alcohol and ultra-pure water ultrasonic cleaning 20min, then putting into mass concentration is in the sodium dodecyl sulfate solution of 0.1%, ultrasonic 20min, dry, obtain the quartz plate of modification or the ito glass of modification, with the ito glass of the quartz plate of modification or modification for substrate utilizes high precision numerical control even glue spin coating instrument in nitrogen atmosphere, with the rotating speed of 1000r/s, the rotational time spin coating 30 times of 20s/ time, obtain the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310236525.0A CN103337377B (en) | 2013-06-14 | 2013-06-14 | A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310236525.0A CN103337377B (en) | 2013-06-14 | 2013-06-14 | A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103337377A CN103337377A (en) | 2013-10-02 |
| CN103337377B true CN103337377B (en) | 2016-03-16 |
Family
ID=49245516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310236525.0A Active CN103337377B (en) | 2013-06-14 | 2013-06-14 | A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103337377B (en) |
Families Citing this family (7)
| 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 |
| CN105199134A (en) * | 2015-10-12 | 2015-12-30 | 湖北工业大学 | Polyaniline-modified graphene conductive composite film and preparation method thereof |
| 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 |
| CN106479175B (en) * | 2016-12-09 | 2019-08-06 | 东华大学 | A kind of preparation method of self-supporting graphene-polyaniline nano-line composite material |
| CN108057880B (en) * | 2017-11-28 | 2021-06-18 | 上海交通大学 | Method for preparing metal photonic crystal by electrodeposition |
| CN108198699B (en) * | 2017-12-08 | 2019-12-17 | 华东理工大学 | Self-supporting graphene film/polyaniline @ polyaniline composite electrode with hierarchical structure, preparation method and application |
| CN111004390B (en) * | 2018-10-08 | 2022-07-08 | 惠州学院 | Preparation method of graphene/polyaniline composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532891A (en) * | 2011-12-23 | 2012-07-04 | 北京航空航天大学 | Graphene/polyaniline nano-fiber composite material and preparation method and application in super capacitor thereof |
| 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 |
| CN102786705A (en) * | 2012-09-04 | 2012-11-21 | 江南大学 | Method for preparing graphene/polyaniline laminated films on basis of layer-by-layer self-assembly technique |
-
2013
- 2013-06-14 CN CN201310236525.0A patent/CN103337377B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102532891A (en) * | 2011-12-23 | 2012-07-04 | 北京航空航天大学 | Graphene/polyaniline nano-fiber composite material and preparation method and application in super capacitor thereof |
| CN102786705A (en) * | 2012-09-04 | 2012-11-21 | 江南大学 | Method for preparing graphene/polyaniline laminated films on basis of layer-by-layer self-assembly technique |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103337377A (en) | 2013-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103337377B (en) | A kind of preparation method of the orderly high power capacity self-supporting film based on graphenic surface epitaxial growth polyaniline | |
| Rajesh et al. | A high performance PEDOT/PEDOT symmetric supercapacitor by facile in-situ hydrothermal polymerization of PEDOT nanostructures on flexible carbon fibre cloth electrodes | |
| Feng et al. | Facile synthesis of shape-controlled graphene–polyaniline composites for high performance supercapacitor electrode materials | |
| Wang et al. | Polyaniline nanotube arrays as high-performance flexible electrodes for electrochemical energy storage devices | |
| Dubal et al. | All-solid-state flexible thin film supercapacitor based on Mn3O4 stacked nanosheets with gel electrolyte | |
| Cui et al. | Rational construction of a 3D hierarchical NiCo 2 O 4/PANI/MF composite foam as a high-performance electrode for asymmetric supercapacitors | |
| Wu et al. | Highly regulated electrodeposition of needle-like manganese oxide nanofibers on carbon fiber fabric for electrochemical capacitors | |
| Qiao et al. | Self-assembled synthesis of hierarchical waferlike porous Li–V–O composites as cathode materials for lithium ion batteries | |
| CN108364797B (en) | Preparation method of carbon nanotube fabric electrode and yarn electrode and application of electrode | |
| Pawar et al. | Transition of hexagonal to square sheets of Co3O4 in a triple heterostructure of Co3O4/MnO2/GO for high performance supercapacitor electrode | |
| Kuang et al. | Influence of the reaction temperature on polyaniline morphology and evaluation of their performance as supercapacitor electrode | |
| CN102723209A (en) | Preparation method for graphene nanosheet/conducting polymer nanowire composite material | |
| CN110183655A (en) | A kind of preparation method of the organic positive electrode of two dimension carbide crystalline base polyimides | |
| CN110993375B (en) | Method for preparing compact-structure RGO/MXene-sulfuric acid supercapacitor flexible electrode in one step and application thereof | |
| CN104377040A (en) | Electrode applied to electrochemical energy storage device and preparation method thereof | |
| CN106449146B (en) | Application of the graphene oxide-polyaniline composite material of three-dimensional structure in capacitor electrode material | |
| Wang et al. | Advanced supercapacitors based on α-Ni (OH) 2 nanoplates/graphene composite electrodes with high energy and power density | |
| CN104616915A (en) | Graphene-ruthenium oxide composite material preparation method | |
| Wei et al. | Integrating carbon dots with porous hydrogels to produce full carbon electrodes for electric double-layer capacitors | |
| CN105885410A (en) | Molybdenum sulfide/polypyrrole/polyaniline ternary composite material as well as preparation method and application thereof | |
| CN104576080A (en) | One-step electrochemical method for preparing graphene/polyaniline (PANI) flexible electrode | |
| CN106971860A (en) | A kind of MnO2The preparation method of@graphene fiber super capacitor electrode materials | |
| Zhang et al. | Mild synthesis route to nanostructured α-MnO2 as electrode materials for electrochemical energy storage | |
| Sun et al. | Size-refinement enhanced flexibility and electrochemical performance of MXene electrodes for flexible waterproof supercapacitors | |
| CN103474619B (en) | A kind of flexible lithium sulphur battery electrode based on carbon tube bank and preparation method thereof and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |