CN104311798A - Preparation method of conductive polymer film having inverse opal structure - Google Patents
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Abstract
The invention discloses a preparation method of a conductive polymer film having an inverse opal structure. The preparation method comprises that an electrochemical polymerization reaction occurs based on polymeric microspheres (comprising polystyrene microspheres or amino-polystyrene microspheres) as templates, and then the conductive polymer film having an inverse opal structure is obtained by impurity removal treatment and polymeric microsphere removal treatment. The preparation method has simple processes, utilizes the polymeric microspheres as hard templates, and can be carried out at a room temperature without harsh reaction conditions. The prepared conductive polymer film having an inverse opal structure has tidy morphology and good structural environment stability.
Description
(1) technical field
The present invention relates to the preparation method of conducting polymer nano material, particularly relate to a kind of preparation method with the conductive polymers electrochomeric films of counter opal structure.
(2) background technology
Along with the development of science and technology, the development of material is day by day tending towards nm regime.Nanometer scale science and technology just demonstrates wide application prospect in information, the energy, environment, chemistry, microelectronics, micro-manufacture, biology, medical science and national defence etc.In the past few decades, the development of inorganic nano material obtains the extensive concern of people, and particularly in preparation method and morphology control, scientific research personnel has carried out a series of deep research.In recent years, the Synthesis and applications of polymer nano material has attracted the interest of people.Polymer nano material has unique photoelectricity performance, good electroconductibility, is easy to realize the advantages such as big area preparation and lower production cost, huge commercial promise is presented, so become the study hotspot of current nano material in photodiode, sensor, indicating meter and solar cell etc.But the finiteness of polymer nano material and complicated preparation process limit its commercial applications.The preparation method of current polymer nano material mainly contains:
(1) hard template method: be prepare the most frequently used method of polymer nano material, usually adopt anodic oxidation aluminium formwork, polycarbonate template and zeolite template etc.
Martin (Nature 1994,369:298; Chem.Mater.1994,6:1627,1996,8:2382) etc. people adopt hard template method, utilize chemical oxidising polymerisation or electrochemical polymerization to prepare polypyrrole, polyaniline and poly-3 methyl thiophene nanotube.
The people (Chem.Commun.2004,882) such as Jyongsik Jang adopt anodised aluminium as template, and have prepared polypyrrole nanotube in conjunction with vapour deposition process.Wherein, the thickness of nanotube can accurately control in the size range of several nanometer.
The nanostructure that hard template method obtains has higher environmental stability, and this method accurately can control size and the pattern of nano material.
(2) soft template method: usually adopt tensio-active agent, liquid crystal and biomolecules etc.
The people (Adv.Funct.Mater.2007,17,431) such as Hyeonseok Yoon adopt AOT molecule to form cylindrical micelle, in non-polar solvent with under the acting in conjunction of iron positively charged ion, prepare polypyrrole nanotube.Wherein iron positively charged ion is used as the oxygenant in chemical polymerization, and AOT micella can be surperficial at it by iron cation-adsorption, to promote carrying out smoothly of reaction.
The form of soft template compares diversity, constructs than being easier to, not needing complicated equipment.But this method less stable, template efficiency is not high.
(3) non-template method: mainly comprise electrochemical polymerization method, chemical polymerization, interfacial polymerization etc.
The people such as Lange (Syn.Met.2001,121,1319) adopt electrochemical polymerization method to prepare polyaniline micro nanometer fiber, wherein using fullerene derivate as hotchpotch.
The people such as Kaner (J.Am.Chem.Soc.2003,125,314) adopt interfacial polymerization, have obtained polyaniline nano fiber under vacuum.Wherein, the diameter of nanofiber is 30-50nm, and length is that 500nm is to several microns.This method is on the basis of chemical oxidising polymerisation, under strongly acidic conditions, take ammonium peroxydisulfate as oxygenant, completes under the system of immiscible water/organic solvent.
Non-template method is without any need for template, and preparation process is fairly simple, convenient, but specific aim is stronger, only has limited material and material could adopt this kind of method.
Comprehensive above-mentioned consideration, adopting polystyrene microsphere hard template method to prepare conducting polymer nano material is desirable selection.
(3) summary of the invention
The object of the invention is to provide a kind of method that preparation easy, with low cost has the conducting polymer thin film of counter opal structure.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
The described conducting polymer thin film with counter opal structure is at polymer microballoon (polystyrene microsphere or aminopolystyrene microballoon) for electrochemical polymerization is carried out on the basis of template, so closes the conducting polymer thin film by going template dissolve polymer microsphere template to obtain having counter opal structure; Its preparation method specifically comprises the following steps:
(1) cleaning is being passed through, even tiling one layer of polymeric microballoon on dry sheet ito glass electrode or ITO-PET flexible electrode, described polymer microballoon is polystyrene microsphere or aminopolystyrene microballoon, ito glass electrode or ITO-PET flexible electrode is slowly made to tilt to plumbness after horizontal positioned 30 ~ 40s, bottom again ito glass electrode or ITO-PET flexible electrode after 10 ~ 20s is put into deionized water and (is collected at electrode base owing to vertically placing rear unnecessary microballoon powder, therefore only electrode base need be put into water) make excess polymer microballoon be distributed to deionized water, finally ito glass is left the water and vertically dry, namely the ito glass electrode containing polymer microballoon template layer or ITO-PET flexible electrode is obtained,
(2) electroanalysis solvent, conductive polymers monomer and supporting electrolyte are added in three-electrode cell be mixed with electrolytic solution, in described electrolytic solution, the starting point concentration of conductive polymers monomer is 0.001 ~ 0.01mol/L, and the concentration of supporting electrolyte is 0.001 ~ 0.1mol/L; Described three-electrode cell with step (1) prepare containing polymer microballoon template layer ito glass electrode or or ITO-PET flexible electrode for working electrode, with gold or platinum electrode for supporting electrode, take silver-silver chloride electrode as reference electrode; Electrolytic solution adopts potentiostatic method to be polymerized in three-electrode cell, polyreaction is carried out under constant potential 1.2 ~ 1.5V condition, in conductive polymers galvanic deposit micro polymer sphere gap on the working electrode (s, when polymerization consumes power reaches 0.02 ~ 0.04C, polymerization terminates, and be polymerized to carry out to working electrode priority the conducting polymer thin film that dedoping process and de-polymer microballoon process obtain having counter opal structure afterwards.
In the present invention, ito glass electrode or ITO-PET flexible electrode adopt commercial goods, general commercial goods is sheet, those skilled in the art can cut into certain size as required, make in the operation of an electrode surface coverage polymer microballoon template layer in step (1), general needs realizes covering completely, but by electrodes conduct face topmost the area area of 1/4th (such as nearly) reserve, be used for pressing from both sides clip when testing and connect electrochemical workstation.
Further, the present invention can control the size of the anti-protein structure of the conducting polymer thin film obtained by the aperture controlling polymer microballoon, the aperture of preferred described polymer microballoon is 600-1000nm, to prepare the eurypyloue conducting polymer thin film of tool, aperture can be selected to be the microballoon of 1.0-6.0 μm of size or other different pore size.
Further, in described step (2), the monomer of conductive polymers preferably has the monomer of the conductive polymers of electrochromism function, be more preferably one of following: 1,4-bis-(2-thiophene) benzene, 1,4-bis-(3-thiophene) benzene or (three (4-(2-thiophene)) triphenylamine), the organic electrochromic material such as thiophene-based and phenyl amines can prepare nano-porous structure by this method substantially.
Further, in described step (2), electroanalysis solvent is preferably acetonitrile.
Further, in described step (2), supporting electrolyte is preferably tetrabutylammonium perchlorate, lithium perchlorate or 4-butyl ammonium fluoroborate.Described supporting electrolyte concentration is in the electrolytic solution preferably 0.01 ~ 0.1mol/L.
Further, in described step (2), reference electrode is biliquid direct type silver/silver chloride electrode, is that the first liquid connects with saturated potassium chloride solution, is that the second liquid connects with supporting electrolyte and corresponding electroanalysis solvent.
Further, in described step (2), polyreaction is carried out under constant potential 1.2 ~ 1.5V condition, is polymerized and terminates when polymerization consumes power reaches 0.02 ~ 0.04C.The thickness of polymeric film can be controlled by constant potential and the state modulator of polymerization consumes power, more than 0.04C, anti-protein structure cannot be obtained.
Further, in described step (2), the concrete grammar of dedoping process is: under current potential-0.4 ~-0.6V, working electrode after polyreaction is directly carried out a dedoping process 200 ~ 300s in the electrolytic solution, then by the working electrode electrolysis solvent wash after a dedoping process, again in the blank solution be made up of supporting electrolyte and electroanalysis solvent, under current potential-0.4 ~-0.6V, carry out secondary dedoping process 200 ~ 300s, obtain the conducting polymer thin film working electrode with microsphere template; In described blank solution, the concentration of supporting electrolyte is 0.001 ~ 0.1mol/L.
Further, in described step (2), the concrete grammar of de-polystyrene microsphere process is: the conducting polymer thin film working electrode with microsphere template is put into template agent removing immersion 24 ~ 48h and polystyrene microsphere is dissolved, finally obtain the conducting polymer thin film with counter opal structure.
Further, described template agent removing is can dissolve polymer microballoon but can not dissolve the material of obtained conductive polymers, is preferably one of following: toluene, tetrahydrofuran (THF).
The present invention is characterized by scanning electron microscope (SEM) pattern to polymeric film, confirms the formation of counter opal structure.
Compared with prior art, the beneficial effect with the preparation method of the conductive polymers electrochomeric films of counter opal structure described in the present invention is mainly reflected in:
(1) preparation method of the present invention is easy, with polystyrene microsphere or aminopolystyrene microballoon for hard template, the counter opal structure conducting polymer thin film pattern of preparation is relatively more neat, structural environment good stability, and do not need harsh reaction conditions, just can operate under room temperature.
(2) the counter opal structure conducting polymer thin film be attached on electrode electrochemically prepared, can directly be used for doing various test, avoids the complex process wanting wiring solution-forming film when product that chemical oxidising polymerisation obtains does various test.
(3) aperture and electrochemical parameter by controlling polymer microballoon can control pattern and the thickness of polymeric film.
(4) polymer monomer by controlling to add can prepare the conductive polymers electrochomeric films of counter opal structure, namely distinct colors change can be produced under different applying current potentials, thus indicating meter can be applied to, the field such as smart window, Electronic Paper.
(5) conducting polymer thin film of the counter opal structure prepared has vesicular structure, increase the specific surface area of polymeric film, shorten the distance that counterion in electrolytic solution enters film, thus improve color conversion speed, improve electrochromic property, be more conducive to its practical application.
(4) accompanying drawing explanation
Fig. 1 is that the polystyrene microsphere single tier templates SEM that the embodiment of the present invention 1 obtains schemes (10.0K);
Fig. 2 is that the polystyrene microsphere single tier templates SEM that the embodiment of the present invention 1 obtains schemes (20.0K);
Fig. 3 is that the conducting polymer thin film SEM with counter opal structure that the embodiment of the present invention 1 obtains schemes (10.0K);
Fig. 4 is that the conducting polymer thin film SEM with counter opal structure that the embodiment of the present invention 1 obtains schemes (20.0K);
Fig. 5 a-5d has the conducting polymer thin film (OP PBTB) of counter opal structure and original conductive polymers (PBTB) film performance comparison diagram;
Fig. 6 is that the conducting polymer thin film SEM with counter opal structure that the embodiment of the present invention 2 obtains schemes (10.0K);
Fig. 7 is that the conducting polymer thin film SEM of the concrete counter opal structure that the embodiment of the present invention 2 obtains schemes (20.0K);
Fig. 8 is that the conducting polymer thin film SEM with counter opal structure that the embodiment of the present invention 3 obtains schemes (10.0K);
Fig. 9 is that the conducting polymer thin film SEM with counter opal structure that the embodiment of the present invention 3 obtains schemes (20.0K);
Figure 10 is that the conducting polymer thin film SEM with counter opal structure that the invention process 4 obtains schemes (20.0K);
Figure 11 is the PBTB/PS composite membrane (20.0K) prepared under polymerization electricity is greater than 0.04C that the invention process 4 obtains.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
The present invention adopts template and constant potential polymerization to prepare counter opal structure conducting polymer thin film, and carries out UV-Vis spectrum test, contrast gradient and time of response test to it.The instrument adopted in whole preparation and test process is electrochemical workstation (CHI660C, Shanghai Chen Hua instrument company), ultraviolet-visible spectrometer (VU-1800, Shimadzu Corporation of Japan) and scanning electronic microscope (Hitachi S-4800, FDAC electronics corporation).
Embodiment 1
Monomer is Isosorbide-5-Nitrae-two (2-thiophene) benzene (BTB), and its structure is as follows:
Operating process:
(1) preparation of polystyrene microsphere single tier templates: be dry area after the ito glass ultrasonic cleaning of 2cm × 4cm, and to take a morsel polystyrene microsphere (2.5%w/v with dropper, microballoon aperture 600nm) the even tiling one deck area of clip (be used for when reserving follow-up test press from both sides) on ito glass, then slowly plumbness is tilted to by after its horizontal positioned 30 ~ 40s, bottom again ito glass after 10 ~ 20s put into fill deionized water culture dish then unnecessary polystyrene microsphere can disperse in deionized water rapidly, finally lifted out the water surface and vertically dried the single tier templates just obtaining polystyrene microsphere and be self-assembled into, and scanning electron microscope (SEM) test (Fig. 1 is carried out to it, shown in 2).
(2) preparation of counter opal structure conducting polymer thin film: monomer (0.0001mol) and tetrabutylammonium perchlorate (TBuA ion is 1:1 with the mol ratio of perchlorate) (0.005mol) are mixed with acetonitrile, is mixed with the mixing solutions 50mL that monomer A is 0.002mol/L, supporting electrolyte concentration 0.1mol/L.Adopt tetrabutylammonium perchlorate's (mol ratio of TBuA ion and perchlorate is 1:1) as supporting electrolyte, three-electrode system selected by electrolyzer, using the ITO conductive glass containing polystyrene microsphere template as working electrode (ito glass as working electrode removes edge section and is cut to 0.9cm × 4cm size before electrochemical polymerization), using polished platinized platinum (surface-brightening is smooth) as supporting electrode (Pt, 2cm × 2cm), reference electrode adopts biliquid direct type silver/silver chloride electrode (Ag/AgCl, saturated potassium chloride solution connects as the first liquid, the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate connects as the second liquid).Under room temperature (25 DEG C) condition, constant potential polymerization is adopted to prepare polymeric film on polystyrene moulding, namely be polymerized under polymerization potential is 1.30V vs.Ag/AgCl, consumes power is 0.03C, after polymerization terminates, working electrode surface deposited the polymeric film of blue layer, dedoping process is carried out to obtained polymeric film, namely in same electrolytic solution, controlling potential is-0.6V vs.Ag/AgCl, a dedoping process 300s is carried out to the working electrode after polyreaction, find that color changes yellow into by blueness, and then by the acetonitrile drip washing 5 times of the working electrode after a dedoping process, in blank solution (i.e. the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate), controlling dedoping current potential is again-0.6V vs.Ag/AgCl, time is 200s, carry out the process of secondary dedoping, obtain the working electrode depositing polymeric film and polystyrene microsphere template.Finally, working electrode obtained above is put into culture dish, pour a certain amount of toluene into, take out after placing 24h, because toluene p-poly-phenyl ethene microballoon has good solubility, finally obtain the conducting polymer thin film with counter opal structure, scanning electron microscope (SEM) test (Fig. 3, shown in 4) is carried out to it.Finally, using the conducting polymer thin film (OP PBTB) of the counter opal structure obtained and pure conducting polymer thin film (PBTB) (pure conducting polymer thin film is the film adopting identical condition Direct Electrochemistry to be polymerized the non-porous structure obtained when not using polystyrene microsphere film on ito glass) as working electrode, electrochemical workstation and ultraviolet-visible spectrometer is utilized to carry out the test (shown in Fig. 5 a-5d) of electrochromic property to it.Find at wavelength to be that 1100nm place is reduced to 0.5s from 1.0s its time of response of fading, the painted time of response has been reduced to 3.1s from 3.6s; And be 620nm place at wavelength, time of response of fading has been reduced to 0.7s from 1.6s, and the painted time of response has been reduced to 3.6s from 4.5s, therefrom we can find out that electrochromic conducting polymer material is prepared into counter opal nano-porous structure can significantly improve its electrochromism response speed.
Embodiment 2
Monomer is Isosorbide-5-Nitrae-two (3-thiophene) benzene, and its structure is as follows:
Electrolytic solution is identical with embodiment 1 with blank solution, and polymerization electricity becomes 0.035C.
Operating process:
(1) preparation of polystyrene microsphere single tier templates: be dry area after the ito glass ultrasonic cleaning of 2cm × 4cm, and to take a morsel polystyrene microsphere (2.5%w/v with dropper, microballoon aperture 600nm) to be evenly laid on ito glass (area being used for pressing from both sides clip when reserving follow-up test), then slowly plumbness is tilted to by after its horizontal positioned 30 ~ 40s, bottom again ito glass after 10 ~ 20s put into fill deionized water culture dish then unnecessary polystyrene microsphere can disperse in deionized water rapidly, finally lifted out the water surface and vertically dried the single tier templates just obtaining polystyrene microsphere and be self-assembled into.
(2) preparation of counter opal structure conducting polymer thin film: monomer A (0.0001mol) and tetrabutylammonium perchlorate (TBuA ion is 1:1 with the mol ratio of perchlorate) (0.005mol) are mixed with acetonitrile, is mixed with the mixing solutions 50mL that monomer A is 0.002mol/L, supporting electrolyte concentration 0.1mol/L.Adopt tetrabutylammonium perchlorate's (mol ratio of TBuA ion and perchlorate is 1:1) as supporting electrolyte, three-electrode system selected by electrolyzer, using the ITO conductive glass containing polystyrene moulding as working electrode (ito glass as working electrode removes edge section and is cut to 0.9cm × 4cm size before electrochemical polymerization), using polished platinized platinum (surface-brightening is smooth) as supporting electrode (Pt, 2cm × 2cm), reference electrode adopts biliquid direct type silver/silver chloride electrode (Ag/AgCl, saturated potassium chloride solution connects as the first liquid, the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate connects as the second liquid).Under room temperature (25 DEG C) condition, constant potential polymerization is adopted to prepare polymeric film on polystyrene moulding, namely be polymerized under polymerization potential is 1.30V vs.Ag/AgCl, consumes power is 0.035C, after polymerization terminates, working electrode surface deposited the polymeric film of blue layer, dedoping process is carried out to obtained polymeric film, namely in same electrolytic solution, controlling potential is-0.6V vs.Ag/AgCl, a dedoping process 300s is carried out to the working electrode after polyreaction, find that color changes yellow into by blueness, and then by the acetonitrile drip washing 5 times of the working electrode after a dedoping process, in blank solution (i.e. the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate), controlling dedoping current potential is again-0.6V vs.Ag/AgCl, time is 200s, carry out the process of secondary dedoping, obtain the working electrode depositing polymeric film and polystyrene microsphere template.Finally, working electrode obtained above is put into culture dish, pour a certain amount of toluene solution into, take out after placing 24h, because toluene p-poly-phenyl ethene microballoon has good solubility, finally obtain the conducting polymer thin film with counter opal structure, scanning electron microscope (SEM) test (Fig. 6, shown in 7) is carried out to it.Owing to being polymerized the increase of electricity, the thickness with the conducting polymer thin film of counter opal structure obtained can being made to increase to some extent, although a some holes can be override, substantially can not affect the electrochromic property of film.
Embodiment 3
Monomer is (three (4-(2-thiophene)) triphenylamine), and its structure is as follows:
Electrolytic solution is identical with embodiment 1 with blank solution, changes the amino polystyrene microsphere (600-1000nm2.5%w/v) of band into unlike microballoon.
Operating process:
(1) preparation of aminopolystyrene microballoon single tier templates: be dry area after the ito glass ultrasonic cleaning of 2cm × 4cm, and to take a morsel aminopolystyrene microballoon (2.5%w/v with dropper, 600nm) be evenly laid on ito glass and (when reserving follow-up test, be used for pressing from both sides the area of clip), then slowly plumbness is tilted to by after its horizontal positioned 30 ~ 40s, bottom again ito glass after 10 ~ 20s put into fill deionized water culture dish then unnecessary aminopolystyrene microballoon can disperse in deionized water rapidly, finally lifted out the water surface and vertically dried the single tier templates just obtaining aminopolystyrene microballoon and be self-assembled into.
(2) preparation of counter opal structure conducting polymer thin film: monomer A (0.0001mol) and tetrabutylammonium perchlorate (TBuA ion is 1:1 with the mol ratio of perchlorate) (0.005mol) are mixed with acetonitrile, is mixed with the mixing solutions 50mL that monomer A is 0.002mol/L, supporting electrolyte concentration 0.1mol/L.Adopt tetrabutylammonium perchlorate's (mol ratio of TBuA ion and perchlorate is 1:1) as supporting electrolyte, three-electrode system selected by electrolyzer, using the ITO conductive glass containing aminopolystyrene template as working electrode (ito glass as working electrode removes edge section and is cut to 0.9cm × 4cm size before electrochemical polymerization), using polished platinized platinum (surface-brightening is smooth) as supporting electrode (Pt, 2cm × 2cm), reference electrode adopts biliquid direct type silver/silver chloride electrode (Ag/AgCl, saturated potassium chloride solution connects as the first liquid, the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate connects as the second liquid).Under room temperature (25 DEG C) condition, constant potential polymerization is adopted to prepare polymeric film on polystyrene moulding, namely be polymerized under polymerization potential is 1.30V vs.Ag/AgCl, consumes power is 0.03C, after polymerization terminates, working electrode surface deposited the polymeric film of blue layer, dedoping process is carried out to obtained polymeric film, namely in same electrolytic solution, controlling potential is-0.6V vs.Ag/AgCl, a dedoping process 300s is carried out to the working electrode after polyreaction, after finding that color changes, and then by the acetonitrile drip washing 5 times of the working electrode after a dedoping process, in blank solution (i.e. the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate), controlling dedoping current potential is again-0.6V vs.Ag/AgCl, time is 200s, carry out the process of secondary dedoping, obtain the working electrode depositing polymeric film and polystyrene microsphere template.Finally, working electrode obtained above is put into culture dish, pour a certain amount of toluene solution into, take out after placing 24h, because toluene p-poly-phenyl ethene microballoon has good solubility, finally obtain the conducting polymer thin film with counter opal structure, scanning electron microscope (SEM) test (Fig. 8, shown in 9) is carried out to it.
Embodiment 4
Monomer is Isosorbide-5-Nitrae-two (2-thiophene) benzene (BTB), and its structure is as follows:
Electrolytic solution is identical with embodiment 1 with blank solution, is promoted to 0.04C unlike polymerization electricity.
Operating process:
(1) preparation of polystyrene microsphere single tier templates: be dry area after the ito glass ultrasonic cleaning of 2cm × 4cm, and to take a morsel polystyrene microsphere (2.5%w/v with dropper, microballoon aperture 600nm) the even tiling one deck area of clip (be used for when reserving follow-up test press from both sides) on ito glass, then slowly plumbness is tilted to by after its horizontal positioned 30 ~ 40s, bottom again ito glass after 10 ~ 20s put into fill deionized water culture dish then unnecessary polystyrene microsphere can disperse in deionized water rapidly, finally lifted out the water surface and vertically dried the single tier templates just obtaining polystyrene microsphere and be self-assembled into.
(2) preparation of counter opal structure conducting polymer thin film: monomer (0.0001mol) and tetrabutylammonium perchlorate (TBuA ion is 1:1 with the mol ratio of perchlorate) (0.005mol) are mixed with acetonitrile, is mixed with the mixing solutions 50mL that monomer A is 0.002mol/L, supporting electrolyte concentration 0.1mol/L.Adopt tetrabutylammonium perchlorate's (mol ratio of TBuA ion and perchlorate is 1:1) as supporting electrolyte, three-electrode system selected by electrolyzer, using the ITO conductive glass containing polystyrene microsphere template as working electrode (ito glass as working electrode removes edge section and is cut to 0.9cm × 4cm size before electrochemical polymerization), using polished platinized platinum (surface-brightening is smooth) as supporting electrode (Pt, 2cm × 2cm), reference electrode adopts biliquid direct type silver/silver chloride electrode (Ag/AgCl, saturated potassium chloride solution connects as the first liquid, the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate connects as the second liquid).Under room temperature (25 DEG C) condition, constant potential polymerization is adopted to prepare polymeric film on polystyrene moulding, namely be polymerized under polymerization potential is 1.30V vs.Ag/AgCl, consumes power is 0.04C, after polymerization terminates, working electrode surface deposited the polymeric film of blue layer, dedoping process is carried out to obtained polymeric film, namely in same electrolytic solution, controlling potential is-0.6V vs.Ag/AgCl, a dedoping process 300s is carried out to the working electrode after polyreaction, find that color changes yellow into by blueness, and then by the acetonitrile drip washing 5 times of the working electrode after a dedoping process, in blank solution (i.e. the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate), controlling dedoping current potential is again-0.6V vs.Ag/AgCl, time is 200s, carry out the process of secondary dedoping.Finally, working electrode obtained above is put into culture dish, pour a certain amount of toluene into, take out after placing 24h, because toluene p-poly-phenyl ethene microballoon has good solubility, finally obtain the conducting polymer thin film with counter opal structure.(shown in Figure 10).It is to be noted when polymerization electricity is greater than 0.04C, the PBTB film obtained can be caused to start to cover PS microballoon on a large scale, so just cannot prepare counter opal structure (shown in Figure 11).
Claims (9)
1. there is a preparation method for the conducting polymer thin film of counter opal structure, comprise the steps:
(1) cleaning is being passed through, even tiling one layer of polymeric microballoon on dry sheet ito glass electrode or ITO-PET flexible electrode, described polymer microballoon is polystyrene microsphere or aminopolystyrene microballoon, ito glass electrode or ITO-PET flexible electrode is slowly made to tilt to plumbness after horizontal positioned 30 ~ 40s, deionized water is put in bottom again ito glass electrode or ITO-PET flexible electrode after 10 ~ 20s makes excess polymer microballoon be distributed to deionized water, finally ito glass is left the water and vertically dry, namely the ito glass electrode containing polymer microballoon template layer or ITO-PET flexible electrode is obtained,
(2) electroanalysis solvent, conductive polymers monomer and supporting electrolyte are added in three-electrode cell be mixed with electrolytic solution, in described electrolytic solution, the starting point concentration of conductive polymers monomer is 0.001 ~ 0.01mol/L, and the concentration of supporting electrolyte is 0.001 ~ 0.1mol/L; Described three-electrode cell with step (1) prepare containing polymer microballoon template layer ito glass electrode or or ITO-PET flexible electrode for working electrode, with gold or platinum electrode for supporting electrode, take silver-silver chloride electrode as reference electrode; Electrolytic solution adopts potentiostatic method to be polymerized in three-electrode cell, polyreaction is carried out under constant potential 1.2 ~ 1.5V condition, in conductive polymers galvanic deposit micro polymer sphere gap on the working electrode (s, when polymerization consumes power reaches 0.02 ~ 0.04C, polymerization terminates, and be polymerized to carry out to working electrode priority the conducting polymer thin film that dedoping process and de-polymer microballoon process obtain having counter opal structure afterwards.
2. preparation method as claimed in claim 1, is characterized in that: the aperture of described polymer microballoon is 600-1000nm.
3. preparation method as claimed in claim 1, it is characterized in that: in described step (2), conductive polymers monomer is the conductive polymers monomer with electrochromism function.
4. preparation method as claimed in claim 3, it is characterized in that: conductive polymers monomer is selected from one of following: 1,4-bis-(2-thiophene) benzene, Isosorbide-5-Nitrae-two (3-thiophene) benzene, (three (4-(2-thiophene)) triphenylamine).
5. preparation method as claimed in claim 1, it is characterized in that: in described step (2), electroanalysis solvent is acetonitrile.
6. preparation method as claimed in claim 1, it is characterized in that: in described step (2), supporting electrolyte is tetrabutylammonium perchlorate, lithium perchlorate or 4-butyl ammonium fluoroborate.
7. the preparation method as described in one of claim 1 ~ 6, it is characterized in that: in described step (2), the concrete grammar of dedoping process is: under current potential-0.4 ~-0.6V, working electrode after polyreaction is directly carried out a dedoping process 200 ~ 300s in the electrolytic solution, then by the working electrode electrolysis solvent wash after a dedoping process, again in the blank solution be made up of supporting electrolyte and electroanalysis solvent, secondary dedoping process 200 ~ 300s is carried out under current potential-0.4 ~-0.6V, obtain the conducting polymer thin film working electrode with microsphere template, in described blank solution, the concentration of supporting electrolyte is 0.001 ~ 0.1mol/L.
8. the preparation method as described in one of claim 1 ~ 6, it is characterized in that: in described step (2), the concrete grammar of de-polystyrene microsphere process is: the conducting polymer thin film working electrode with microsphere template is put into template agent removing immersion 24 ~ 48h and polystyrene microsphere is dissolved, finally obtain the conducting polymer thin film with counter opal structure.
9. preparation method as claimed in claim 8, is characterized in that: described template agent removing is one of following: toluene, tetrahydrofuran (THF).
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| CN104610544A (en) * | 2015-02-16 | 2015-05-13 | 哈尔滨工业大学 | Preparation method of thermal-control polyimide material and method for preparing devices from material |
| CN109289540A (en) * | 2018-09-21 | 2019-02-01 | 武汉纺织大学 | Has micropore-nano pore structure nanofiber porous membrane and preparation method thereof |
| CN110850584A (en) * | 2019-11-29 | 2020-02-28 | 京东方科技集团股份有限公司 | Electronic paper display device and electronic equipment |
| CN112842333A (en) * | 2020-12-31 | 2021-05-28 | 华中科技大学 | Visual glucose concentration detection microneedle patch, preparation method and application |
| CN112969309A (en) * | 2020-08-28 | 2021-06-15 | 重庆康佳光电技术研究院有限公司 | Welding method of circuit board and light-emitting device, display module, panel and welding flux |
| CN115368879A (en) * | 2022-09-22 | 2022-11-22 | 南京工程学院 | High-thermal-conductivity film material and preparation method thereof |
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| CN104610544A (en) * | 2015-02-16 | 2015-05-13 | 哈尔滨工业大学 | Preparation method of thermal-control polyimide material and method for preparing devices from material |
| CN109289540A (en) * | 2018-09-21 | 2019-02-01 | 武汉纺织大学 | Has micropore-nano pore structure nanofiber porous membrane and preparation method thereof |
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| CN112969309B (en) * | 2020-08-28 | 2022-04-19 | 重庆康佳光电技术研究院有限公司 | Welding method of circuit board and light-emitting device, display module, panel and welding flux |
| CN112842333A (en) * | 2020-12-31 | 2021-05-28 | 华中科技大学 | Visual glucose concentration detection microneedle patch, preparation method and application |
| CN115368879A (en) * | 2022-09-22 | 2022-11-22 | 南京工程学院 | High-thermal-conductivity film material and preparation method thereof |
| CN115368879B (en) * | 2022-09-22 | 2024-01-30 | 南京工程学院 | High-heat-conductivity film material and preparation method thereof |
| CN115745424A (en) * | 2022-11-14 | 2023-03-07 | 广州天赐高新材料股份有限公司 | Porous conductive polymer material and preparation method and application thereof |
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