CN100395646C - Electrochromism device with polyaniline-polyvinyl alcohol compound film and preparation method thereof - Google Patents
Electrochromism device with polyaniline-polyvinyl alcohol compound film and preparation method thereof Download PDFInfo
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- CN100395646C CN100395646C CNB2005101106930A CN200510110693A CN100395646C CN 100395646 C CN100395646 C CN 100395646C CN B2005101106930 A CNB2005101106930 A CN B2005101106930A CN 200510110693 A CN200510110693 A CN 200510110693A CN 100395646 C CN100395646 C CN 100395646C
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Abstract
The present invention belongs to the technical field of off-color material, and particularly relates to an electrochromic device with a polyaniline and polyvinyl alcohol compound film and a preparing method thereof which has the advantages of simple technology and easy control. The performance of the polyaniline and polyvinyl alcohol compound film can be changed by changing monomer concentration and the species of acid to be doped. Compared with a polyaniline film, the polyaniline and polyvinyl alcohol compound film has good mechanical performance and bonding performance, good electric activity and short response time, reversibly changes the color from no color to purple under the action of external voltage, and has long cyclic service life. The color of the electrochromic device assembled by the compound film is changed into no color, yellow, green, blue and purple in different electric potentials, the transmittivity in the position of 600 nm is changed from 38% to 75%, and the cyclic service life of the device reaches 1327 times.
Description
Technical field
The invention belongs to the off-color material technical field, be specifically related to a kind of preparation method who contains the electrochromic device of polyaniline-polyvinyl alcohol composite membrane.
Background technology
The electrochromism phenomenon is meant that the optical property of material with extra electric field reversible variation takes place, and utilizes this character of material can be made into the adjustable electrochomeric glass device of color and light penetration or reflectivity.Traditional electrochromic device is made up of base plate glass and electrochromic system; sheet glass is selected transparent ITO (tin indium oxide) electro-conductive glass usually; electrochromic system generally comprises electrochromic film, ion storage film and ion conductor film; it is on glass that three-layer thin-film can be deposited on base plate successively; two-layer base plate glass plays electrode on the one hand; on the other hand electrochromic system is clipped in the middle; thereby the protection electrochromic system exempts from the destruction of extraneous factor, prolongs the serviceable life of device.When applying voltage between the two-layer electro-conductive glass, electrochemical reaction takes place in the electrochromic film, cause its structural change, the result of structural change is the change color of variable color film, thereby causes that light penetration changes.In addition, when institute's making alive is reverse, variable color film generation reversed reaction, reversible variation also takes place in color thereupon.
According to employed electrolytical difference, the electrochomeric glass device can be divided into liquid-type, semi-solid type and solid type etc., semi-solid type is generally selected gel electrolyte, it can replace ion storage film and ion conductor film, good ionic conductivity is arranged and be easy to film forming, the material therefor safety non-pollution, the electrochomeric glass device that is assembled into, can be when guaranteeing color changeable effect, the weight that can save electrochromic device is greatly simplified its packaging technology.
The electrochomeric glass device can be widely used as the energy-saving window of building etc., if the variable color film is deposited on the planar metal plate with fine reflecting effect, then can make the rearview mirror assemblies of automobile etc., have the accommodation reflex light intensity, avoid occurring the advantage of high light dazzle.
The variable color film can be selected inorganic material or organic material for use, compare with inorganic off-color material, conducting polymer composite has very big advantage as off-color material, can adopt simply and easily directly film forming on the base plate electro-conductive glass of electrochemical method, and film forming is even and change color abundant.The electropolymerization polyaniline film is exactly wherein a kind of.Yet at present the polyaniline variable color film of preparation exists that mechanical property is relatively poor, film and electro-conductive glass substrate bond shortcoming such as not firm.For this reason, can improve the performance of polyaniline film by the compound composite membrane that obtains polyaniline of host material with itself and good mechanical properties.Method of modifying mainly contains 2 kinds, and a kind of is to prepare the matrix film in advance on electrode, then this electrode in containing the reaction solution of aniline monomer electric polymerization reaction is taken place as working electrode, thereby obtain polyaniline composite film on electrode.Another kind is directly aniline monomer, matrix material to be dissolved in the electrolytic solution together, and electropolymerization once obtains polyaniline composite film simultaneously.No matter adopt which kind of mode, one of key factor of the selection of matrix material.Require it can form cellular structure so that its can and polyaniline carry out effectively compound, also should have simultaneously the good mechanical performance and and the good adhesive property of electrode surface.Available matrix material has polyvinyl alcohol (PVA), cellulose acetate, polymethylmethacrylate, polycarbonate etc. usually.Wherein, polyvinyl alcohol film has desirable network structure (1. Cho M S, Park S Y, Hwang J Y, et al.Synthesis and electrical properties ofpolymer composites with polyaniline nanoparticles[J] .Materials Science and Engineering:C, 2004,24 (1-2): 15-18. are Mirmohseni A 2., Wallace G G.Preparation and characterization ofprocessable electroactive polyaniline-polyvinyl alcohol composite[J] .Polymer 2003,44,3523-3528), aniline monomer, micromolecule such as electrolyte can be easy to be diffused in the polyvinyl alcohol (PVA), arrive the conductive glass electrode surface-discharge, realize the original position electropolymerization of aniline, so inner from polyvinyl alcohol (PVA), and polyaniline constantly generates, diffusion at last grows in the whole polyvinyl alcohol (PVA), forms the polyaniline/polyvinyl alcohol composite membrane.This composite membrane not only has the doping of polyaniline and goes the performance of mixing, and polyvinyl alcohol (PVA) also can improve the electrochemical stability of composite membrane by the transformation that suppresses the complete quinoid of polyaniline simultaneously.
The employing polyvinyl alcohol (PVA) is matrix material, deposits research existing report (Wang Hui, Zheng Jianbang, the Wu Hongcai of polyaniline to form the polyaniline/polyvinyl alcohol conductive composite film thereon with electrochemical oxidation process.Electrochemical process prepares the performance of polyaniline/polyvinyl alcohol conducting film.Semiconductor optoelectronic, 53-55), but does not see that it carries out the research of electrochromic property at 2000 the 21st the 1st phases of volume.
Summary of the invention
The objective of the invention is to propose a kind of preparation method with electrochromic device that contains the polyaniline-polyvinyl alcohol composite membrane of excellent mechanical performances and adhesive property.
The present invention proposes a kind of electrochromic device that contains the polyaniline-polyvinyl alcohol composite membrane, form by conductive layer 1, polyaniline-polyvinyl alcohol composite film 2, electrolyte membrane layer 3, conductive glass layer 4 successively from bottom to top, wherein electrolyte membrane layer 3 all around is covered with ambroin layer 5, is distributed with respectively on conductive layer 1, the conductive glass layer 4 and draws lead 1a, draws lead 4a.
Among the present invention, described conductive layer is a kind of (as ordinary stainless steel plate, coated plate, the platinum plating plate) of indium tin oxide-coated glass layer or sheet metal, and conductive glass layer is the indium tin oxide-coated glass layer.
The present invention proposes a kind of preparation method who contains the electrochromic device of polyaniline-polyvinyl alcohol composite membrane, it is characterized in that concrete steps are:
(1) preparation of polyaniline-polyvinyl alcohol composite membrane
At conductive layer (1) top casting polyvinyl alcohol water solution, under the room temperature dry 36-72 hour, obtain being coated with the electrode of polyvinyl alcohol film; With the electrode that is coated with polyvinyl alcohol film that makes is working electrode, saturated calomel electrode is a contrast electrode, platinum electrode is to electrode, constitute three-electrode system, electrolyte solution is an inorganic acid aqueous solution, aniline monomer is dissolved in the electrolyte solution, adopt constant potential polymerization electropolymerization, polymerization time is 3～10 minutes, and current potential is 0.21～0.60V, promptly makes polyaniline-polyvinyl alcohol original position composite film on conductive layer, wherein, the mass percent of polyvinyl alcohol (PVA) in aqueous solution is 0.5～4wt%, and the volumetric molar concentration of inorganic acid aqueous solution is 0.01～2mol/L, and the aniline monomer volumetric molar concentration is 0.1～1mol/L;
(2) preparation of dielectric film
Electrolytic salt was descended dry 36-56 hour at 90-110 ℃, be dissolved among the carbonic allyl ester PC, being mixed with volumetric molar concentration is electrolytic salt/PC solution of 1.0-1.8mol/L, adds polymetylmethacrylate then, under 45-55 ℃ of temperature, placed 60-90 hour, be mixed with gel electrolyte; Employing is cast into embrane method, and this gel electrolyte is cast on the conductive glass layer that acetone cleans, and makes electrolyte membrane layer, and prepared electrolyte membrane layer drying is stand-by; Wherein, the mass content of polymethylmethacrylate is 15～30% of a gel electrolyte quality;
(3) device is synthetic
Polyaniline-polyvinyl alcohol original position composite film and electrolyte membrane layer are bonded together, use epoxy sealing around conductive layer and the conductive glass layer, treat that epoxy resin solidifies after, promptly get required electrochromic device.
Among the present invention, described mineral acid is a kind of of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid.
Among the present invention, described electrolytic salt is a kind of in perchlorate (as lithium perchlorate, sodium perchlorate, potassium perchlorate etc.), hydrochloride (lithium chloride, sodium chloride, potassium chloride etc.) or the sulfate (lithium sulfate, sodium sulphate, glazier's salt etc.) etc.
Good conditions of the present invention is:
Among the present invention, the mass percent of polyvinyl alcohol (PVA) in aqueous solution is 1～2.5wt%.
Among the present invention, the volumetric molar concentration of inorganic acid aqueous solution is 0.8～1.2mol/L.
The present invention adopts the constant potential oxidative polymerization method electrically conductive polyaniline to be deposited on the polyvinyl alcohol film that adheres in advance on the conductive layer, obtained having the polyaniline/polyvinyl alcohol composite membrane of excellent mechanical performances and adhesive property, in certain potential change scope, the composite membrane that the present invention makes has better electrochromic property and electrochemical activity than polyaniline film.And can adopt this composite membrane and gel electrolyte assembling electrochromic device.
Polyaniline-polyvinyl alcohol original position composite membrane is tested in perchloric acid solution, can be seen, along with the difference of externally-applied potential, the color of composite membrane can become colorless respectively, yellow, green, blueness or purple.If current potential reversible cycle in a scope changes, then the color of composite membrane is also with the reversible variation of corresponding generation.Corresponding with the composite membrane change color is the variation of the spectral absorption of composite membrane in visible-range, and along with the difference of externally-applied potential, the visible absorption of composite membrane takes place by significant the variation.
Following p-poly-phenyl amine-polyvinyl alcohol (PVA) original position composite membrane and electrochromic device performance characterization are as follows:
1. electroactive test
Utilize CHI-830 type electrochemical analyser, adopt three-electrode system, with the electrode that deposits the polyaniline-polyvinyl alcohol composite membrane is that working electrode, 232 type saturated calomel electrodes are that contrast electrode, 213 type platinum electrodes are to electrode, 1mol/L perchloric acid is electrolyte solution, carry out cyclic voltammetry scan with different sweep velocitys, record current-electric potential relation curve characterizes the electroactive of composite membrane with the size of peak current.
2. electric look property testing
Observation method of naked eye: in the electroactive test of above-mentioned three-electrode system, the situation that the color of visual inspection composite membrane changes with the continuous variation of current potential.And write down the corresponding relation of corresponding current potential and color.
Spectroelectrochemistry: be working electrode with the ITO/PVA-PAN glass electrode, the Ag/AgCl electrode is a contrast electrode, platinum electrode is in the three-electrode system to electrode, with 1mol/L perchloric acid is electrolyte solution, exporting certain constant potential by ZF-3 type potentiostat is loaded on the ITO/PVA-PAN working electrode, output current reaches stationary value after treating the several seconds, behind the composite membrane colour stable, utilize Agilent 8453 ultraviolet spectrum analyzers in 400～1000nm scope composite membrane to be carried out the UV, visible light photoscanning, scanning reference benchmark is the ito glass electrode that is coated with the PVA film.
3. current-responsive time test
Adopt the three-electrode system identical with electroactive test, utilize CHI-830 type electrochemical analyser, with 1mol/L perchloric acid is electrolyte solution, the working electrode of giving to deposit the polyaniline-polyvinyl alcohol composite membrane in advance applies the constant potential of 0.5V, treat outputting current steadily reach stationary value, composite membrane color reach stable after, use peak value instead to be respectively+0.5V and-square wave of 0.4V carries out electric potential scanning, the scanning current potential cycle is 32s, simultaneously record current curve over time.
4. variable color device performance test
The visible light transmissive spectral measurement of device adopts Agilent 8453E ultraviolet-visible spectrophotometer, does reference with air.The optical response time of device adopts the dynamic method of ultraviolet-visible spectrophotometer, and wavelength is selected 600nm, and test interval was 15 seconds.The CHI830 electrochemical analyser is adopted in the current-responsive time of device and life test, be connected on the extraction electrode of device together with the contrast electrode of electrochemical analyser with to electrode, and the chuck of working electrode connects on another extraction electrode of device, sensitivity is set to maximum, current-responsive time test current potential is respectively-0.6V and+1.35V, this moment, device was respectively colourless and purple; Cyclic voltammetry is selected in life test for use, potential range-0.6V～+ 1.35V, sweep speed 100mV/s.
Among the present invention, the preparation method of polyaniline-polyvinyl alcohol original position composite membrane is easy, can improve the mechanical property of composite membrane, and composite membrane and electro-conductive glass bonding better improves the serviceable life of composite membrane simultaneously.The result shows after tested, and composite membrane shows preferable electrochromism and long serviceable life, and the electrochromic device of making thus is functional.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Number in the figure: 1 is conductive layer, and 1a is the lead of drawing on the conductive layer, and 2 is polyaniline-polyvinyl alcohol original position composite membrane, and 3 is dielectric film, and 4 is the ITO transparent conducting glass, and 4a is the lead of drawing respectively on the electro-conductive glass, and 5 is the ambroin layer.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
Used instrument and equipment is: platinized platinum electrode, 1 * 1cm
2, 213 types; Saturated calomel electrode, 232 types; Platinum electrode, the Ag/AgCl contrast electrode; Ito glass, side's resistance 15 Ω/; Electrochemical analyser, the CHI-830 type; Agilent 8453 ultraviolet spectrum analyzers; ZF-3 type potentiostat; Two compartment glass electrolytic cells.
With area is 3.5 * 2.0cm
2The ITO electro-conductive glass clean with acetone and dry, horizontal positioned, the concentration of casting thereon is the polyvinyl alcohol water solution of 1wt%, under the room temperature dry 36 hours, obtains being coated with the indium-tin oxide electrode of polyvinyl alcohol film; With the ITO electro-conductive glass that is coated with polyvinyl alcohol film is that working electrode, saturated calomel electrode are that contrast electrode, 213 type platinum electrodes are for constituting three-electrode system to electrode.Electropolymerization solution is 1mol/L perchloric acid and 0.3mol/L aniline, polymerization current potential 0.24V (contrast electrode relatively), and polymerization time is 5 minutes.The composite membrane that polymerization is obtained repeatedly washes with deionized water, washes out surface mass.Be-0.4 when apply current potential to composite membrane～-during 0.1V, composite membrane is colourless, composite membrane does not have tangible absorption peak when-0.35V; Current potential is-0.1～+ during 0.2V, composite membrane is yellow, composite membrane does not have tangible absorption peak when+0.05V; Current potential is+0.2～+ during 0.36V, composite membrane is green, the absorption peak of composite membrane is at the 720nm place when+0.25V; Current potential is+0.36～+ during 0.5V, composite membrane is blue, the absorption peak of composite membrane is at the 680nm place when+0.45V; Current potential is+0.5～+ during 0.9V, composite membrane is a purple, the absorption peak of composite membrane is at the 670nm place when+0.6V.The cyclic voltammetry curve of composite membrane has a tangible oxidation peak and two reduction peak, and the position of oxidation peak is at+0.35V place, the position of reduction peak+0.61V and+the 0.10V place.To composite membrane apply+during the current potential of 0.5V, the current-responsive time is 10.0 seconds, apply-during the current potential of 0.4V, the current-responsive time also is 10.0 seconds.
12 gram lithium perchlorates were descended dry 48 hours at 100 ℃, obtain the Lithium perchlorate anhydrous, it is dissolved in the carbonic allyl ester, the addition of carbonic allyl ester is 50 milliliters, is mixed with the LiClO that volumetric molar concentration is 1.5mol/L
4/ PC adds polymethylmethacrylate 23.1 gram then, places 72 hours under 50 ℃ of constant temperature, can be mixed with the polymethylmethacrylate mass concentration and be 25% PMMA-LiClO
4-PC gel electrolyte.
Polyaniline-polyvinyl alcohol original position composite film and electrolyte membrane layer are bonded together, use epoxy sealing around the conductive glass layer, treat that epoxy resin solidifies after, promptly get required electrochromic device.
After testing, when give the variable color device apply-during the current potential of 0.6V, device is the colourless of homogeneous transparent, is 75% at the light penetration of 400～800nm, see through the peak and occur; When the current potential that applies during for+0.6V, device shows light yellow, has one at 500nm place significantly through the peak, and transmitance is 72%.Increase with current potential, the color of device deepens gradually, by green (+0.95V) change to blueness (+1.30V) at last for purple (+1.55V), the visible light transmissivity of device reduces gradually, the peak that sees through of device also moves to the shortwave direction gradually, violet shift takes place, have one to see through the peak at the 475nm place during purple, transmitance is 38%.In apply round-robin voltage scanning process to device, device can change the color that different potentials is corresponding different to continuous reversible between the purple colourless.No matter device becomes yellow, green or purple, and its color is all very even, does not occur and can not fade fully or coloring phenomenon.To device apply+during the current potential of 1.5V, the current-responsive time of device is 50 seconds, the optical response time at the 600nm place is 170 seconds, applies-during the current potential of 0.6V, the current-responsive time is 60 seconds, the optical response time at the 600nm place is 300 seconds.To device through 1327 times repeatedly after the electric potential scanning, its optical response time does not change basically, to device apply-during the current potential of 0.6V, device is colourless, is 65% at the light penetration of 400～800nm, sees through the peak and occurs, apply+during the current potential of 1.5V, device is a purple, has one significantly to see through the peak at the 460nm place, and transmitance is 47%.
Embodiment 2
Used instrument and equipment is: platinized platinum electrode, 1 * 1cm
2, 213 types; Saturated calomel electrode, 232 types; Platinum electrode, the Ag/AgCl contrast electrode; Ito glass, side's resistance 15 Ω/; Electrochemical analyser, the CHI-830 type; Agilent 8453 ultraviolet spectrum analyzers; ZF-3 type potentiostat; Two compartment glass electrolytic cells.
With area is 3.5 * 2.0cm
2The ITO electro-conductive glass clean with acetone and dry, horizontal positioned, the concentration of casting thereon is the polyvinyl alcohol water solution of 1wt%, under the room temperature dry 48 hours, obtains being coated with the indium-tin oxide electrode of polyvinyl alcohol film; With the ITO electro-conductive glass that is coated with polyvinyl alcohol film is that working electrode, saturated calomel electrode are that contrast electrode, 213 type platinum electrodes are for constituting three-electrode system to electrode.It is 1mol/L hydrochloric acid that electropolymerization solution is selected volumetric molar concentration for use, and middle adding volumetric molar concentration is a 0.3mol/L aniline in solution, polymerization current potential 0.24V (contrast electrode relatively), and polymerization time is 5 minutes.
The composite membrane that polymerization is obtained repeatedly washes with deionized water, washes out surface mass.After testing, be-0.4 when apply current potential to composite membrane～-during 0.05V, composite membrane is colourless, the absorption peak of composite membrane is at the 810nm place when-0.35V; Current potential is-0.05～+ during 0.2V, composite membrane is a yellow green, the absorption peak of composite membrane is at the 780nm place when+0.05V; Current potential is+0.2～+ during 0.36V, composite membrane is blue, the absorption peak of composite membrane is at the 750nm place when+0.25V; Current potential is+0.36～+ during 0.9V, composite membrane is a purple, the absorption peak of composite membrane is at the 550nm place when+0.45V.The electric potential scanning scope is-0.4～+ 0.9V, when sweep speed was 50mV/s, the cyclic voltammetry curve of composite membrane had a tangible oxidation peak and two reduction peak, the position of oxidation peak is at+0.48V place, the position of reduction peak+0.45V and+the 0.10V place.To composite membrane apply+during the current potential of 0.5V, the current-responsive time is 14.0 seconds, apply-during the current potential of 0.4V, the current-responsive time is 10.5 seconds.
24.2 gram sodium sulphate were descended dry 48 hours at 100 ℃, obtain anhydrous sodium sulfate, it is dissolved in the carbonic allyl ester, the addition of carbonic allyl ester is 50 milliliters, is mixed with the NaClO that volumetric molar concentration is 1.5mol/L
4/ PC adds polymethylmethacrylate 17.7 gram then, places 72 hours under 50 ℃ of constant temperature, can be mixed with the polymethylmethacrylate mass concentration and be 20% PMMA-Na
2SO
4-PC gel electrolyte.
Polyaniline-polyvinyl alcohol original position composite film and electrolyte membrane layer are bonded together, use epoxy sealing around the conductive glass layer, treat that epoxy resin solidifies after, promptly get required electrochromic device.
Embodiment 3
Used instrument and equipment is: platinized platinum electrode, 1 * 1cm
2, 213 types; Saturated calomel electrode, 232 types; Platinum electrode, the Ag/AgCl contrast electrode; Ito glass, side's resistance 15 Ω/; Electrochemical analyser, the CHI-830 type; Agilent 8453 ultraviolet spectrum analyzers; ZF-3 type potentiostat; Two compartment glass electrolytic cells.
With area is 3.5 * 2.0cm
2The ITO electro-conductive glass clean with acetone and dry, horizontal positioned, the concentration of casting thereon is the polyvinyl alcohol water solution of 2.5wt%, under the room temperature dry 60 hours, obtains being coated with the indium-tin oxide electrode of polyvinyl alcohol film; With the ITO electro-conductive glass that is coated with polyvinyl alcohol film is that working electrode, saturated calomel electrode are that contrast electrode, 213 type platinum electrodes are for constituting three-electrode system to electrode.Electropolymerization solution is 1mol/L sulfuric acid and 0.3mol/L aniline, polymerization current potential 0.24V (contrast electrode relatively), and polymerization time is 10 minutes.The composite membrane that polymerization is obtained repeatedly washes with deionized water, washes out surface mass.Be-0.4 when apply current potential to composite membrane～-during 0.14V, composite membrane is colourless, the absorption peak of composite membrane is at the 800nm place when-0.35V; Current potential is-0.14～+ during 0.2V, composite membrane is a yellow green, the absorption peak of composite membrane is at the 750nm place when+0.05V; Current potential is+0.2～+ during 0.4V, composite membrane is blue, the absorption peak of composite membrane is at the 680nm place when+0.25V; Current potential is+0.4～+ during 0.9V, composite membrane is a purple, the absorption peak of composite membrane is at the 630nm place when+0.45V.The cyclic voltammetry curve of composite membrane has tangible two oxidation peak and two reduction peak, the position of oxidation peak+0.25V and+0.85V place, the position of reduction peak is at+0.73V and+0.05V place.To composite membrane apply+during the current potential of 0.5V, the current-responsive time is 11.5 seconds, apply-during the current potential of 0.4V, the current-responsive time is 11.0 seconds.
5.6 gram potassium chloride were descended dry 48 hours at 100 ℃, obtain anhydrous potassium chloride, it is dissolved in the carbonic allyl ester, the addition of carbonic allyl ester is 50 milliliters, is mixed with the NaClO that volumetric molar concentration is 1.5mol/L
4/ PC adds polymethylmethacrylate 21.9 gram then, places 72 hours under 50 ℃ of constant temperature, can be mixed with the polymethylmethacrylate mass concentration and be 25% PMMA-KCl-PC gel electrolyte.
Polyaniline-polyvinyl alcohol original position composite film and electrolyte membrane layer are bonded together, use epoxy sealing around the conductive glass layer, treat that epoxy resin solidifies after, promptly get required electrochromic device.
Embodiment 4
Used instrument and equipment is: platinized platinum electrode, 1 * 1cm
2, 213 types; Saturated calomel electrode, 232 types; Platinum electrode, the Ag/AgCl contrast electrode; Ito glass, side's resistance 15 Ω/; Ordinary stainless steel plate; Electrochemical analyser, the CHI-830 type; Agilent 8453 ultraviolet spectrum analyzers; ZF-3 type potentiostat; Two compartment glass electrolytic cells.
With area is 3.5 * 2.0cm
2Ordinary stainless steel plate clean with acetone and dry, horizontal positioned, the concentration of casting thereon is the polyvinyl alcohol water solution of 2.5wt%, under the room temperature dry 56 hours, obtains being coated with the corrosion resistant plate electrode of polyvinyl alcohol film; With the corrosion resistant plate that is coated with polyvinyl alcohol film is that working electrode, saturated calomel electrode are that contrast electrode, 213 type platinum electrodes are for constituting three-electrode system to electrode.Electropolymerization solution is 0.1mol/L nitric acid and 0.1mol/L aniline, polymerization current potential 0.21V (contrast electrode relatively), and polymerization time is 3 minutes, obtains polyaniline-polyvinyl alcohol original position composite membrane.The composite membrane that polymerization is obtained repeatedly washes with deionized water, washes out surface mass.Be-0.4 when apply current potential to composite membrane～+ during 0.05V, composite membrane is yellow; Current potential is+0.05～+ during 0.16V, composite membrane is green; Current potential is+0.16～+ during 0.3V, composite membrane is blue; Current potential is+0.3～+ during 0.5V, composite membrane is a purple.The cyclic voltammetry curve of composite membrane has a tangible oxidation peak and two reduction peak, and the position of oxidation peak is at+0.1V place, the position of reduction peak+0.2V and+the 0.05V place.To composite membrane apply+during the current potential of 0.5V, the current-responsive time is 2.0 seconds, apply-during the current potential of 0.4V, the current-responsive time also is 2.0 seconds.
10.5 gram sodium perchlorates were descended dry 48 hours at 100 ℃, obtain anhydrous sodium perchlorate, it is dissolved in the carbonic allyl ester, the addition of carbonic allyl ester is 50 milliliters, is mixed with the NaClO that volumetric molar concentration is 1.5mol/L
4/ PC adds polymethylmethacrylate 17.3 gram then, places 72 hours under 50 ℃ of constant temperature, can be mixed with the polymethylmethacrylate mass concentration and be 20% PMMA-NaClO
4-PC gel electrolyte.
Polyaniline-polyvinyl alcohol original position composite film and electrolyte membrane layer are bonded together, use epoxy sealing around stainless steel flaggy and the conductive glass layer, treat that epoxy resin solidifies after, promptly get required electrochromic device.
Claims (3)
1. preparation method who contains the electrochromic device of polyaniline-polyvinyl alcohol composite membrane is characterized in that concrete steps are:
(1) preparation of polyaniline-polyvinyl alcohol composite membrane
At conductive layer (1) top casting polyvinyl alcohol water solution, under the room temperature dry 36-72 hour, obtain being coated with the electrode of polyvinyl alcohol film; With the electrode that is coated with polyvinyl alcohol film that makes is working electrode, saturated calomel electrode is a contrast electrode, platinum electrode is to electrode, constitute three-electrode system, electrolyte solution is an inorganic acid aqueous solution, aniline monomer is dissolved in the electrolyte solution, adopt constant potential polymerization electropolymerization, polymerization time is 3～10 minutes, and current potential is 0.21～0.60V, promptly makes polyaniline-polyvinyl alcohol original position composite film on conductive layer, wherein, the mass percent of polyvinyl alcohol (PVA) in aqueous solution is 0.5～4wt%, and the volumetric molar concentration of inorganic acid aqueous solution is 0.01～2mol/L, and the aniline monomer volumetric molar concentration is 0.1～1mol/L;
(2) preparation of dielectric film
Electrolytic salt was descended dry 36-56 hour at 90-110 ℃, be dissolved among the carbonic allyl ester PC, being mixed with volumetric molar concentration is electrolytic salt/PC solution of 1.0-1.8mol/L, adds polymetylmethacrylate then, under 45-55 ℃ of temperature, placed 60-90 hour, be mixed with gel electrolyte; Employing is cast into embrane method, and this gel electrolyte is cast on the conductive glass layer that acetone cleans, and makes electrolyte membrane layer, and prepared electrolyte membrane layer drying is stand-by; Wherein, the mass content of polymethylmethacrylate is 15～30% of a gel electrolyte quality;
(3) device is synthetic
Polyaniline-polyvinyl alcohol original position composite film and electrolyte membrane layer are bonded together, use epoxy sealing around conductive layer and the conductive glass layer, treat that epoxy resin solidifies after, promptly get required electrochromic device;
Wherein, described mineral acid is a kind of of hydrochloric acid, nitric acid, sulfuric acid or perchloric acid, and described electrolytic salt is a kind of of sodium perchlorate, hydrochloride or sulfate.
2. the preparation method who contains the electrochromic device of polyaniline-polyvinyl alcohol composite membrane according to claim 1 is characterized in that the mass percent of polyvinyl alcohol (PVA) in aqueous solution is 1～2.5wt%.
3. the preparation method who contains the electrochromic device of polyaniline-polyvinyl alcohol composite membrane according to claim 1, the volumetric molar concentration that it is characterized in that inorganic acid aqueous solution is 0.1～1.5mol/L.
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| WO2008049275A1 (en) * | 2006-10-25 | 2008-05-02 | Feng Chia University | Flexible electromic apparatus |
| CN101225178B (en) * | 2007-12-24 | 2011-04-06 | 天津大学 | Method for preparing polyaniline conductive composite film by in-situ polymerization |
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