CN103965864A - Purpurine compound electrochromic material and electrochromic device thereof - Google Patents
Purpurine compound electrochromic material and electrochromic device thereof Download PDFInfo
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Abstract
The invention provides an electrochromic device. The electrochromic device comprises a first electrode, a second electrode opposite to the first electrode, and an dielectric layer, wherein an electrochromic layer is arranged on either the first electrode or the second electrode; the dielectric layer is arranged between the first electrode and the second electrode; the electrochromic layer on the first electrode comprises an electrochromic material; the electrochromic material is a purpurine compound electrochromic material, specifically, dichloride,1-(carbazol-N-hexyl)-1'-(phosphonic acid-2-ethyl)-4,4'-bipyridine salt; the second electrode comprises triphenylamine substances. The novel electrochromic material, provided by the invention, utilizes the novel matching method, and is made into electrochromic electrodes matched with each other; the electrochromic device obtained by assembling is short in color changing time, high in transmittivity difference, and stable in performance; the preparation technology can be popularized widely, and is suitable for practical production and wide application.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of purpurine compound electrochromic material and electrochromic device thereof.
Background technology
Electrochromism refers to that the optical properties (as transmitance, color etc.) of material issues raw reversible colour-change at extra electric field, and have this character material we be referred to as electrochromic material, the device with this function is electrochromic device.Based on this performance, this device can be applicable to electrochromic intelligent dimming glass window, electrochromic display device and automobile automatic anti-glare rear vision mirror.
Electrochromic (ECW) is an effective controller for solar, and it can regulate injecting of visible and part near infrared light, and only the voltage of 1～3V can be realized this function.Compare with solar control device with traditional sunshade, it has many advantages: common window shutter or curtain outside window landscape cover completely, and ECW has overcome this shortcoming, and convenient comfortable dazzle control and heat management are provided; Very power saving of ECW driving itself (even can photovoltaic drive), also can include central electrical management in, it has almost unlimited Colour selection, and can block direct projection and the diffuse scattering irradiation of sunlight, optionally absorb or reflect extraneous thermal radiation and inner thermodiffusion, reduce office block and residential houses and keep nice and cool and keep warm consumed mass energy winter in summer; Meanwhile, energy consumption is low, especially when it consumes during in constant painted or bleached state almost nil.
Summary of the invention
Cause the application of device in order to expand electricity, increase the electric cycle life that causes device, the object of the present invention is to provide a kind of purpurine compound electrochromic material.
Another object of the present invention is to provide containing a kind of electrochromic device.
In order to realize object of the present invention, technical scheme of the present invention is as follows:
A kind of purpurine compound electrochromic material, it is compound dichloride 1-(carbazole-N-hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt, its structural formula is as follows:
Prepare a method for purpurine compound electrochromic material, it comprises the steps (can with reference to figure 1):
(1) bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
Take in proportion 4,4'-Bipyridine and 2-phosphonic acid ethyl bromide diethyl ester, after being dissolved in organic solvent, at 50～80 DEG C, reflux 20～30 hours, obtain solid brominated 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(2) dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
By the bromination 1-of step (1) gained (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt is put in and in organic solvent, is heated to 100～150 DEG C of backflows, drip wherein 1 subsequently, 6-dibromo-hexane, react after 12～48 hours, obtain dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(3) dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt synthetic
Sodium hydroxide is placed in to dimethyl sulfoxide (DMSO) (DMSO) and stirs, add carbazole and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt, stirs under room temperature 5～6 hours; Filter, DMSO is removed in underpressure distillation; Said mixture is dissolved in methyl alcohol, adds hydrochloric acid to make phosphonic acid ester take off esterification; In water, ethyl acetate, wash respectively, obtain pure dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt (CV).
Preferably, step (1) also comprises post-processing step: the mixture underpressure distillation after refluxing is removed to desolventizing, and with low polar organic solvent (ether or sherwood oil) washing precipitation, obtain the solid brominated 1-of pale yellow (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
Preferably, described in step (1), the amount of substance of 4,4'-Bipyridine, 2-phosphonic acid ethyl bromide diethyl ester and organic solvent and volume ratio are 1:0.8～1.2:1～5mol/mol/L.Preferred, 4,4'-Bipyridine described in step (1), 2-phosphonic acid ethyl bromide diethyl ester mol ratio are 1:1.
Described in step (1), organic solvent is preferably acetonitrile, ethyl acetate etc.
Preferably, step (2) also comprises post-processing step: mixture underpressure distillation is removed to organic solvent, and with low polar organic solvent (ether or sherwood oil) washing precipitation, obtain dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
Preferably, organic solvent described in step (2) is methyl alcohol, water or its mixture etc.
Preferably, described in step (2) 1,6-dibromo-hexane and bromination 1-(diethyl phosphonate-2-ethyl)-4, the mol ratio of 4 ' bipyridine salt is 1:0.7～1.2.
Preferably, the mass volume ratio of sodium hydroxide described in step (3) and dimethyl sulfoxide (DMSO) (DMSO) is 1g:10～20mL.
Preferably, carbazole and dibrominated 1-described in step (3) (bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4, the ratio of 4 ' bipyridine salt and DMSO is 2～5mol:1mol:5～10L.
The present invention also provides a kind of electrochromic device, and it comprises the first electrode (being working electrode) and second electrode (to electrode) relative with this first electrode; Electrochromic layer in any of described the first electrode or the second electrode; And be arranged on the dielectric layer between described the first electrode and the second electrode; Wherein said electrochromic layer comprises above-mentioned electrochromic material.
Preferably, described the first electrode comprises: the first electrically conducting transparent substrate, be placed in the semiconductor porous film of the first electrically conducting transparent substrate surface, and be adsorbed in the above-mentioned electrochromic material on porous, electrically conductive semiconductor film surface, described electrochromic material contacts with dielectric layer.
Preferably, described the second electrode comprises: the second electrically conducting transparent substrate, and be placed in the semiconductor porous film of the second electrically conducting transparent substrate surface, and be adsorbed in the triphenylamine material on porous, electrically conductive semiconductor film surface, described triphenylamine material contacts with dielectric layer.
Preferably, described triphenylamine material is (4-pentanoic) benzylphosphonic acid (TPA), and its structural formula is as follows:
The preparation method of described (4-pentanoic) benzylphosphonic acid is as follows: triphenylamine aldehyde and sodium borohydride are added in the mixing solutions of toluene and methyl alcohol, stir 4～12 hours under ice bath, the 4-p-diaminodiphenyl phenylcarbinol that obtains having reduced.Again by the 4-p-diaminodiphenyl phenylcarbinol obtaining and triethyl-phosphite under nitrogen protection, taking zinc bromide as catalyzer, under room temperature, stir 20～36 hours.Mix products is filtered, after drying under reduced pressure, add methanol hydrochloride solution, reflux 5～10 hours, use H
2o and washed with dichloromethane three times, obtain light green (4-pentanoic) benzylphosphonic acid (TPA).
Described electrochromic device principle of work following (as shown in Figure 2):
When switch A is in closure state, and B is in the time of open-circuit condition, and electric current is propagated counterclockwise along wire.Working electrode loses electronics, and purpurine compound changes positive monovalent cation free radical into by divalence Zhenyang ionic condition, changes mazarine state into from vitreous state; Now, owing to obtaining the electronics of equivalent, be there is to redox reaction in electrode, also change deep green state into from vitreous state.And in electrolytic solution now, due to the electric charge gain and loss of electrode surface, lithium ion and hexafluorophosphoricacid acid ions are shifted to respectively working electrode and to electrode.Now, device is in colored state.
During in colored state, open switch B at device, Closing Switch A, electric current just flows clockwise along wire.Working electrode obtains electronics, is oxidized to transparent positive divalent cation in the purpurine compound of navy blue positive monovalent cation free radical state, and to electrode materials generation reduction reaction, deep green state takes off to colourless state.Now, device is in vitreous state.
So, just realize device painted by being clear to, then by the painted conversion to vitreous state.
Preferably, described electrically conducting transparent substrate is TCO.TCO (Transparent Conductive Oxide) glass, plates the conductive oxide film of layer of transparent uniformly by physics or chemical plating method at surface of plate glass, we are referred to as TCO glass this glass.TCO conductive glass has ITO (indium tin oxide-coated glass) conventionally, AZO (zinc oxide aluminum conductive glass) and FTO (fluoridize and mix indium tin oxide-coated glass).Preferred, what in the present invention, use is that electrically conducting transparent substrate all adopts FTO glass, and it is the SnO of doped with fluorine
2transparent conducting glass (SnO
2: F).SnO
2be a kind of broad-band gap oxide semiconductor to visible transparent, energy gap 3.7-4.0eV, has positive tetrahedron rutile structure.After having mixed fluorine, SnO
2that film has is good to visible ray light transmission, uv-absorbing coefficient is large, resistivity is low, the advantages such as antiacid alkali ability is strong under stable chemical performance and room temperature.The more important thing is, FTO is than ITO, and AZO glass, has very high thermostability, and at 500 DEG C, conductivity is still very stable.
Preferably, described semiconductor porous film is transparent nano titanium dioxide.
Preferably, described dielectric layer is the electrolytic solution being sealed between two transparency electrodes, and its effect is conveying electronic.It is high that electrolytic solution need possess transmitance, and visible region is without obvious absorption peaks, and have certain conductivity.Electrolytic solution can be any electrolytic solution that can satisfy condition that can buy on market.Preferred, the propylene carbonate that described electrolytic solution is lithium hexafluoro phosphate and NSC 11801 mixing solutions.Wherein the concentration of lithium hexafluoro phosphate is 0.1～0.5mol/L, and the volume ratio of propylene carbonate and NSC 11801 is 1～1:2.
Beneficial effect of the present invention:
Dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4 providing in the present invention, 4 ' bipyridine salt compound, there is good electrochromic property as cathode electrochromic material, electrochromism transmitance difference is high, difference window is large, in visible region, (50%) and near infrared region all have the good rate variance that sees through, and stability is high.Anode electrochromic material (4-pentanoic) benzylphosphonic acid providing in the present invention simultaneously, utilize phosphoric acid to modify, be fixed on electrochromism electrode, can prepare Novel anode electrochromism electrode, equally, this material possesses higher electrochromism transmitance and stability.
Two kinds of electrochromism electrodes that adopt in the present invention are all first to adopt cladding process to make porous nano semiconductor film, and recycling dipping absorption method is prepared from.This preparation method has abandoned original expensive vacuum plating and conductive substrates has been required to high electrochemical deposition method, and big area commercialization is implemented.
The novel electrochromic material that the present invention is synthetic, utilizes new matching process, and is prepared into the electrochromism electrode of mutual coupling, the electrochromic device variable color time that assembling obtains is short, sees through rate variance high, and stable performance, technology of preparing can large-scale popularization, is suitable for actual production and widespread use.
In sum, novel purpurine compound electrochromic device provided by the invention has good transmitance difference; And this device has stable cycle performance and very short switching time, be specially adapted to the dimming glass of electrochromic.
Brief description of the drawings
Fig. 1 is the method steps figure that the present invention prepares purpurine compound electrochromic material;
Fig. 2 is electrochromic device fundamental diagram of the present invention;
Fig. 3 is the spectral quality of electrochromic device of the present invention;
Fig. 4 is the spectrogram of electrochromic device of the present invention under different cycle indexes;
Fig. 5 is the spectrogram of electrochromic device of the present invention under different cycle indexes;
Fig. 6 is that embodiment 5 electrochromic devices that compare with the present invention are at spectral quality;
Fig. 7 is that embodiment 6 electrochromic devices that compare with the present invention are at spectral quality;
Fig. 8 is embodiment 6 electrochromic devices that compare from the present invention spectrograms under different cycle indexes.
Embodiment
Further describe by the following examples the present invention.
The material using in the present invention is as 4,4 '-dipyridyl, 2-phosphonic acid ethyl bromide diethyl ester, carbazole, triphenylamine aldehyde, triethyl-phosphite is to be provided by Alfa aesar company, the mineral compound example hydrochloric acid using, sodium hydroxide, and organic solvent etc. is to be provided by Chemical Reagent Co., Ltd., Sinopharm Group.The instrument electrochemical workstation (model: 660D) of testing is purchased in Shanghai Chen Hua Instrument Ltd., and ultraviolet-visible-near infrared spectrometer (model: V670) is purchased in Japan Spectroscopy Corporation.
The preparation of embodiment 1 purpurine compound electrochromic material
(1) bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
Claim 4,4 '-dipyridyl 3g (0.02mol) is placed in there-necked flask, is dissolved in acetonitrile solvent 20ml, and 2-phosphonic acid ethyl bromide diethyl ester 3.76g (0.016mol) is dissolved in acetonitrile 30ml, slowly be added drop-wise in above-mentioned there-necked flask, at 80 DEG C, reflux 20 hours.Aftertreatment: said mixture underpressure distillation is removed to acetonitrile solvent, and use ether washing precipitation, obtain the solid brominated 1-of pale yellow (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
(2) dibrominated 1-(bromine hexyl)-1 '-(phosphonic acid ester-2-ethyl)-4,4 ' bipyridine salt synthetic
Synthetic bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4g (0.01mol) heats and puts 100 DEG C of backflows in methyl alcohol (50ml), drip 1,6 '-dibromo-hexane 2.03g (0.008mol) is set up and states solution, after 24 hours, aftertreatment is the same.
(3) dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt synthetic
Sodium hydroxide 5g is dissolved in 50ml DMSO and is stirred, add carbazole 2.17g (0.012mol) and dibrominated 1-(carbazole-N-hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4.2g (0.006mol), stirs under room temperature 6 hours.Filter, DMSO is removed in underpressure distillation.Said mixture is dissolved in methyl alcohol, adds hydrochloric acid to make phosphonic acid ester take off esterification.In water, ethyl acetate, wash respectively, obtain pure CV.
The preparation of embodiment 2 purpurine compound electrochromic materials
(1) bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
Claim 4,4 '-dipyridyl 3g (0.02mol) is placed in there-necked flask, is dissolved in acetonitrile solvent 20ml, and 2-phosphonic acid ethyl bromide diethyl ester 4.7g (0.02mol) is dissolved in acetonitrile 30ml, slowly be added drop-wise in above-mentioned there-necked flask, at 80 DEG C, reflux 20 hours.Aftertreatment: said mixture underpressure distillation is removed to acetonitrile solvent, and use ether washing precipitation, obtain the solid brominated 1-of pale yellow (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
(2) dibrominated 1-(bromine hexyl)-1 '-(phosphonic acid ester-2-ethyl)-4,4 ' bipyridine salt synthetic
Synthetic bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4g (0.01mol) heats and puts 100 DEG C of backflows in methyl alcohol (50ml), drip 1,6 '-dibromo-hexane 2.43g (0.01mol) is set up and states solution, after 24 hours, aftertreatment is the same.
(3) dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt synthetic
Sodium hydroxide 10g is dissolved in 100ml DMSO and is stirred, add carbazole 3.26g (0.018mol) and dibrominated 1-(carbazole-N-hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4.2g (0.006mol), stirs under room temperature 6 hours.Filter, DMSO is removed in underpressure distillation.Said mixture is dissolved in methyl alcohol, adds hydrochloric acid to make phosphonic acid ester take off esterification.In water, ethyl acetate, wash respectively, obtain pure CV.
The preparation of embodiment 3 purpurine compound electrochromic materials
(1) bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
Claim 4,4 '-dipyridyl 3g (0.02mol) is placed in there-necked flask, is dissolved in acetonitrile solvent 20ml, and 2-phosphonic acid ethyl bromide diethyl ester 5.6g (0.024mol) is dissolved in acetonitrile 30ml, slowly be added drop-wise in above-mentioned there-necked flask, at 80 DEG C, reflux 20 hours.Aftertreatment: said mixture underpressure distillation is removed to acetonitrile solvent, and use ether washing precipitation, obtain the solid brominated 1-of pale yellow (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
(2) dibrominated 1-(bromine hexyl)-1 '-(phosphonic acid ester-2-ethyl)-4,4 ' bipyridine salt synthetic
Synthetic bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4g (0.01mol) heats and puts 100 DEG C of backflows in methyl alcohol (50ml), drip 1,6 '-dibromo-hexane 3.47g (0.014mol) is set up and states solution, after 24 hours, aftertreatment is the same.
(3) dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt synthetic
Sodium hydroxide 15g is dissolved in 150ml DMSO and is stirred, add carbazole 5.44g (0.03mol) and dibrominated 1-(carbazole-N-hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4.2g (0.006mol), stirs under room temperature 6 hours.Filter, DMSO is removed in underpressure distillation.Said mixture is dissolved in methyl alcohol, adds hydrochloric acid to make phosphonic acid ester take off esterification.In water, ethyl acetate, wash respectively, obtain pure CV.
Embodiment 4 electrochromic device preparations
Apply semiconductor porous film at electrically conducting transparent substrate surface, after thermal treatment, be placed in respectively working electrode material and the solution of electrode materials is adsorbed, obtain working electrode and to electrode;
By described working electrode, electrolytic solution with electrode is assembled to the working electrode, electrolytic solution and the electrochromic device to electrode that are comprised successively.
From aforesaid method, the present invention is preparation work electrode and to electrode first, and then assembles.
The preparation process of working electrode is: first on FTO conductive glass, apply one deck porous semiconductor nano-titanium dioxide film, then heat-treat, then on the film surface obtaining, adsorb dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt:
To electrode: first apply one deck porous semiconductor nano-titanium dioxide film on FTO conductive glass, then heat-treat, then absorption (4-pentanoic) benzylphosphonic acid on the film surface obtaining:
Employing is scraped the skill in using a kitchen knife in cookery at electrically conducting transparent substrate surface coated with nano titanium deoxid film, and it is dry under room temperature after titanium dioxide coating nano pulp on FTO glass surface that the skill in using a kitchen knife in cookery is scraped in concrete employing, is preferably 15-30min time of drying.After being dried completely, it is heat-treated, make its crystalline form be converted to Detitanium-ore-type, and then realize absorption and electric transmission function.The temperature of this step thermal treatment process is preferably 400-500 DEG C, and preferably the time is 15-30min.
After heat treatment step, just can carry out absorption process, absorption process can adopt technology well known to those skilled in the art, be specially: cooling the transparent nano titanium deoxid film after thermal treatment putting after room temperature immersed in working electrode solution and adsorbed, this solution particular methanol is as solvent, adsorption time is preferably 24～48 hours, with guarantee absorption reach just when.
Employing is scraped the skill in using a kitchen knife in cookery at electrically conducting transparent substrate surface coated with nano titanium deoxid film, and it is dry under room temperature after titanium dioxide coating nano pulp on FTO glass surface that the skill in using a kitchen knife in cookery is scraped in concrete employing, is preferably 15-30min time of drying.After being dried completely, it is heat-treated, make its crystalline form be converted to Detitanium-ore-type, and then realize absorption and electric transmission function.The temperature of this step thermal treatment process is preferably 400-500 DEG C, and preferably the time is 15-30min.
After heat treatment step, just can carry out absorption process, absorption process can adopt technology well known to those skilled in the art, be specially: cooling the transparent nano titanium deoxid film after thermal treatment putting after room temperature immersed in working electrode solution and adsorbed, this solution particular methanol is as solvent, adsorption time is preferably 24～48 hours, with guarantee absorption reach just when.
Electrolytic solution preferably adopts the propylene carbonate of lithium hexafluoro phosphate and the mixing solutions of NSC 11801.Wherein the concentration of lithium hexafluoro phosphate is 0.1～0.5mol/L, and the volume ratio of propylene carbonate and NSC 11801 is 1～2:1.Preferred, the volume ratio of NSC 11801 and propylene carbonate is 1:1.
Assembling Photoelectrochromic device: the granulated glass sphere that is first 100 microns by two component cements with diameter mixes, and is then coated in working electrode film edge, and stays next injection port; Will be to electrode cap on working electrode, make the nano titanium dioxide film of electrode relatively with the nano-titanium dioxide film of electrochromism electrode, use clamp two plate electrodes.After two component cements solidify, take off fixture, utilize 1 milliliter of syringe that electrolytic solution is injected between two plate electrodes by the injection port staying in advance, after filling, with two component cements, injection port is sealed again.After assembling, obtain electrochromic device.
After device has been assembled, we have also carried out a series of research to the electrochromic device based on this kind of material.Figure 3 shows that the spectral quality of device.As seen from the figure, this electrochromic device is in the time seeing through state (Fig. 3 solid black lines), within the scope of 400nm～1200nm, transmitance is all more than 50%, the large maximum 66.6% at 600nm place, and device is when colored state (Fig. 3 black dotted lines), within the scope of 680～800nm, the transmitance value of device only, below 2%, has a Schwellenwert 1.24% at 730nm place.By can be calculated, it is maximum that this device transmitance difference (△ %T=Tt (λ)-Td (λ)) reaches at 670nm place, is 63%, in addition, in near-infrared region, this device also has certain transmitance difference, is 29% at 1200nm place.Figure can find out thus, and this device has good optical property.
Fig. 4 and Figure 5 shows that the spectrogram of device under different cycle indexes, this test are to measure this device under fixed wave length, spectroscopic data repeatedly of circulation.Fig. 4 is at the transmittance of 650nm place device and the cyclic curve of time, as seen from the figure, device has stable cycle performance, this device is forwarded between vitreous state and is mutually changed and can complete within 1 second by colored state, after 1000 circulations, device transmitance is changed back and forth 62.5% (seeing through state) and 4.8% (colored state), after 150,000 circulations, the transmitance of device does not vary widely, in 58.14% and 9.3% conversion mutually.At 1000nm place, device transmitance circulates between 44.7% and 15.2% as shown in Figure 5, after 150,000 times, between 52.4% and 15.3%.As can be seen here, this device is after 150,000 circulations, and it is little that performance reduces degree.
The contrast experiment of embodiment 5 electrochromic devices
Apply semiconductor porous film at electrically conducting transparent substrate surface, after thermal treatment, be placed in respectively working electrode material and the solution of electrode materials is adsorbed, obtain working electrode and to electrode;
By described working electrode, electrolytic solution with electrode is assembled to the working electrode, electrolytic solution and the electrochromic device to electrode that are comprised successively.
From aforesaid method, the present invention is preparation work electrode and to electrode first, and then assembles.
The preparation process of working electrode is identical with embodiment 4;
Preparation to electrode:
Prussian blue to electrode materials selection, adopt electrochemical deposition method preparation.
The Prussian blue preparation to electrode: first prepare electroplate liquid, the each constituent concentration of electroplate liquid: 0.05MFeCl3; 0.05M K
3[Fe
3+(CN)
6]; 0.05M HCl.Using cleaned ITO conductive glass as electrically conducting transparent substrate, Ag silk is as reference electrode, in the electroplate liquid preparing, (ITO conducting surface is relative with Pt as electrode is immersed simultaneously for Pt, and ensure can not be in contact with one another between 3 electrodes), first select chronoamperometry to electroplate that (each parameter is: take-off potential-0.05V, noble potential-0.05V, low potential-0.07V, negative sense step, the working hour is 2s); Finally ito glass is taken out, use deionized water clean surface, on air drying stand-by (surface can lid layer filter paper prevent koniology contaminated surface).
Electrolytic solution preferably adopts the propylene carbonate of lithium hexafluoro phosphate and the mixing solutions of NSC 11801.Wherein the concentration of lithium hexafluoro phosphate is 0.1～0.5mol/L, and the volume ratio of propylene carbonate and NSC 11801 is with embodiment 4.
Assembling electrochromic device step is with embodiment 2.
After device has been assembled, we have also carried out a series of research to the electrochromic device based on this kind of material.This device can be realized the painted and process of fading under ± 2.3V.Figure 6 shows that the spectral signature figure of this device under painted and bleached state, solid black lines is the spectral response value of this device under bleached state, and dotted line is the spectrogram under colored state.As can be seen from the figure, this device transmitance maximum value under bleached state can reach 63.58% (536nm place), minimum 43.5% (the 800nm place) that reach; Under colored state, transmitance maximum value is 50% (480nm place), and minimum value is 13.4% (716nm).And see through rate variance only up to 37.6% (650nm), be difficult to meet actual user demand.
The contrast experiment of embodiment 6 electrochromic devices
Apply semiconductor porous film at electrically conducting transparent substrate surface, after thermal treatment, be placed in respectively working electrode material and the solution of electrode materials is adsorbed, obtain working electrode and to electrode;
By described working electrode, electrolytic solution with electrode is assembled to the working electrode, electrolytic solution and the electrochromic device to electrode that are comprised successively.
From aforesaid method, first the present invention prepares to make electrode and to electrode, and then assembles.
Working electrode with to the preparation process of electrode with case study on implementation 4.
Electrolytic solution adopts the propylene carbonate mixing solutions of lithium perchlorate (0.1mol/L).
Assembling electrochromic device is with case 4.
After device has been assembled, we have also carried out a series of research to the electrochromic device based on this kind of material.This device can be realized the painted and process of fading under ± 2.3V.Figure 7 shows that the spectral signature figure of this device under painted and bleached state, solid black lines is the spectral response value of this device under bleached state, and dotted line is the spectrogram under colored state.As can be seen from the figure, this device under bleached state transmitance at 500～900nm place all higher than 60%, reach maximum value 66.7% to 544nm place; Under colored state, transmitance maximum value is 21% (664nm place), and minimum value is 5.9% (484nm).See through rate variance and can reach 54% (512nm place).Matching between purpurine compound and triphenylamine has been achieved the outstanding spectral quality of this device.Figure 8 shows that this device circulates (solid line) and 10,000 circulations spectrum cycle specificity of (dotted line) afterwards at 1000 times respectively at 650nm place.This device circulation 10,000 times after, the transmitance under bleached state only reaches 27.2%, degradation 50%, stability is good not.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. an electrochromic device, it comprises the first electrode and second electrode relative with this first electrode; Electrochromic layer in any of described the first electrode or the second electrode; And be arranged on the dielectric layer between described the first electrode and the second electrode;
Wherein, the electrochromic layer on described the first electrode comprises electrochromic material; Described electrochromic material is purpurine compound electrochromic material, is specially compound dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt, and its structural formula is as follows:
Described the second electrode comprises triphenylamine material.
2. electrochromic device as claimed in claim 1, is characterized in that, the preparation method of described purpurine compound electrochromic material, comprises the steps:
(1) bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
Take in proportion 4,4'-Bipyridine and 2-phosphonic acid ethyl bromide diethyl ester, after being dissolved in organic solvent, at 50～80 DEG C, reflux 20～30 hours, obtain solid brominated 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(2) dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
By the bromination 1-of step (1) gained (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt is put in and in organic solvent, is heated to 100～150 DEG C of backflows, drip wherein 1 subsequently, 6 '-dibromo-hexane, react after 12～48 hours, obtain dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(3) dichloride 1-(carbazole-N-hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
Sodium hydroxide is dissolved in dimethyl sulfoxide (DMSO) and is stirred, add carbazole and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt, stirs under room temperature 5～6 hours; Filter, DMSO is removed in underpressure distillation; Said mixture is dissolved in methyl alcohol, adds hydrochloric acid to make phosphonic acids take off esterification; In water, ethyl acetate, wash respectively, obtain pure dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt.
3. electrochromic device as claimed in claim 1, it is characterized in that, described the first electrode comprises: the first electrically conducting transparent substrate, be placed in the semiconductor porous film of the first electrically conducting transparent substrate surface, with the described electrochromic material that is adsorbed in porous, electrically conductive semiconductor film surface, described electrochromic material contacts with dielectric layer.
4. electrochromic device as claimed in claim 1, it is characterized in that, described the second electrode comprises: the second electrically conducting transparent substrate, be placed in the semiconductor porous film of the second electrically conducting transparent substrate surface, with the described triphenylamine material that is adsorbed in porous, electrically conductive semiconductor film surface, described triphenylamine material contacts with dielectric layer.
5. the electrochromic device as described in claim 1 or 4, is characterized in that, described triphenylamine material is (4-pentanoic) benzylphosphonic acid.
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