CN102965096A - Purpurine compound electrochromic material and electrochromic device thereof - Google Patents
Purpurine compound electrochromic material and electrochromic device thereof Download PDFInfo
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- CN102965096A CN102965096A CN201210475279XA CN201210475279A CN102965096A CN 102965096 A CN102965096 A CN 102965096A CN 201210475279X A CN201210475279X A CN 201210475279XA CN 201210475279 A CN201210475279 A CN 201210475279A CN 102965096 A CN102965096 A CN 102965096A
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Abstract
The invention provides a purpurine compound electrochromic material which is a compound of dichloro-1-(carbazole-N-hexyl)-1'-(diethyl phosphate-2-ethyl)-4,4' bipyridinium salt. The invention also provides an electrochromic device comprising the purpurine compound electrochromic material. The novel electrochromic material is prepared into mutually matched electrochromic electrodes by using a new matching method; the assembled electrochromic device is short in discoloration time, high in transmittance difference and stable in performance; and the preparation technology can be widely popularized and is suitable for actual production and extensive use.
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
The optical properties (such as transmitance, color etc.) that electrochromism refers to material issues at extra electric field and gives birth to reversible colour-change, and have this character material we be referred to as electrochromic material, the device with this function then 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 the solar control device with traditional sunshade, it has many advantages: common window shutter or curtain outside window landscape cover fully, and ECW has then 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 the 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 the thermal radiation in the reflection external world and the thermodiffusion of inside, reduce office block and residential houses and keep feeling nice and cool and the warm mass energy that consumes of maintenance in winter in summer; Simultaneously, energy consumption is low, especially consumes almost nil when it is in constant painted or bleached state.
Summary of the invention
Cause the application of device in order to expand electricity, increase the cycle life that electricity causes device, the object of the present invention is to provide a kind of purpurine compound electrochromic material.
Another object of the present invention provides and contains a kind of electrochromic device.
In order to realize purpose 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:
A kind of method for preparing 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 by weighing in proportion 4,4'-Bipyridine and 2-bromine diethyl diethyl phosphonate, be dissolved in the organic solvent after, 50 ~ 80 ℃ of lower backflows 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
Bromination 1-(diethyl phosphonate-2-ethyl)-4 with step (1) gained, 4 ' bipyridine salt is put in and is heated to 100 ~ 150 ℃ of backflows in the organic solvent, wherein drip 1 with backward, the 6-dibromo-hexane, react after 12 ~ 48 hours, get 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
Place dimethyl sulfoxide (DMSO) (DMSO) to stir in sodium hydroxide, add carbazole and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt stirred under the room temperature 5 ~ 6 hours; Filter, DMSO is removed in underpressure distillation; Said mixture is dissolved in the methyl alcohol, adds hydrochloric acid and 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 desolventizing after will refluxing, 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, the amount of substance of 4,4'-Bipyridine described in the step (1), 2-bromine diethyl diethyl phosphonate and organic solvent and volume ratio are 1:0.8 ~ 1.2:1 ~ 5mol/mol/L.Preferred, 4,4'-Bipyridine described in the step (1), 2-bromine diethyl diethyl phosphonate mol ratio are 1:1.
Organic solvent is preferably acetonitrile, ethyl acetate etc. described in the step (1).
Preferably, step (2) also comprises post-processing step: organic solvent is removed in the mixture underpressure distillation, 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 the step (2) is methyl alcohol, water or its mixture etc.
Preferably, described in the 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 the step (3) and dimethyl sulfoxide (DMSO) (DMSO) is 1g:10 ~ 20mL.
Preferably, carbazole and dibrominated 1-described in the 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 on any of described the first electrode or the second electrode; And be arranged on 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, place 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 place 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-p-diaminodiphenyl) phenmethyl phosphonic acids (TPA), and its structural formula is as follows:
The preparation method of described (4-p-diaminodiphenyl) phenmethyl phosphonic acids is as follows: triphenylamine aldehyde and sodium borohydride are added in the mixing solutions of toluene and methyl alcohol, stirred the 4-p-diaminodiphenyl phenylcarbinol that obtains reducing under the ice bath 4 ~ 12 hours.Again with the 4-p-diaminodiphenyl phenylcarbinol that obtains and triethyl-phosphite under nitrogen protection, take zinc bromide as catalyzer, stirred under the room temperature 20 ~ 36 hours.Mix products is filtered, behind the drying under reduced pressure, add methanol hydrochloride solution, refluxed 5 ~ 10 hours, use H
2O and washed with dichloromethane three times obtain light green (4-p-diaminodiphenyl) phenmethyl phosphonic acids (TPA).
Described electrochromic device principle of work following (as shown in Figure 2):
A is in closure state when switch, and B is when being in open-circuit condition, and electric current is propagated counterclockwise along wire.Working electrode loses electronics, and the purpurine compound changes positive monovalent cation free radical into by divalence Zhenyang ionic condition, changes the mazarine state into from vitreous state; At this moment, redox reaction owing to obtain the electronics of equivalent, is occured in electrode, also change the deep green state into from vitreous state.And in the electrolytic solution of this moment, because the electric charge gain and loss of electrode surface, lithium ion and hexafluorophosphoricacid acid ions are shifted to respectively working electrode and are reached electrode.At this moment, device is in colored state.
When device is in colored state, open switch B, Closing Switch A, electric current just flow clockwise along wire.Working electrode obtains electronics, and the purpurine compound that is in navy blue positive monovalent cation free radical state is oxidized to transparent positive divalent cation, and to electrode materials generation reduction reaction, the deep green state takes off to colourless state.At this moment, device is in vitreous state.
So, realized that just device is painted by being clear to, again by 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 at surface of plate glass uniformly by physics or chemical plating method, and we are referred to as TCO glass this glass.The TCO conductive glass has ITO (indium tin oxide-coated glass) usually, AZO(zinc oxide aluminum conductive glass) and FTO(fluoridize mix indium tin oxide-coated glass).Preferred, what use among the present invention is that the 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 the positive tetrahedron rutile structure.After having mixed fluorine, SnO
2That film has is good to the visible light light transmission, the uv-absorbing coefficient is large, resistivity is low, the advantages such as antiacid alkali ability is strong under stable chemical performance and the room temperature.The more important thing is that FTO is than ITO, AZO glass has very high thermostability, and is still very stable at 500 ℃ of lower conductivities.
Preferably, described semiconductor porous film is transparent nano titanium dioxide.
Preferably, described dielectric layer is the electrolytic solution that is sealed between two transparency electrodes, and its effect is conveying electronic.Electrolytic solution need possess the transmitance height, and the visible region is without obvious absorption peaks, and certain conductivity is arranged.Electrolytic solution can be any electrolytic solution that can satisfy condition that can buy on the market.Preferred, described electrolytic solution is propylene carbonate and the NSC 11801 mixing solutions of lithium hexafluoro phosphate.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:
The dichloride 1-that provides among the present invention (carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt compound, as cathode electrochromic material good electrochromic property is arranged, electrochromism transmitance difference is high, the difference window is large, (50%) and near infrared region all have the good rate variance that sees through in the visible region, and stability is high.Anode electrochromic material (4-p-diaminodiphenyl) the phenmethyl phosphonic acids that provides among simultaneously the present invention, utilize phosphoric acid to modify, be fixed on the electrochromism electrode, can prepare Novel anode electrochromism electrode, equally, this material possesses higher electrochromism transmitance and stability.
Two kinds of electrochromism electrodes that adopt among the present invention all are to adopt first cladding process to make the 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 high electrochemical deposition method, so that the big area commercialization is implemented.
The novel electrochromic material that the present invention synthesizes utilizes new matching process, and it is prepared into the electrochromism electrode of mutual coupling, the electrochromic device variable color time that assembling obtains is short, and it is high to see through rate variance, and stable performance, but the technology of preparing 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, is specially adapted to the dimming glass of electrochromic.
Description of 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 for embodiment 5 electrochromic devices that compare with the present invention at spectral quality;
Fig. 7 for embodiment 6 electrochromic devices that compare with the present invention at spectral quality;
Fig. 8 is the spectrogram of embodiment 6 electrochromic devices under different cycle indexes that compares from the present invention.
Embodiment
Further describe by the following examples the present invention.
The material that uses among the present invention is such as 4,4 '-dipyridyl, 2-bromine diethyl diethyl phosphonate, carbazole, triphenylamine aldehyde, triethyl-phosphite are to be provided by Alfa aesar company, employed mineral compound example hydrochloric acid, sodium hydroxide, and organic solvent etc. is to be provided by Chemical Reagent Co., Ltd., Sinopharm Group.The instrument electrochemical workstation of testing (model: 660D) purchase Instr Ltd. in Shanghai occasion China, ultraviolet-visible-near infrared spectrometer (model: V670) purchase in Japanese light splitting Co., Ltd..
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) places there-necked flask, is dissolved among the acetonitrile solvent 20ml, and 2-bromine diethyl diethyl phosphonate 3.76g (0.016mol) is dissolved among the acetonitrile 30ml, slowly be added drop-wise in the above-mentioned there-necked flask, 80 ℃ of lower backflows 20 hours.Aftertreatment: acetonitrile solvent is removed in the said mixture underpressure distillation, and used the 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) 100 ℃ of backflows are put in heating in methyl alcohol (50ml), drip 1, and 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 among the 50ml DMSO stirs, 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) stirred 6 hours under the room temperature.Filter, DMSO is removed in underpressure distillation.Said mixture is dissolved in the methyl alcohol, adds hydrochloric acid and 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) places there-necked flask, is dissolved among the acetonitrile solvent 20ml, and 2-bromine diethyl diethyl phosphonate 4.7g (0.02mol) is dissolved among the acetonitrile 30ml, slowly be added drop-wise in the above-mentioned there-necked flask, 80 ℃ of lower backflows 20 hours.Aftertreatment: acetonitrile solvent is removed in the said mixture underpressure distillation, and used the 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) 100 ℃ of backflows are put in heating in methyl alcohol (50ml), drip 1, and 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 among the 100ml DMSO stirs, 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) stirred 6 hours under the room temperature.Filter, DMSO is removed in underpressure distillation.Said mixture is dissolved in the methyl alcohol, adds hydrochloric acid and 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) places there-necked flask, is dissolved among the acetonitrile solvent 20ml, and 2-bromine diethyl diethyl phosphonate 5.6g (0.024mol) is dissolved among the acetonitrile 30ml, slowly be added drop-wise in the above-mentioned there-necked flask, 80 ℃ of lower backflows 20 hours.Aftertreatment: acetonitrile solvent is removed in the said mixture underpressure distillation, and used the 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) 100 ℃ of backflows are put in heating in methyl alcohol (50ml), drip 1, and 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 among the 150ml DMSO stirs, 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) stirred 6 hours under the room temperature.Filter, DMSO is removed in underpressure distillation.Said mixture is dissolved in the methyl alcohol, adds hydrochloric acid and make phosphonic acid ester take off esterification.In water, ethyl acetate, wash respectively, obtain pure CV.
The preparation of embodiment 4 electrochromic devices
Apply semiconductor porous film at the electrically conducting transparent substrate surface, after the thermal treatment, place respectively working electrode material and the solution of electrode materials is adsorbed, obtain working electrode and to electrode;
Assemble the working electrode that is comprised successively, electrolytic solution and to the electrochromic device of electrode with described working electrode, electrolytic solution with to electrode.
By aforesaid method as can be known, the present invention is preparation work electrode and to electrode at first, and then assembles.
The preparation process of working electrode is: at first apply one deck porous semiconductor nano-titanium dioxide film at the FTO conductive glass, then heat-treat, then adsorb dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4 at the film surface that obtains, 4 ' bipyridine salt:
To electrode: at first apply one deck porous semiconductor nano-titanium dioxide film at the FTO conductive glass, then heat-treat, film surface absorption (4-p-diaminodiphenyl) the phenmethyl phosphonic acids that is then 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 concrete the employing scraped skill in using a kitchen knife in cookery drying under room temperature behind the titanium dioxide coating nano pulp on the FTO glass surface, is preferably 15-30min time of drying.After drying is complete, 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 ℃, and the preferred time is 15-30min.
Behind the heat treatment step, just can carry out absorption process, absorption process can adopt technology well known to those skilled in the art, be specially: the transparent nano titanium deoxid film after thermal treatment cooling is put to immerse in the working electrode solution after the room temperature adsorb, 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 concrete the employing scraped skill in using a kitchen knife in cookery drying under room temperature behind the titanium dioxide coating nano pulp on the FTO glass surface, is preferably 15-30min time of drying.After drying is complete, 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 ℃, and the preferred time is 15-30min.
Behind the heat treatment step, just can carry out absorption process, absorption process can adopt technology well known to those skilled in the art, be specially: the transparent nano titanium deoxid film after thermal treatment cooling is put to immerse in the working electrode solution after the room temperature adsorb, 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: be that 100 microns granulated glass sphere mixes with two component cements with diameter first, then be coated in the working electrode film edge, and stay 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 anchor clamps, utilize 1 milliliter of syringe that electrolytic solution is injected between two plate electrodes by the injection port that stays in advance, with two component cements injection port is sealed again after filling with.Assemble and obtain electrochromic device after complete.
After set of devices installed into, we had also carried out a series of research to the electrochromic device based on this kind material.Figure 3 shows that the spectral quality of device.As seen from the figure, this electrochromic device is when seeing through state (Fig. 3 solid black lines), in 400nm ~ 1200nm scope, transmitance is all more than 50%, the large maximum 66.6% at the 600nm place, and device is when being in colored state (Fig. 3 black dotted lines), in 680 ~ 800nm scope, the transmitance value of device has a Schwellenwert 1.24% only below 2% at the 730nm place.By can be calculated, it is maximum that this device transmitance difference (△ %T=Tt (λ)-Td (λ)) reaches at the 670nm place, is 63%, and in addition, in the near-infrared region, this device also has certain transmitance difference, is 29% at the 1200nm place.Figure can find out thus, and this device has good optical property.
Fig. 4 with Figure 5 shows that the spectrogram of device under different cycle indexes, this test is to measure this device under fixed wave length, circulation spectroscopic data repeatedly.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 to mutually to change between the vitreous state by colored state and can finish within 1 second, after through 1000 circulations, the device transmitance sees through state at 62.5%() and the 4.8%(colored state) back and forth conversion, after 150,000 circulations, the transmitance of device does not vary widely, in 58.14% and 9.3% mutually conversion.At the 1000nm place, the device transmitance circulates between 44.7% and 15.2% as shown in Figure 5, after 150,000 times, between 52.4% and 15.3%.This shows that this device is after circulating through 150,000 times, it is little that performance reduces degree.
The contrast experiment of embodiment 5 electrochromic devices
Apply semiconductor porous film at the electrically conducting transparent substrate surface, after the thermal treatment, place respectively working electrode material and the solution of electrode materials is adsorbed, obtain working electrode and to electrode;
Assemble the working electrode that is comprised successively, electrolytic solution and to the electrochromic device of electrode with described working electrode, electrolytic solution with to electrode.
By aforesaid method as can be known, the present invention is preparation work electrode and to electrode at first, and then assembles.
The preparation process of working electrode is identical with embodiment 4;
Preparation to electrode:
Prussian blue to the electrode materials selection, adopt the electrochemical deposition method preparation.
Prussian blue preparation to electrode: at first prepare electroplate liquid, each constituent concentration of electroplate liquid: 0.05MFeCl3; 0.05M K
3[Fe
3+(CN)
6]; 0.05M HCl.With cleaned ITO conductive glass as the electrically conducting transparent substrate, the Ag silk is as reference electrode, (the ITO conducting surface is relative with Pt in the electroplate liquid for preparing as electrode is immersed simultaneously for Pt, and guarantee to be in contact with one another between 3 electrodes), at first select chronoamperometry to electroplate that (each parameter is: take-off potential-0.05V, noble potential-0.05V, low potential-0.07V, the negative sense step, the working hour is 2s); At last ito glass is taken out, use the deionized water clean surface, on air drying stand-by (surface can lid layer filter paper prevent the 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.
The assembling electrochromic device step is with embodiment 2.
After set of devices installed into, we had also carried out a series of research to the electrochromic device based on this kind material.This device can be realized painted under ± 2.3V and the process of fading.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 then is the spectrogram under the colored state.As can be seen from the figure, this device transmitance maximum value under bleached state can reach the 63.58%(536nm place), the minimum 43.5%(800nm place that reaches); Under colored state, the transmitance maximum value is the 50%(480nm place), minimum value is 13.4%(716nm).And see through rate variance only up to 37.6%(650nm), be difficult to satisfy actual user demand.
The contrast experiment of embodiment 6 electrochromic devices
Apply semiconductor porous film at the electrically conducting transparent substrate surface, after the thermal treatment, place respectively working electrode material and the solution of electrode materials is adsorbed, obtain working electrode and to electrode;
Assemble the working electrode that is comprised successively, electrolytic solution and to the electrochromic device of electrode with described working electrode, electrolytic solution with to electrode.
By aforesaid method as can be known, the present invention at first 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).
The assembling electrochromic device is with case 4.
After set of devices installed into, we had also carried out a series of research to the electrochromic device based on this kind material.This device can be realized painted under ± 2.3V and the process of fading.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 then is the spectrogram under the colored state.As can be seen from the figure, this device transmitance under bleached state all is higher than 60% at 500 ~ 900nm place, reaches maximum value 66.7% to the 544nm place; Under colored state, the transmitance maximum value is the 21%(664nm place), minimum value is 5.9%(484nm).See through rate variance and can reach the 54%(512nm place).Matching between purpurine compound and the triphenylamine has been achieved the outstanding spectral quality of this device.Figure 8 shows that this device at the 650nm place respectively in the rear spectrum cycle specificity of (dotted line) of 1000 circulation (solid line) and 10,000 times circulations.This device the circulation 10,000 times after, the transmitance under the bleached state only reaches 27.2%, degradation 50%, stability is good not.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (10)
1. purpurine compound electrochromic material, it is compound dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt, its structural formula is as follows:
2. method for preparing the described purpurine compound of claim 1 electrochromic material, it comprises the steps:
(1) bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt synthetic
Take by weighing in proportion 4,4'-Bipyridine and 2-bromine diethyl diethyl phosphonate, be dissolved in the organic solvent after, 50 ~ 80 ℃ of lower backflows 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
Bromination 1-(diethyl phosphonate-2-ethyl)-4 with step (1) gained, 4 ' bipyridine salt is put in and is heated to 100 ~ 150 ℃ of backflows in the organic solvent, wherein drip 1 with backward, 6 '-dibromo-hexane, react after 12 ~ 48 hours, get 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 the dimethyl sulfoxide (DMSO) stirs, add carbazole and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt stirred under the room temperature 5 ~ 6 hours; Filter, DMSO is removed in underpressure distillation; Said mixture is dissolved in the methyl alcohol, adds hydrochloric acid and 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. method as claimed in claim 2 is characterized in that, step (1) and/or step (2) also comprise post-processing step: the mixture underpressure distillation desolventizing after will refluxing, and with low polar organic solvent washing precipitation.
4. method as claimed in claim 2 is characterized in that, amount of substance and the volume ratio of 4,4'-Bipyridine described in the step (1), 2-bromine diethyl diethyl phosphonate and organic solvent are 1:0.8 ~ 1.2:100 ~ 500mol/mol/mL.
5. method as claimed in claim 2 is characterized in that, described in the step (2) 1, and 6 '-dibromo-hexane and bromination 1-(diethyl phosphonate-2-ethyl)-4, the mol ratio of 4 ' bipyridine salt is 1:0.7 ~ 1.2.
6. method as claimed in claim 2 is characterized in that, carbazole and dibrominated 1-described in the step (3) (bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4, and the molar ratio of 4 ' bipyridine salt is 2 ~ 5:1.
7. electrochromic device, it comprises the first electrode and second electrode relative with this first electrode; Electrochromic layer on any of described the first electrode or the second electrode; And be arranged on dielectric layer between described the first electrode and the second electrode; Wherein said electrochromic layer comprises the described electrochromic material of claim 1.
8. electrochromic device as claimed in claim 7, it is characterized in that, described the first electrode comprises: the first electrically conducting transparent substrate, place the semiconductor porous film of the first electrically conducting transparent substrate surface, with the described electrochromic material of claim 1 that is adsorbed in porous, electrically conductive semiconductor film surface, described electrochromic material contacts with dielectric layer.
9. electrochromic device as claimed in claim 7, it is characterized in that, described the second electrode comprises: the second electrically conducting transparent substrate, place the semiconductor porous film of the second electrically conducting transparent substrate surface, with the triphenylamine material that is adsorbed in porous, electrically conductive semiconductor film surface, described triphenylamine material contacts with dielectric layer.
10. electrochromic device as claimed in claim 9 is characterized in that, described triphenylamine material is (4-p-diaminodiphenyl) phenmethyl phosphonic acids.
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