CN102965096B - Purpurine compound electrochromic material and electrochromic device thereof - Google Patents
Purpurine compound electrochromic material and electrochromic device thereof Download PDFInfo
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- CN102965096B CN102965096B CN201210475279.XA CN201210475279A CN102965096B CN 102965096 B CN102965096 B CN 102965096B CN 201210475279 A CN201210475279 A CN 201210475279A CN 102965096 B CN102965096 B CN 102965096B
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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
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 then 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 realize this function.Compare with solar control device with traditional sunshade, it has many advantages: common window shutter or curtain will cover by landscape outside window completely, and ECW then overcomes this shortcoming, provides convenient comfortable giddy light by dominated and heat management; ECW driving itself very power saving (even can photovoltaic drive), also central electrical management can be included in, it has almost unlimited Colour selection, and direct projection and the diffuse scattering irradiation of sunlight can be blocked, the optionally thermal radiation of absorption or reflect ambient and the thermodiffusion of inside, reduces office block and residential houses kept feeling nice and cool and warm the consumed mass energy of maintenance in winter in summer; Meanwhile, energy consumption is low, especially consumes almost nil when it is in constant painted or bleached state.
Summary of the invention
In order to expand the application of electroluminescent device, increasing the cycle life of electroluminescent 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, and 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) synthesis of bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
Take 4,4'-Bipyridine and 2-bromine diethyl diethyl phosphonate in proportion, be dissolved in after in organic solvent, reflux 20 ~ 30 hours at 50 ~ 80 DEG C, obtain solid brominated 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(2) synthesis of dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
By the bromination 1-(diethyl phosphonate-2-ethyl)-4 of step (1) gained, 4 ' bipyridine salt is put in organic solvent and is heated to 100 ~ 150 DEG C of backflows, subsequently to wherein dripping 1,6-dibromo-hexane, react after 12 ~ 48 hours, obtain dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(3) synthesis of dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt
Sodium hydroxide is placed in dimethyl sulfoxide (DMSO) (DMSO) to stir, adds carbazole and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt, stirred at ambient temperature 5 ~ 6 hours; Filter, underpressure distillation removing DMSO; Said mixture is dissolved in methyl alcohol, adds hydrochloric acid and make phosphonic acid ester take off esterification; Wash in water, ethyl acetate 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: by the mixture underpressure distillation after backflow except 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, the amount of substance of 4,4'-Bipyridine described in 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 step (1), 2-bromine diethyl diethyl phosphonate 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: by mixture underpressure distillation removing 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, the mol ratio of 1,6-dibromo-hexane described in step (2) and bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt is 1:0.7 ~ 1.2.
Preferably, described in step (3), the mass volume ratio of sodium hydroxide and dimethyl sulfoxide (DMSO) (DMSO) is 1g:10 ~ 20mL.
Preferably, the ratio of carbazole described in step (3) and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt and DMSO is 2 ~ 5mol:1mol:5 ~ 10L.
Present invention also offers a kind of electrochromic device, it comprises the first electrode (i.e. working electrode) and second electrode (to electrode) relative with this first electrode; Described first electrode or the second electrode any one on electrochromic layer; And the dielectric layer be arranged between described first electrode and the second electrode; Wherein said electrochromic layer comprises above-mentioned electrochromic material.
Preferably, described first electrode comprises: the first transparent conductive substrate, be placed in the semiconductor porous film on the first transparent conductive 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 second electrode comprises: the second transparent conductive substrate, is placed in the semiconductor porous film on the second transparent conductive substrate surface, and is adsorbed in the triphenylamine material on porous, electrically conductive semiconductor film surface, and 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, stirs 4 ~ 12 hours, obtain the 4-p-diaminodiphenyl phenylcarbinol reduced under ice bath.Again by the 4-p-diaminodiphenyl phenylcarbinol that obtains and triethyl-phosphite under nitrogen protection, take zinc bromide as catalyzer, stirred at ambient temperature 20 ~ 36 hours.Mix products is filtered, after drying under reduced pressure, adds methanol hydrochloride solution, reflux 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):
When switch A is in closure state, and when B is in open-circuit condition, electric current is propagated counterclockwise along wire.Working electrode loses electronics, and viologen compound is changed to positive monovalent cation free radical by the positive cationic state of divalence, changes mazarine state into from vitreous state; Now, to electrode owing to obtaining the electronics of equivalent, there is redox reaction, 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 shift to working electrode and respectively to electrode.Now, device is in colored state.
When device is in colored state, open switch B, close switch A, electric current is just along wire clockwise flow.Working electrode obtains electronics, and the viologen compound being in navy blue positive monovalent cation free radical state is oxidized to transparent positive divalent cation, and to electrode materials generation reduction reaction, deep green state takes off to colorless state.Now, device is in vitreous state.
So, just achieve device painted by being clear to, then by the painted conversion to vitreous state.
Preferably, described transparent conductive substrate is TCO.TCO(Transparent Conductive Oxide) glass, plate the conductive oxide film of layer of transparent at surface of plate glass uniformly by physics or chemical plating method, this glass we be referred to as TCO glass.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, use transparent conductive substrate all to adopt FTO glass in the present invention, 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 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, compared to ITO, 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 be sealed in the electrolytic solution between two transparency electrodes, and its effect is conveying electronic.It is high that electrolytic solution need possess transmitance, and without obvious absorption peaks, and there is certain conductivity visible region.Electrolytic solution can be any electrolytic solution that can satisfy condition that market can be bought.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:
Dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4 provided in the present invention, 4 ' bipyridylium compound, good electrochromic property is had as cathode electrochromic material, electrochromism transmitance difference is high, difference window is large, all have good in rate variance at visible region (50%) and near infrared region, stability is high.Anode electrochromic material (4-p-diaminodiphenyl) the phenmethyl phosphonic acids provided in the present invention simultaneously, utilize phosphoric acid to modify, be fixed on electrochromic electrode, Novel anode electrochromic electrode can be prepared, equally, this material possesses higher electrochromism transmitance and stability.
The two kinds of electrochromic electrode adopted in the present invention are all first adopt cladding process to make porous nano semiconductor film, and recycling dipping absorption method is prepared from.This preparation method has abandoned the vacuum plating of original high cost and has required high electrochemical deposition method to conductive substrates, and big area commercialization is implemented.
The novel electrochromic material of the present invention's synthesis, utilizes new matching process, and is prepared into the electrochromic electrode of coupling mutually, the electrochromic device Coloring Time that assembling obtains is short, high through rate variance, and stable performance, technology of preparing can large-scale popularization, is suitable for actual production and widespread use.
In sum, novel viologen 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.
Accompanying drawing explanation
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 index;
Fig. 5 is the spectrogram of electrochromic device of the present invention under different cycle index;
Fig. 6 is that embodiment 5 electrochromic device that compares with the present invention is at spectral quality;
Fig. 7 is that embodiment 6 electrochromic device that compares with the present invention is at spectral quality;
Fig. 8 is the spectrogram of embodiment 6 electrochromic device under different cycle index compared from the present invention.
Embodiment
Further describe the present invention by the following examples.
The material used in the present invention is as 4,4 '-dipyridyl, 2-bromine diethyl diethyl phosphonate, carbazole, triphenylamine aldehyde, triethyl-phosphite is provided by Alfa aesar company, the mineral compound example hydrochloric acid used, sodium hydroxide, and organic solvent etc. is provided by Chemical Reagent Co., Ltd., Sinopharm Group.The instrument electrochemical workstation (model: 660D) tested 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) synthesis of bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
Claim 4,4 '-dipyridyl 3g (0.02mol) is placed in there-necked flask, is dissolved in acetonitrile solvent 20ml, is dissolved in acetonitrile 30ml by 2-bromine diethyl diethyl phosphonate 3.76g (0.016mol), slowly be added drop-wise in above-mentioned there-necked flask, reflux 20 hours at 80 DEG C.Aftertreatment: by said mixture underpressure distillation removing acetonitrile solvent, and by washed with diethylether precipitation, obtain the solid brominated 1-of pale yellow (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
(2) synthesis of dibrominated 1-(bromine hexyl)-1 '-(phosphonic acid ester-2-ethyl)-4,4 ' bipyridine salt
Synthetic bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4g(0.01mol) heat in methyl alcohol (50ml) and put 100 DEG C of backflows, drip 1,6 '-dibromo-hexane 2.03g (0.008mol) is set up and states solution, after 24 hours, aftertreatment is the same.
(3) synthesis of dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt
Sodium hydroxide 5g is dissolved in 50ml DMSO and 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 at ambient temperature 6 hours.Filter, underpressure distillation removing DMSO.Said mixture is dissolved in methyl alcohol, adds hydrochloric acid and make phosphonic acid ester take off esterification.Wash in water, ethyl acetate respectively, obtain pure CV.
The preparation of embodiment 2 purpurine compound electrochromic material
(1) synthesis of bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
Claim 4,4 '-dipyridyl 3g (0.02mol) is placed in there-necked flask, is dissolved in acetonitrile solvent 20ml, is dissolved in acetonitrile 30ml by 2-bromine diethyl diethyl phosphonate 4.7g (0.02mol), slowly be added drop-wise in above-mentioned there-necked flask, reflux 20 hours at 80 DEG C.Aftertreatment: by said mixture underpressure distillation removing acetonitrile solvent, and by washed with diethylether precipitation, obtain the solid brominated 1-of pale yellow (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
(2) synthesis of dibrominated 1-(bromine hexyl)-1 '-(phosphonic acid ester-2-ethyl)-4,4 ' bipyridine salt
Synthetic bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4g(0.01mol) heat in methyl alcohol (50ml) and put 100 DEG C of backflows, drip 1,6 '-dibromo-hexane 2.43g (0.01mol) is set up and states solution, after 24 hours, aftertreatment is the same.
(3) synthesis of dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt
Sodium hydroxide 10g is dissolved in 100ml DMSO and 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 at ambient temperature 6 hours.Filter, underpressure distillation removing DMSO.Said mixture is dissolved in methyl alcohol, adds hydrochloric acid and make phosphonic acid ester take off esterification.Wash in water, ethyl acetate respectively, obtain pure CV.
The preparation of embodiment 3 purpurine compound electrochromic material
(1) synthesis of bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
Claim 4,4 '-dipyridyl 3g (0.02mol) is placed in there-necked flask, is dissolved in acetonitrile solvent 20ml, is dissolved in acetonitrile 30ml by 2-bromine diethyl diethyl phosphonate 5.6g (0.024mol), slowly be added drop-wise in above-mentioned there-necked flask, reflux 20 hours at 80 DEG C.Aftertreatment: by said mixture underpressure distillation removing acetonitrile solvent, and by washed with diethylether precipitation, obtain the solid brominated 1-of pale yellow (diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt.
(2) synthesis of dibrominated 1-(bromine hexyl)-1 '-(phosphonic acid ester-2-ethyl)-4,4 ' bipyridine salt
Synthetic bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt 4g(0.01mol) heat in methyl alcohol (50ml) and put 100 DEG C of backflows, drip 1,6 '-dibromo-hexane 3.47g (0.014mol) is set up and states solution, after 24 hours, aftertreatment is the same.
(3) synthesis of dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt
Sodium hydroxide 15g is dissolved in 150ml DMSO and 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 at ambient temperature 6 hours.Filter, underpressure distillation removing DMSO.Said mixture is dissolved in methyl alcohol, adds hydrochloric acid and make phosphonic acid ester take off esterification.Wash in water, ethyl acetate respectively, obtain pure CV.
Prepared by embodiment 4 electrochromic device
At transparent conductive substrate surface-coated semiconductor porous film, after thermal treatment, be placed in working electrode material respectively and the solution of electrode materials is adsorbed, obtaining working electrode and to electrode;
By described working electrode, electrolytic solution with assemble electrode, the working electrode comprised successively, electrolytic solution and the electrochromic device to electrode.
From aforesaid method, the present invention is first preparation work electrode and to electrode, 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 obtained, 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 on the film surface obtained, adsorb (4-p-diaminodiphenyl) phenmethyl phosphonic acids:
Employing scrapes the skill in using a kitchen knife in cookery at transparent conductive substrate surface-coated nano-titanium dioxide film, and concrete employing scrapes skill in using a kitchen knife in cookery drying under room temperature after titanium dioxide coating nano pulp on FTO glass surface, and time of drying is preferably 15-30min.After drying completely, it is heat-treated, makes 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 the preferred time is 15-30min.
After heat treatment step, just absorption process can be carried out, absorption process can adopt technology well known to those skilled in the art, be specially: immerse in working electrode solution after room temperature is put in the transparent nano titanium deoxid film cooling after thermal treatment and adsorb, this solution particular methanol is as solvent, adsorption time is preferably 24 ~ 48 hours, with guarantee absorption reach just when.
Employing scrapes the skill in using a kitchen knife in cookery at transparent conductive substrate surface-coated nano-titanium dioxide film, and concrete employing scrapes skill in using a kitchen knife in cookery drying under room temperature after titanium dioxide coating nano pulp on FTO glass surface, and time of drying is preferably 15-30min.After drying completely, it is heat-treated, makes 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 the preferred time is 15-30min.
After heat treatment step, just absorption process can be carried out, absorption process can adopt technology well known to those skilled in the art, be specially: immerse in working electrode solution after room temperature is put in the transparent nano titanium deoxid film cooling after thermal treatment and 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: first two component is mixed with the granulated glass sphere that diameter is 100 microns, be then coated in working electrode film edge, and stay next injection port; To electrode cap on the working electrode (s, make the nano titanium dioxide film of electrode relative with the nano-titanium dioxide film of electrochromic electrode, use clamp two plate electrode.After two component solidifies, take off fixture, utilize 1 milliliter of syringe to inject between two plate electrodes by electrolytic solution by the injection port stayed in advance, with two component, injection port is sealed again after filling.Electrochromic device is obtained after assembling.
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 when 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 when device is in 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, this device transmitance difference (△ %T=Tt (λ)-Td (λ)) reaches maximum at 670nm place, is 63%, and 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 index, this test measures 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 forwards mutual conversion between vitreous state to by colored state and can complete within 1 second, through 1000 times circulation after, device transmitance at 62.5%(through state) and 4.8%(colored state) change back and forth, through 150,000 times circulate after, the transmitance of device does not vary widely, and mutually changes at 58.14% and 9.3%.As shown in Figure 5 at 1000nm place, device transmitance circulates between 44.7% and 15.2%, 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 device
At transparent conductive substrate surface-coated semiconductor porous film, after thermal treatment, be placed in working electrode material respectively and the solution of electrode materials is adsorbed, obtaining working electrode and to electrode;
By described working electrode, electrolytic solution with assemble electrode, the working electrode comprised successively, electrolytic solution and the electrochromic device to electrode.
From aforesaid method, the present invention is first preparation work electrode and to electrode, and then assembles.
The preparation process of working electrode is identical with embodiment 4;
Preparation to electrode:
Select Prussian blue to electrode materials, adopt electrochemical deposition method preparation.
The Prussian blue preparation to electrode: first prepare electroplate liquid, 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, (ITO conducting surface is relative with Pt as immersing electrode in the electroplate liquid for preparing simultaneously for Pt, and ensure can not contact with each other between 3 electrodes), first (each parameter is: take-off potential-0.05V, noble potential-0.05V, low potential-0.07V to select chronoamperometry to carry out electroplating, negative sense step, the working hour is 2s); Finally ito glass is taken out, by washed with de-ionized water surface, in atmosphere dried for standby (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 realize 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 then 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), minimumly reach 43.5%(800nm place); Under colored state, transmitance maximum value is 50%(480nm place), minimum value is 13.4%(716nm).And through rate variance only up to 37.6%(650nm), be difficult to satisfied actual user demand.
The contrast experiment of embodiment 6 electrochromic device
At transparent conductive substrate surface-coated semiconductor porous film, after thermal treatment, be placed in working electrode material respectively and the solution of electrode materials is adsorbed, obtaining working electrode and to electrode;
By described working electrode, electrolytic solution with assemble electrode, the working electrode comprised successively, electrolytic solution and the electrochromic device to electrode.
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 realize 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 then 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), minimum value is 5.9%(484nm).54%(512nm place is can reach) through rate variance.Matching between viologen compound and triphenylamine has achieved the outstanding spectral quality of this device.Figure 8 shows that the spectrum cycle specificity that this device circulates (solid line) and circulates rear (dotted line) for 10,000 times at 1000 times at 650nm place respectively.This device is after circulation 10,000 times, and the transmitance under bleached state only reaches 27.2%, and 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 (6)
1. a purpurine compound electrochromic material, it is compound dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt, and its structural formula is as follows:
2. prepare a method for purpurine compound electrochromic material described in claim 1, it comprises the steps:
(1) synthesis of bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
Take 4,4'-Bipyridine and 2-phosphonic acid ethyl bromide diethyl ester in proportion, be dissolved in after in organic solvent, reflux 20 ~ 30 hours at 50 ~ 80 DEG C, obtain solid brominated 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(2) synthesis of dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
By the bromination 1-(diethyl phosphonate-2-ethyl)-4 of step (1) gained, 4 ' bipyridine salt is put in organic solvent and is heated to 100 ~ 150 DEG C of backflows, subsequently to wherein dripping 1,6 '-dibromo-hexane, react after 12 ~ 48 hours, obtain dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt;
(3) synthesis of dichloride 1-(carbazole-N-hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt
Sodium hydroxide is dissolved in dimethyl sulfoxide (DMSO) and stirs, add carbazole and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt, stirred at ambient temperature 5 ~ 6 hours; Filter, underpressure distillation removing DMSO; Said mixture is dissolved in methyl alcohol, adds hydrochloric acid and make phosphonic acids take off esterification; Wash in water, ethyl acetate respectively, obtain pure dichloride 1-(carbazole-N-hexyl)-1 '-(phosphonic acids-2-ethyl)-4,4 ' bipyridine salt.
3. method as claimed in claim 2, it is characterized in that, step (1) and/or step (2) also comprise post-processing step: by the mixture underpressure distillation after backflow except desolventizing, and with low polar organic solvent washing precipitation.
4. method as claimed in claim 2, it is characterized in that, amount of substance and the volume ratio of 4,4'-Bipyridine, 2-phosphonic acid ethyl bromide diethyl ester and organic solvent described in step (1) are 1:0.8 ~ 1.2:100 ~ 500mol/mol/mL.
5. method as claimed in claim 2, is characterized in that, described in step (2) 1, the mol ratio of 6 '-dibromo-hexane and bromination 1-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt is 1:0.7 ~ 1.2.
6. method as claimed in claim 2, it is characterized in that, the amount of substance ratio of carbazole described in step (3) and dibrominated 1-(bromine hexyl)-1 '-(diethyl phosphonate-2-ethyl)-4,4 ' bipyridine salt is 2 ~ 5:1.
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