CN105199709B - A kind of electrochromic material and preparation method thereof - Google Patents
A kind of electrochromic material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of electrochromic material and preparation method thereof, the electrochromic material is prepared from by electrochemical polymerization method in boron trifluoride diethyl etherate system by 4,5 ethylenedioxy indole of monomer.Poly- (4, the 5 ethylenedioxy indole) material that the present invention is prepared has that excellent electrochromic property, heat stability are good, electrical conductivity is higher, have good pliability and self-supporting, and preparation process energy consumption is little.
Description
Technical field
The present invention relates to have the material and preparation method of excellent conductive performance, and in particular to a kind of that there is self-supporting property
With poly- (4, the 5- ethylenedioxy indole) material of electrochromic property and preparation method thereof, belong to electrochromic polymeric compounds material neck
Domain.
Background technology
《State natural sciences fund " 12 " development plan》Research emphasis field include study emphasis photoelectricity material
The design of material and preparation, the preparation of photoelectricity antetype device and performance characterization, and electrochromic material and device development are also current
One of study hotspot of domestic and international photoelectric functional material.Comprehensive literature report, the electrochromic material of present people's research and development
Mainly there are following a few big class：Inorganic electrochromic material, organic molecule electrochromic material and Polymer Electrochromic material
Material, the latter, because having good use and processing characteristics, are the emphasis of current research.In macromolecular material, thiophene Type of Collective
Thing and polyaniline chemical stability are good, and electrochromic property is excellent, are the off-color materials being most extensively concerned.It is related both at home and abroad to lead
In domain, the current less applied research to indoles polymer in electrochromic material.
Indoles polymer belongs to the main chain conjugated type conducting polymer in macromolecular material, is that a class is of good performance latent
In electrochromism functional material：Indole is made up of phenyl ring and pyrrole ring, shows that polybenzazole may have the property of polyphenyl and polypyrrole concurrently
Energy；The indoles polymer of electrochemical synthesis has preferable heat stability, relatively stable in doped electrical conductivity；And by
Participate in conjugated system in phenyl ring, show the property of uniqueness, the presence of phenyl ring allows quinoid and benzenoid structure to resonate, in oxygen
Because near infrared absorption experiences the change of colored-colorless during change, this color change is different from other conducting polymers, therefore will
Indoles polymer is with good market prospect and business potential in being applied to electrochromic material.
According to prior art, the preparation of indoles conducting polymer is primarily present following shortcoming：1st, electrochemical polymerization legal system
During standby indoles conducting polymer, oxidizing potential is higher, and energy resource consumption is larger.2nd, the polybenzazole class for preparing in neutral solution is led
Electric polymer, the polymer for obtaining mostly is granule or powder, and mechanical performance is poor, it is difficult to carry out practical application.
The content of the invention
The invention provides a kind of novel electrochromic polymeric material, by monomer 4,5- ethylenedioxies indole is using electrification
Method polymerization is generated, and the structure of 4,5- ethylenedioxy indole is as shown in Figure 1.The preparation method step of the polymeric material is such as
Under：
(1) Ag silks are put in the hydrochloric acid solution that concentration is 4-8mol/L, under Jing constant potential 1.4-1.7V, are electrolysed 50-150s
Afterwards, the red AgCl adhesive layers of Surface Creation, as reference electrode.Ito glass electrode is clean with alcohol wipe, used as work electricity
Pole.Sand papering of the stainless steel electrode with 1200 mesh, is rinsed successively and is dried up with water, ethanol, acetone afterwards, as to electrode.
(2) solid 4 is weighed, 5- ethylenedioxy indole 0.0170-0.0180g are dissolved in 5mL boron trifluoride diethyl etherate (BFEE) solution, match somebody with somebody
It is set to the reaction solution of 4,5- ethylenedioxy indole monomer concentration 0.019-0.021mol/L.By three electrode groups in step (1)
Get togather, be put in the boron trifluoride ether solution containing 4,5- ethylenedioxy indole monomers, apply 0.43-0.65V.vs.SCE's
Voltage, reacts certain hour.(3) working electrode in step (2) is taken out, to adhering to superincumbent poly- (4,5- ethylenedioxies
Indole) the further subsequent treatment of material.
Using 4,5- ethylenedioxies indole as the monomer for preparing electrochromic polymeric compounds material in the present invention, it is a kind of
New indole analog derivative, its 4,5 introduce two oxygen atoms.Compared with other indole derivatives, 4,5- ethylenedioxies
Indole has advantages below：1) 4, the hydrogen of 5 is replaced by ethylenedioxy ring, reduces its energy level, so as to the process in electropolymerization
In can hinder α positions occur side reaction, obtain high-quality polymeric film；2) introducing of ethylenedioxy ring can reduce polymer
Current potential during oxidation (doping) state, the stability for making doped polymer more excellent and higher electric conductivity.
BFEE is adopted in technical scheme as the solution system of electrochemical polymerization.BFEE is a kind of in itself
Lewis is sour, a kind of itself not just solution, can be used as supporting electrolyte, with higher ionic conductivity, therefore
There are electrocatalysises.Contain phenyl ring on indole derivatives, can interact with the boron trioxide in BFEE solution systems, ether
π-complex is generated, the delocalization energy of phenyl ring is reduced, so as to reduce the oxidizing potential of indole, is conducive to the reduction of energy consumption.Simultaneously
The addition of ether also enhances the total acidity of system, also improves the ionic conductivity of solution, and then accelerates indole derivativeses
With the coupling speed of its cation, rate of polymerization is improve.
Poly- (4, the 5- ethylenedioxy indole) electrochromic material that the present invention is prepared, it is with porous spherical structure, described
The aperture size of polymer is micron order, and 10000 times of amplification is as shown in Figure 2 afterwards under an electron microscope.It has solid fluorescence
Property, is Yellow luminous thing, has excellent electrochromic property, add after voltage can between yellowish-brown and bottle green possibility of reversal
Change, and thiophene-based electrochromic polymeric compounds are typically presented blueness.Its mechanical performance and heat stability is good, has higher under room temperature
Electrical conductivity, and be not in safety problem.It also has good pliability and self-supporting property, can intactly from work
Remove on electrode, can greatly extend the range of application in real life.Prepare poly- (4,5- ethylenedioxy indole) material oxidation
Current potential is low, energy consumption is little, advantageously reduces cost, the potential quality for possessing industrialized production popularization.
Description of the drawings
The monomer structure of 4,5 ethylenedioxies of Fig. 1-indole
The stereoscan photograph of poly- (4, the 5- ethylenedioxy indole) films of Fig. 2
The spectroelectrochemistry curve of poly- (4, the 5- ethylenedioxy indole) films of Fig. 3
Transmitance-time graphs of the Fig. 4 poly- (4,5- ethylenedioxy indole) at 675nm
Fig. 54,5- ethylenedioxy indole (A) and remove the infrared spectrum of doped poly- (4,5- ethylenedioxy indole) film (B)
Figure
Poly- (4, the 5- ethylenedioxy indole) fluorescence spectras of Fig. 6
Poly- (4,5- ethylenedioxy indole) the thermogravimetric curve figures of Fig. 7
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, but technical scheme implement and not only
The description being limited in embodiment.
Embodiment 1
(1) Ag silks are put in the hydrochloric acid solution that concentration is 4mol/L, Jing after being electrolysed 100s under constant potential 1.7V, surface life
Into red AgCl adhesive layers, as reference electrode.Ito glass electrode is clean with alcohol wipe, used as working electrode.Rustless steel
Sand papering of the electrode with 1200 mesh, is rinsed successively and is dried up with water, ethanol, acetone afterwards, as to electrode.
(2) solid 4 is weighed, 5- ethylenedioxy indole 0.0175g are dissolved in 5mL boron trifluoride ether solutions, are configured to
The reaction solution of 4,5- ethylenedioxy indole monomer concentration 0.02mol/L.Three electrode groups in step (1) are got togather, is put into and is contained
In having the boron trifluoride ether solution of 4,5- ethylenedioxy indole monomers, apply the voltage of 0.5V.vs.SCE, react 50s.
(3) working electrode in step (2) is taken out, is entered to adhering to superincumbent poly- (4,5- ethylenedioxy indole) material
One step subsequent treatment.
Embodiment 2
(1) Ag silks are put in the hydrochloric acid solution that concentration is 8mol/L, Jing after being electrolysed 60s under constant potential 1.4V, surface life
Into red AgCl adhesive layers, as reference electrode.Ito glass electrode is clean with alcohol wipe, used as working electrode.Rustless steel
Sand papering of the electrode with 1200 mesh, is rinsed successively and is dried up with water, ethanol, acetone afterwards, as to electrode.
(2) solid 4 is weighed, 5- ethylenedioxy indole 0.0175g are dissolved in 5mL boron trifluoride ether solutions, are configured to
The reaction solution of 4,5- ethylenedioxy indole monomer concentration 0.02mol/L.Three electrode groups in step (1) are got togather, is put into and is contained
In having the boron trifluoride ether solution of 4,5- ethylenedioxy indole monomers, apply the voltage of 0.5V.vs.SCE, react 50s.
(3) working electrode in step (2) is taken out, is entered to adhering to superincumbent poly- (4,5- ethylenedioxy indole) material
One step subsequent treatment.
Embodiment 3
(1) Ag silks are put in the hydrochloric acid solution that concentration is 6mol/L, Jing after being electrolysed 100s under constant potential 1.5V, surface life
Into red AgCl adhesive layers, as reference electrode.Ito glass electrode is clean with alcohol wipe, used as working electrode.Rustless steel
Sand papering of the electrode with 1200 mesh, is rinsed successively and is dried up with water, ethanol, acetone afterwards, as to electrode.
(2) solid 4 is weighed, 5- ethylenedioxy indole 0.018g are dissolved in 5mL boron trifluoride ether solutions, are configured to 4,
The reaction solution of 5- ethylenedioxy indole monomer concentration 0.021mol/L.Three electrode groups in step (1) are got togather, be put into containing
In the boron trifluoride ether solution of 4,5- ethylenedioxy indole monomers, apply the voltage of 0.5V.vs.SCE, react 45s.
(3) working electrode in step (2) is taken out, is entered to adhering to superincumbent poly- (4,5- ethylenedioxy indole) material
One step subsequent treatment.
Embodiment 4
(1) Ag silks are put in the hydrochloric acid solution that concentration is 6mol/L, Jing after being electrolysed 100s under constant potential 1.5V, surface life
Into red AgCl adhesive layers, as reference electrode.Ito glass electrode is clean with alcohol wipe, used as working electrode.Rustless steel
Sand papering of the electrode with 1200 mesh, is rinsed successively and is dried up with water, ethanol, acetone afterwards, as to electrode.
(2) solid 4 is weighed, 5- ethylenedioxy indole 0.0175g are dissolved in 5mL boron trifluoride ether solutions, are configured to
The reaction solution of 4,5- ethylenedioxy indole monomer concentration 0.02mol/L.Three electrode groups in step (1) are got togather, is put into and is contained
In having the boron trifluoride ether solution of 4,5- ethylenedioxy indole monomers, apply the voltage of 0.5V.vs.SCE, react 50s.
(3) ITO electrode is taken out, is positioned at the light admission port of ultraviolet spectrophotometer, apply -0.5～1.2V's
Voltage the method using combining with spectral absorption, obtain the spectroelectrochemistry curve of thin polymer film as shown in figure 3, explanation
The thin polymer film of preparation has electrochromic property, and color change interval is between yellowish-brown to bottle green.
Embodiment 5
(1) Ag silks are put in the hydrochloric acid solution that concentration is 6mol/L, Jing after being electrolysed 100s under constant potential 1.5V, surface life
Into red AgCl adhesive layers, as reference electrode.Ito glass electrode is clean with alcohol wipe, used as working electrode.Rustless steel
Sand papering of the electrode with 1200 mesh, is rinsed successively and is dried up with water, ethanol, acetone afterwards, as to electrode.
(2) solid 4 is weighed, 5- ethylenedioxy indole 0.0175g are dissolved in 5mL boron trifluoride ether solutions, are configured to
The reaction solution of 4,5- ethylenedioxy indole monomer concentration 0.02mol/L.Three electrode groups in step (1) are got togather, is put into and is contained
In having the boron trifluoride ether solution of 4,5- ethylenedioxy indole monomers, apply the voltage of 0.5V.vs.SCE, react 50s.
(3) ITO electrode is taken out, is positioned at the light admission port of ultraviolet spectrophotometer, using square wave current potential and light
Spectrum absorbs the method for combining, and changes primary voltage at interval of 5s, and under the scanning of square-wave voltage -0.5V and 1.2V, record is poly-
(4, the 5- ethylenedioxy indole) optic response of film at 675nm, as shown in Figure 4.Can draw from figure at 675nm, light
Contrast is 26%, needs 2.1s to colour, and 2.5s is reduced, and coloration efficiency is 108cm2C-1, this is significantly larger than what document was recorded
Value (the 50-70cm of polypyrrole2C-1)。
Embodiment 6
(1) Ag silks are put in the hydrochloric acid solution that concentration is 6mol/L, Jing after being electrolysed 100s under constant potential 1.5V, surface life
Into red AgCl adhesive layers, as reference electrode.Ito glass electrode is clean with alcohol wipe, used as working electrode.Rustless steel
Sand papering of the electrode with 1200 mesh, is rinsed successively and is dried up with water, ethanol, acetone afterwards, as to electrode.
(2) solid 4 is weighed, 5- ethylenedioxy indole 0.0175g are dissolved in 5mL boron trifluoride ether solutions, are configured to
The reaction solution of 4,5- ethylenedioxy indole monomer concentration 0.02mol/L.Three electrode groups in step (1) are got togather, is put into and is contained
In having the boron trifluoride ether solution of 4,5- ethylenedioxy indole monomers, apply the voltage of 0.5V.vs.SCE, react 10000s.
(3) polymeric film is scraped with pocket knife, and is soaked in being placed on distilled water 3 days, use repeatedly acetone and steaming afterwards
Distilled water is rinsed, and 48h is vacuum dried at 60 DEG C, and the electrical conductivity of resulting polymers thin film is 0.21S cm-1, and there is self-supporting
Matter and good pliability.
(4) the present embodiment is shown in Fig. 5-A, the Fourier transformation of resulting polymers using the Fourier transform infrared spectrogram of monomer
Infrared spectrum is shown in Fig. 5-B.As seen from the figure, in 3394cm-1Characteristic absorption peak of the strong and narrow peak that place occurs for N-H,
1561cm-1The absworption peak at place is the stretching vibration of N-H keys and deformation vibration respectively, in 725cm-1With 762cm-1The absworption peak at place
It is C2With C3The C-H out-of-plane bending vibration characteristic peaks of position.In fig. 2,3397cm-1Characteristic absorption peak of the peak that place occurs for N-H,
Positioned at 792cm-1And 1084cm-1The peak at place is 1,2,3,4, the out-of-plane vibration of substituted phenyl ring c h bond and the peak of in plane vibration,
C on indole ring2With C3The C-H stretching vibration peaks of position disappear, and illustrate that monomer may there occurs polymerization in the prosposition of indole.
(5) fluorescence spectrum of the present embodiment resulting polymers is shown in Fig. 6, positioned at the excitation spectrum that the peak of 468nm is polymer
Peak, positioned at the emission spectrum that the peak of 581nm is the polymer, illustrates that the polymer is a kind of yellow luminous material.
(6) thermogravimetric curve of the present embodiment resulting polymers is shown in Fig. 7, when temperature rises to 1000K, the polymer it is surplus
Surplus still has 62%, illustrates that the polymer has good heat stability.
Claims (10)
1. a kind of electrochromic material, it is characterised in that the structural formula of the electrochromic material is as shown below：
2. electrochromic material as claimed in claim 1, it is characterised in that：The electrochromic material is by monomer 4,5- dioxies
Ethylene indole is prepared from by electrochemical polymerization method in boron trifluoride diethyl etherate system.
3. electrochromic material as claimed in claim 2, it is characterised in that：The polymerization adopts three-electrode system.
4. the method according to the arbitrary electrochromic material of claim 1-3 is prepared, it is characterised in that：By three combination of electrodes
Afterwards, it is put in the boron trifluoride ether solution containing 4,5- ethylenedioxy indole monomer concentration for 0.019-0.021mol/L, applies
Plus after the voltage response certain hour of 0.43-0.65V.vs.SCE, working electrode is removed, to attachment superincumbent poly- (4,5-
Ethylenedioxy indole) the further subsequent treatment of material.
5. method according to claim 4, it is characterised in that after three electrode groups are got togather, be put into the trifluoro of 0.02mol/L
Change the voltage for applying 0.5V.vs.SCE in borate ether solution, react 50s.
6. the method as described in claim 4 or 5, it is characterised in that：Using AgCl as reference electrode, ito glass electrode is made
For working electrode, stainless steel electrode is used as to electrode.
7. method as claimed in claim 6, it is characterised in that：Ag silks are put in the hydrochloric acid solution that concentration is 4-8mol/L,
Jing after being electrolysed 50-150s under constant potential 1.4-1.7V, the red AgCl adhesive layers of Surface Creation, as reference electrode.
8. method as claimed in claim 7, it is characterised in that：Concentration of hydrochloric acid solution is 6mol/L, and constant potential is 1.5V, electrolysis
Time 100s.
9. method as claimed in claim 6, it is characterised in that：Sand papering of the stainless steel electrode with 1200 mesh, afterwards with water,
Ethanol, acetone are rinsed successively and are dried up, used as to electrode.
10. method as claimed in claim 6, it is characterised in that：Ito glass electrode is clean with alcohol wipe, used as work electricity
Pole.
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| CN106290529B (en) * | 2016-08-04 | 2018-12-25 | 北京工业大学 | A kind of test of electrochromic material cyclical stability and analysis method based on the double step chronometric analysis technologies of multi-cycle |
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