CN111908509B - Tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material and preparation method thereof - Google Patents
Tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material and preparation method thereof Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 239000000463 material Substances 0.000 title claims abstract description 81
- 229920000123 polythiophene Polymers 0.000 title claims abstract description 51
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002077 nanosphere Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000004544 sputter deposition Methods 0.000 claims description 43
- 238000000151 deposition Methods 0.000 claims description 35
- 230000008021 deposition Effects 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 230000001588 bifunctional effect Effects 0.000 claims description 24
- 239000004793 Polystyrene Substances 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004040 coloring Methods 0.000 claims description 13
- 239000002356 single layer Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000004005 microsphere Substances 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000005562 fading Methods 0.000 claims description 8
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 8
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 7
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000002441 reversible effect Effects 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 8
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- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
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- 230000001351 cycling effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
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- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
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- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
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Abstract
The invention provides a tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material and a preparation method thereof. The electrochromic capacitor dual-function material ordered hollow sphere array has a porous hierarchical structure and a network structure, and during preparation, FTO conductive glass is used as a substrate, and a hollow tungsten trioxide nanosphere array is sequentially prepared on the surface of the substrate and coated with a polythiophene layer and a tungsten trioxide layer. The invention realizes that the tungsten trioxide hollow nanospheres are uniformly distributed on the substrate, the polythiophene is in a porous structure and uniformly coats the surface of the hollow nanospheres, the tungsten trioxide at the outermost layer improves the overall stability of the material, the invention realizes the combination of a tungsten trioxide inorganic material and a polythiophene organic material on a nanoscale, the electrochromic and capacitance performances are greatly improved, the advantage complementation is realized, the specific surface area of the dual-function material is increased, and the dynamic process of the reaction is obviously enhanced.
Description
Technical Field
The invention relates to the technical field of functional films, in particular to a tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitive bifunctional material and a preparation method thereof.
Background
Electrochromic materials are of great interest because of their color tunability and reversible tunability in optical properties (transmittance, absorbance or reflectance) driven at low voltages, and are promising energy-saving application materials. Pseudocapacitance is considered another promising energy storage application in addition to batteries, where charge insertion/extraction by reversible redox reactions can be used to store energy. In addition, when a reversible redox reaction of rapid charge transfer occurs in the pseudocapacitor, due to similar working principles, certain specific electrode materials may undergo an electrochromic process simultaneously, including tungsten trioxide materials and polythiophene materials. The tungsten trioxide material is obtained from WO in that it is composed of a three-dimensional network6The octahedron is formed, abundant channels can be provided for transporting small ions, switchable color change and charging and discharging processes are facilitated, and the octahedron is suitable for outdoor application due to good environmental stability. However, to date, optical contrast, response time, cycling stability and some other performance metrics have not been satisfactory, particularly for bulk WO3The ion transport capacity is very limited for the compact structure of (2). While organic materials have the advantage of fast reaction rates, they are relatively poorly chemically stable. Therefore, the preparation of organic-inorganic hybrid structure materials is an effective method for improving the electrochromic and capacitive performance.
Disclosure of Invention
In view of this, the object of the invention is: provides a tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material and a preparation method thereof. The invention simultaneously utilizes the tungsten trioxide as an inorganic material and the polythiophene as an organic material, has an ordered hollow sphere array, a porous hierarchical structure and a network structure, can effectively improve the electron transmission speed and the ion diffusion rate, quickens the reaction kinetic process, and greatly improves the reaction speed and the cycle stability of the electrochromic capacitor dual-function material.
In order to achieve the above object, the present invention provides the following technical solutions:
a tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor bifunctional material is characterized in that: the double-function material has a porous hierarchical structure and a network structure, the double-function material takes a tungsten trioxide hollow nanosphere as a core, polythiophene as a first shell layer and tungsten trioxide as a second shell layer, the diameter of the tungsten oxide hollow nanosphere is 400-600nm, the polythiophene as a porous structure, the thickness of the double-function material is 40-50nm, the average pore diameter of the double-function material is 2-3nm, the double-function material is uniformly coated on the tungsten trioxide hollow nanosphere, and the thickness of the second shell layer is 20-30nm and is uniformly coated on the surface of the first shell layer.
Preferably, the bifunctional material has a hollow array structure and has a large specific surface area.
Preferably, the dual-functional material can realize rapid reversible change between transparent and dark blue under macroscopic view, has excellent electrochromic performance, has the visible light modulation amplitude of 85-97%, the near infrared light modulation amplitude of 85-95%, the complete coloring time of 2-5 s and the fading time of 3-7 s, and has the capacity of 40-60 mf/cm2The multiplying power performance reaches 70% -80%; the dual-functional material realizes the storage and the release of electric quantity during the coloring and fading processes.
A preparation method of a tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor bifunctional material comprises the following steps:
(1) mixing the polystyrene microsphere dispersion liquid, ethanol and acetone to obtain a suspension;
(2) putting deionized water and cleaned FTO conductive glass into a culture dish, sequentially dripping the suspension and the triton on onto the surface of the deionized water, taking out the FTO conductive glass, and naturally drying to obtain the single-layer PS ball film-coated FTO conductive glass;
(3) at vacuum degree 2 x 10-4WO with a purity of 99.99% and a Pa of less than3The single-layer PS ball film packet is used as a target material in the step (2)Performing radio frequency reactive deposition sputtering on the surface of the coated FTO conductive glass, wherein the radio frequency reactive deposition sputtering is performed in an oxygen-argon mixed atmosphere;
(4) soaking the FTO conductive glass treated in the step (3) in a tetrahydrofuran solution for 12-24h so as to remove the single-layer PS sphere template and obtain a hollow structure;
(5) taking the FTO conductive glass treated in the step (4) as a working electrode, a platinum wire as a counter electrode, an Ag/AgCl electrode as a reference electrode, dissolving lithium perchlorate and 3, 4-ethylenedioxythiophene monomer in propylene carbonate solution as a polymerization electrolyte, soaking the working electrode in the polymerization electrolyte for 0.5-1h, performing ultrasonic treatment for 10-20min, applying 0.3-0.6V voltage for 10-60 s, and finally performing constant current deposition on the working electrode;
(6) rinsing the product obtained in the step (5) with ethanol and deionized water respectively, and then placing the product on filter paper and baking the product with an infrared lamp;
(7) performing magnetron sputtering again on the product obtained in the step (6) under the vacuum degree of 2 x 10-4WO with a purity of 99.99% and a Pa of less than3The radio frequency reaction deposition sputtering is carried out in the mixed atmosphere of oxygen and argon as the target material.
Preferably, the volume ratio of the polystyrene microsphere dispersion liquid to the ethanol to the acetone in the step (1) is 5:5:2, and the mass concentration of the polystyrene microsphere dispersion liquid is 8-10%.
Preferably, the FTO conductive glass in step (2) is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 10-20min before use, and then placed in a vacuum oven for drying for standby.
Preferably, the volume fraction of oxygen gas generated by the radio frequency reactive deposition sputtering in the step (3) is 10-50%, the sputtering power is 50-100W, the sputtering pressure is 1.0-3.0 Pa, the sputtering time is 10-30 minutes, and the working distance is 5-10 cm.
Preferably, the concentration of the lithium perchlorate in the step (5) is 0.2mol/L, and the concentration of the 3, 4-ethylenedioxythiophene monomer is 0.1 mol/L.
Preferably, the deposition current of the galvanostatic deposition in step (5) is 2.5mA/cm2-3.5mA/cm2At the time of depositionThe time is 10s-20 s.
Preferably, the volume fraction of oxygen gas generated by the radio frequency reactive deposition sputtering in the step (7) is 10-50%, the sputtering power is 50-100W, the sputtering pressure is 1.0-3.0 Pa, the sputtering time is 10-30 minutes, and the working distance is 5-10 cm.
The poly 3, 4-ethylenedioxythiophene is a common conductive polymer, has high conductivity, belongs to a cathode coloring material with tungsten oxide, has a similar reflection wavelength to visible light in a coloring state and is similar to the tungsten oxide, and the combination of the poly 3, 4-ethylenedioxythiophene and the tungsten oxide can greatly shorten the response time and greatly improve the contrast ratio in the aspect of electrochromic performance. The unique hollow tungsten oxide nanosphere array and the polythiophene with the porous structure increase the active specific surface area of a sample, accelerate the transmission of electrons and ions, remarkably enhance the kinetic process of a reversible reaction, and play an excellent role in protecting the whole material, particularly an organic material, by coating the inner and outer oxide layers, thereby improving the stability and the cycle life of the material.
The tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material provided by the invention has an ordered hollow sphere array, a porous hierarchical structure and a network structure, and is characterized in that FTO conductive glass is used as a substrate, three layers are sequentially wrapped on the surface of the substrate, the tungsten trioxide hollow spheres are used as a bottom layer, polythiophene is used as a first shell layer, and tungsten trioxide is used as a second shell layer. The invention realizes that the tungsten trioxide hollow nanospheres are uniformly distributed on the substrate, the polythiophene is in a porous structure and uniformly coats the surface of the hollow nanospheres, the tungsten trioxide is coated on the outermost layer, the overall stability of the material is improved, the invention realizes the combination of a tungsten trioxide inorganic material and a polythiophene organic material on a nanoscale, realizes the advantage complementation, simultaneously increases the specific surface area of a bifunctional material, remarkably enhances the dynamic process of the reaction, and thus improves the electrochromic and capacitance performances.
Compared with the prior art, the method has the following beneficial effects:
1. the electrochromic material has an ordered hollow sphere array, a porous hierarchical structure and a network structure, can effectively improve the electron transmission speed and the ion diffusion rate, accelerate the reaction kinetics process, reduce the fading voltage of the film, and greatly improve the reaction speed and the cycling stability of the material;
2. two cathode coloring materials with similar coloring state colors can enter a coloring state and a fading state simultaneously, so that the optical modulation amplitude of a visible waveband and a near-infrared waveband of the electrochromic material is greatly improved;
3. the organic/inorganic interfaces of tungsten trioxide and polythiophene are effectively hybridized, and the complementary advantages are achieved;
4. the preparation method has the characteristics of simplicity, stability, controllable size and thickness, and is favorable for large-scale industrial production.
Drawings
FIG. 1 is an electron microscope scan of a tungsten trioxide hollow structure obtained in step (4) of example 1; the tungsten oxide at the innermost layer obtained by magnetron sputtering is shown as a hollow nanosphere array.
FIG. 2 is an electron microscope scan of the polythiophene coated shell obtained after step (5) of example 1; the appearance of the material is shown after electrochemical polythiophene coating.
FIG. 3 is an electron microscope scanning image of the electrochromic capacitive dual-function material of tungsten trioxide/polythiophene/tungsten trioxide obtained after step (7) of the example; the appearance of the material after the completion of the whole preparation process is shown, and the hollow array structure is still maintained.
FIG. 4 is a spectrum of visible light and near infrared band transmittance of the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitive bifunctional material prepared in example 1; the prepared material has large optical modulation amplitude in both visible light and near infrared wave bands.
FIG. 5 is a schematic diagram of the kinetic electrochromic properties of the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitive dual-function material prepared in example 1 (633nm, ± 1V); the prepared material has quick response speed.
FIG. 6 is an electrochromic efficiency chart (633nm) of the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitive bifunctional material prepared in example 1; the prepared material has higher coloring efficiency.
FIG. 7 is a graph showing the comparison between the initial state kinetics and the post-cycle kinetics of 6000 cycles of the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitive dual-function material prepared in example 1 (633nm, + -1V); the prepared material has good electrochromic cycling stability.
FIG. 8 is a curve of surface capacitance versus current density for the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitive dual-function material prepared in example 2; the prepared material also has good capacitance.
FIG. 9 shows that the electrochromic capacitive dual-function material of tungsten trioxide/polythiophene/tungsten trioxide prepared in example 2 is at 0.14mA/cm2A charge-discharge curve under current density and a corresponding transmittance change chart thereof; the prepared material can complete the coloring and fading process while carrying out the charging and discharging process.
FIG. 10 is a graph showing the capacitance change of the electrochromic capacitive dual-function material of tungsten trioxide/polythiophene/tungsten trioxide prepared in example 2 after 2000 cycles; the prepared material has good capacitance cycling stability.
Detailed Description
In order to facilitate understanding of the present invention for those skilled in the art, the present invention will be further described with reference to the accompanying drawings and examples.
Example 1
A preparation method of a tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor bifunctional material comprises the following steps:
(1) mixing the polystyrene microsphere dispersion liquid, ethanol and acetone to obtain a suspension; the volume ratio of the polystyrene microsphere dispersion liquid to the ethanol to the acetone is 5:5:2, and the mass concentration of the polystyrene microsphere dispersion liquid is 8%;
(2) putting deionized water and cleaned FTO conductive glass into a culture dish, sequentially dripping the suspension and the triton on onto the surface of the deionized water, taking out the FTO conductive glass, and naturally drying to obtain the single-layer PS ball film-coated FTO conductive glass;
(3) at vacuum degree 2 x 10-4WO with a purity of 99.99% and a Pa of less than3Performing radio frequency reactive deposition sputtering on the surface of the FTO conductive glass wrapped by the single-layer PS sphere film in the step (2) as a target material, wherein the radio frequency reactive deposition sputtering is performed in an oxygen-argon mixed atmosphere; the volume fraction of oxygen in the mixed atmosphere is 10%, the sputtering power of the sputtering deposition is 50W, the sputtering pressure is 1.0Pa, the sputtering time is 10 minutes, and the working distance is 5 cm.
(4) And (4) soaking the FTO conductive glass treated in the step (3) in a tetrahydrofuran solution for 24h so as to remove the single-layer PS sphere template and obtain a hollow structure.
(5) Taking the FTO conductive glass treated in the step (4) as a working electrode, a platinum wire as a counter electrode, an Ag/AgCl electrode as a reference electrode, dissolving lithium perchlorate and 3, 4-ethylenedioxythiophene monomer in propylene carbonate solution as a polymerization electrolyte, firstly soaking the working electrode in the polymerization electrolyte for 1h, carrying out ultrasonic treatment for 20min, then applying 0.6V voltage for treatment for 30 s, and finally carrying out constant current deposition on the working electrode; wherein the concentration of the lithium perchlorate is 0.2mol/L, the concentration of the 3, 4-ethylenedioxythiophene monomer is 0.1mol/L, and the deposition current of the constant current deposition is 2.5mA/cm2The deposition time was 10 s.
(6) Rinsing the product obtained in the step (5) with ethanol and deionized water respectively, and then placing the product on filter paper and baking the product with an infrared lamp;
(7) performing magnetron sputtering again on the product obtained in the step (6) under the vacuum degree of 2 x 10-4WO with a purity of 99.99% and a Pa of less than3The target material is subjected to the radio frequency reaction deposition sputtering in an oxygen-argon mixed atmosphere; the volume fraction of oxygen in the mixed atmosphere is 10%, the sputtering power of the sputtering deposition is 50W, the sputtering pressure is 1.0Pa, the sputtering time is 10 minutes, and the working distance is 5 cm.
The tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor bifunctional material prepared by the embodiment has an ordered hollow sphere array, a porous hierarchical structure and a network structure, and is prepared by taking FTO (fluorine-doped tin oxide) conductive glass as a substrate, sequentially wrapping three layers on the surface of the substrate, taking the tungsten trioxide hollow spheres as a bottom layer, taking polythiophene as a first shell layer and taking tungsten trioxide as a second shell layer. A scan image of the electrochromic capacitive bifunctional material prepared in this embodiment after step (4) is finished is shown in fig. 1, and an ordered hollow sphere array is represented, scan images of the electrochromic capacitive bifunctional material after steps (5) and (7) are respectively shown in fig. 2 and fig. 3, a hierarchical multilayer shell structure and an organic-inorganic hybrid structure are represented, and a visible light and near-infrared band transmittance spectrum of embodiment 1 is shown in fig. 4; the dynamic electrochromic performance is schematically shown (633nm +/-1V) in a graph of FIG. 5, the electrochromic efficiency is shown in a graph of FIG. 6, and the electrochromic cycle stability is shown in a graph of FIG. 7.
Except for the ordered hollow sphere array and the porous hierarchical structure, the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-functional material prepared by the embodiment has excellent electrochromic performance, and has the advantages of visible and near-infrared dual-band large-range modulation (the visible light modulation reaches 96% and the near-infrared light modulation reaches 91%), short reaction time (completely coloring for 4s and fading for 3s), high coloring efficiency, excellent cycle stability and the like.
Example 2
A preparation method of a tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material comprises the following specific steps:
(1) mixing the polystyrene microsphere dispersion liquid, ethanol and acetone to obtain a suspension; the mass concentration of the polystyrene microsphere dispersion is 10%.
(2) Putting deionized water and cleaned FTO conductive glass into a culture dish, sequentially dripping the suspension and triton on onto the surface of the deionized water, then taking out the FTO conductive glass, and naturally drying to obtain the FTO conductive glass wrapped by the single-layer PS ball film;
(3) at vacuum degree 2 x 10-4WO with a purity of 99.99% and a Pa of less than3Performing radio frequency reactive deposition sputtering on the surface of the FTO conductive glass wrapped by the single-layer PS sphere film in the step (2) as a target material, wherein the radio frequency reactive deposition sputtering is performed in an oxygen-argon mixed atmosphere; the volume fraction of oxygen in the mixed atmosphere is 50%, the sputtering power of the sputtering deposition is 100W, the sputtering pressure is 3.0Pa, the sputtering time is 30 minutes, and the working distance is 10 cm.
(4) And (4) soaking the FTO conductive glass treated in the step (3) in a tetrahydrofuran solution for 24h so as to remove the single-layer PS sphere template and obtain a hollow structure.
(5) Taking the FTO conductive glass treated in the step (4) as a working electrode, a platinum wire as a counter electrode, an Ag/AgCl electrode as a reference electrode, dissolving lithium perchlorate and 3, 4-ethylenedioxythiophene monomer in propylene carbonate solution as a polymerization electrolyte, firstly soaking the working electrode in the polymerization electrolyte for 1h, carrying out ultrasonic treatment for 20min, then applying 0.6V voltage for treatment for 60 s, and finally carrying out constant current deposition on the working electrode; wherein the concentration of the lithium perchlorate is 0.2mol/L, the concentration of the 3, 4-ethylenedioxythiophene monomer is 0.1mol/L, and the deposition current of the constant current deposition is 3.5mA/cm2The deposition time was 20 s.
(6) Rinsing the product obtained in the step (5) with ethanol and deionized water respectively, and then placing the product on filter paper and baking the product with an infrared lamp;
(7) performing magnetron sputtering again on the product obtained in the step (6) under the vacuum degree of 2 x 10-4WO with a purity of 99.99% and a Pa of less than3The target material is subjected to the radio frequency reaction deposition sputtering in an oxygen-argon mixed atmosphere; the volume fraction of oxygen in the mixed atmosphere is 50%, the sputtering power of the sputtering deposition is 100W, the sputtering pressure is 3.0Pa, the sputtering time is 30 minutes, and the working distance is 10 cm.
The tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor bifunctional material prepared in this embodiment has an ordered hollow sphere array, a porous hierarchical structure network structure, excellent electrochromic performance, electrochromic/capacitor bifunctional characteristics and excellent cycling stability, fig. 8 is a surface capacitance corresponding current density curve of the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor bifunctional material prepared in example 2, and fig. 9 is a graph of the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor bifunctional material prepared in example 2 at 0.14mA/cm2A charge-discharge curve under current density and a corresponding transmittance change chart, and fig. 10 is a capacitance change chart of the tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material prepared in example 2, which is circulated for 2000 cycles.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor bifunctional material is characterized in that: the double-function material has a porous hierarchical structure and a network structure, the double-function material takes a tungsten trioxide hollow nanosphere as a core, polythiophene as a first shell layer and tungsten trioxide as a second shell layer, the diameter of the tungsten oxide hollow nanosphere is 400-600nm, the polythiophene as a porous structure, the thickness of the double-function material is 40-50nm, the average pore diameter of the double-function material is 2-3nm, the double-function material is uniformly coated on the tungsten trioxide hollow nanosphere, and the thickness of the second shell layer is 20-30nm and is uniformly coated on the surface of the first shell layer.
2. The tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitive bifunctional material as claimed in claim 1, wherein the bifunctional material has a hollow array structure and a large specific surface area.
3. The tungsten trioxide/polythiophene/tungsten trioxide electrochromic capacitor dual-function material as claimed in claim 1, wherein the dual-function material can realize rapid reversible change between transparent and dark blue under macroscopic view, has excellent electrochromic performance, the visible light modulation amplitude is 85% -97%, the near infrared light modulation amplitude is 85-95%, the complete coloring time is 2-5 s, the fading time is 3-7 s, and the capacity of the functional material reaches 40-60 mf/cm2The multiplying power performance reaches 70% -80%; the dual-functional material realizes the storage and the release of electric quantity during the coloring and fading processes.
4. A preparation method of the tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor bifunctional material as defined in any one of claims 1-3, comprising the following steps:
(1) mixing the polystyrene microsphere dispersion liquid, ethanol and acetone to obtain a suspension;
(2) putting deionized water and cleaned FTO conductive glass into a culture dish, sequentially dripping the suspension and the triton on onto the surface of the deionized water, taking out the FTO conductive glass, and naturally drying to obtain the single-layer PS ball film-coated FTO conductive glass;
(3) at vacuum degree 2 x 10-4WO with a purity of 99.99% and a Pa of less than3Performing radio frequency reactive deposition sputtering on the surface of the FTO conductive glass wrapped by the single-layer PS sphere film in the step (2) as a target material, wherein the radio frequency reactive deposition sputtering is performed in an oxygen-argon mixed atmosphere;
(4) soaking the FTO conductive glass treated in the step (3) in a tetrahydrofuran solution for 12-24h so as to remove the single-layer PS sphere template and obtain a hollow structure;
(5) taking the FTO conductive glass treated in the step (4) as a working electrode, a platinum wire as a counter electrode, an Ag/AgCl electrode as a reference electrode, dissolving lithium perchlorate and 3, 4-ethylenedioxythiophene monomer in propylene carbonate solution as a polymerization electrolyte, soaking the working electrode in the polymerization electrolyte for 0.5-1h, performing ultrasonic treatment for 10-20min, applying 0.3-0.6V voltage for 10-60 s, and finally performing constant current deposition on the working electrode;
(6) rinsing the product obtained in the step (5) with ethanol and deionized water respectively, and then placing the product on filter paper and baking the product with an infrared lamp;
(7) performing magnetron sputtering again on the product obtained in the step (6) under the vacuum degree of 2 x 10-4WO of purity of 99.99% at Pa or less3The radio frequency reaction deposition sputtering is carried out in the mixed atmosphere of oxygen and argon as the target material.
5. The preparation method of the tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor bifunctional material as claimed in claim 4, wherein the volume ratio of the polystyrene microsphere dispersion liquid to the ethanol to the acetone in the step (1) is 5:5:2, and the mass concentration of the polystyrene microsphere dispersion liquid is 8-10%.
6. The preparation method of the tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor bifunctional material as claimed in claim 4, wherein in the step (2), the FTO conductive glass is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 10-20min before use, and then placed in a vacuum oven for drying for later use.
7. The preparation method of the tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor dual-functional material according to claim 4, wherein the volume fraction of oxygen gas sputtered in the step (3) through the radio frequency reactive deposition is 10-50%, the sputtering power is 50-100W, the sputtering pressure is 1.0-3.0 Pa, the sputtering time is 10-30 minutes, and the working distance is 5-10 cm.
8. The preparation method of the tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor bifunctional material as claimed in claim 4, wherein the concentration of the lithium perchlorate in the step (5) is 0.2mol/L, and the concentration of the 3, 4-ethylenedioxythiophene monomer is 0.1 mol/L.
9. The method for preparing the tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitive bifunctional material according to claim 4, wherein the deposition current of the galvanostatic deposition in the step (5) is 2.5mA/cm2-3.5mA/cm2The deposition time is 10s-20 s.
10. The preparation method of the tungsten trioxide/polythiophene/tungsten trioxide/electrochromic capacitor dual-functional material according to claim 4, wherein the volume fraction of oxygen gas generated by the radio frequency reactive deposition sputtering in the step (7) is 10-50%, the sputtering power is 50-100W, the sputtering pressure is 1.0-3.0 Pa, the sputtering time is 10-30 minutes, and the working distance is 5-10 cm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060733A (en) * | 2015-07-16 | 2015-11-18 | 浙江大学 | Electrochromic film adopting amorphous/crystalline tungsten trioxide core-shell structure and preparation method of film |
| AU2014336895B2 (en) * | 2013-10-16 | 2016-11-24 | Suzhou Hans Energy Storage Technology Co., Ltd. | Tungsten-based material super battery and supercapacitor |
| CN106987244A (en) * | 2017-05-15 | 2017-07-28 | 电子科技大学 | A kind of composite electrochromic material and preparation method thereof |
| WO2017133074A1 (en) * | 2016-02-02 | 2017-08-10 | 付国东 | Nanocomposite photothermally-responsive system, resin material and smart glass |
| CN107033892A (en) * | 2017-05-09 | 2017-08-11 | 合肥工业大学 | A kind of polythiophene/tungsten trioxide nano-rod electrochromic material and preparation method thereof |
| KR20190008764A (en) * | 2017-07-17 | 2019-01-25 | 엘지디스플레이 주식회사 | Chromic nanoparticles, discoloring device including the same and display device including the same |
| CN110684521A (en) * | 2019-08-28 | 2020-01-14 | 合肥工业大学 | Covalently bonded tungsten trioxide nanowire/polythiophene electrochromic material and preparation method thereof |
-
2020
- 2020-08-05 CN CN202010776780.4A patent/CN111908509B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2014336895B2 (en) * | 2013-10-16 | 2016-11-24 | Suzhou Hans Energy Storage Technology Co., Ltd. | Tungsten-based material super battery and supercapacitor |
| CN105060733A (en) * | 2015-07-16 | 2015-11-18 | 浙江大学 | Electrochromic film adopting amorphous/crystalline tungsten trioxide core-shell structure and preparation method of film |
| WO2017133074A1 (en) * | 2016-02-02 | 2017-08-10 | 付国东 | Nanocomposite photothermally-responsive system, resin material and smart glass |
| CN107033892A (en) * | 2017-05-09 | 2017-08-11 | 合肥工业大学 | A kind of polythiophene/tungsten trioxide nano-rod electrochromic material and preparation method thereof |
| CN106987244A (en) * | 2017-05-15 | 2017-07-28 | 电子科技大学 | A kind of composite electrochromic material and preparation method thereof |
| KR20190008764A (en) * | 2017-07-17 | 2019-01-25 | 엘지디스플레이 주식회사 | Chromic nanoparticles, discoloring device including the same and display device including the same |
| CN110684521A (en) * | 2019-08-28 | 2020-01-14 | 合肥工业大学 | Covalently bonded tungsten trioxide nanowire/polythiophene electrochromic material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Designed growth of WO3/PEDmodulated electrochromic propertiesOT core/shell hybrid nanorod arrays with;Yingdi Shi et al.;《Chemical Engineering Journal》;20180825;第355卷;第942-951页 * |
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