CN113737241A - Ionic liquid doped water-soluble polythiophene composite film and preparation method and application thereof - Google Patents

Ionic liquid doped water-soluble polythiophene composite film and preparation method and application thereof Download PDF

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CN113737241A
CN113737241A CN202111070414.8A CN202111070414A CN113737241A CN 113737241 A CN113737241 A CN 113737241A CN 202111070414 A CN202111070414 A CN 202111070414A CN 113737241 A CN113737241 A CN 113737241A
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ionic liquid
deposition
water
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composite film
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CN113737241B (en
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蒋海云
吴威
梁榕莲
张维莉
曾海兰
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Hunan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C03C2217/948—Layers comprising indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/115—Deposition methods from solutions or suspensions electro-enhanced deposition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene

Abstract

The invention provides an ionic liquid doped water-soluble polythiophene composite film and a preparation method and application thereof, belonging to the technical field of electrochromism. Firstly, sodium polystyrene sulfonate (PSS) is doped and put into a reactor containing 3,4 Ethylene Dioxythiophene (EDOT) and lithium perchlorate (LiClO)4) In the aqueous solution of Sodium Dodecyl Benzene Sulfonate (SDBS), a large amount of evenly dispersed anionic water deposition solution is obtained to replace the traditional organic solvent-based deposition solution; meanwhile, the ionic liquid is added to promote the uniform dispersion of EDOT in the aqueous solution and increase free movement ions in the solution; and then carrying out electrochemical deposition by using an electrochemical workstation to obtain the ionic liquid doped water-soluble polythiophene composite film. The invention adopts an in-situ electrochemical polymerization method and realizes the preparation of the PEDOT by water-soluble deposition through secondary doping to obtain the PEDOT-doped aqueous solutionThe obtained film has high electrochromic performance, high cycle stability and high electrochemical activity.

Description

Ionic liquid doped water-soluble polythiophene composite film and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochromism, in particular to an ionic liquid doped water-soluble polythiophene composite film and a preparation method and application thereof.
Background
At present, the world enters the fourth industrial revolution era with low carbon, energy conservation, environmental protection and new energy as the leading factors, the research of sustainable development and environment-friendly materials becomes increasingly active research field, and people continuously research and develop novel intelligent and renewable materials and industrialized technology to meet the development and the demand of the era. Electrochromic technology is an emerging industrialized technology. The intelligent dimming window is developed and applied to continuously changing the lives of people, such as an automobile intelligent anti-dazzle mirror, an airplane intelligent dimming porthole, a dimmable home intelligent shutter and the like. How to obtain electrochromic materials with good controllability, stability and high color change efficiency has rapidly become the focus of current research.
PEDOT (polymer of 3, 4-ethylenedioxythiophene) is an electrochromic material with excellent performance, and has the advantages of simple molecular structure, excellent conductivity, easiness in control and higher coloring efficiency. Under the action of an applied voltage, the PEDOT electrochromic film can generate oxidation-reduction reaction, and reversible color conversion from dark blue in a reduction state to light blue in an oxidation state can be realized. Therefore, the PEDOT film has wide application in the field of electrochromism, such as intelligent windows, anti-dazzling glasses, flexible displays and the like. However, PEDOT is hardly soluble in water and other common solvents, and when polymerization occurs using an aqueous solution as an electrolyte, radicals of the thiophene group of EDOT (3, 4-ethylenedioxythiophene) itself react with water molecules, thereby inhibiting polymerization of EDOT in the aqueous solution. Meanwhile, in the process of polymerization of the PEDOT film, the formed molecular structure is compact, and the transition of electrons can be hindered, so that the electrochromic performance of the PEDOT film is reduced. Therefore, the solubility and electrochromic properties of the PEDOT film are still to be improved.
Disclosure of Invention
In view of the above, the present invention provides an ionic liquid doped water-soluble polythiophene composite membrane, and a preparation method and an application thereof. The ionic liquid doped water-soluble polythiophene composite film prepared by the method disclosed by the invention is excellent in electrochromic performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an ionic liquid doped water-soluble polythiophene composite film, which comprises the following steps:
mixing sodium polystyrene sulfonate, 3, 4-ethylenedioxythiophene, lithium perchlorate, sodium dodecyl benzene sulfonate and water to obtain an anionic water deposition solution;
mixing ionic liquid with the anionic water deposition solution to obtain deposition solution;
and carrying out electrochemical deposition by using the deposition solution to obtain the ionic liquid doped water-soluble polythiophene composite film.
Preferably, the ionic liquid is 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt, 1-ethyl-3-methylimidazole perchlorate or 1-ethyl-3-methylimidazole p-toluenesulfonate.
Preferably, the mass ratio of the 3, 4-ethylenedioxythiophene to the lithium perchlorate is 8.925: 0.3197-0.638.
Preferably, the mass ratio of the 3, 4-ethylenedioxythiophene to the ionic liquid is 8.925: 5-8.
Preferably, the mass ratio of the 3, 4-ethylenedioxythiophene to the ionic liquid is 8.925: 6.
Preferably, the mass ratio of the 3, 4-ethylenedioxythiophene to the sodium dodecyl benzene sulfonate is 8.925: 4.5-8.
Preferably, the electrochemical deposition is performed using an Auto-lab electrochemical workstation in combination with a three-electrode system, with indium tin oxide conductive glass as the WE, a platinum sheet as the CE, and a silver chloride glass tube as the RE.
Preferably, the deposition voltage of the electrochemical deposition is 0.1-1.2V, and the number of deposition turns is 10-25.
The invention also provides the ionic liquid doped water-soluble polythiophene composite film prepared by the preparation method of the technical scheme.
The invention also provides the application of the ionic liquid doped water-soluble polythiophene composite film in the technical scheme in the field of electrochromism.
The invention provides a preparation method of an ionic liquid doped water-soluble polythiophene (PEDOT: PSS/EMI-TSFI) composite film, which comprises the following steps: mixing sodium polystyrene sulfonate, 3, 4-ethylenedioxythiophene, lithium perchlorate, sodium dodecyl benzene sulfonate and water to obtain an anionic water deposition solution; mixing ionic liquid with the anionic water deposition solution to obtain deposition solution; and carrying out electrochemical deposition by using the deposition solution to obtain the ionic liquid doped water-soluble polythiophene composite film. The invention firstly prepares sodium polystyrene sulfonate (PSS), 3,4 Ethylene Dioxythiophene (EDOT) and lithium perchlorate (LiClO)4) Mixing Sodium Dodecyl Benzene Sulfonate (SDBS) and water to obtain a deposition solution containing a large amount of uniformly dispersed anions to replace the conventional organic solvent-based deposition solution, and simultaneously adding an ionic liquid (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide [ EMI-TFSI ]]1-Ethyl-3-methylimidazole perchlorate [ HOEtMIm-Cl ]]Or 1-ethyl-3-methylimidazole p-toluenesulfonate [ Hemin-Tos ]]) So as to promote the uniform dispersion of EDOT in water, increase free moving ions in the deposition solution, and then carry out electrochemical deposition by using an electrochemical workstation to obtain the ionic liquid doped water-soluble polythiophene composite film. The preparation method adopts an in-situ electrochemical polymerization method, realizes the water-soluble deposition preparation of PEDOT through secondary doping, and the obtained film has high electrochromic performance, high cycle stability and electrochemical activity.
Drawings
FIG. 1 is an electron micrograph of a PEDOT: PSS/EMI-TSFI composite film prepared in example 1;
FIG. 2 is an infrared spectrum of a PEDOT/PSS/EMI-TSFI composite film prepared in example 1;
FIG. 3 is a spectrum test chart of a PEDOT/PSS/EMI-TSFI composite film prepared in example 1;
FIG. 4 is a graph showing the stability test of the PEDOT/PSS/EMI-TSFI composite film prepared in example 1;
FIG. 5 is a spectrum test chart of a PEDOT/PSS/HOEtMIm-Cl composite film prepared in example 2;
FIG. 6 is a graph showing the stability test of the PEDOT/PSS/HOEtMIm-Cl composite film prepared in example 2;
FIG. 7 is a spectrum test chart of a PEDOT/PSS/Hemin-Tos composite film prepared in example 3;
FIG. 8 is a graph showing the stability test of the PEDOT/PSS/Hemin-Tos composite film prepared in example 3.
Detailed Description
The invention provides a preparation method of an ionic liquid doped water-soluble polythiophene composite film, which comprises the following steps;
mixing sodium polystyrene sulfonate, 3, 4-ethylenedioxythiophene, lithium perchlorate, sodium dodecyl benzene sulfonate and water to obtain an anionic water deposition solution;
mixing ionic liquid with the anionic water deposition solution to obtain deposition solution;
and carrying out electrochemical deposition by using the deposition solution to obtain the ionic liquid doped water-soluble polythiophene composite film.
The invention mixes sodium polystyrene sulfonate, 3,4 ethylene dioxythiophene, lithium perchlorate, sodium dodecyl benzene sulfonate and water to obtain anion water deposition solution.
In the invention, the mass ratio of the 3, 4-ethylenedioxythiophene to the lithium perchlorate is preferably 8.925: 0.3197-0.638, and more preferably 8.925: 0.523.
In the invention, the mass ratio of the 3, 4-ethylenedioxythiophene to the sodium dodecyl benzene sulfonate is preferably 8.925: 4.5-8, and more preferably 8.925: 5.
In the invention, EDOT and LiClO are preferably added at normal temperature4And adding SDBS into deionized water respectively, stirring uniformly by ultrasonic to obtain a mixed solution, and adding sodium polystyrene sulfonate into the mixed solution.
In the present invention, the volume ratio of the mixed solution to the sodium polystyrene sulfonate is preferably 1: 1.
In the invention, the dosage ratio of the 3, 4-ethylenedioxythiophene to the sodium polystyrene sulfonate is preferably 8.925g: 30-50 mL, and more preferably 8.925g:40 mL.
After the anionic water deposition solution is obtained, the ionic liquid and the anionic water deposition solution are mixed to obtain the deposition solution.
In the present invention, the ionic liquid is preferably 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt (EMI-TSFI), 1-ethyl-3-methylimidazole perchlorate salt (HOEtMIm-Cl) or 1-ethyl-3-methylimidazole p-toluenesulfonate salt (Hemin-Tos), and the sources of the 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazole perchlorate salt and 1-ethyl-3-methylimidazole p-toluenesulfonate salt are not particularly limited and commercially available products well known to those skilled in the art may be used.
In the invention, the mass ratio of the 3, 4-ethylenedioxythiophene to the ionic liquid is preferably 8.925: 5-8, and more preferably 8.925: 6.
The present invention preferably drops the ionic liquid into the anionic water deposition solution.
After the deposition solution is obtained, the invention carries out electrochemical deposition by using the deposition solution to obtain the ionic liquid doped water-soluble polythiophene composite film.
In the present invention, the electrochemical deposition is preferably performed using an Auto-lab electrochemical workstation in combination with a three-electrode system, preferably using Indium Tin Oxide (ITO) conductive glass as WE, platinum sheet as CE, and silver chloride glass tube as RE.
In the invention, the deposition voltage of the electrochemical deposition is preferably 0.1-1.2V, more preferably 0.5-1V, and the number of deposition turns is preferably 10-25, more preferably 15.
In the present invention, it is preferable to use CH separately before the electrochemical deposition3COCH3、C2H5OH、H2And O, carrying out ultrasonic treatment on the ITO conductive glass for 15-20 min, independently putting each ITO conductive glass into a small test tube for ultrasonic treatment in the ultrasonic process, putting the ITO conductive glass subjected to ultrasonic treatment into an oven for drying for 2h, and then putting the ITO conductive glass in a culture dish for sealed storage for later use.
The invention also provides the ionic liquid doped water-soluble polythiophene composite film (PEDOT: PSS/EMI-TSFI film) prepared by the preparation method in the technical scheme.
The invention also provides the application of the ionic liquid doped water-soluble polythiophene composite film in the technical scheme in the field of electrochromism.
In order to further illustrate the present invention, the ionic liquid doped water-soluble polythiophene composite film and the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A preparation method of an ionic liquid doped water-soluble polythiophene composite film comprises the following steps:
0.3197g of LiClO were weighed using an electronic balance430mL of LiClO was prepared4The aqueous solution was ultrasonically mixed well, 8.925g of EDOT and 4.5g of SDBS were weighed and slowly added dropwise, respectively, and the mixture was ultrasonically treated for 30 min. 30mL of the PSS solution was measured using a graduated cylinder and added to the above solution to obtain an aqueous deposition solution containing a large amount of uniformly dispersed anions.
And 5g of ionic liquid EMI-TFSI is weighed and mixed into the solution, and deposition liquid is obtained after uniform ultrasonic mixing.
The resulting deposition solution was poured into an electrolytic cell and subjected to in situ electrochemical polymerization using an Auto-lab electrochemical workstation in combination with a three-electrode system, in which 9mm x 50mm Indium Tin Oxide (ITO) conductive glass was used as WE, platinum sheet (Pt) was used as CE, and silver chloride (Ag/AgCl) (in saturated 3.0M NaCl solution) glass tube was used as RE. The deposition method is cyclic voltammetry, the deposition voltage is 1.2V, and the number of deposition turns is 10, so that the electrochromic PEDOT/PSS/EMI-TSFI film with a uniform surface is obtained.
FIG. 1 is an electron micrograph of a PEDOT: PSS/EMI-TSFI composite film prepared in example 1,
FIG. 2 is an infrared spectrum of the PEDOT/PSS/EMI-TSFI composite film prepared in example 1, and it can be seen from FIG. 2 that the main peak of the infrared spectrum is 1486cm-1，1364cm-1，1182cm-1，1055cm-1，893cm-1，756cm-1。
FIG. 3 is a spectrum test chart of the PEDOT/PSS/EMI-TSFI composite film prepared in example 1. from FIG. 3, it can be seen that the maximum transmittance difference reaches 34.6%, and the film undergoes reversible color conversion from dark blue in the reduced state to light blue in the oxidized state.
FIG. 4 is a graph showing stability tests of the PEDOT/PSS/EMI-TSFI composite film prepared in example 1. As can be seen from FIG. 4, after 1000 cycles of cyclic discoloration, the transmittance difference of the film remains constant and the electrochromic properties are stable.
Example 2
A preparation method of an ionic liquid doped water-soluble polythiophene composite film comprises the following steps:
0.523g of LiClO was weighed using an electronic balance440mL of LiClO was prepared4The aqueous solution is evenly mixed by ultrasonic, 8.925g of EDOT and 6g of SDBS are weighed and respectively and slowly dripped, and ultrasonic treatment is carried out for 30 min. 40mL of the PSS solution was measured using a graduated cylinder and added to the above solution to obtain an aqueous deposition solution containing a large amount of uniformly dispersed anions.
6g of ionic liquid 1-ethyl-3-methylimidazole perchlorate (HOEtMIm-Cl) is weighed and mixed into the solution, and deposition solution is obtained after ultrasonic mixing is carried out uniformly.
The resulting deposition solution was poured into an electrolytic cell and subjected to in situ electrochemical polymerization using an Auto-lab electrochemical workstation in combination with a three-electrode system, in which 9mm x 50mm Indium Tin Oxide (ITO) conductive glass was used as WE, platinum sheet (Pt) was used as CE, and silver chloride (Ag/AgCl) (in saturated 3.0M NaCl solution) glass tube was used as RE. The deposition method is cyclic voltammetry, the deposition parameter is 1.2V, the number of deposition turns is 15, and the electrochromic PEDOT/PSS/HOEtMIm-Cl film with uniform surface is obtained.
FIG. 5 is a spectrum test chart of a PEDOT/PSS/HOEtMIm-Cl composite film prepared in example 2. from FIG. 5, it can be seen that the maximum transmittance difference reaches 32.3%, and the film undergoes reversible color conversion from dark blue in a reduced state to light blue in an oxidized state.
FIG. 6 is a graph showing stability tests of PEDOT/PSS/HOEtMIm-Cl composite films prepared in example 2. As can be seen from FIG. 6, after 1000 cycles of cyclic discoloration, the transmittance difference of the films remained constant, and the electrochromic properties were stable.
Example 3
A preparation method of an ionic liquid doped water-soluble polythiophene composite film comprises the following steps:
0.638g of LiClO was weighed using an electronic balance450mL of LiClO was prepared4The aqueous solution is evenly mixed by ultrasonic, 8.925g of EDOT and 7g of SDBS are weighed and respectively and slowly dripped, and ultrasonic treatment is carried out for 30 min. 50mL of the PSS solution was measured using a graduated cylinder and added to the above solution to obtain an aqueous deposition solution containing a large amount of uniformly dispersed anions.
8g of ionic liquid 1-ethyl-3-methylimidazole p-toluenesulfonate (Hemin-Tos) is weighed and mixed into the solution, and deposition solution is obtained after ultrasonic mixing is carried out uniformly.
The resulting deposition solution was poured into an electrolytic cell and subjected to in situ electrochemical polymerization using an Auto-lab electrochemical workstation in combination with a three-electrode system, in which 9mm x 50mm Indium Tin Oxide (ITO) conductive glass was used as WE, platinum sheet (Pt) was used as CE, and silver chloride (Ag/AgCl) (in saturated 3.0M NaCl solution) glass tube was used as RE. The deposition method is cyclic voltammetry, the deposition voltage is 1.2V, the number of deposition turns is 25, and the electrochromic PEDOT/PSS/Hemin-Tos film with uniform surface is obtained.
FIG. 7 is a spectrum test chart of the PEDOT/PSS/Hemin-Tos composite film prepared in example 3. from FIG. 7, it can be seen that the maximum transmittance difference reaches 33.2%, and the film undergoes reversible color conversion from dark blue in the reduced state to light blue in the oxidized state.
FIG. 8 is a graph showing stability tests of the PEDOT/PSS/Hemin-Tos composite film prepared in example 3. As can be seen from FIG. 8, after 1000 cycles of cyclic discoloration, the transmittance difference of the film remains constant and the electrochromic properties are stable.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. The preparation method of the ionic liquid doped water-soluble polythiophene composite film is characterized by comprising the following steps of:
mixing sodium polystyrene sulfonate, 3, 4-ethylenedioxythiophene, lithium perchlorate, sodium dodecyl benzene sulfonate and water to obtain an anionic water deposition solution;
mixing ionic liquid with the anionic water deposition solution to obtain deposition solution;
and carrying out electrochemical deposition by using the deposition solution to obtain the ionic liquid doped water-soluble polythiophene composite film.
2. The method according to claim 1, wherein the ionic liquid is 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazole perchlorate salt, or 1-ethyl-3-methylimidazole p-toluenesulfonate salt.
3. The preparation method according to claim 1, wherein the mass ratio of the 3, 4-ethylenedioxythiophene to the lithium perchlorate is 8.925: 0.3197-0.638.
4. The preparation method according to claim 1, wherein the mass ratio of the 3, 4-ethylenedioxythiophene to the ionic liquid is 8.925: 5-8.
5. The preparation method according to claim 4, wherein the mass ratio of the 3, 4-ethylenedioxythiophene to the ionic liquid is 8.925: 6.
6. The preparation method according to claim 1, wherein the mass ratio of the 3, 4-ethylenedioxythiophene to the sodium dodecyl benzene sulfonate is 8.925: 4.5-8.
7. The method of claim 1, wherein the electrochemical deposition is performed using an Auto-lab electrochemical workstation in combination with a three-electrode system using indium tin oxide conductive glass as WE, platinum sheet as CE, and silver chloride glass tube as RE.
8. The method according to claim 1, wherein the electrochemical deposition has a deposition voltage of 0.1 to 1.2V and a number of deposition cycles of 10 to 25.
9. The ionic liquid doped water-soluble polythiophene composite film prepared by the preparation method of any one of claims 1-8.
10. The use of the ionic liquid doped water-soluble polythiophene composite membrane of claim 9 in the field of electrochromism.
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US20100084600A1 (en) * 2008-06-09 2010-04-08 Shahzada Ahmad Process for the preparation of solid polymer electrolytes using ionic liquids

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