CN112764285A - Electrochromic device based on polyvinyl alcohol-polyacrylic acid hydrogel electrolyte and preparation method and application thereof - Google Patents
Electrochromic device based on polyvinyl alcohol-polyacrylic acid hydrogel electrolyte and preparation method and application thereof Download PDFInfo
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- -1 1-butyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 6
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- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical group [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 2
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—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
- G02F1/01—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
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—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
- G02F1/01—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
- 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
- G02F2001/164—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 the electrolyte is made of polymers
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The electrochromic device is of a layered structure, and the layered structure sequentially comprises a transparent conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a transparent conductive electrode 2 from top to bottom. And provides a preparation method of an electrochromic device based on a polyvinyl alcohol-polyacrylic acid hydrogel electrolyte, which comprises the steps of preparing the polyvinyl alcohol-polyacrylic acid hydrogel electrolyte with high transmittance, high ionic conductivity, excellent electrochemical and thermal stability, and assembling the electrochromic device by using the polyvinyl alcohol-polyacrylic acid hydrogel electrolyte as the electrolyte. The device has the advantages of simple preparation process, energy conservation and environmental protection, can realize large-scale change of color and transmittance under an external electric field, has excellent comprehensive performance, and has huge application prospect in the fields of intelligent windows, energy-saving glass and the like.
Description
Technical Field
The invention relates to an electrochromic device based on a polyvinyl alcohol-polyacrylic acid hydrogel electrolyte, and a preparation method and application thereof.
Background
Electrochromism refers to a reversible change in color and transmittance in appearance by a redox reaction of a material when a certain voltage is applied, resulting in a change in optical absorption, transmittance, or reflectance. Therefore, the electrochromic material and the device have wide application prospects in the aspects of displays, electronic paper, intelligent windows and military camouflage.
A typical electrochromic device is composed of five layers: transparent conductive electrode-electrochromic layer-electrolyte layer-ion storage layer-transparent conductive electrode. The electrolyte layer is used as an important component of the electrochromic device, plays roles of ion conduction and electronic insulation, and forms a built-in electric field for the device and provides ions for charge compensation. At present, the electrolyte layer is mainly classified into a liquid electrolyte, a solid electrolyte, and a gel electrolyte. The liquid electrolyte has complete dissociation, low system viscosity, low ionic motion resistance and high mobility, but the device has poor packaging effect and poor thermal stability; the solid electrolyte is easy to process into a film, has high stability after packaging, but has low ionic conductivity and poor device interface binding property; the gel electrolyte has the advantages of both liquid electrolyte and solid electrolyte, and has high ionic conductivity, high stability and high mechanical strength, so that the gel electrolyte is widely applied to electrochromic devices.
The hydrogel has the characteristics similar to the structural characteristics of natural biological tissues and extracellular matrixes, and has the advantages of good light transmittance, excellent mechanical properties, environmental stability and the like, so that the hydrogel electrolyte has good application prospects in the fields of electrochemical devices and sensors. Polyvinyl alcohol (PVA) and polyacrylic acid (PAA) are two water-soluble polymers that have been extensively studied. PVA has high strength, excellent film forming performance and good biocompatibility, and PAA has stimulation responsiveness and biocompatibility. In the past, the PVA and PAA are blended to prepare the hydrogel, and the hydrogel is applied to the fields of artificial muscle, osmotic separation, stimulus response and the like, but the research in the electrochromic field is rarely reported.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polyvinyl alcohol-polyacrylic acid (PVA-PAA) hydrogel electrolyte and a preparation method of an electrochromic device thereof, wherein the hydrogel electrolyte has the characteristics of high transmittance, high ionic conductivity and good electrochemical and environmental stability, the electrochromic device based on the PVA-PAA hydrogel electrolyte is assembled, and different color changing effects and transmittance adjustment of the device are realized through electric field control, so that the electrochromic device is expected to be applied to the fields of intelligent glass, displays and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrochromic device is of a layered structure, and the layered structure sequentially comprises a transparent conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a transparent conductive electrode 2 from top to bottom, wherein the transparent conductive electrode 1 is Indium Tin Oxide (ITO) glass or polyethylene glycol terephthalate (ITO-PET), the conductive electrode 2 is ITO glass or ITO-PET, the electrochromic layer is a thiophene polymer, the ion storage layer is poly (3, 4-ethylenedioxythiophene) (PEDOT), and the electrolyte layer is a polyvinyl alcohol-polyacrylic acid (PVA-PAA) hydrogel electrolyte.
A preparation method of an electrochromic device based on a polyvinyl alcohol-polyacrylic acid hydrogel electrolyte comprises the following steps:
(1) preparation of polyvinyl alcohol-polyacrylic acid hydrogel electrolyte: adding polyvinyl alcohol (shown as a formula I) and polyacrylic acid (shown as a formula II) in a set proportion into a solvent, and mixing at a set temperature to obtain PVA-PAA (shown as a formula III); adding electrolyte with set content into the solution, pouring the obtained solution into a mould, and freezing and thawing at set temperature for set time to obtain PVA-PAA hydrogel electrolyte;
(2) preparation of electrochromic layer: in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), bithiophene triphenylamine (TBTPA) (shown in formula IV) with set concentration, an electrolyte and an organic solvent are used as electrolyte, transparent conductive substrate ITO glass or ITO-PET is used as the working electrode, a polymer PTBTPA film is prepared by adopting a constant potential electrolysis method, and is cleaned and dried by chromatographic grade acetonitrile to obtain an electrochromic layer;
(3) preparation of ion storage layer: in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), 3, 4-Ethylenedioxythiophene (EDOT) (shown as a formula V) with set concentration, an electrolyte and an organic solvent are used as electrolyte, transparent conductive substrate ITO glass or ITO-PET is used as the working electrode, a constant potential electrolysis method is adopted to prepare a polymer PEDOT film, and chromatographic grade acetonitrile is used for cleaning and drying to obtain an ion storage layer;
(4) assembling the electrochromic device: and (3) cutting the PVA-PAA hydrogel electrolyte, attaching the PVA-PAA hydrogel electrolyte to the electrode covered by the PEDOT film prepared in the step (3), attaching the electrode covered by the PTBTPA film prepared in the step (2) to the surface of the electrode, and packaging the periphery of the device to finally obtain the electrochromic device.
Further, in the step (1), the mass ratio of polyvinyl alcohol/polyacrylic acid is 100: 1-1: 1; the solvent is deionized water or water/dimethyl sulfoxide mixed solution; the dissolving temperature is 60-120 ℃.
Further, in the step (1), the electrolyte is lithium perchlorate or zinc trifluoromethanesulfonate; the mass ratio of the electrolyte to the polyvinyl alcohol-polyacrylic acid PVA-PAA is 0.01: 1-1: 1; the freezing and thawing temperature in the step (1) is-30-0 ℃, and the freezing and thawing time is 3-24 h.
Furthermore, in the step (2), the auxiliary electrode is a platinum electrode/titanium electrode, and the reference electrode is an Ag/AgCl electrode; the electrolyte is tetrabutylammonium perchlorate, lithium perchlorate or 1-butyl-3-methylimidazolium tetrafluoroborate; the organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or propylene carbonate; TBTPA monomer concentration of 1X 10-4～2×10-3mol/L, and the electrolyte concentration is 0.05-0.2 mol/L.
Further, in the step (2), the polymerization voltage of the constant potential electrolysis method is 1.1-1.4V, and the polymerization electric quantity is 0.02-0.1C; after the polymerization is finished, the dedoping is carried out under the voltage of-0.2 to-0.6V, and the dedoping time is 60 to 100 seconds.
Further, in the step (3), the auxiliary electrode is a platinum electrode/titanium electrode, and the reference electrode is an Ag/AgCl electrode; the electrolyte is tetrabutylammonium hexafluorophosphate or 1-butyl-3-methyl bis (trifluoromethanesulfonyl) imide; the organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or propylene carbonate; EDOT monomer concentration of 2X 10-4～10×10-3mol/L, and the electrolyte concentration is 0.05-0.2 mol/L.
Further, in the step (3), the polymerization voltage of the constant potential electrolysis method is 1.1-1.4V, and the polymerization electric quantity is 0.02-0.1C; after the polymerization is finished, the dedoping is carried out under the voltage of-0.2 to-0.6V, and the dedoping time is 60 to 100 seconds.
Further, in the step (4), the device package adopts epoxy resin glue or UV light curing glue.
The application of the electrochromic device based on the polyvinyl alcohol-polyacrylic acid hydrogel electrolyte realizes the adjustment of different color changing effects and transmittance of the device through electric field control, and the electrochromic device is applied to intelligent glass or a display.
The electrochromic device based on the PVA-PAA hydrogel electrolyte is characterized by an electrochemical workstation and an ultraviolet spectrophotometer, and the device can realize reversible change from orange yellow to blue under different voltages.
The invention has the beneficial effects that:
(1) a high transmittance (75%), high ionic conductivity (> 10-4S*cm-1) The novel PVA-PAA hydrogel electrolyte with excellent electrochemical and thermal stability is used as an electrolyte layer to assemble an electrochromic device, and the color and transmittance of the device can be adjusted under different voltages.
(2) The device is simple in preparation process, energy-saving and environment-friendly, has excellent comprehensive performance (optical contrast is 34.5%, response time is 0.7s, and fading is 1.7s), and has huge application prospects in the fields of intelligent glass, electronic paper and the like.
Drawings
FIG. 1 is a schematic diagram of the structure of an electrochromic device based on a PVA-PAA hydrogel electrolyte.
FIG. 2 is the transmittance of the PVA-PAA hydrogel electrolyte in examples 1 to 3.
FIG. 3 is an electrochemical impedance diagram of PVA-PAA hydrogel electrolytes of examples 1 to 3
Fig. 4 is a plot of the absorption spectrum of the device of example 2 over the full band at different voltages.
FIG. 5 shows the optical contrast and response time of the device of example 2 in a certain wavelength band.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
Referring to fig. 1 to 3, an electrochromic device based on a polyvinyl alcohol-polyacrylic acid hydrogel electrolyte is a layered structure, and the layered structure sequentially comprises a transparent conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a transparent conductive electrode 2 from top to bottom, wherein the transparent conductive electrode 1 for searching books is Indium Tin Oxide (ITO) glass or polyethylene terephthalate (ITO-PET), the conductive electrode 2 is ITO glass or ITO-PET, the electrochromic layer is a thiophene polymer, the ion storage layer is poly (3, 4-ethylenedioxythiophene) (PEDOT), and the electrolyte layer is a polyvinyl alcohol-polyacrylic acid (PVA-PAA) hydrogel electrolyte.
A preparation method of an electrochromic device based on PVA-PAA hydrogel electrolyte comprises the following steps:
(1) adding polyvinyl alcohol and polyacrylic acid in a mass ratio of 20:1 into a solvent, and dissolving at 80 ℃ to obtain polyvinyl alcohol-polyacrylic acid PVA-PAA; LiClO is added4Adding the solution (polyvinyl alcohol-polyacrylic acid PVA-PAA) into the solution, wherein the mass ratio of the polyvinyl alcohol-polyacrylic acid PVA-PAA to the electrolyte is 1:0.075, pouring the obtained solution into a mould, and freezing and thawing at-18 ℃ for 24h to obtain a PVA-PAA hydrogel electrolyte;
(2) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), 0.75mmol/L of bithiophene triphenylamine (TBTPA), electrolyte and organic solvent are used as electrolyte, transparent conductive substrate ITO glass is used as the working electrode, 1.2V constant potential and-0.6V de-doping are adopted to prepare a polymer PTBTPA film, and the polymer PTBTPA film is cleaned and dried by chromatographic grade acetonitrile to obtain an electrochromic layer;
(3) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), 5mmol/L of 3, 4-Ethylenedioxythiophene (EDOT), electrolyte and an organic solvent are used as electrolyte, transparent conductive substrate ITO glass is used as the working electrode, 1.3V constant potential and-0.5V de-doping are adopted to prepare a polymer PEDOT film, and the polymer PEDOT film is cleaned by chromatographic grade acetonitrile and dried to obtain an ion storage layer;
(4) cutting the PVA-PAA hydrogel electrolyte, attaching the PVA-PAA hydrogel electrolyte to an electrode covered by the prepared PEDOT film, attaching the electrode covered by the prepared PTBTPA film to the surface of the electrode, and packaging the periphery of the device by adopting epoxy resin glue to finally obtain the electrochromic device.
Example 2
Referring to fig. 1 to 5, a method for preparing an electrochromic device based on a PVA-PAA hydrogel electrolyte includes the following steps:
(1) adding polyvinyl alcohol and polyacrylic acid in a mass ratio of 20:1 into a solvent, and dissolving at 120 ℃ to obtain polyvinyl alcohol-polyacrylic acid PVA-PAA; LiClO is added4Adding the solution (polyvinyl alcohol-polyacrylic acid PVA-PAA) into the solution, wherein the mass ratio of the polyvinyl alcohol-polyacrylic acid PVA-PAA to the electrolyte is 1:0.150, pouring the obtained solution into a mould, and performing freeze thawing at-18 ℃ for 18h to obtain a PVA-PAA hydrogel electrolyte;
(2) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), 0.75mmol/L of bithiophene triphenylamine (TBTPA), electrolyte and organic solvent are used as electrolyte, transparent conductive substrate ITO glass is used as the working electrode, 1.2V constant potential and-0.6V de-doping are adopted to prepare a polymer PTBTPA film, and the polymer PTBTPA film is cleaned and dried by chromatographic grade acetonitrile to obtain an electrochromic layer;
(3) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), 5mmol/L of 3, 4-Ethylenedioxythiophene (EDOT), electrolyte and an organic solvent are used as electrolyte, transparent conductive substrate ITO glass is used as the working electrode, 1.4V constant potential and-0.6V de-doping are adopted to prepare a polymer PEDOT film, and the polymer PEDOT film is cleaned by chromatographic grade acetonitrile and dried to obtain an ion storage layer;
(4) cutting the PVA-PAA hydrogel electrolyte, attaching the PVA-PAA hydrogel electrolyte to an electrode covered by the prepared PEDOT film, attaching the electrode covered by the prepared PTBTPA film to the surface of the electrode, and packaging the periphery of the device by adopting epoxy resin glue to finally obtain the electrochromic device.
Example 3
Referring to fig. 1 to 3, a method for preparing an electrochromic device based on a PVA-PAA hydrogel electrolyte includes the following steps:
(1) adding polyvinyl alcohol and polyacrylic acid in a mass ratio of 20:1 into a solvent, and dissolving at 120 ℃ to obtain polyvinyl alcohol-polyacrylic acid PVA-PAA; LiClO is added4Adding the solution (polyvinyl alcohol-polyacrylic acid PVA-PAA) into the solution, wherein the mass ratio of the polyvinyl alcohol-polyacrylic acid PVA-PAA to the electrolyte is 1:0.225, pouring the obtained solution into a mould, and freezing and thawing at-18 ℃ for 3h to obtain a PVA-PAA hydrogel electrolyte;
(2) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), 0.75mmol/L of bithiophene triphenylamine (TBTPA), electrolyte and organic solvent are used as electrolyte, transparent conductive substrate ITO glass is used as the working electrode, 1.2V constant potential and-0.6V de-doping are adopted to prepare a polymer PTBTPA film, and the polymer PTBTPA film is cleaned and dried by chromatographic grade acetonitrile to obtain an electrochromic layer;
(3) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), 5mmol/L of 3, 4-Ethylenedioxythiophene (EDOT), electrolyte and an organic solvent are used as electrolyte, transparent conductive substrate ITO glass is used as the working electrode, 1.4V constant potential and-0.6V de-doping are adopted to prepare a polymer PEDOT film, and the polymer PEDOT film is cleaned by chromatographic grade acetonitrile and dried to obtain an ion storage layer;
(4) cutting the PVA-PAA hydrogel electrolyte, attaching the PVA-PAA hydrogel electrolyte to an electrode covered by the prepared PEDOT film, attaching the electrode covered by the prepared PTBTPA film to the surface of the electrode, and packaging the periphery of the device by adopting epoxy resin glue to finally obtain the electrochromic flexible device.
Example 4
Referring to fig. 1 to 3, a method for preparing an electrochromic device based on a PVA-PAA hydrogel electrolyte includes the following steps:
(1) adding polyvinyl alcohol and polyacrylic acid in a mass ratio of 100:1 into a solvent, and dissolving at 120 ℃ to obtain polyvinyl alcohol-polyacrylic acid PVA-PAA; LiClO is added4Adding the solution (polyvinyl alcohol-polyacrylic acid PVA-PAA) into the solution, wherein the mass ratio of the polyvinyl alcohol-polyacrylic acid PVA-PAA to the electrolyte is 1:1, pouring the obtained solution into a mould, and performing freeze thawing at-30 ℃ for 24 hours to obtain a PVA-PAA hydrogel electrolyte;
(2) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), the ratio of 2 x 10 is-3Preparing a polymer PTBTPA film by taking mol/L bithiophene triphenylamine (TBTPA), electrolyte and an organic solvent as electrolyte and transparent conductive substrate ITO glass as a working electrode and adopting 1.4V constant potential and-0.6V dedoping, and cleaning and drying the polymer PTBTPA film by using chromatographic grade acetonitrile to obtain an electrochromic layer;
(3) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), the ratio of 10 multiplied by 10-3Preparing a polymer PEDOT film by taking mol/L3, 4-Ethylenedioxythiophene (EDOT), electrolyte and an organic solvent as electrolyte, taking transparent conductive substrate ITO glass as a working electrode and adopting 1.4V constant potential and-0.6V de-doping, cleaning with chromatographic grade acetonitrile and drying to obtain an ion storage layer;
(4) cutting the PVA-PAA hydrogel electrolyte, attaching the PVA-PAA hydrogel electrolyte to an electrode covered by the prepared PEDOT film, attaching the electrode covered by the prepared PTBTPA film to the surface of the electrode, and packaging the periphery of the device by adopting epoxy resin glue to finally obtain the electrochromic flexible device.
Example 5
Referring to fig. 1 to 3, a method for preparing an electrochromic device based on a PVA-PAA hydrogel electrolyte includes the following steps:
(1) adding polyvinyl alcohol and polyacrylic acid in a mass ratio of 1:1 into a solvent, and dissolving at 60 ℃ to obtain polyvinyl alcohol-polyacrylic acid PVA-PAA; LiClO is added4Adding into the above solution (polyethylene)Enol-polyacrylic acid PVA-PAA), the mass ratio of the polyvinyl alcohol-polyacrylic acid PVA-PAA to the electrolyte is 1:0.01, the obtained solution is poured into a mould, and freeze thawing is carried out for 3 hours at the temperature of 0 ℃, thus obtaining the PVA-PAA hydrogel electrolyte;
(2) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), the ratio of 1 x 10 is-4Preparing a polymer PTBTPA film by taking mmol/L bithiophene triphenylamine (TBTPA), electrolyte and an organic solvent as electrolyte and transparent conductive substrate ITO glass as a working electrode and adopting 1.1V constant potential and-0.2V dedoping, and cleaning and drying the polymer PTBTPA film by using chromatographic grade acetonitrile to obtain an electrochromic layer;
(3) in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), the ratio of 2 x 10 is-4Preparing a polymer PEDOT film by taking mol/L3, 4-Ethylenedioxythiophene (EDOT), electrolyte and an organic solvent as electrolyte, taking transparent conductive substrate ITO glass as a working electrode and adopting 1.1V constant potential and-0.2V de-doping, cleaning with chromatographic grade acetonitrile and drying to obtain an ion storage layer;
(4) cutting the PVA-PAA hydrogel electrolyte, attaching the PVA-PAA hydrogel electrolyte to an electrode covered by the prepared PEDOT film, attaching the electrode covered by the prepared PTBTPA film to the surface of the electrode, and packaging the periphery of the device by adopting epoxy resin glue to finally obtain the electrochromic flexible device.
Example 6
The application of the electrochromic device based on the polyvinyl alcohol-polyacrylic acid hydrogel electrolyte realizes the adjustment of different color changing effects and transmittance of the device through electric field control, and the electrochromic device is applied to intelligent glass or a display.
The embodiments described in this specification are merely illustrative of implementations of the inventive concepts, which are intended for purposes of illustration only. The scope of the present invention should not be construed as being limited to the particular forms set forth in the examples, but rather as being defined by the claims and the equivalents thereof which can occur to those skilled in the art upon consideration of the present inventive concept.
Claims (10)
1. The electrochromic device based on the polyvinyl alcohol-polyacrylic acid hydrogel electrolyte is characterized by being of a layered structure, wherein the layered structure sequentially comprises a transparent conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a transparent conductive electrode 2 from top to bottom, wherein the transparent conductive electrode 1 for searching books is Indium Tin Oxide (ITO) glass or polyethylene glycol terephthalate (ITO-PET), the conductive electrode 2 is ITO glass or ITO-PET, the electrochromic layer is a thiophene polymer, the ion storage layer is poly (3, 4-ethylenedioxythiophene), and the electrolyte layer is the polyvinyl alcohol-polyacrylic acid hydrogel electrolyte.
2. A method for preparing an electrochromic device based on a polyvinyl alcohol-polyacrylic acid hydrogel electrolyte according to claim 1, comprising the steps of:
(1) preparation of polyvinyl alcohol-polyacrylic acid hydrogel electrolyte: adding polyvinyl alcohol and polyacrylic acid in a set proportion into a solvent, and mixing at a set temperature to obtain polyvinyl alcohol-polyacrylic acid PVA-PAA; adding electrolyte with set content into the solution, pouring the obtained solution into a mould, and freezing and thawing at set temperature for set time to obtain PVA-PAA hydrogel electrolyte;
(2) preparation of electrochromic layer: in a three-electrode system, bithiophene triphenylamine TBTPA with set concentration, electrolyte and organic solvent are used as electrolyte, transparent conductive substrate ITO glass or ITO-PET is used as a working electrode, a constant potential electrolysis method is adopted to prepare a polymer PTBTPA film, and the polymer PTBTPA film is cleaned and dried by chromatographic grade acetonitrile to obtain an electrochromic layer;
(3) preparation of ion storage layer: in a three-electrode system, 3, 4-ethylenedioxythiophene EDOT with set concentration, an electrolyte and an organic solvent are used as electrolyte, transparent conductive substrate ITO glass or ITO-PET is used as a working electrode, a polymer PEDOT film is prepared by adopting a constant potential electrolysis method, and the polymer PEDOT film is cleaned and dried by chromatographic grade acetonitrile to obtain an ion storage layer;
(4) assembling the electrochromic device: and (3) cutting the PVA-PAA hydrogel electrolyte, attaching the PVA-PAA hydrogel electrolyte to the electrode covered by the PEDOT film prepared in the step (3), attaching the electrode covered by the PTBTPA film prepared in the step (2) to the surface of the electrode, and packaging the periphery of the device to finally obtain the electrochromic device.
3. The preparation method according to claim 2, wherein in the step (1), the mass ratio of polyvinyl alcohol/polyacrylic acid is 100:1 to 1: 1; the solvent is deionized water or water/dimethyl sulfoxide mixed solution; the dissolving temperature is 60-120 ℃.
4. The production method according to claim 2 or 3, wherein in the step (1), the electrolyte is lithium perchlorate or zinc trifluoromethanesulfonate; the mass ratio of the electrolyte to the polyvinyl alcohol-polyacrylic acid PVA-PAA is 0.01: 1-1: 1; the freezing and thawing temperature in the step (1) is-30-0 ℃, and the freezing and thawing time is 3-24 h.
5. The production method according to claim 2 or 3, wherein in the step (2), the auxiliary electrode is a platinum/titanium electrode, and the reference electrode is an Ag/AgCl electrode; the electrolyte is tetrabutylammonium perchlorate, lithium perchlorate or 1-butyl-3-methylimidazolium tetrafluoroborate; the organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or propylene carbonate; TBTPA monomer concentration of 1X 10-4～2×10-3mol/L, and the electrolyte concentration is 0.05-0.2 mol/L.
6. The method according to claim 2 or 3, wherein in the step (2), the polymerization voltage of the potentiostatic electrolysis method is 1.1 to 1.4V, and the polymerization capacity is 0.02 to 0.1C; after the polymerization is finished, the dedoping is carried out under the voltage of-0.2 to-0.6V, and the dedoping time is 60 to 100 seconds.
7. The production method according to claim 2 or 3, wherein in the step (3), the auxiliary electrode is a platinum/titanium electrode, and the reference electrode is an Ag/AgCl electrode; the electrolyte is tetrabutylammonium hexafluorophosphate or 1-butyl-3-methyl bis (trifluoromethanesulfonyl) imide; the organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or carbonAcrylic acid ester; EDOT monomer concentration of 2X 10-4～10×10-3mol/L, and the electrolyte concentration is 0.05-0.2 mol/L.
8. The method according to claim 2 or 3, wherein in the step (3), the polymerization voltage of the potentiostatic electrolysis method is 1.1 to 1.4V, and the polymerization capacity is 0.02 to 0.1C; after the polymerization is finished, the dedoping is carried out under the voltage of-0.2 to-0.6V, and the dedoping time is 60 to 100 seconds.
9. The method according to claim 2 or 3, wherein in the step (4), the device package is made of epoxy glue or UV light-cured glue.
10. Use of an electrochromic device based on a polyvinyl alcohol-polyacrylic acid hydrogel electrolyte according to claim 1 for the application in smart glasses or displays, with different color effects and adjustment of the transmittance of the device being achieved by electric field control.
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