CN112666770B - Electrochromic flexible device based on P (SPMA-MMA) hydrogel electrolyte and preparation method and application thereof - Google Patents
Electrochromic flexible device based on P (SPMA-MMA) hydrogel electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The electrochromic flexible device is of a layered structure, and the layered structure sequentially comprises a conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a conductive electrode 2 from top to bottom. And a preparation method of an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte, and provides a preparation method of a poly (3-sulfopropyl methacrylate potassium salt-methyl methacrylate) hydrogel electrolyte with high transmittance, high ionic conductivity and excellent electrochemical and thermal stability, and the electrochromic flexible device is assembled by using the electrolyte layer. The device is simple in preparation process, energy-saving and environment-friendly, can realize reversible change of color and transmittance under different voltages, is excellent in comprehensive performance, and has huge application prospects in the fields of portable and wearable flexible display such as intelligent watches and color electronic paper.
Description
Technical Field
The invention relates to an electrochromic flexible device based on a poly (3-sulfopropyl methacrylate potassium salt-methyl methacrylate) (P (SPMA-MMA)) hydrogel electrolyte, and a preparation method and application thereof.
Background
Electrochromism means that under the action of a certain voltage, a material undergoes an oxidation-reduction reaction, so that the optical absorption rate, the transmittance or the reflectance of the material are changed, and the appearance shows reversible change of color. Due to the special property, 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: a transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and another transparent conductive layer. Wherein the electrolyte layer acts as an ion conducting layer, separating the electrochromic layer from the ion storage layer, but allowing ions to pass through, which directly affects the diffusion, intercalation/deintercalation rates of the ions, thereby affecting the performance of the electrochromic device. At present, electrolytes are mainly classified into liquid electrolytes, solid electrolytes, and gel electrolytes. The ionic conductivity of the liquid electrolyte is high, but the defects of unstable chemical property, difficult packaging, easy leakage in use and the like exist when the electrochromic device is assembled; the solid electrolyte does not contain a solvent, so that the working stability is high after the encapsulation, but the ionic conductivity is low, the requirement of quick response of the electrochromic device is difficult to meet, and in addition, the interface combination of the solid electrolyte and the adjacent active layer belongs to rigid combination, so that the separation of the electrolyte and the active layer is easy to occur, and the device is failed; in contrast, gel electrolytes are widely used in electrochromic devices due to their advantages of high ionic conductivity, ease of assembly, and the like.
The hydrogel has similar characteristics to natural biological tissues and extracellular matrix structures, and has the advantages of good transmittance, excellent mechanical properties, good environmental stability and the like. In recent years, hydrogel electrolytes have been studied and applied primarily in the fields of electrochemical devices and sensors due to their high ionic conductivity, excellent mechanical properties, and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of an electrochromic flexible device based on a poly (3-sulfopropyl methacrylate potassium salt-methyl methacrylate) (P (SPMA-MMA)) hydrogel electrolyte, which develops a novel poly (3-sulfopropyl methacrylate potassium salt-methyl methacrylate) (P (SPMA-MMA)) hydrogel electrolyte with high transmittance, high ionic conductivity and good electrochemical and environmental stability, and finally assembles the electrochromic flexible device based on the hydrogel electrolyte; the adjustment of different color changing effects and transmittance of the device is realized through electric field control, so that the device is expected to be applied to the fields of portable, wearable and other flexible displays.
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrochromic flexible device is of a layered structure, and the layered structure sequentially comprises a conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a conductive electrode 2 from top to bottom, wherein the conductive electrode 1 is an indium tin oxide-polyethylene terephthalate (ITO-PET) flexible electrode, the conductive electrode 2 is an ITO-PET flexible electrode, the electrochromic layer is a thiophene polymer, the ion storage layer is poly (3, 4-ethylenedioxythiophene) (PEDOT), and the electrolyte layer is a P (SPMA-MMA) hydrogel electrolyte.
A preparation method of an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte comprises the following steps:
(1) preparation of P (SPMA-MMA) hydrogel electrolyte: adding a potassium methacrylate 3-sulfopropyl ester (shown as a formula I), methyl methacrylate (shown as a formula II) and an initiator into a reaction solvent together according to a set proportion, and polymerizing at a set temperature to obtain P (SPMA-MMA) (shown as a formula III); adding P (SPMA-MMA) into a glycerol/water mixed solution containing electrolyte with a certain concentration, and drying at a set temperature to remove part of water to obtain the P (SPMA-MMA) hydrogel electrolyte;
(2) preparation of electrochromic layer: in a three-electrode system (comprising a reference electrode, an auxiliary electrode and a working electrode), Taking Bithiophene Triphenylamine (TBTPA) (shown as a formula IV) with a set concentration, an electrolyte and an organic solvent as electrolyte, taking a transparent conductive substrate ITO-PET as the working electrode, preparing a polymer PTBTPA film by adopting a constant potential electrolysis method, cleaning with chromatographic grade acetonitrile and drying to obtain an electrochromic layer;
(3) preparation of an 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, a transparent conductive substrate ITO-PET is used as the working electrode, a polymer PEDOT film is prepared by adopting a constant potential electrolysis method, and the polymer PEDOT film is cleaned by chromatographic grade acetonitrile and dried to obtain an ion storage layer;
(4) assembling the electrochromic flexible device: cutting a P (SPMA-MMA) hydrogel electrolyte, attaching the cut P (SPMA-MMA) 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 flexible device.
Further, in the step (1), the mass ratio of 3-sulfopropyl methacrylate potassium salt to methyl methacrylate is 1: 1-1: 10; the initiator is benzoyl peroxide, and the mass ratio of the benzoyl peroxide to the 3-sulfopropyl methacrylate potassium salt is 1: 100-1: 1000.
Further, in the step (1), the reaction solvent is N, N-dimethylformamide and water, and the mass ratio of the N, N-dimethylformamide to the water is 1: 1-1: 20; the polymerization temperature is 30-120 ℃, and the polymerization time is 12-24 h.
Furthermore, in the step (1), the electrolyte is lithium perchlorate or zinc trifluoromethanesulfonate, and the mass ratio of the P (SPMA-MMA) to the electrolyte is 1: 0.01-1: 1; the mass ratio of the glycerol to the water is 1: 1-1: 100.
Further, in the step (1), the drying temperature is 30-120 ℃, and the drying time is 0.5-10 h.
Further, 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 tetrabutyl ammonium perchlorate and lithium perchlorateOr 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 -3 mol/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 -3 mol/L, and the electrolyte concentration is 0.05-0.2 mol/L.
Further, in the step (3), the constant potential electrolytic polymerization voltage 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.
An application of an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte realizes adjustment of different color changing effects and transmittance of the device through electric field control, and is applied to portable and wearable flexible display equipment.
Electrochromic flexible devices based on P (SPMA-MMA) hydrogel electrolytes, which can reversibly change from orange yellow to blue at different voltages, were characterized by an electrochemical workstation and an ultraviolet spectrophotometer.
Compared with the prior art, the invention has the following beneficial effects:
(1) a high transmittance (> 85%), high ionic conductivity (> 10) has been developed -4 S*cm -1 ) Novel hydrogel electrolyte having excellent electrochemical and thermal stability, and electrochromic flexible device assembled using the same as electrolyte layerThe device can realize the adjustment of the color and the transmittance of the device under different voltages.
(2) The device is simple in preparation process, energy-saving and environment-friendly, has excellent comprehensive performance (optical contrast is 31%, response time is 0.48s, and fading is 1.1s), and has huge application prospect in portable and wearable flexible display fields such as intelligent watches and colored electronic paper.
Drawings
FIG. 1 is a schematic diagram of the structure of an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte.
FIG. 2 is the transmittance of the hydrogel electrolyte of examples 1-3P (SPMA-MMA).
FIG. 3 is a graph of the electrochemical impedance of the hydrogel electrolyte of examples 1-3P (SPMA-MMA).
FIG. 4 is a cyclic voltammogram of the hydrogel electrolyte of example 2P (SPMA-MMA).
FIG. 5 is the optical contrast and response time of the electrochromic flexible device of example 2 based on P (SPMA-MMA) hydrogel electrolyte.
The invention is further described below with reference to the accompanying drawings.
Example 1
Referring to fig. 1 to 3, an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte is a layered structure, and the layered structure sequentially includes, from top to bottom, a conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a conductive electrode 2, where the conductive electrode 1 is an indium tin oxide-polyethylene terephthalate (ITO-PET) flexible electrode, the conductive electrode 2 is an ITO-PET flexible electrode, the electrochromic layer is a thiophene polymer, the ion storage layer is poly (3, 4-ethylenedioxythiophene) (PEDOT), and the electrolyte layer is a P (SPMA-MMA) hydrogel electrolyte.
A preparation method of an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte comprises the following steps:
(1) adding 3-sulfopropyl methacrylate potassium salt, methyl methacrylate and an initiator into a reaction solvent according to the mass ratio of 1:1, and polymerizing at 70 ℃ to obtain P (SPMA-MMA), wherein the initiator is benzoyl peroxide, the mass ratio of the benzoyl peroxide to the 3-sulfopropyl methacrylate potassium salt is 1:500, the reaction solvent is N, N-dimethylformamide and water, and the mass ratio of the N, N-dimethylformamide to the water is 1: 10; the polymerization time is 16 h; adding P (SPMA-MMA) into a glycerol/water mixed solution containing zinc trifluoromethanesulfonate, wherein the mass ratio of the P (SPMA-MMA) to the zinc trifluoromethanesulfonate is 1:0.075, the mass ratio of the P (SPMA-MMA) to the mixed solution is 1:10, and the mass ratio of the glycerol to the water is 1:20, drying at 80 ℃ for 2h to remove part of water to obtain the P (SPMA-MMA) 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, a transparent conductive substrate ITO-PET is used as the working electrode, a polymer PTBTPA film is prepared by adopting 1.2V constant potential and minus 0.6V dedoping, and 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, a transparent conductive substrate ITO-PET is used as the working electrode, a polymer PEDOT film is prepared by adopting 1.4V constant potential and-0.6V dedoping, and is cleaned by chromatographic grade acetonitrile and dried to obtain an ion storage layer;
(4) cutting a P (SPMA-MMA) hydrogel electrolyte, attaching the cut P (SPMA-MMA) 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 2
Referring to fig. 1 to 5, a method for preparing an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte includes the steps of:
(1) adding 3-sulfopropyl methacrylate potassium salt, methyl methacrylate and an initiator into a reaction solvent according to the mass ratio of 1:5, and polymerizing at 30 ℃ to obtain P (SPMA-MMA), wherein the initiator is benzoyl peroxide, the mass ratio of the benzoyl peroxide to the 3-sulfopropyl methacrylate potassium salt is 1:100, the reaction solvent is N, N-dimethylformamide and water, and the mass ratio of the N, N-dimethylformamide to the water is 1: 1; the polymerization time is 12 h; adding P (SPMA-MMA) into a glycerol/water mixed solution containing zinc trifluoromethanesulfonate, wherein the mass ratio of the P (SPMA-MMA) to the zinc trifluoromethanesulfonate is 1:0.15, the mass ratio of the P (SPMA-MMA) to the mixed solution is 1:10, and the mass ratio of glycerol to water is 1:1, drying at 30 ℃ for 10 hours to remove part of water to obtain a P (SPMA-MMA) 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, a transparent conductive substrate ITO-PET is used as the working electrode, a polymer PTBTPA film is prepared by adopting 1.2V constant potential and minus 0.6V dedoping, and 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, a transparent conductive substrate ITO-PET is used as the working electrode, a polymer PEDOT film is prepared by adopting 1.4V constant potential and-0.6V dedoping, and is cleaned by chromatographic grade acetonitrile and dried to obtain an ion storage layer;
(4) cutting a P (SPMA-MMA) hydrogel electrolyte, attaching the cut P (SPMA-MMA) 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 3
Referring to fig. 1 to 3, a method for preparing an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte includes the steps of:
1) adding 3-sulfopropyl methacrylate potassium salt, methyl methacrylate and an initiator into a reaction solvent according to the mass ratio of 1:10, and polymerizing at 100 ℃ to obtain P (SPMA-MMA), wherein the initiator is benzoyl peroxide, the mass ratio of the benzoyl peroxide to the 3-sulfopropyl methacrylate potassium salt is 1:1000, the reaction solvent is N, N-dimethylformamide and water, and the mass ratio of the N, N-dimethylformamide to the water is 1: 20; the polymerization time is 24 h; adding P (SPMA-MMA) into a glycerol/water mixed solution containing zinc trifluoromethanesulfonate, wherein the mass ratio of the P (SPMA-MMA) to the zinc trifluoromethanesulfonate is 0.225, the mass ratio of the P (SPMA-MMA) to the mixed solution is 1:10, and the mass ratio of the glycerol to the water is 1:100, drying at 120 ℃ for 0.5h to remove part of water to obtain the P (SPMA-MMA) 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, a transparent conductive substrate ITO-PET is used as the working electrode, a polymer PTBTPA film is prepared by adopting 1.2V constant potential and minus 0.6V dedoping, and 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, a transparent conductive substrate ITO-PET is used as the working electrode, a polymer PEDOT film is prepared by adopting 1.4V constant potential and-0.6V dedoping, and is cleaned by chromatographic grade acetonitrile and dried to obtain an ion storage layer;
(4) cutting a P (SPMA-MMA) hydrogel electrolyte, attaching the cut P (SPMA-MMA) 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 flexible device based on a P (SPMA-MMA) hydrogel electrolyte includes the steps of:
1) adding 3-sulfopropyl methacrylate potassium salt, methyl methacrylate and an initiator into a reaction solvent according to the mass ratio of 1:10, and polymerizing at 100 ℃ to obtain P (SPMA-MMA), wherein the initiator is benzoyl peroxide, the mass ratio of the benzoyl peroxide to the 3-sulfopropyl methacrylate potassium salt is 1:1000, the reaction solvent is N, N-dimethylformamide and water, and the mass ratio of the N, N-dimethylformamide to the water is 1: 20; the polymerization time is 24 h; adding P (SPMA-MMA) into a glycerol/water mixed solution containing zinc trifluoromethanesulfonate, wherein the mass ratio of the P (SPMA-MMA) to the zinc trifluoromethanesulfonate is 0.225, the mass ratio of the P (SPMA-MMA) to the mixed solution is 1:10, and the mass ratio of the glycerol to the water is 1:100, drying at 120 ℃ for 0.5h to remove part of water to obtain the P (SPMA-MMA) 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 -3 Preparing a polymer PTBTPA film by taking mol/L bithiophene triphenylamine (TBTPA), electrolyte and an organic solvent as electrolyte and a transparent conductive substrate ITO-PET as a working electrode and adopting 1.4V constant potential and-0.6V de-doping, 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 -3 Preparing a polymer PEDOT film by taking mol/L3, 4-Ethylenedioxythiophene (EDOT), electrolyte and an organic solvent as electrolyte and a transparent conductive substrate ITO-PET as a working electrode and adopting 1.4V constant potential and-0.6V dedoping, cleaning with chromatographic grade acetonitrile and drying to obtain an ion storage layer;
(4) cutting a P (SPMA-MMA) hydrogel electrolyte, attaching the cut P (SPMA-MMA) 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 adhesive to finally obtain the electrochromic flexible device.
Example 5
Referring to fig. 1 to 3, a method for preparing an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte includes the steps of:
1) adding 3-sulfopropyl methacrylate potassium salt, methyl methacrylate and an initiator into a reaction solvent according to the mass ratio of 1:10, and polymerizing at 100 ℃ to obtain P (SPMA-MMA), wherein the initiator is benzoyl peroxide, the mass ratio of the benzoyl peroxide to the 3-sulfopropyl methacrylate potassium salt is 1:1000, the reaction solvent is N, N-dimethylformamide and water, and the mass ratio of the N, N-dimethylformamide to the water is 1: 20; the polymerization time is 24 h; adding P (SPMA-MMA) into a glycerol/water mixed solution containing zinc trifluoromethanesulfonate, wherein the mass ratio of the P (SPMA-MMA) to the zinc trifluoromethanesulfonate is 0.225, the mass ratio of the P (SPMA-MMA) to the mixed solution is 1:10, and the mass ratio of the glycerol to the water is 1:100, drying at 120 ℃ for 0.5h to remove part of water, thus obtaining the P (SPMA-MMA) 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 -4 Preparing a polymer PTBTPA film by taking mol/L bithiophene triphenylamine (TBTPA), electrolyte and an organic solvent as electrolyte and a transparent conductive substrate ITO-PET as a working electrode and adopting 1.1V constant potential and-0.2V de-doping, 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 -4 Preparing a polymer PEDOT film by taking mol/L3, 4-Ethylenedioxythiophene (EDOT), electrolyte and an organic solvent as electrolyte and a transparent conductive substrate ITO-PET as a working electrode and adopting 1.1V constant potential and-0.2V dedoping, cleaning with chromatographic grade acetonitrile and drying to obtain an ion storage layer;
(4) cutting a P (SPMA-MMA) hydrogel electrolyte, attaching the cut P (SPMA-MMA) 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
An application of an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte realizes adjustment of different color changing effects and transmittance of the device through electric field control, and is applied to portable and wearable flexible display equipment.
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 embodiments, but is to be accorded the widest scope consistent with the principles and equivalents thereof as contemplated by those skilled in the art.
Claims (10)
1. The electrochromic flexible device is characterized in that the electrochromic flexible device is of a layered structure, and the layered structure sequentially comprises a conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a conductive electrode 2 from top to bottom, wherein the conductive electrode 1 is an indium tin oxide-polyethylene terephthalate flexible electrode, the conductive electrode 2 is an ITO-PET flexible electrode, the electrochromic layer is a thiophene polymer, the ion storage layer is poly (3, 4-ethylenedioxythiophene), and the electrolyte layer is a P (SPMA-MMA) hydrogel electrolyte.
2. A method for preparing an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte according to claim 1, characterized in that it comprises the following steps:
(1) preparation of P (SPMA-MMA) hydrogel electrolyte: adding 3-sulfopropyl methacrylate potassium salt, methyl methacrylate and an initiator into a reaction solvent according to a set proportion, and polymerizing at a set temperature to obtain P (SPMA-MMA); adding P (SPMA-MMA) into a glycerol/water mixed solution containing electrolyte with a set concentration, and drying at a set temperature to remove part of water to obtain the P (SPMA-MMA) hydrogel electrolyte;
(2) preparation of electrochromic layer: in a three-electrode system, bithiophene triphenylamine with set concentration, an electrolyte and an organic solvent are used as electrolyte, a transparent conductive substrate ITO-PET is used as a 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 an 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, a transparent conductive substrate 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 using chromatographic grade acetonitrile to obtain an ion storage layer;
(4) assembling the electrochromic flexible device: cutting a P (SPMA-MMA) hydrogel electrolyte, attaching the cut P (SPMA-MMA) 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 flexible device.
3. The method according to claim 2, wherein in the step (1), the mass ratio of the 3-sulfopropyl methacrylate potassium salt to the methyl methacrylate is 1:1 to 1: 10; the initiator is benzoyl peroxide, and the mass ratio of the benzoyl peroxide to the 3-sulfopropyl methacrylate potassium salt is 1: 100-1: 1000.
4. The preparation method according to claim 2 or 3, wherein in the step (1), the reaction solvent is N, N-dimethylformamide and water, and the mass ratio of N, N-dimethylformamide to water is 1: 1-1: 20; the polymerization temperature is 30-120 ℃, and the polymerization time is 12-24 h.
5. The production method according to claim 2 or 3, wherein in the step (1), the electrolyte is lithium perchlorate or zinc trifluoromethanesulfonate, and the mass ratio of P (SPMA-MMA) to the electrolyte is 1: 0.01-1: 1; the mass ratio of the glycerol to the water is 1: 1-1: 100.
6. The method according to claim 2 or 3, wherein in the step (1), the drying temperature is 30 ℃ to 120 ℃ and the drying time is 0.5h to 10 h.
7. The 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 -3 mol/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 (2), the polymerization voltage of the potentiostatic electrolysis method is 1.1 to 1.4V, and the polymerization electric quantity 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 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 propylene carbonate; EDOT monomer concentration of 2X 10 -4 ～10×10 -3 mol/L, the concentration of the electrolyte is 0.05-0.2 mol/L;
in the step (3), the constant potential electrolytic polymerization voltage is 1.1-1.4V, and the polymerization electric quantity is 0.02-0.1C; after the polymerization is finished, carrying out de-doping at a voltage of-0.2 to-0.6V for 60 to 100 s;
in the step (4), the device packaging adopts epoxy resin glue or UV light curing glue.
10. Use of an electrochromic flexible device based on a P (SPMA-MMA) hydrogel electrolyte according to claim 1, for the adjustment of different color-changing effects and transmittance of the device by electric field control, in portable, wearable flexible display devices.
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