CN112666770B - Electrochromic Flexible Device Based on P(SPMA-MMA) Hydrogel Electrolyte and Its Preparation and Application - Google Patents

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

Electrochromic flexible devices based on P(SPMA-MMA) hydrogel electrolyte and their fabrication Preparation method and application

technical field

The invention relates to an electrochromic flexible device based on poly(3-propyl methacrylate sulfonate potassium salt-methyl methacrylate) (P(SPMA-MMA)) hydrogel electrolyte, a preparation method and the same application.

Background technique

Electrochromism means that under the action of a certain voltage, the material undergoes a redox reaction, resulting in a change in its optical absorption, transmittance or reflectance, and the appearance is reflected as a reversible change in color. Due to this special property, electrochromic materials and devices have broad application prospects in displays, electronic paper, smart windows, and military camouflage.

A typical electrochromic device consists of five layers: a transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, and another transparent conductive layer. Among them, the electrolyte layer acts as an ion conductive layer, which separates the electrochromic layer from the ion storage layer, but allows ions to pass through, which directly affects the diffusion and insertion/extraction rates of ions, thereby affecting the performance of electrochromic devices. At present, electrolytes are mainly divided into liquid electrolytes, solid electrolytes and gel electrolytes. Liquid electrolytes have high ionic conductivity, but when assembling electrochromic devices, there are often defects such as unstable chemical properties, difficult to package, and easy to leak during use; solid electrolytes have high stability after packaging because they do not contain solvents, but their ionic conductivity It is difficult to meet the requirements of fast response of electrochromic devices. In addition, the interface between the solid electrolyte and the adjacent active layer is a rigid bond, and the separation of the electrolyte and the active layer is prone to cause device failure. In contrast, gel electrolytes Due to its high ionic conductivity and easy assembly, it is widely used in electrochromic devices.

Hydrogels have attracted extensive attention due to their similar properties to natural biological tissues and extracellular matrix structures, as well as good permeability, excellent mechanical properties, and good environmental stability. In recent years, hydrogel electrolytes have been preliminarily studied and applied in the fields of electrochemical devices and sensors due to their high ionic conductivity and excellent mechanical properties.

SUMMARY OF THE INVENTION

In order to overcome the deficiencies of the prior art, the present invention provides an electrochromic electrolyte based on poly(3-propyl methacrylate sulfonate potassium salt-methyl methacrylate) (P(SPMA-MMA)) hydrogel electrolyte Fabrication of flexible devices, development of a novel hydrogel electrolyte based on poly(3-propyl methacrylate potassium salt-methyl methacrylate) (P(SPMA-MMA)) with high permeability The electrochromic flexible device based on hydrogel electrolyte is finally assembled; the different color changing effects and transmittance adjustment of the device are realized by electric field control, which is expected to be applied to portable , wearable and other flexible display fields.

In order to achieve the above object, the present invention adopts the following technical solutions:

An electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, the electrochromic flexible device is a layered structure, and the layered structure from top to bottom is a conductive electrode 1, an electrochromic layer, an electrolyte layer, an ion storage layer and a conductive electrode 2, wherein the conductive electrode 1 is an indium tin oxide-polyethylene terephthalate (ITO-PET) flexible electrode, and 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 P(SPMA-MMA) hydrogel electrolyte, comprising the following steps:

(1) Preparation of P(SPMA-MMA) hydrogel electrolyte: a set ratio of potassium 3-sulfopropyl methacrylate (as shown in formula I) and methyl methacrylate (as shown in formula II) shown), the initiator are added to the reaction solvent together, and at the set temperature, the polymerization is obtained to obtain P (SPMA-MMA) (as shown in formula III); P (SPMA-MMA) is added to the glycerol/water containing a certain concentration of electrolyte In the mixed solution, drying at the set temperature to remove part of the water, namely obtain the P(SPMA-MMA) hydrogel electrolyte;

(2) Preparation of electrochromic layer: in a three-electrode system (including a reference electrode, an auxiliary electrode, and a working electrode), a set concentration of dithiophene triphenylamine (TBTPA) (as shown in formula IV), electrolyte , the organic solvent is the electrolyte, the transparent conductive substrate ITO-PET is used as the working electrode, the polymer PTBTPA film is prepared by the constant potential electrolysis method, and the electrochromic layer is obtained by washing and drying with chromatographic grade acetonitrile;

(3) Preparation of ion storage layer: in a three-electrode system (including a reference electrode, an auxiliary electrode, and a working electrode), a set concentration of 3,4-ethylenedioxythiophene (EDOT) (as shown in formula V) , electrolyte and organic solvent are used as electrolyte, and transparent conductive substrate ITO-PET is used as working electrode, and polymer PEDOT film is prepared by potentiostatic electrolysis method, washed with chromatographic grade acetonitrile and dried to obtain ion storage layer;

(4) Assembly of the electrochromic flexible device: cut the P(SPMA-MMA) hydrogel electrolyte, and stick it on the electrode covered by the PEDOT film prepared in step (3). The covered electrodes are face-to-face and packaged on the periphery of the device to finally obtain an electrochromic flexible device.

Further, in the step (1), the material ratio of 3-propyl methacrylate potassium salt and methyl methacrylate is 1:1 to 1:10; the initiator is benzoyl peroxide, The mass ratio of benzoyl peroxide to 3-sulfopropyl methacrylate potassium salt is 1:100-1:1000.

Still further, in the step (1), the reaction solvent is N,N-dimethylformamide and water, and the mass ratio is 1:1 to 1:20; the polymerization temperature is 30°C to 120°C, and the polymerization time is 12～24h.

Further, in the step (1), the electrolyte is lithium perchlorate or zinc trifluoromethanesulfonate, the mass ratio of P(SPMA-MMA) to the electrolyte is 1:0.01 to 1:1; the mass ratio of glycerol to water 1:1 to 1:100.

Further, in the step (1), the drying temperature is 30°C～120°C, and the drying time is 0.5h～10h.

Further, in the step (2), the auxiliary electrode is a platinum electrode/titanium electrode, the reference electrode is an Ag/AgCl electrode; the electrolyte is tetrabutylammonium perchlorate, lithium perchlorate or 1-butyl-3- Methylimidazole tetrafluoroborate; the organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or propylene carbonate; the concentration of TBTPA monomer is 1×10 ^-4 to 2×10 ^-3 mol/L, and the electrolyte concentration It is 0.05～0.2mol/L.

Further, in the step (2), the polymerization voltage of the potentiostatic electrolysis method is 1.1-1.4V, and the polymerization electricity is 0.02-0.1C; The time is 60 to 100s.

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-methylbis(tris(tributyl)) Fluoromethanesulfonyl)imide salt; the organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or propylene carbonate; the EDOT monomer concentration is 2×10 ^-4 -10×10 ^-3 mol/L, and the electrolyte concentration It is 0.05～0.2mol/L.

Further, in the step (3), the potentiostatic electropolymerization voltage is 1.1-1.4V, and the polymerization electricity is 0.02-0.1C; For 60 ~ 100s.

Further, in the step (4), epoxy resin glue or UV light curing glue is used for device encapsulation.

The application of an electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, which realizes the adjustment of different color changing effects and transmittance of the device through electric field control, and is applied to portable and wearable flexible display devices.

Electrochromic flexible devices based on P(SPMA-MMA) hydrogel electrolytes were characterized by electrochemical workstation and UV spectrophotometer, which can reversibly change from orange-yellow to blue at different voltages.

Compared with the prior art, the beneficial effects of the present invention are mainly reflected in:

(1) A new hydrogel electrolyte with high transmittance (>85%), high ionic conductivity (>10* ^-4 S*cm ^-1 ), excellent electrochemical and thermal stability was developed, and the It serves as an electrolyte layer to assemble an electrochromic flexible device, which can adjust the color and transmittance of the device under different voltages.

(2) The device preparation process is simple, energy-saving and environmentally friendly, and has excellent overall performance (optical contrast ratio of 31%, response time coloring 0.48s, fading 1.1s), and has huge potential in the field of portable and wearable flexible displays such as smart watches and color electronic paper. application prospects.

Description of drawings

Figure 1 is a schematic diagram of the structure of electrochromic flexible devices based on P(SPMA-MMA) hydrogel electrolyte.

Figure 2 is the permeability of Example 1-3P (SPMA-MMA) hydrogel electrolyte.

Figure 3 is an electrochemical impedance plot of Example 1-3P (SPMA-MMA) hydrogel electrolyte.

Figure 4 is a cyclic voltammetry curve of Example 2P (SPMA-MMA) hydrogel electrolyte.

5 is the optical contrast and response time of the electrochromic flexible device based on the P(SPMA-MMA) hydrogel electrolyte in Example 2.

The present invention will be further described below with reference to the accompanying drawings.

Example 1

1 to 3, an electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, the electrochromic flexible device is a layered structure, and the layered structure is in order from top to bottom Conductive electrode 1, electrochromic layer, electrolyte layer, ion storage layer and conductive electrode 2, wherein the conductive electrode 1 is an indium tin oxide-polyethylene terephthalate (ITO-PET) flexible electrode, and the conductive electrode 2 It 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 P(SPMA-MMA) hydrogel electrolyte, comprising the following steps:

(1) adding the methacrylic acid 3-sulfopropyl methacrylate potassium salt, methyl methacrylate and the initiator together with the material ratio of 1:1 to the reaction solvent, and polymerizing at 70° C. to obtain P(SPMA- MMA), initiator is benzoyl peroxide, and the mass ratio of benzoyl peroxide and 3-sulfopropyl methacrylate potassium salt is 1:500, and the reaction solvent is N,N-dimethylformamide and water , its mass ratio is 1:10; the polymerization time is 16h; P(SPMA-MMA) is added to the glycerol/water mixed solution containing zinc trifluoromethanesulfonate, P(SPMA-MMA) and trifluoromethanesulfonic acid The mass ratio of zinc is 1:0.075, the mass ratio of P(SPMA-MMA) and the mixed solution is 1:10, and the mass ratio of glycerol and water is 1:20. After drying at 80°C for 2 hours to remove part of the water, P( SPMA-MMA) hydrogel electrolyte;

(2) In the three-electrode system (including reference electrode, auxiliary electrode and working electrode), 0.75mmol/L dithiophene triphenylamine (TBTPA), electrolyte and organic solvent were used as electrolyte, and transparent conductive substrate ITO-PET was used as electrolyte. As the working electrode, the polymer PTBTPA film was prepared by 1.2V constant potential and -0.6V de-doping, washed with chromatographic grade acetonitrile and dried to obtain the electrochromic layer;

(3) In a three-electrode system (including a reference electrode, an auxiliary electrode, and a working electrode), 5 mmol/L 3,4-ethylenedioxythiophene (EDOT), an electrolyte, and an organic solvent were used as the electrolyte, and a transparent conductive substrate was used as the electrolyte. ITO-PET is the working electrode, using 1.4V constant potential, -0.6V de-doping to prepare the polymer PEDOT film, washing with chromatographic grade acetonitrile and drying to obtain the ion storage layer;

(4) The P(SPMA-MMA) hydrogel electrolyte was cut and attached to the electrode covered by the prepared PEDOT film, and the electrode covered by the prepared PTBTPA film was attached face to face, and epoxy resin glue was used on the periphery of the device. encapsulation, and finally an electrochromic flexible device is obtained.

Example 2

1 to 5, a preparation method of an electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, comprising the following steps:

(1) adding the methacrylic acid 3-sulfopropyl methacrylate potassium salt, methyl methacrylate, the initiator with the material ratio of 1:5 to the reaction solvent, and polymerizing at 30 ° C to obtain P(SPMA- MMA), the initiator is benzoyl peroxide, and the mass ratio of benzoyl peroxide and 3-sulfopropyl methacrylate potassium salt is 1:100, and the reaction solvent is N,N-dimethylformamide and water , its mass ratio is 1:1; the polymerization time is 12h; P(SPMA-MMA) is added to the glycerol/water mixed solution containing zinc trifluoromethanesulfonate, P(SPMA-MMA) and trifluoromethanesulfonic acid The mass ratio of zinc is 1:0.15, the mass ratio of P(SPMA-MMA) and the mixed solution is 1:10, and the mass ratio of glycerol and water is 1:1. After drying at 30°C for 10h to remove part of the water, P( SPMA-MMA) hydrogel electrolyte;

(2) In the three-electrode system (including reference electrode, auxiliary electrode and working electrode), 0.75mmol/L dithiophene triphenylamine (TBTPA), electrolyte and organic solvent were used as electrolyte, and transparent conductive substrate ITO-PET was used as electrolyte. As the working electrode, the polymer PTBTPA film was prepared by 1.2V constant potential and -0.6V de-doping, washed with chromatographic grade acetonitrile and dried to obtain the electrochromic layer;

(3) In a three-electrode system (including a reference electrode, an auxiliary electrode, and a working electrode), 5 mmol/L 3,4-ethylenedioxythiophene (EDOT), an electrolyte, and an organic solvent were used as the electrolyte, and a transparent conductive substrate was used as the electrolyte. ITO-PET is the working electrode, using 1.4V constant potential, -0.6V de-doping to prepare the polymer PEDOT film, washing with chromatographic grade acetonitrile and drying to obtain the ion storage layer;

(4) The P(SPMA-MMA) hydrogel electrolyte was cut and attached to the electrode covered by the prepared PEDOT film, and the electrode covered by the prepared PTBTPA film was attached face to face, and epoxy resin glue was used on the periphery of the device. encapsulation, and finally an electrochromic flexible device is obtained.

Example 3

1 to 3, a preparation method of an electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, comprising the following steps:

1) adding the 3-sulfopropyl methacrylate potassium salt of 1:10 in the amount of the substance to the reaction solvent together with methyl methacrylate and an initiator, and polymerizing at 100 ° C to obtain P(SPMA-MMA) ), the initiator is benzoyl peroxide, the mass ratio of benzoyl peroxide and 3-sulfopropyl methacrylate potassium salt is 1:1000, and the reaction solvent is N,N-dimethylformamide and water, The mass ratio is 1:20; the polymerization time is 24h; P(SPMA-MMA) is added to the glycerol/water mixed solution containing zinc trifluoromethanesulfonate, P(SPMA-MMA) and zinc trifluoromethanesulfonate The mass ratio of 0.225, the mass ratio of P(SPMA-MMA) and the mixed solution is 1:10, the mass ratio of glycerol and water is 1:100, and drying at 120 ° C for 0.5h to remove part of the water, that is, P(SPMA- MMA) hydrogel electrolyte;

(2) In the three-electrode system (including reference electrode, auxiliary electrode and working electrode), 0.75mmol/L dithiophene triphenylamine (TBTPA), electrolyte and organic solvent were used as electrolyte, and transparent conductive substrate ITO-PET was used as electrolyte. As the working electrode, the polymer PTBTPA film was prepared by 1.2V constant potential and -0.6V de-doping, washed with chromatographic grade acetonitrile and dried to obtain the electrochromic layer;

(3) In a three-electrode system (including a reference electrode, an auxiliary electrode, and a working electrode), 5 mmol/L 3,4-ethylenedioxythiophene (EDOT), an electrolyte, and an organic solvent were used as the electrolyte, and a transparent conductive substrate was used as the electrolyte. ITO-PET is the working electrode, using 1.4V constant potential, -0.6V de-doping to prepare the polymer PEDOT film, washing with chromatographic grade acetonitrile and drying to obtain the ion storage layer;

(4) The P(SPMA-MMA) hydrogel electrolyte was cut and attached to the electrode covered by the prepared PEDOT film, and the electrode covered by the prepared PTBTPA film was attached face to face, and epoxy resin glue was used on the periphery of the device. encapsulation, and finally an electrochromic flexible device is obtained.

Example 4

1 to 3, a preparation method of an electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, comprising the following steps:

1) adding the 3-sulfopropyl methacrylate potassium salt of 1:10 in the amount of the substance to the reaction solvent together with methyl methacrylate and an initiator, and polymerizing at 100 ° C to obtain P(SPMA-MMA) ), the initiator is benzoyl peroxide, the mass ratio of benzoyl peroxide and 3-sulfopropyl methacrylate potassium salt is 1:1000, and the reaction solvent is N,N-dimethylformamide and water, The mass ratio is 1:20; the polymerization time is 24h; P(SPMA-MMA) is added to the glycerol/water mixed solution containing zinc trifluoromethanesulfonate, P(SPMA-MMA) and zinc trifluoromethanesulfonate The mass ratio of P(SPMA-MMA) is 0.225, the mass ratio of P(SPMA-MMA) and the mixed solution is 1:10, and the mass ratio of glycerol and water is 1:100. After drying at 120°C for 0.5h to remove part of the water, P(SPMA- MMA) hydrogel electrolyte;

(2) In the three-electrode system (including reference electrode, auxiliary electrode and working electrode), 2×10 ^-3 mol/L dithiophene triphenylamine (TBTPA), electrolyte and organic solvent are used as electrolytes, and transparent conductive materials are used as electrolytes. The substrate ITO-PET is the working electrode, and the polymer PTBTPA film is prepared by using 1.4V constant potential and -0.6V de-doping, which is washed with chromatographic grade acetonitrile and dried to obtain the electrochromic layer;

(3) In a three-electrode system (including reference electrode, auxiliary electrode and working electrode), 10×10 ^-3 mol/L 3,4-ethylenedioxythiophene (EDOT), electrolyte and organic solvent were used as electrolytes , using the transparent conductive substrate ITO-PET as the working electrode, using 1.4V constant potential, -0.6V de-doping to prepare the polymer PEDOT film, washing with chromatographic grade acetonitrile and drying to obtain the ion storage layer;

(4) The P(SPMA-MMA) hydrogel electrolyte was cut and attached to the electrode covered by the prepared PEDOT film, and the electrode covered by the prepared PTBTPA film was attached face to face, and epoxy resin glue was used on the periphery of the device. encapsulation, and finally an electrochromic flexible device is obtained.

Example 5

1 to 3, a preparation method of an electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, comprising the following steps:

1) adding the 3-sulfopropyl methacrylate potassium salt of 1:10 in the amount of the substance to the reaction solvent together with methyl methacrylate and an initiator, and polymerizing at 100 ° C to obtain P(SPMA-MMA) ), the initiator is benzoyl peroxide, the mass ratio of benzoyl peroxide and 3-sulfopropyl methacrylate potassium salt is 1:1000, and the reaction solvent is N,N-dimethylformamide and water, The mass ratio is 1:20; the polymerization time is 24h; P(SPMA-MMA) is added to the glycerol/water mixed solution containing zinc trifluoromethanesulfonate, P(SPMA-MMA) and zinc trifluoromethanesulfonate The mass ratio of 0.225, the mass ratio of P(SPMA-MMA) and the mixed solution is 1:10, the mass ratio of glycerol and water is 1:100, and drying at 120 ° C for 0.5h to remove part of the water, that is, P(SPMA- MMA) hydrogel electrolyte;

(2) In the three-electrode system (including reference electrode, auxiliary electrode and working electrode), 1×10 ^-4 mol/L dithiophene triphenylamine (TBTPA), electrolyte and organic solvent are used as electrolytes, and transparent conductive materials are used as electrolytes. The substrate ITO-PET is the working electrode, and the polymer PTBTPA film is prepared by 1.1V constant potential and -0.2V de-doping, which is washed with chromatographic grade acetonitrile and dried to obtain the electrochromic layer;

(3) In a three-electrode system (including reference electrode, auxiliary electrode and working electrode), 2×10 ^-4 mol/L 3,4-ethylenedioxythiophene (EDOT), electrolyte and organic solvent were used as electrolytes , using the transparent conductive substrate ITO-PET as the working electrode, using a 1.1V constant potential, -0.2V de-doping to prepare a polymer PEDOT film, washing with chromatographic grade acetonitrile and drying to obtain an ion storage layer;

(4) The P(SPMA-MMA) hydrogel electrolyte was cut and attached to the electrode covered by the prepared PEDOT film, and the electrode covered by the prepared PTBTPA film was attached face to face, and epoxy resin glue was used on the periphery of the device. encapsulation, and finally an electrochromic flexible device is obtained.

Example 6

The application of an electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte, which realizes the adjustment of different color changing effects and transmittance of the device through electric field control, and is applied to portable and wearable flexible display devices.

The content described in the embodiments of the present specification is merely an enumeration of the implementation forms of the inventive concept, and is only used for illustration purposes. The protection scope of the present invention should not be construed as being limited to the specific forms stated in this embodiment, and the protection scope of the present invention also extends to equivalent technical means that those of ordinary skill in the art can think of according to the inventive concept.

Claims (10)

1. an electrochromic flexible device based on P (SPMA-MMA) hydrogel electrolyte, it is characterized in that, described electrochromic flexible device is a layered structure, and described layered structure is electrically conductive sequentially from top to bottom Electrode 1, electrochromic layer, electrolyte layer, ion storage layer and conductive electrode 2, wherein, conductive electrode 1 is indium tin oxide-polyethylene terephthalate flexible electrode, and conductive electrode 2 is 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 preparation method of the electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte as claimed in claim 1, is characterized in that, described preparation method comprises the following steps: (1) Preparation of P(SPMA-MMA) hydrogel electrolyte: add a set proportion of potassium 3-sulfopropyl methacrylate, methyl methacrylate, and an initiator into the reaction solvent, and in the set P(SPMA-MMA) is obtained by polymerization at a fixed temperature; P(SPMA-MMA) is added to a glycerol/water mixed solution containing an electrolyte of a set concentration, and dried at a set temperature to remove part of the water, to obtain P(SPMA- MMA) hydrogel electrolyte; (2) Preparation of electrochromic layer: In a three-electrode system, a set concentration of dithiophene triphenylamine, an electrolyte and an organic solvent was used as the electrolyte, and the transparent conductive substrate ITO-PET was used as the working electrode. The polymer PTBTPA film was prepared by the method, washed with chromatographic grade acetonitrile and dried to obtain the electrochromic layer; (3) Preparation of ion storage layer: In a three-electrode system, a set concentration of 3,4-ethylenedioxythiophene EDOT, an electrolyte, and an organic solvent were used as the electrolyte, and the transparent conductive substrate ITO-PET was used as the working electrode. The polymer PEDOT film was prepared by potentiostatic electrolysis, washed with chromatographic grade acetonitrile and dried to obtain an ion storage layer; (4) Assembly of the electrochromic flexible device: cut the P(SPMA-MMA) hydrogel electrolyte, and stick it on the electrode covered by the PEDOT film prepared in step (3). The covered electrodes are face-to-face and packaged on the periphery of the device to finally obtain an electrochromic flexible device. 3. preparation method as claimed in claim 2, is characterized in that, in described step (1), the material amount ratio of 3-sulfopropyl methacrylate potassium salt and methyl methacrylate is 1:1 ～1:10; the initiator is benzoyl peroxide, and the mass ratio of benzoyl peroxide to 3-propyl 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 its mass ratio is 1:1～1 : 20; the polymerization temperature is 30℃～120℃, and the polymerization time is 12h～24h. 5. preparation method as claimed in claim 2 or 3 is characterized in that, in described step (1), electrolyte is lithium perchlorate or zinc trifluoromethanesulfonate, and the quality of P (SPMA-MMA) and electrolyte The ratio is 1:0.01～1:1; the mass ratio of glycerin and water is 1:1～1:100. 6 . The preparation method according to claim 2 or 3 , wherein, in the step (1), the drying temperature is 30° C.˜120° C., and the drying time is 0.5 h˜10 h. 7 . 7. The preparation method according to claim 2 or 3, wherein in the step (2), the auxiliary electrode is a platinum electrode/titanium electrode, the reference electrode is an Ag/AgCl electrode; the electrolyte is a tetrabutyl high Ammonium chlorate, lithium perchlorate or 1-butyl-3-methylimidazolium tetrafluoroborate; organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or propylene carbonate; TBTPA monomer concentration is 1 ×10 ^-4 to 2×10 ^-3 mol/L, and the electrolyte concentration is 0.05 to 0.2 mol/L. 8. The preparation method according to claim 2 or 3, characterized in that, in the step (2), the potentiostatic electrolysis polymerization voltage is 1.1-1.4V, and the polymerization electricity is 0.02-0.1C; after the polymerization, the De-doping is performed at a voltage of -0.2 to -0.6 V, and the de-doping time is 60 to 100 s. 9. The preparation method according to claim 2 or 3, wherein 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 tetrabutylhexanone Ammonium fluorophosphate or 1-butyl-3-methylbis(trifluoromethanesulfonyl)imide salt; organic solvent is chromatographic grade dichloromethane, acetonitrile, dichloromethane or propylene carbonate; EDOT monomer concentration is 2 ×10 ^-4 ～10×10 ^-3 mol/L, the electrolyte concentration is 0.05～0.2 mol/L; In the step (3), the potentiostatic electropolymerization voltage is 1.1-1.4V, and the polymerization electricity is 0.02-0.1C; after the polymerization, de-doping is performed at a voltage of -0.2--0.6 V, and the de-doping time is 60 ~100s; In the step (4), the device packaging adopts epoxy resin glue or UV light curing glue. 10. An application of the electrochromic flexible device based on P(SPMA-MMA) hydrogel electrolyte as claimed in claim 1, which realizes the adjustment of different color-changing effects and transmittance of the device through electric field control, and is applied to portable , wearable flexible display devices.

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