阅读说明：本技术 一种高性能全固态聚合物电致变色器件及其制备方法 (High-performance all-solid-state polymer electrochromic device and preparation method thereof ) 是由 张�诚 杨园园 吕晓静 徐欣佳 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种高性能全固态聚合物电致变色器件及其制备方法,所述的高性能全固态聚合物电致变色器件结构依次包括：透明导电电极一、电致变色层、电解质层、离子储存层、透明导电电极二。通过选择PANI薄膜作为电致变色层,PEDOT:PSS为离子储存层,两种聚合物材料在施加电压时均表现为从透明到深色的颜色变化,因此获得了高光学对比度、快速响应的全固态聚合物电致变色器件,在智能眼镜、防眩目后视镜领域具有潜在的应用。且所述操作过程简单,原料成本低,且制备过程安全无污染,符合绿色生产的要求和保护环境的生态理念。(The invention discloses a high-performance all-solid-state polymer electrochromic device and a preparation method thereof, wherein the high-performance all-solid-state polymer electrochromic device sequentially comprises the following structures: the device comprises a first transparent conductive electrode, an electrochromic layer, an electrolyte layer, an ion storage layer and a second transparent conductive electrode. By selecting the PANI film as an electrochromic layer and the PEDOT: PSS as an ion storage layer, the two polymer materials show color change from transparent to dark color when voltage is applied, so that the all-solid-state polymer electrochromic device with high optical contrast and quick response is obtained, and has potential application in the fields of intelligent glasses and anti-glare rearview mirrors. And the operation process is simple, the raw material cost is low, the preparation process is safe and pollution-free, and the requirements of green production and the ecological concept of environment protection are met.)

1. A high-performance all-solid-state polymer electrochromic device is characterized in that: the structure of the high-performance all-solid-state polymer electrochromic device sequentially comprises: the device comprises a first transparent conductive electrode, an electrochromic layer, an electrolyte layer, an ion storage layer and a second transparent conductive electrode; the first transparent conductive electrode is composed of a first substrate and a first transparent conductive layer; the second transparent conductive electrode is composed of a second substrate and a second transparent conductive layer; the first substrate or the second substrate is glass, polybutylene terephthalate, polyurethane or polydimethylsiloxane respectively and independently; the first transparent conducting layer or the second transparent conducting layer is indium tin oxide, fluorine-doped tin oxide or silver nanowire respectively and independently; the electrochromic layer is a PANI film; the ion storage layer is PEDOT: (ii) a PSS polymer film.

2. A method for preparing the high-performance all-solid-state polymer electrochromic device according to claim 1, wherein: the method comprises the following steps:

(1) in a three-electrode electrolytic cell system, aniline is used as a monomer, sulfuric acid is used as a supporting electrolyte, water is used as a solvent, a mixed solution obtained by mixing is used as an electrolyte, a first transparent conductive electrode is used as a working electrode, and a PANI film deposited on the first transparent conductive electrode is obtained by adopting an electrochemical polymerization method at room temperature; in the mixed solution, the initial final concentration of the aniline monomer is 0.3-0.7 mol/L, and the initial final concentration of the supporting electrolyte sulfuric acid is 0.5-1.5 mol/L;

(2) polyethylene dioxythiophene-poly (styrenesulfonate) PEDOT: and PSS is dissolved in deionized water to obtain an aqueous solution of poly (ethylenedioxythiophene) -poly (styrene sulfonate), and the aqueous solution of poly (ethylenedioxythiophene) -poly (styrene sulfonate) is spin-coated on the second transparent conductive electrode by a spin-coating method to obtain PEDOT: PSS, oven dried to yield PEDOT: (ii) a PSS polymer film; the PEDOT: the mass ratio of the PSS to the water is 1: 90-1: 99;

(3) mixing a plasticizer and a polymer binder, heating and swelling, and marking as a system A; adding a supporting electrolyte into the mixed solvent, and carrying out ultrasonic treatment until the supporting electrolyte is completely dissolved, and marking as a system B; mixing the system A and the system B, performing ultrasonic treatment until the mixture is uniform, and performing rotary evaporation on the obtained solution to remove part of the solvent to obtain a gel-state electrolyte; the mass ratio of the plasticizer to the polymer binder is 1: 2-1: 5; the mass ratio of the supporting electrolyte to the mixed solvent is 1: 5-7;

(4) and (3) attaching a 3M glue frame with a square hole to the PEDOT prepared in the step (2): uniformly dripping the gel-state electrolyte obtained in the step (3) onto the second transparent conductive electrode covered by the PSS film into the 3M rubber frame, and then covering the first transparent conductive electrode covered by the PANI film prepared in the step (1) on the 3M rubber frame to ensure that the ratio of PEDOT: and respectively closely attaching the PSS film and the PANI film to the two sides of the rubber frame and forming a closed space with the rubber frame, and then drying the obtained device in an oven to finally obtain the all-solid-state polymer electrochromic device.

3. The method of claim 2, wherein: in the step (1), the voltage is 0.5-1.0V, the polymerization electric quantity is 0.04-0.08C, after the polymerization is finished, the polymer is obtained by dedoping for 50-70 s under the negative potential of-0.4-minus 0.8V, and then the polymer is dried for 4-8 h in a vacuum drying oven at the temperature of 60-80 ℃, and the PANI film deposited on the first transparent conductive substrate is obtained after rinsing and drying.

4. The method of claim 2, wherein: in the step (2), the spin coating parameters are as follows: the rotating speed is 1000-2000 rpm, and the time is 50-70 s.

5. The method of claim 2, wherein: in the step (2), the drying temperature is 120-140 ℃, and the drying time is 10-15 min.

6. The method of claim 2, wherein: in the step (3), the polymer binder is polymethyl methacrylate, polyvinylidene fluoride, polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene or polyacrylonitrile; the plasticizer is propylene carbonate, ethylene carbonate, dimethyl carbonate or diethyl carbonate.

7. The method of claim 2, wherein: in the step (3), the electrolyte is lithium perchlorate, lithium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate or 1-butyl-3-methylimidazolium bistrifluoromethylsulfimide.

8. The method of claim 2, wherein: in the step (3), the mixed solvent is a mixed solution of acetonitrile and dichloromethane, and the mass ratio of the acetonitrile to the dichloromethane is 1: 3 to 5.

9. The method of claim 2, wherein: in the step (4), the drying temperature of the electrochromic device is 40-70 ℃, and the drying time is 15-20 hours.

Technical Field

The invention relates to a preparation method of an all-solid-state polymer electrochromic device with high optical contrast and quick response, and has potential application in the fields of intelligent glasses, anti-dazzle rearview mirrors and the like.

Background

At present, most of electrochromic devices are liquid-state devices and solid-state devices. Among them, the liquid electrochromic device has problems of easy leakage, low safety, poor stability and the like because of existence of electrochromic materials or electrolyte materials in a liquid state, so that research and development of the solid electrochromic device are particularly important.

Among many conductive polymer materials, Polyaniline (PANI) has received great attention due to its characteristics of good thermal and chemical stability, easy film formation, low price, and the like. In particular, PANI exhibits multiple redox states at different potentials and thus different color changes. PANI is transparent in the reduced state, turns green in the intermediate oxidation state, and appears blue in the oxidation state, and thus is widely studied and applied as an electrochromic material.

Although PANI has been studied earlier as an electrochromic material, it is mostly applied to liquid electrochromic devices as an electrochromic layer, and the practical application is limited due to poor performance, especially insufficient transparency during color conversion. Therefore, the PANI material is used as the electrochromic layer, a high-performance all-solid-state polymer electrochromic device is developed, and the practical application of the device is further expanded.

Disclosure of Invention

The invention aims to provide an all-solid-state polymer electrochromic device and a preparation method and application thereof, aiming at the problems of easy leakage and poor electrochemical stability of a liquid device structure in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

the structure of a high-performance all-solid-state polymer electrochromic device sequentially comprises: the device comprises a first transparent conductive electrode, an electrochromic layer, an electrolyte layer, an ion storage layer and a second transparent conductive electrode; the first transparent conductive electrode is composed of a first substrate and a first transparent conductive layer; the second transparent conductive electrode is composed of a second substrate and a second transparent conductive layer; the first substrate or the second substrate is glass, polybutylene terephthalate (PET), polyurethane or Polydimethylsiloxane (PDMS); the first transparent conducting layer or the second transparent conducting layer is indium tin oxide, fluorine-doped tin oxide or silver nanowire respectively and independently; the electrochromic layer is a PANI film; the ion storage layer is PEDOT: (ii) a PSS polymer film.

Further, the high-performance all-solid-state polymer electrochromic device is prepared according to the following method:

(1) in a three-electrode electrolytic cell system, aniline is used as a monomer, sulfuric acid is used as a supporting electrolyte, water is used as a solvent, a mixed solution obtained by mixing is used as an electrolyte, a first transparent conductive electrode is used as a working electrode, and a PANI film deposited on the first transparent conductive electrode is obtained by adopting an electrochemical polymerization method at room temperature; in the mixed solution, the initial final concentration of the aniline monomer is 0.3-0.7 mol/L, and the initial final concentration of the supporting electrolyte sulfuric acid is 0.5-1.5 mol/L;

(2) polyethylene dioxythiophene-poly (styrenesulfonate) PEDOT: and PSS is dissolved in deionized water to obtain an aqueous solution of poly (ethylenedioxythiophene) -poly (styrene sulfonate), and the aqueous solution of poly (ethylenedioxythiophene) -poly (styrene sulfonate) is spin-coated on the second transparent conductive electrode by a spin-coating method to obtain PEDOT: PSS, oven dried to yield PEDOT: (ii) a PSS polymer film; the PEDOT: the mass ratio of the PSS to the water is 1: 90-1: 99;

(3) mixing a plasticizer and a polymer binder, heating and swelling, and marking as a system A; adding a supporting electrolyte into the mixed solvent, and carrying out ultrasonic treatment until the supporting electrolyte is completely dissolved, and marking as a system B; mixing the system A and the system B, performing ultrasonic treatment until the mixture is uniform, and performing rotary evaporation on the obtained solution to remove part of the solvent to obtain a gel-state electrolyte; the mass ratio of the plasticizer to the polymer binder is 1: 2-1: 5; the mass ratio of the supporting electrolyte to the mixed solvent is 1: 5-7;

(4) and (3) attaching a 3M glue frame with a square hole to the PEDOT prepared in the step (2): uniformly dripping the gel-state electrolyte obtained in the step (3) onto the second transparent conductive electrode covered by the PSS film into the 3M rubber frame, and then covering the first transparent conductive electrode covered by the PANI film prepared in the step (1) on the 3M rubber frame to ensure that the ratio of PEDOT: and respectively closely attaching the PSS film and the PANI film to the two sides of the rubber frame and forming a closed space with the rubber frame, and then drying the obtained device in an oven to finally obtain the all-solid-state polymer electrochromic device.

Further, in the step (1), the voltage is 0.5-1.0V, the polymerization electric quantity is 0.04-0.08C, after the polymerization is finished, the polymer is dedoped for 50-70 s at a negative potential of-0.4-0.8V, the polymer is obtained after leaching, and then the polymer is dried for 4-8 h in a vacuum drying oven at the temperature of 60-80 ℃, and the PANI film deposited on the first transparent conductive substrate is obtained after leaching and drying.

Further, in the step (2), the spin coating parameters are as follows: the rotating speed is 1000-2000 rpm, and the time is 50-70 s.

Further, in the step (2), the drying temperature is 120-140 ℃, and the drying time is 10-15 min.

Further, in the step (3), the polymer binder is polymethyl methacrylate (PMMA), polyvinylidene fluoride, polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene or polyacrylonitrile; the plasticizer is propylene carbonate, ethylene carbonate, dimethyl carbonate or diethyl carbonate.

Further, in the step (3), the electrolyte is lithium perchlorate, lithium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate or 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide.

Further, in the step (3), the mixed solvent is a mixed solution of acetonitrile and dichloromethane, and the mass ratio of the acetonitrile to the dichloromethane is 1: 3 to 5.

Further, in the step (4), the drying temperature of the electrochromic device is 40-70 ℃, and the drying time is 15-20 hours.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the invention, the PANI film is selected as the electrochromic layer, the PEDOT and the PSS are selected as the ion storage layer, and the two polymer materials show color change from transparent to dark color when voltage is applied, so that the all-solid-state polymer electrochromic device with high optical contrast and quick response is obtained, and the all-solid-state polymer electrochromic device has potential application in the fields of intelligent glasses and anti-glare rearview mirrors.

(2) The method has the advantages of simple operation process, low raw material cost, safe and pollution-free preparation process, and accords with the requirements of green production and the ecological concept of environmental protection.

Drawings

FIG. 1 is a schematic diagram of an all-solid-state electrochromic device; 1. the device comprises a first transparent conductive electrode 2, an electrochromic layer 3, an electrolyte layer 4, an ion storage layer 5 and a second transparent conductive electrode.

FIG. 2 is a color change effect graph of a device prepared in example 5.

FIG. 3 is a graph of the full band transmission of the device prepared in example 5 after scanning at 1100-300 nm.

FIG. 4 is the optical contrast at 630nm for the device prepared in example 5.

FIG. 5 is a response time test chart at a wavelength of 630nm for a device prepared in example 5.

Detailed Description

The invention is further described below by means of specific examples, without restricting its scope to these.

The raw materials and reagents used in the invention are all available from the market.