CN115840317A - Complementary type electro-dimming device - Google Patents

Abstract

The invention provides a complementary type electro-dimming device, which comprises a first conductive substrate, an electrochromic film layer, an electrolyte layer and a second conductive substrate which are arranged in sequence; the electrolyte layer includes reversibly deposited ions. Compared with the prior art, the invention introduces reversible deposition/dissolution reaction between metal ions and metal oxides into the electrochromic device for the first time, and utilizes the reversible deposition/dissolution reaction as a charge release/storage medium of the device, thereby effectively solving the problem of mismatching of the traditional counter electrode material (such as nickel oxide, prussian blue and the like) and the electrochemical process of the electrochromic thin film layer, and realizing stable circulation for five thousand times. Further preferably, the electrochromic light modulator with ultraviolet-visible-infrared full-spectrum modulation performance and high cycle stability can be realized by reasonably selecting and matching the electrochromic thin film layer, the electrolyte layer and the protective electrode layer.

Description

A Complementary Electroluminescence Dimming Device

technical field

The invention belongs to the technical field of electrochromism, and in particular relates to a complementary electroluminescence adjustment device.

Background technique

Electrochromic technology can cause significant and reversible changes in the optical properties of materials such as transmittance, absorptivity, reflectivity, etc. by applying an external bias voltage. Electrochromic technology is considered to be the most potential technology for building smart windows due to its good control effect on light and heat.

The traditional electroluminescent device consists of three parts, namely, the cathode electrochromic material (working electrode) which plays the role of dominant color change and transmittance modulation, and the anode electrochromic material (working electrode) which plays charge balance, ion storage, and auxiliary color change. material (counter electrode), and cations that can be reversibly intercalated/intercalated in the anodic and anodic color-changing materials.

Tungsten trioxide (WO ₃ ) thin film is regarded as the most scientifically and commercially valuable cathodic electrochromic material because of its colorless and transparent, high transmittance modulation window and excellent cycle stability. In traditional electroluminescent devices, the anode electrochromic materials are usually nickel oxide, Prussian blue, etc., but the electrochemical process matching between these materials and tungsten trioxide thin film is poor, which is reflected in two points: 1. Anode The charge storage capacity of the electrochromic film is an order of magnitude lower than that of the tungsten trioxide film; 2. The anodic electrochromic film is more prone to ion capture than the tungsten trioxide film during the cycle. This makes the assembled devices prone to bubbles and attenuation of transmittance modulation ability during the cycle process.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide a complementary electroluminescent device with complementary colors, full-spectrum shielding and long-term cycling stability.

The present invention provides a complementary electroluminescent device, comprising sequentially setting a first conductive substrate, an electrochromic thin film layer, an electrolyte layer and a second conductive substrate;

The electrolyte layer includes reversibly deposited ions.

Preferably, the electrochromic film layer is selected from one or more of inorganic color-changing material layer, polymer color-changing material layer and organic small molecule color-changing material layer;

The inorganic color-changing material layer is formed of an inorganic color-changing material; the inorganic color-changing material is selected from tungsten trioxide and/or vanadium pentoxide;

The polymer color-changing material layer is formed of a polymer color-changing material; the polymer color-changing material is one or more of polythiophene, polyaniline and their derivatives;

The organic small molecule color-changing material layer is formed of an organic small molecule color-changing material; the organic small molecule color-changing material is viologen and/or its derivatives.

Preferably, the reversible deposition ions are selected from Mn ²⁺ and/or Pb ²⁺ .

Preferably, the concentration of reversibly deposited ions in the electrolyte layer is 0.1-1 mol/L.

Preferably, the electrolyte layer also includes an ionic salt that participates in the electrochemical reaction of the electrochromic thin film layer to produce color changes and a solvent required for dissolving the ionic salt.

Preferably, the cation of the ionic salt includes H ⁺ ; the concentration of the cation of the ionic salt in the electrolyte layer is 0.1-5 mol/L; and the solvent is water.

Preferably, the cation of the ionic salt also includes one or more of alkali metal ions, alkaline earth metal ions and Al ³⁺ ; the alkali metal ions are selected from Li ⁺ and/or Na ⁺ ; the alkaline earth metal ions Selected from Mg ²⁺ and/or Ca ²⁺ ; the molar ratio of one or more of the alkali metal ions, alkaline earth metal ions and Al ³⁺ to H ⁺ is 1:9-9:1.

Preferably, a protective electrode layer is also included; the protective electrode layer is disposed between the electrolyte layer and the second conductive substrate; the protective electrode layer includes one or more of titanium dioxide, carbon materials and acid-resistant metal materials.

Preferably, the first conductive substrate and the second conductive substrate are independently selected from indium tin oxide glass or fluorine-doped tin oxide glass.

Preferably, it includes a first conductive substrate, a tungsten trioxide layer, an electrolyte layer, a titanium dioxide layer and a second conductive substrate arranged in sequence;

The electrolyte layer includes Mn ²⁺ and/or Pb ²⁺ .

The invention provides a complementary electroluminescent device, which comprises sequentially setting a first conductive substrate, an electrochromic thin film layer, an electrolyte layer and a second conductive substrate; the electrolyte layer includes reversible deposited ions. Compared with the prior art, the present invention introduces the reversible deposition/dissolution reaction between metal ions and metal oxides into the electrochromic device for the first time, and uses it as the charge release/storage medium of the device, effectively solving the problem of traditional counter electrode materials (such as nickel oxide, Prussian blue, etc.) and the electrochemical process of the electrochromic thin film layer do not match the problem, and achieved five thousand stable cycles.

Further preferably, the present invention can realize an electroluminescent device with ultraviolet-visible-infrared full-spectrum modulation performance and high cycle stability by rationally selecting and matching the electrochromic film layer, electrolyte layer and protective electrode layer.

Further preferably, the solvent of the electrolyte layer of the complementary electroluminescent device provided by the present invention is water, which is green and safe.

The experimental results show that the structure of the complementary electroluminescent device provided by the present invention abandons the traditional counter electrode material and only uses titanium dioxide with high transmittance as the corrosion-resistant protective layer, so that the device can be used in the visible light region in the faded state. It has high transmittance (ie T _bleach ~78%).

In addition, the deposited manganese dioxide has complementary colors to the tungsten trioxide in the colored state, and the device in the colored state can realize the full-spectrum shielding effect of ultraviolet-visible-infrared (ie, T _color ~ 0%).

When the device is in the colored state, tungsten trioxide and manganese dioxide are respectively located on the working electrode and the counter electrode in the form of a thin film, which makes the device have an excellent memory effect. When the voltage is removed, the transmittance in the colored state changes less than 20 minutes. 1%.

Description of drawings

Fig. 1 is a schematic cross-sectional structure diagram of a complementary electroluminescent device provided by the present invention;

Fig. 2 is the mechanism diagram of the coloring and fading process of the complementary electroluminescent device provided by the present invention;

Fig. 3 is a comparative diagram of transmittance modulation spectra of WO ₃ film (left) and Mn ²⁺ /MnO ₂ reversible deposition/dissolution (right) in Example 4 of the present invention;

Fig. 4 is the transmittance spectrum of WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ devices at different voltages in Example 4 of the present invention;

Fig. 5 is the transient transmittance response spectrum of WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ devices in Example 4 of the present invention;

Fig. 6 is a memory effect diagram of WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ devices in Example 4 of the present invention;

Fig. 7 is a comparative graph of transmittance spectra of WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ devices before and after 5000 cycles in Example 4 of the present invention;

Fig. 8 is a transmittance modulation spectrum diagram of WO ₃ //H ⁺ , Pb ²⁺ //TiO ₂ device in Example 4 of the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The invention provides a complementary electroluminescent device, which comprises sequentially setting a first conductive substrate, an electrochromic thin film layer, an electrolyte layer and a second conductive substrate; the electrolyte layer includes reversible deposited ions.

Referring to FIG. 1 , FIG. 1 is a schematic cross-sectional view of a complementary electro-dimming device provided by the present invention.

The complementary electroluminescent device provided by the present invention includes a first conductive substrate; the first conductive substrate can be a conductive substrate well known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably conductive glass, more preferably Indium tin oxide (ITO) glass or fluorine-doped tin oxide (FTO) glass is preferred.

The conductive glass is provided with an electrochromic thin film layer; the thickness of the electrochromic thin film layer is preferably 50-1000nm, more preferably 100-800nm, more preferably 300-800nm, more preferably 400-600nm, most preferably is 500nm; the electrochromic thin film layer is preferably one or more of an inorganic color-changing material layer, a polymer color-changing material layer and an organic small molecule color-changing material layer; the inorganic color-changing material layer is formed by an inorganic color-changing material; The inorganic color-changing material is preferably tungsten trioxide and/or vanadium pentoxide; the polymer color-changing material layer is formed by a polymer color-changing material; the polymer color-changing material is preferably polythiophene; the organic small molecule color-changing material layer It is formed by an organic small molecule color-changing material; the organic small molecule color-changing material is preferably viologen.

An electrolyte layer is provided on the electro-thin film layer; the thickness of the electrolyte layer is preferably 50-500 μm, more preferably 100-500 μm, more preferably 200-400 μm, most preferably 300 μm; the electrolyte layer A non-conductive frame is arranged around to prevent the electrolyte from flowing out; the electrolyte layer includes reversible deposition ions; the reversible deposition ions are metal ions that can undergo reversible deposition/dissolution reactions between metal ions and metal oxides. In the invention, it is preferably Mn ²⁺ and/or Pb ^{2 +} ; the concentration of reversibly deposited ions in the electrolyte layer is preferably 0.1-1 mol/L, more preferably 0.2-0.8 mol/L, and even more preferably 0.4-0.6 mol /L, most preferably 0.5mol/L; In the present invention, the electrolyte layer also includes participating in the electrochemical reaction of the electrochromic thin film layer and producing an ionic salt and a solvent required for dissolving the ionic salt; The cation of the ionic salt, that is, the guest ion preferably includes H ⁺ ; in the present invention, the cation preferably includes one or more of alkali metal ions, alkaline earth metal ions and Al ³⁺ in addition to H ⁺ ; the alkali metal The ions are preferably Li ⁺ and/or Na ⁺ ; the alkaline earth metal ions are preferably Mg ²⁺ and/or Ca ²⁺ ; one or more of the alkali metal ions, alkaline earth metal ions and Al ³⁺ are combined with H The molar ratio of ⁺ is 1:9 to 9:1, more preferably 3:7 to 7:3, more preferably 4:6 to 6:4, most preferably 5:5 to 6:4; the electrolyte The concentration of the cation of the ionic salt in the layer is preferably 0.1-5 mol/L, more preferably 0.5-4 mol/L, more preferably 0.5-2 mol/L, more preferably 0.6-1.5 mol/L, more preferably 0.8-1.2 mol/L, preferably 1mol/L; the anions in the electrolyte layer can be those well-known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably ClO ₄ ^- and/or SO ₄ ^{2 -} ; the solvent is a single or mixed solvent known to those skilled in the art that can dissolve ionic salts and provide active oxygen (that is, contain O ^2- ), preferably water in the present invention, which has green and safe characteristics.

The electrolyte layer is provided with a second conductive substrate; the second conductive substrate can be a conductive substrate well known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably conductive glass, more preferably indium oxide Tin glass or fluorine-doped tin oxide glass; the second conductive substrate and the electrochromic film layer do not conduct electrons with each other, and a non-conductive frame is preferably arranged between them, and an electrolyte layer is inside the non-conductive frame.

Since the second conductive substrate will be corroded by the hydrogen-ion-containing electrolyte under long-term cycles, the conductivity will be significantly reduced, so the complementary electroluminescent device provided by the present invention preferably further includes a protective electrode layer; the protective electrode layer is set Between the electrolyte layer and the second conductive substrate; the protective electrode layer preferably includes one or more of titanium dioxide, carbon materials and acid-resistant metal materials, more preferably a titanium dioxide layer; the thickness of the protective electrode layer Preferably it is 0.1-10 micrometers, More preferably, it is 0.5-5 micrometers, More preferably, it is 1-2 micrometers.

The complementary electroluminescent device provided by the present invention most preferably includes a first conductive substrate, a tungsten trioxide layer, an electrolyte layer, a titanium dioxide layer, and a second conductive substrate arranged in sequence; the electrolyte layer includes Mn ²⁺ and/or or Pb ²⁺ .

The present invention introduces the reversible deposition/dissolution reaction between metal ions and metal oxides into the electrochromic device for the first time, and uses it as the charge release/storage medium of the device, effectively solving the problem of traditional counter electrode materials (such as nickel oxide, Prussian blue etc.) and the electrochemical process of the electrochromic film layer do not match the problem, and achieved five thousand stable cycles; at the same time, through reasonable selection and matching of the electrochromic film layer, electrolyte layer and protective electrode layer, UV -Electro-tunable devices with visible-infrared full-spectrum modulation performance and high cycle stability.

The present invention also provides a method for preparing the above-mentioned complementary electroluminescent device, comprising the following steps: S1) depositing an electrochromic film layer on the first conductive substrate to obtain a color-changing electrode; S2) converting the electrochromic electrode of the color-changing electrode The color-changing thin film layer and the second conductive substrate are placed face to face, and a non-conductive frame is made between them. The non-conductive frame reserves an electrolyte inlet, and then the electrolyte is injected between the color-changing electrode and the second conductive substrate through the electrolyte inlet to form Electrolyte layer, closing the inlet of the electrolyte to obtain a complementary electroluminescent device.

The first conductive substrate, the electrochromic thin film layer, the electrolyte layer and the second conductive substrate are the same as those described above, and will not be repeated here.

In the present invention, preferably, a protective electrode layer is also formed on the second conductive substrate, and the electrochromic film layer of the color-changing electrode is placed face to face with the protective electrode layer of the second conductive substrate, and then a non-conductive frame is made between them.

In order to further illustrate the present invention, a complementary electroluminescent device provided by the present invention will be described in detail below in conjunction with embodiments.

The reagents used in the following examples are all commercially available.

Example 1

Preparation of Electrochromic Film WO ₃ Thin Film

a. Preparation of peroxypolytungstate (PPTA) solution

First weigh 6g of tungsten powder into a 1L (or larger) beaker, then add 60mL of 30% hydrogen peroxide solution under magnetic stirring, and the solution releases a lot of heat. When the reaction solution was cooled to room temperature, a milky white suspension was obtained, and the reaction solution was filtered twice to obtain a translucent white solution. The solution was transferred to a 250mL round bottom flask, refluxed at 51°C for 12h, refluxed at 65°C for 2h, and reacted at 85°C for 30min to obtain a yellow transparent PPTA solution. Add 60 mL of ethanol to the reaction solution and continue to reflux at 50° C. for 24 h. The finally obtained solution was stored in a refrigerator at 4° C. for about 7 days for further aging to obtain a yellow PPTA sol.

b. Preparation of WO ₃ film by electrodeposition

Place the conductive substrate (ITO glass) in an equal proportion of water, ethanol, and acetone solution for ultrasonic cleaning. The cleaned conductive substrate is used as the working electrode, the platinum sheet is used as the counter electrode, and the silver wire is used as the reference electrode. CHI660D electrochemical workstation is used. Three-electrode system for electrodeposition. Chronoamperometry was used for electrodeposition, the deposition voltage range was -0.55 to -0.56V, and the deposition time was 150s. After the deposition, the film was soaked in ethanol solution for about 1 minute to remove the residual PPTA solution on the film surface. Then place the film in a muffle furnace for annealing at 300° C. for 30 minutes, and cool to room temperature to obtain a WO ₃ film with a thickness of 500 nm.

Example 2

Preparation of protective layer _TiO2 thin film

a. Preparation of _TiO2 slurry

Measure 10 mL of titanium tetraisopropoxide, dissolve it in 20 mL of glacial acetic acid, and slowly add 10 mL of deionized water. At this time, the hydrolyzate of titanium tetraisopropoxide will be separated out in the form of precipitation, and will gradually dissolve after continuous stirring, and the solution will return to a transparent state. This solution was placed in a 50mL reactor and reacted at 200°C for 4h. After cooling to room temperature, _TiO2 slurry and mother liquor will be generated in the reactor. The mother liquor is introduced into another beaker for later use, and the TiO ₂ slurry is taken out.

b. Preparation of _TiO2 thin films by doctor blade method

Add a little mother liquor to the prepared TiO ₂ slurry to obtain a suitable viscosity for scraping coating, and use it after stirring evenly. Cut the FTO glass with a suitable size as the substrate, place the conductive surface on the test bench, cover its two ends with 3M adhesive tape with a thickness of about 1 μm, and stick it on the test bench. Take a little _TiO2 slurry, spread it flat with a scraper, and tear off the tape to get a _TiO2 film with uniform thickness. Finally, we heat-treated the film at 450°C for 30 minutes to obtain the final TiO ₂ film with a thickness of 1 μm.

Example 3

Electrolyte preparation

Preparation of a.1M HClO ₄ solution

Add about 200mL of deionized water into a 500mL beaker, slowly add 41mL of 70% perchloric acid into the deionized water under stirring, transfer to a 500mL volumetric flask after cooling, and add deionized water to make the volume to 500mL, A 1M solution of _HClO4 was obtained.

b. Preparation of 1M Al(ClO ₄ ) ₃ solution

Add 0.10 mol of aluminum perchlorate to 100 mL of deionized water to prepare a 1M Al(ClO ₄ ) ₃ solution.

c. Preparation of electrolyte containing deposited ions

1M HClO ₄ solution and 1M Al(ClO ₄ ) ₃ solution are mixed in proportion to obtain a mixed electrolyte with different ion ratios and a fixed cation concentration of 1M. Take 20mL of the mixed electrolyte, add 0.01mol of manganese sulfate (or lead perchlorate) to it, and obtain the electrolyte used.

Example 4

Assembly of electro-dimming devices

1) according to the step of embodiment 1, prepare electrochromic film WO ₃ film on ITO glass by electrodeposition method, obtain color-changing electrode;

According to the step of embodiment 2, on the FTO glass, scrape coating method is prepared protection layer TiO _thin film, obtains protection electrode;

2) Place the electrochromic film of the color-changing electrode and the protective layer of the protective electrode facing each other, use ultraviolet curing glue to make a frame between the color-changing electrode and the protective electrode, and set the electrolyte inlet, between the color-changing electrode and the protective electrode Glass beads (300 μm in diameter) are placed between them to control the gap between the color-changing electrode and the catalytic electrode. After solidification, the electrolyte described in Example 3 is injected into the framework to obtain an electrolyte layer ( The thickness is the thickness of glass beads), and then sealed and cured with ultraviolet curing glue to obtain an electroluminescent device, the structure of which is shown in Figure 1. According to the different ionic salts in the electrolyte used, the devices can be named as WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ and WO ₃ //H ⁺ , Mn ²⁺ //TiO ₂ and so on.

In Example 4 of the present invention, tungsten trioxide thin film and titanium dioxide thin film are respectively used as working electrode and protective electrode (or counter electrode), and manganese ions (or lead ions, etc.) are added to the aqueous proton electrolyte as electrolyte layer. Among them, the tungsten trioxide film mainly plays a role in regulating the optical transmittance in the device, and the titanium dioxide film can prevent the exposed counter electrode (such as FTO glass) from being corroded by hydrogen ions in the electrolyte, while the manganese ions in the electrolyte ( or lead ions) by reversibly depositing/dissolving manganese dioxide (or lead dioxide) on the protective electrode to balance the electrochemical process of the working electrode tungsten trioxide film, and at the same time it can play a color complementary role with the colored tungsten trioxide .

Taking WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ devices as an example, the working mechanism of the device is shown in Figure 2. During the coloring process, the WO ₃ electrode is applied with a negative bias (such as -1.7V), and the H ⁺ and Al ³⁺ in the electrolyte layer are embedded in the WO 3 film as guest ions under the applied negative pressure, and electrons are also injected into the WO ₃ film. In the film, W ⁶⁺ is reduced (forming W ⁵⁺ or W ⁴⁺ ), and the film changes from colorless to dark blue; at this time, the Mn ²⁺ in the electrolyte layer loses electrons on the surface of the protective electrode TiO ₂ , and the solvent H ₂ O reacts to form yellow-brown MnO ₂ deposited on the surface of TiO ₂ electrode. The fading process of the device is the opposite, the working electrode is applied with a positive bias (such as +1.0V), electrons and guest ions are deintercalated from the WO ₃ film, and the film turns from dark blue to colorless; MnO ₂ on the counter electrode After gaining electrons, it is reductively dissolved by H ⁺ in the electrolyte, and the counter electrode changes from yellow-brown to colorless and transparent. The discoloration process on the working and guard electrodes of the device can be represented by Equations 1.1 and 1.2, respectively:

In order to verify the color complementary superposition effect of WO ₃ thin film and MnO ₂ thin film, the in situ permeation of WO ₃ and 0.5mol/L Mn ²⁺ /MnO ₂ in proton electrolyte (1M HClO ₄ solution) are shown in Figure 3, respectively. Overrate Modulation Spectrum. It can be seen that the modulation ability of WO ₃ film to visible light is concentrated in the 450-800nm band (there is an obvious bulging peak in the 350-450nm band, and the transmittance is about 30%-40%, so it is displayed in blue), while Mn ²⁺ / _MnO2 's ability to modulate visible light is concentrated in the 350-450nm band (while there is almost no transmittance modulation ability in the 600-800nm band, that is, ΔT<20%), and the superposition of the two can show a better color complementary effect.

Figure 4 is a WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ device (the concentration ratio of H ⁺ and Al ³⁺ is 4:6, the total concentration of H ⁺ and Al ³⁺ is 1M, Mn The concentration of ²⁺ is 0.5M) and the transmittance modulation spectrum in the 300-1500nm band under different driving voltages. The test is to use the electrochemical workstation CHI660D in combination with the ultraviolet-visible-near-infrared spectrophotometer. After applying the specified voltage to the device through the electrochemical workstation for a period of time, the spectrophotometer is used to test the transmittance spectrum of the band to be tested. Under the driving voltage of +1.0V, the device is in a faded state and is colorless and transparent, and the average transmittance of the device is greater than 70% in the range of visible light. When a driving voltage of -1.2V is applied for 60s, the device appears dark blue, almost all near-infrared light is shielded, and the transmittance of 400-600nm of visible light is still about 30%, which is due to the low driving voltage. Under the condition, the device charge is insufficient, the working electrode WO ₃ is not completely colored, and the deposition amount of MnO ₂ on the counter electrode is insufficient. Further increase the driving voltage to -1.5V, the shielding effect of the device on visible light is significantly improved, the peak transmittance of the device is about 5%, the average transmittance is less than 1%, and the transmittance is 0 in the range of 600-1500nm, the color of the device Appears as opaque black. Until the drive is -1.7V, the transmittance of the device is less than 1% in the whole spectral range.

Figure 5 is a WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ device (the concentration ratio of H ⁺ and Al ³⁺ is 4:6, the total concentration of H ⁺ and Al ³⁺ is 1M, Mn The concentration of ²⁺ is 0.5M) under the square wave voltage of -1.5V (60s) and +1.0V (60s) at 660nm transient transmittance response spectrum. The coloring and fading response time of the device can be calculated from the figure (the time required for the device to fully reach its 90% transmittance modulation in its colored or faded state), WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ The coloring time of the device was 9.9s and the fading time was 6.4s.

Figure 6 is a WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ device (the concentration ratio of H ⁺ and Al ³⁺ is 4:6, the total concentration of H ⁺ and Al ³⁺ is 1M, Mn The concentration of ²⁺ is 0.5M) under the off-circuit condition after coloring at -1.5V for 60s, the real-time transmittance (at 660nm) of the device changes within 1200s. It can be seen from the figure that the transmittance of the device changes less than 1% within 20 minutes, showing an excellent memory effect. This is because when the device with this structure is in the colored state, the positive and negative charges are stored in the tungsten trioxide film of the working electrode and the manganese dioxide film of the counter electrode respectively. There will be direct contact, and the electrolyte layer only conducts ions and hardly conducts electrons, and it is difficult for spontaneous electron gain and loss to occur between the films, so that it can maintain a colored state for a long time. The excellent memory effect enables the device to maintain the colored state without additional voltage, which helps to realize smart windows of buildings with low energy consumption.

Figure 7 is a WO ₃ //H ⁺ , Al ³⁺ , Mn ²⁺ //TiO ₂ device (the concentration ratio of H ⁺ and Al ³⁺ is 4:6, the total concentration of H ⁺ and Al ³⁺ is 1M, Mn Concentration of ²⁺ is 0.5M) under the square wave voltage of -1.5V, 20s and +1.0V, 20s, the comparison chart of the transmittance modulation spectrum before and after 5000 coloring and fading cycles. Compared with the initial state, the device still maintains more than 95% of the initial state modulation capability after 5000 cycles. The slight decrease in the transmittance spectrum of the device in the faded state is due to the fact that the protective electrode titanium dioxide, as a cathodic electrochromic material, will embed a small amount of guest ions during the cycle, resulting in slight coloring. The transmittance spectrum in the faded state of the device has almost no decay before and after 5000 cycles, which proves that the working electrode and the counter electrode reaction of the device with this structure have a good electrochemical matching.

The device structure designed in the present invention, in addition to using the reversible electrochemical reaction of Mn ²⁺ /MnO ₂ , also has good scalability, such as using the reversible electrochemical reaction of Pb ²⁺ /PbO ₂ which has a similar reaction mechanism. The chemical deposition/dissolution reaction is used as the counter electrode reaction of the device, and its reaction process is shown in the reaction equation 1.3:

Figure 8 is WO ₃ //H ⁺ , Pb ²⁺ //TiO ₂ device (H ⁺ concentration is 1M, Pb ²⁺ concentration is 0.5M) colored state (-2.0V, 60s) and faded state (+1.0V , 60s) transmittance modulation spectrum. The device in the faded state still maintains an average transmittance of more than 70% in the visible light range. In the colored state, it can achieve full shielding at wavelengths greater than 600nm, but there is still a peak at 400nm, which is due to the absorbance of lead dioxide and the two Manganese oxide is relatively weak, and the deposition potential of Pb ²⁺ is higher than that of Mn ²⁺ , but the device can still appear opaque blue-black in the colored state.

Claims (10)

1. A complementary type electro-dimming device is characterized by comprising a first conductive substrate, an electrochromic film layer, an electrolyte layer and a second conductive substrate which are sequentially arranged;

the electrolyte layer includes reversibly deposited ions.

2. The complementary type electro-dimmer device according to claim 1, wherein the electrochromic thin film layer is selected from one or more of an inorganic color-changing material layer, a polymer color-changing material layer and an organic small molecule color-changing material layer;

the inorganic color-changing material layer is formed by an inorganic color-changing material; the inorganic color-changing material is selected from tungsten trioxide and/or vanadium pentoxide;

the polymer color-changing material layer is formed by a polymer color-changing material; the high-molecular color-changing material is one or more of polythiophene, polyaniline and derivatives thereof;

the organic micromolecule color-changing material layer is formed by an organic micromolecule color-changing material; the organic micromolecular color-changing material is viologen and/or derivatives thereof.

3. The complementary electroluminescent dimming device of claim 1, wherein the reversibly deposited ions are selected from Mn ^{2 +} And/or Pb ²⁺ 。

4. A complementary electro-dimmer device as claimed in claim 1, wherein the concentration of reversibly depositable ions in the electrolyte layer is between 0.1 and 1mol/L.

5. The complementary electro-dimmer device of claim 1, wherein the electrolyte layer further comprises an ionic salt that participates in the electrochemical reaction of the electrochromic thin film layer and produces a color change and a solvent required to dissolve the ionic salt.

6. The complementary electro-dimmer device of claim 5, wherein the cation of said ionic salt comprises H ⁺ (ii) a The concentration of cations of the ionic salt in the electrolyte layer is 0.1-5 mol/L; the solvent is water.

7. The complementary electro-dimmer device of claim 6, wherein the cations of said ionic salt further comprise alkali metal ions, alkaline earth metal ions and Al ³⁺ One or more of; the alkali metal ion is selected from Li ⁺ And/or Na ⁺ (ii) a The alkaline earth metal ion is selected from Mg ²⁺ And/or Ca ²⁺ (ii) a The alkali metal ion, the alkaline earth metal ion and Al ³⁺ With H ⁺ In a molar ratio of 1:9 to 9:1.

8. a complementary electro-dimmer device as claimed in claim 1, further comprising a guard electrode layer; the protective electrode layer is arranged between the electrolyte layer and the second conductive substrate; the protective electrode layer comprises one or more of titanium dioxide, a carbon material and an acid-resistant metal material.

9. A complementary electro-dimmer device as claimed in claim 1, wherein the first and second conductive substrates are each independently selected from indium tin oxide glass or fluorine doped tin oxide glass.

10. The complementary electro-dimmer device of claim 1, comprising a first conductive substrate, a tungsten trioxide layer, an electrolyte layer, a titanium dioxide layer, and a second conductive substrate arranged in this order;

the electrolyte layer comprises Mn ²⁺ And/or Pb ²⁺ 。

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