CN110376816B

CN110376816B - Self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel and preparation method thereof

Info

Publication number: CN110376816B
Application number: CN201910639591.XA
Authority: CN
Inventors: 方华靖; 武文婷; 汪宏
Original assignee: Xian Jiaotong University
Current assignee: Xian Jiaotong University
Priority date: 2019-07-16
Filing date: 2019-07-16
Publication date: 2021-01-15
Anticipated expiration: 2039-07-16
Also published as: CN110376816A

Abstract

A self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel and a preparation method thereof comprise the following steps; 1) cleaning and airing FTO conductive glass; 2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide; 3) spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on FTO conductive glass by adopting a sol-gel spin coating method, forming a film, and then annealing to obtain a transparent tungsten oxide-based electrochromic film; 4) preparing a polyacrylamide hydrogel; 5) infiltrating the polyacrylamide hydrogel with an aluminum chloride solution to obtain aluminum chloride hydrogel; 6) packaging the aluminum chloride hydrogel with the transparent tungsten oxide-based electrochromic film obtained in the step 3) through common glass adhered with the aluminum electrode to obtain an electrochromic intelligent window device; 7) connecting the hydrogel pen with the transparent tungsten oxide-based electrochromic film obtained in the step 3) to obtain the voltage-driven erasable ion writing screen. The preparation method is simple and easy to realize.

Description

Self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel and preparation method thereof

Technical Field

The invention relates to the technical field of intelligent window technology and ion screen display, in particular to a self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel and a preparation method thereof.

Background

Electrochromism refers to the fact that under the driving of an electric field, through electrochemical reaction, lasting and reversible transformation of optical properties (absorption rate, transmittance or reflectivity) of a substance is achieved, and then reversible changes of color and transparency are expressed. The electrochromic device has great application prospect in the photoelectric field due to the characteristic that the electrochromic device can realize reversible regulation and control of the transmittance of visible light and infrared light at will. The electrochromic device can play the roles of building energy saving, display and the like, so that the electrochromic device can be used for specific applications of devices such as electrochromic intelligent windows, anti-dazzle rearview mirrors, electrochromic displays and the like.

At present, the electrochromic device has a complex structure, and the interface transmission and industrial manufacturing cost are increased. The electrochromic device requires driving of an applied voltage in both processes of achieving the coloring and decoloring.

Disclosure of Invention

In order to solve the technical problems, the invention aims to provide a self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel and a preparation method thereof.

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

the self-powered tungsten oxide-based electrochromic device based on the aluminum ion hydrogel is an electrochromic intelligent window and a non-voltage-driven erasable ion writing screen respectively.

The preparation method of the self-powered tungsten oxide-based electrochromic device based on the aluminum ion hydrogel comprises the following steps;

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

3) spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on FTO conductive glass by adopting a sol-gel spin coating method, forming a film, and then annealing to obtain a transparent tungsten oxide-based electrochromic film;

4) preparing a polyacrylamide hydrogel;

5) infiltrating the polyacrylamide hydrogel with an aluminum chloride solution to obtain aluminum chloride hydrogel;

6) packaging the aluminum chloride hydrogel with the transparent tungsten oxide-based electrochromic film obtained in the step 3) through common glass adhered with the aluminum electrode to obtain an electrochromic intelligent window device;

7) connecting the hydrogel pen with the transparent tungsten oxide-based electrochromic film obtained in the step 3) to obtain the voltage-driven erasable ion writing screen.

The specific operation of the step 1) is as follows: conducting ultrasonic cleaning on the conductive glass by using deionized water, acetone and ethanol in sequence, and airing in a dust-free environment.

The specific operation of the step 2) is as follows:

reacting 1g of tungsten powder with 2-8ml of hydrogen peroxide in an ice-water bath, taking the supernatant after the reaction, drying at 50-70 ℃ to obtain a tungsten complex, then ultrasonically dispersing in ethanol for 1-3h, standing for 2-5 h, and filtering to obtain precursor sol of tungsten oxide; mixing 40g of molybdenum oxide powder with 80-100ml of ethanol, carrying out ball milling for 2-3h, standing for 3h, and taking supernatant to obtain a molybdenum oxide solution; mixing the obtained tungsten oxide precursor sol with a molybdenum oxide solution to obtain a precursor sol compounded by tungsten oxide and molybdenum oxide;

the volume ratio of the tungsten oxide precursor sol to the molybdenum oxide solution is 1: 1.

the step 3) adopts a sol-gel spin coating method, and when the specific operations of spin coating the precursor sol on the FTO conductive glass and forming the film are carried out, the spin coating is carried out in a mode of multiple times of glue coating, wherein the specific operations of each time of glue coating are as follows: and spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on the FTO conductive glass by using a sol-gel spin-coating method, spin-coating (the rotating speed is 1000-2000r/min, the spin-coating time is 6-20s), and heating for 5-20 min at the temperature of 100-200 ℃ on a heating plate after the spin-coating is finished.

The annealing treatment condition is that the temperature is raised to 400 ℃ at the temperature raising rate of 5-20 ℃/min, the temperature is preserved for 30-60 min, and then the temperature is cooled to the room temperature along with the furnace.

The specific operation of the step 4) is as follows:

dissolving acrylamide, N, N ' -methylene bisacrylamide, ammonium persulfate and N, N, N ', N ' -tetramethyl ethylenediamine in water to obtain a mixed solution, stirring the mixed solution at room temperature for 10-30min, injecting the mixed solution into a mold, and placing the mold into a incubator at 50-60 ℃ for heat preservation for 3-5h to obtain polyacrylamide hydrogel;

the molar concentrations of acrylamide, N, N ' -methylenebisacrylamide, ammonium persulfate, and N, N, N ', N ' -tetramethylethylenediamine in the mixed solution were 2.2 mM, 1.32mM, 3.74mM, and 0.1mM, respectively.

The specific operation of the step 5) is as follows:

and infiltrating the polyacrylamide hydrogel with 0.2M-2M aluminum chloride aqueous solution with the same volume until the polyacrylamide hydrogel reaches diffusion balance to obtain the aluminum chloride hydrogel corresponding to 0.1M-1M.

The concrete operation of encapsulating the aluminum chloride hydrogel in the step 6) with the transparent tungsten oxide-based electrochromic film obtained in the step 3) through common glass adhered with the aluminum electrode is as follows:

and (3) packaging aluminum chloride hydrogel on the tungsten oxide-based electrochromic film by adopting silicon rubber, and then pasting common glass adhered with the aluminum electrode together to package the electrochromic intelligent window device.

In the step 7), the hydrogel pen is connected with the transparent tungsten oxide-based electrochromic film obtained in the step 3), and the specific operation is as follows:

packaging aluminum chloride hydrogel and an aluminum electrode into a hydrogel pen, wherein the aluminum electrode is connected with the transparent tungsten oxide-based electrochromic film during writing, and the hydrogel pen is in contact with the electrochromic film; during erasing, a hydrogen peroxide solution with a very low concentration acts on the electrochromic film.

The invention has the beneficial effects that:

when the self-powered oxide-based electrochromic device based on the aluminum ion hydrogel and the preparation method thereof are specifically operated, the tungsten oxide-based thin film is formed by spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on FTO conductive glass, wherein the molybdenum oxide also has an electrochromic effect, so that the tungsten oxide-based electrochromic thin film has a larger light control range.

In addition, the electrochromic device is prepared based on the aluminum ion hydrogel, and when the electrochromic device is applied to an electrochromic intelligent window, the coloring process does not need the action of external voltage and is driven by internal potential; the decoloring process is realized by low voltage (1V), and the method has the advantages of energy conservation and environmental protection. The electrochromic device of the all-aluminum system with the hydrogel pen interacts with the hydrogen peroxide solution with extremely low concentration, so that the writing and erasing processes of the writing screen are realized without external voltage driving, and a new direction is provided for the application of the electrochromic device. The two devices are simple in preparation method, easy to realize and wide in application prospect in the aspects of aircraft portholes, intelligent homes or intelligent electronics and the like.

Drawings

Fig. 1 is a schematic structural diagram of an electrochromic device.

Fig. 2 is a transmission spectrum of an electrochromic smart window in a colored state and a decolored state.

FIG. 3 shows in-situ transmission spectra of electrochromic smart window self-powering process at red light (660nm), blue light (435nm) and green light (520nm), respectively.

FIG. 4 is a graph of multiple writing-erasing light transmittance of the rewritable ion writing panel driven by no voltage.

FIG. 5 is a write-erase photo of a non-voltage driven erasable ion writing screen.

Detailed Description

The present invention will be described in further detail with reference to examples.

Referring to fig. 1, the self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel according to the present invention has a sandwich structure, wherein the tungsten oxide-based electrochromic film, the aluminum ion hydrogel, and the common glass adhered to the aluminum electrode respectively form each layer of material of the structure.

The preparation method of the self-powered tungsten oxide-based electrochromic device based on the aluminum ion hydrogel comprises the following steps:

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

4) preparing a polyacrylamide hydrogel;

The specific operation of the step 1) is as follows: conducting ultrasonic cleaning on the conductive glass by using deionized water, acetone and ethanol in sequence, and then airing in a dust-free environment.

The specific operation of the step 2) is as follows:

reacting 1g of tungsten powder with 5ml of hydrogen peroxide in an ice-water bath, taking the supernatant after the reaction, drying at 50-70 ℃ to obtain a tungsten complex, then ultrasonically dispersing in ethanol for 1-3h, standing for 2-5 h, and filtering to obtain precursor sol of tungsten oxide; mixing 40g of molybdenum oxide powder with 80-100ml of ethanol, ball-milling for 1-3h, standing for 3h, and taking supernatant to obtain a molybdenum oxide solution; mixing the obtained tungsten oxide precursor sol with a molybdenum oxide solution to obtain a precursor sol compounded by tungsten oxide and molybdenum oxide;

The specific operation of the step 4) is as follows:

The specific operation of the step 5) is as follows:

Step 6) the specific operation of encapsulating the aluminum chloride hydrogel with the transparent tungsten oxide-based electrochromic film obtained in step 3) through common glass adhered with the aluminum electrode is as follows:

Step 7) connecting the hydrogel pen with the transparent tungsten oxide-based electrochromic film obtained in the step 3), and specifically operating as follows:

Example one

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

4) preparing a polyacrylamide hydrogel;

The specific operation of the step 2) is as follows:

reacting 1g of tungsten powder with 2ml of hydrogen peroxide in an ice-water bath, drying the reacted supernatant at 70 ℃ to obtain a tungsten complex, ultrasonically dispersing the tungsten complex in ethanol for 1 hour, standing for 3 hours, and filtering to obtain precursor sol of tungsten oxide; mixing 40g of molybdenum oxide powder with 80ml of ethanol, carrying out ball milling for 1h, standing for 3h, and taking supernatant to obtain a molybdenum oxide solution; and mixing the obtained tungsten oxide precursor sol with a molybdenum oxide solution to obtain the precursor sol compounded by tungsten oxide and molybdenum oxide.

in the step 3), a sol-gel spin coating method is adopted, precursor sol is spin-coated on the FTO conductive glass, and during the specific operation of film forming, a mode of multiple times of coating is adopted for spin coating, wherein the specific operation of each time of coating is as follows: and spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on the FTO conductive glass by using a sol-gel spin-coating method, wherein the spin-coating speed is 1000r/min, the spin-coating time is 8s, and after the spin-coating is finished, heating the FTO conductive glass for 10min by using a heating plate at 200 ℃.

The annealing condition is that the temperature is raised to 400 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 30min, and then the temperature is cooled to the room temperature along with the furnace.

The specific operation of the step 4) is as follows: dissolving acrylamide, N, N ' -methylene bisacrylamide, ammonium persulfate and N, N, N ', N ' -tetramethyl ethylenediamine in water to obtain a mixed solution, stirring the mixed solution at room temperature for 10min, injecting the mixed solution into a mold, and placing the mold into a 50 ℃ incubator to preserve heat for 4h to obtain the polyacrylamide hydrogel. Wherein the molar concentrations of the acrylamide, the N, N ' -methylene-bisacrylamide, the ammonium persulfate and the N, N, N ', N ' -tetramethyl-ethylenediamine in the mixed solution are respectively 2.2M, 1.32mM, 3.74mM and 0.1 mM.

The specific operation of the step 5) is as follows:

and infiltrating the polyacrylamide hydrogel into 2M aluminum chloride aqueous solution with the same volume until the polyacrylamide hydrogel reaches diffusion balance, and obtaining the corresponding 1M aluminum chloride hydrogel.

Example two

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

4) preparing a polyacrylamide hydrogel;

The specific operation of the step 1) is as follows: the conductive glass is ultrasonically cleaned by deionized water, acetone and ethanol in sequence and is dried in a dust-free environment.

The specific operation of the step 2) is as follows:

reacting 1g of tungsten powder with 4ml of hydrogen peroxide in an ice-water bath, taking the supernatant after the reaction, drying at 60 ℃ to obtain a tungsten complex, then ultrasonically dispersing in ethanol for 2h, standing for 2h, and filtering to obtain precursor sol of tungsten oxide; mixing 40g of molybdenum trioxide powder with 90ml of ethanol, performing ball milling for 1h, standing for 3h, and taking supernatant to obtain a molybdenum trioxide solution; and mixing the obtained tungsten oxide precursor sol with a molybdenum trioxide solution to obtain the precursor sol compounded by tungsten oxide and molybdenum oxide.

The volume ratio of the tungsten oxide precursor sol to the molybdenum trioxide solution is 1: 1.

in the step 3), a sol-gel spin coating method is adopted, precursor sol is spin-coated on the FTO conductive glass, and during the specific operation of film forming, a mode of multiple times of coating is adopted for spin coating, wherein the specific operation of each time of coating is as follows: and spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on the FTO conductive glass by using a sol-gel spin-coating method, wherein the spin-coating speed is 1500r/min, the spin-coating time is 8s, and after the spin-coating is finished, heating the FTO conductive glass for 10min by using a heating plate at 200 ℃.

The annealing treatment in the step 3) comprises the following specific operations: and (3) heating the sample obtained by spin coating to 350 ℃ at the heating rate of 15 ℃/min, preserving the heat for 1h, and then cooling to room temperature along with the furnace.

The specific operation of the step 4) is as follows: dissolving acrylamide, N, N ' -methylene bisacrylamide, ammonium persulfate and N, N, N ', N ' -tetramethyl ethylenediamine in water to obtain a mixed solution, stirring the mixed solution at room temperature for 0.5h, injecting the mixed solution into a mold, and placing the mold into a 55 ℃ incubator for heat preservation for 5h to obtain the polyacrylamide hydrogel. Wherein the molar concentrations of the acrylamide, the N, N ' -methylene-bisacrylamide, the ammonium persulfate and the N, N, N ', N ' -tetramethyl-ethylenediamine in the mixed solution are respectively 2.2M, 1.32mM, 3.74mM and 0.1 mM.

The specific operation of the step 5) is as follows:

packaging aluminum chloride hydrogel and an aluminum electrode into a hydrogel pen, wherein during writing, the aluminum electrode is connected with the transparent tungsten oxide-based electrochromic film, and the hydrogel pen is in contact with the electrochromic film; during erasing, a hydrogen peroxide solution with a very low concentration acts on the electrochromic film.

EXAMPLE III

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

4) preparing a polyacrylamide hydrogel;

The specific operation of the step 2) is as follows:

reacting 1g of tungsten powder with 6ml of hydrogen peroxide in an ice-water bath, taking the supernatant after the reaction, drying at 65 ℃ to obtain a tungsten complex, then ultrasonically dispersing in ethanol for 1h, standing for 3h, and filtering to obtain precursor sol of tungsten oxide; mixing 40g of molybdenum trioxide powder with 100ml of ethanol, performing ball milling for 1h, standing for 3h, and taking supernatant to obtain a molybdenum trioxide solution; and mixing the obtained tungsten oxide precursor sol with a molybdenum trioxide solution to obtain the precursor sol compounded by tungsten oxide and molybdenum oxide.

in the step 3), a sol-gel spin coating method is adopted, precursor sol is spin-coated on the FTO conductive glass, and during the specific operation of film forming, a mode of multiple times of coating is adopted for spin coating, wherein the specific operation of each time of coating is as follows: and spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on the FTO conductive glass by using a sol-gel spin-coating method, wherein the spin-coating speed is 1000r/min, the spin-coating time is 10s, and after the spin-coating is finished, heating the FTO conductive glass for 10min by using a heating plate to 150 ℃.

The annealing treatment in the step 3) comprises the following specific operations: and heating the sample obtained by spin coating to 300 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 30min, and then cooling to room temperature along with the furnace.

The specific operation of the step 5) is as follows:

and infiltrating the polyacrylamide hydrogel with 1M of aluminum chloride aqueous solution with the same volume until the polyacrylamide hydrogel reaches diffusion balance, and obtaining aluminum chloride hydrogel corresponding to 0.5M.

Example four

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

4) preparing a polyacrylamide hydrogel;

The specific operation of the step 2) is as follows:

reacting 1g of tungsten powder with 8ml of hydrogen peroxide in an ice-water bath, drying the reacted supernatant at 70 ℃ to obtain a tungsten complex, ultrasonically dispersing the tungsten complex in ethanol for 3 hours, standing for 5 hours, and filtering to obtain precursor sol of tungsten oxide; mixing 40g of molybdenum trioxide powder with 100ml of ethanol, carrying out ball milling for 3h, standing for 3h, and taking supernatant to obtain a molybdenum trioxide solution; and mixing the obtained tungsten oxide precursor sol with a molybdenum trioxide solution to obtain the precursor sol compounded by tungsten oxide and molybdenum oxide.

in the step 3), a sol-gel spin coating method is adopted, precursor sol is spin-coated on the FTO conductive glass, and during the specific operation of film forming, a mode of multiple times of coating is adopted for spin coating, wherein the specific operation of each time of coating is as follows: and spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on the FTO conductive glass by using a sol-gel spin-coating method, wherein the spin-coating speed is 2000r/min, the spin-coating time is 20s, and after the spin-coating is finished, heating the FTO conductive glass for 20min by using a heating plate at 200 ℃.

The annealing treatment in the step 3) comprises the following specific operations: and heating the sample obtained by spin coating to 400 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 60min, and then cooling to room temperature along with the furnace.

The specific operation of the step 4) is as follows: dissolving acrylamide, N, N ' -methylene bisacrylamide, ammonium persulfate and N, N, N ', N ' -tetramethyl ethylenediamine in water to obtain a mixed solution, stirring the mixed solution at room temperature for 30min, injecting the mixed solution into a mold, and placing the mold into a 60 ℃ incubator for heat preservation for 5h to obtain the polyacrylamide hydrogel. Wherein the molar concentrations of the acrylamide, the N, N ' -methylene-bisacrylamide, the ammonium persulfate and the N, N, N ', N ' -tetramethyl-ethylenediamine in the mixed solution are respectively 2.2M, 1.32mM, 3.74mM and 0.1 mM.

The specific operation of the step 5) is as follows:

and infiltrating the polyacrylamide hydrogel into 2M aluminum chloride aqueous solution with the same volume until the polyacrylamide hydrogel reaches diffusion balance, so as to obtain the corresponding 2M aluminum chloride hydrogel.

EXAMPLE five

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

4) preparing a polyacrylamide hydrogel;

The specific operation of the step 2) is as follows:

reacting 1g of tungsten powder with 2ml of hydrogen peroxide in an ice-water bath, drying the reacted supernatant at 50 ℃ to obtain a tungsten complex, ultrasonically dispersing the tungsten complex in ethanol for 1 hour, standing for 2 hours, and filtering to obtain precursor sol of tungsten oxide; mixing 40g of molybdenum trioxide powder with 80ml of ethanol, carrying out ball milling for 2 hours, standing for 3 hours, and taking supernatant to obtain a molybdenum trioxide solution; and mixing the obtained tungsten oxide precursor sol with a molybdenum trioxide solution to obtain the precursor sol compounded by tungsten oxide and molybdenum oxide.

in the step 3), a sol-gel spin coating method is adopted, precursor sol is spin-coated on the FTO conductive glass, and during the specific operation of film forming, a mode of multiple times of coating is adopted for spin coating, wherein the specific operation of each time of coating is as follows: and spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on the FTO conductive glass by using a sol-gel spin-coating method, wherein the spin-coating speed is 1000r/min, the spin-coating time is 6s, and after the spin-coating is finished, heating the FTO conductive glass for 5min by using a heating plate at 100 ℃.

The annealing treatment in the step 3) comprises the following specific operations: and heating the sample obtained by spin coating to 300 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 30min, and then cooling to room temperature along with the furnace.

The specific operation of the step 4) is as follows: dissolving acrylamide, N, N ' -methylene bisacrylamide, ammonium persulfate and N, N, N ', N ' -tetramethyl ethylenediamine in water to obtain a mixed solution, stirring the mixed solution at room temperature for 10min, injecting the mixed solution into a mold, and placing the mold into a 50 ℃ incubator for heat preservation for 3h to obtain the polyacrylamide hydrogel. Wherein the molar concentrations of the acrylamide, the N, N ' -methylene-bisacrylamide, the ammonium persulfate and the N, N, N ', N ' -tetramethyl-ethylenediamine in the mixed solution are respectively 2.2M, 1.32mM, 3.74mM and 0.1 mM.

The specific operation of the step 5) is as follows:

and infiltrating the polyacrylamide hydrogel with 0.2M of aluminum chloride aqueous solution with the same volume until the polyacrylamide hydrogel reaches diffusion equilibrium to obtain aluminum chloride hydrogel corresponding to 0.1M.

According to the manufacturing process of embodiment 1, as can be seen from fig. 2, the upper color state and the decolored state of the electrochromic device can reach 51% in the visible light modulation range, referring to fig. 3, the self-powered process of the electrochromic smart window device respectively adopts in-situ transmission spectra at three colors (red light 660nm, green light 520nm, and blue light 435nm), and the light modulation ranges in the coloring process can respectively reach 49%, 45%, and 40%; FIG. 4 is a light transmittance diagram of multiple writing-erasing of the erasable ion writing screen driven by no voltage, the light modulation range of writing and erasing is about 45%, and the display function is ensured; from fig. 5, the writing-erasing process of the voltage-less driving erasable ion writing panel can be understood.

Claims

1. The preparation method of the self-powered tungsten oxide-based electrochromic device based on the aluminum ion hydrogel is characterized by comprising the following steps;

1) cleaning and airing FTO conductive glass;

2) preparing precursor sol compounded by tungsten oxide and molybdenum oxide;

4) preparing a polyacrylamide hydrogel;

6) and (3) packaging the aluminum chloride hydrogel with the transparent tungsten oxide-based electrochromic film obtained in the step 3) through common glass adhered with the aluminum electrode to obtain the electrochromic intelligent window device.

2. The method for preparing a self-powered tungsten oxide based electrochromic device based on aluminum ion hydrogel according to claim 1, wherein the specific operation of step 1) is as follows: conducting ultrasonic cleaning on the conductive glass by using deionized water, acetone and ethanol in sequence, and airing in a dust-free environment.

3. A method for preparing a self-powered tungsten oxide based electrochromic device based on aluminum ion hydrogel according to claim 1, wherein the specific operation of step 2) is:

4. a method for preparing a self-powered tungsten oxide based electrochromic device based on aluminum ion hydrogel according to claim 1, wherein the sol-gel spin coating method is adopted in step 3), and during the specific operations of spin coating the precursor sol on the FTO conductive glass and forming the film, the spin coating is performed by multiple times of glue coating, wherein the specific operations of each time of glue coating are as follows: spin-coating a precursor sol compounded by tungsten oxide and molybdenum oxide on FTO conductive glass by using a sol-gel spin-coating method, wherein the spin-coating speed is 1000-2000r/min, the spin-coating time is 6-20s, and after the spin-coating is finished, heating is carried out on a heating plate at 100-200 ℃ for 5-20 min;

5. A method for preparing a self-powered tungsten oxide based electrochromic device based on aluminum ion hydrogel according to claim 1, wherein the specific operation of step 4) is:

6. A method for preparing a self-powered tungsten oxide based electrochromic device based on aluminum ion hydrogel according to claim 1, wherein the specific operation of step 5) is:

7. A method for preparing a self-powered tungsten oxide based electrochromic device based on aluminum ion hydrogel according to claim 1, wherein the step 6) of encapsulating the aluminum chloride hydrogel with the transparent tungsten oxide based electrochromic film obtained in the step 3) through common glass adhered with an aluminum electrode comprises the following specific operations: