CN117608136A - Electrochromic device with multiple optical states and preparation method and application thereof - Google Patents

Abstract

The invention discloses a electrochromic device with multiple optical states and a patterning structure, a manufacturing method thereof and application thereof in the electrochromic anti-counterfeiting field. Comprises a top transparent electrode layer, a colorful structural color layer, an electrolyte layer, an electrochromic layer and a base transparent electrode layer which are sequentially combined from top to bottom. The effect is as follows: can provide more optical information and provide a new strategy for designing advanced multi-dimensional anti-counterfeiting devices. The structural colors can be displayed and hidden by actively adjusting the voltage and passively changing the background. But also has a pronounced angle-dependent iridescence so that more optical information can be carried. Various patterns can be prepared by a mature method such as engraving or laser etching of PC films, etc., without affecting the multi-dimensional optical properties thereof. The prepared photonic crystal is more ordered, more saturated and more obvious in structural color characteristics in an electrochromic device. The inherent pattern of the device of the invention can be skillfully changed into different preset background patterns.

Description

Electrochromic device with multiple optical states and preparation method and use thereof

Technical field

The invention belongs to the field of optoelectronic technology and relates to an electrochromic device. Specifically, it relates to a color electrochromic device with multiple optical states and a patterned structure, its production method and its application in the field of electrochromic anti-counterfeiting.

Background technique

Electrochromism is a phenomenon that can reversibly change its optical state (absorbance, transmittance, reflectivity, etc.) under external voltage stimulation. Among them, materials with electrochromic properties are called electrochromic materials. They can undergo a redox reaction under the action of an external electric field, and in the process, the optical properties and color of the material will also change.

A device composed of functional layers such as electrochromic materials is called an electrochromic device. It is mainly composed of functional layers such as an electrochromic layer, an electrolyte layer, an ion storage layer, and two transparent conductive electrodes. Electrochromic devices have many advantages such as no dead spots, no backlight, high contrast, low driving voltage, rich colors, wide operating temperature range and low manufacturing cost. The most important thing is that when the voltage of the electrochromic device is removed, its color can be maintained for a period of time without changing. This color memory effect helps save energy and reduce costs. These unique tunable optical properties enable electrochromic devices to be widely used in various fields, such as smart windows, sensors, wearable devices, supercapacitors, anti-glare rearview mirrors, electronic paper, and displays. Although electrochromic devices have outstanding advantages and wide applications, the color change of traditional electrochromic devices is limited to switching between the colored state and the faded state of the material. In particular, inorganic electrochromic materials have the disadvantage of a single color. This limits the application of electrochromic devices in real life.

Structural color, also known as physical color, is generated by the interaction between light and complex periodic micro-nano structures (including refraction, reflection, interference, diffraction, absorption, scattering, plasmon resonance, etc.). Structural color has High brightness, high saturation, high spatial resolution, angle dependence, environmental friendliness and versatility. In recent years, the extensive development of structural color electrochromic devices has shown a wealth of advantages. Combining structural color and electrochromism can provide more combinations of electrochromic colors, which can enrich the color range of traditional electrochromic devices and expand electrochromic color-tuning strategies.

In the existing technical literature (Nano Letters 2021, 21, 4500-4507), Mei et al. directly embedded colloidal photonic crystal SiO2 with bright structural colors into the electrolyte layer of traditional electrochromic devices, and selected a black electrolyte. Chromochromic polymer serves as the background color layer. Black electrochromic polymers are used to switch from black to colorless at different voltages, simulating the color display effect of structural colors under changing backgrounds. On a white background, the device can switch between the blue structural color and transparency of the colloidal photonic crystal through voltage regulation. And you can use changes in the background color of the environment to passively hide and display structural colors.

However, this method mixes the electrolyte and photonic crystal material together and cannot be separated. Simple and rapid preparation of structural color patterned electrochromic devices cannot be achieved. Moreover, there are too many defects in the photonic crystal assembly process, the color saturation is low, and the angle dependence is not obvious.

In the existing technical literature (Chemical Engineering Journal 2022, 429, 132437), Wang et al. were inspired by the color mixing strategy of gecko structural colors and pigment colors in nature. By mixing thermochromic microcapsules, viologen-based electrochromic materials and PS@PEA colloidal photonic crystal materials, and using shear-induced assembly technology, a structural color electrochromic device with dual response to temperature and voltage was prepared. , which can achieve active (electrochromic) and passive (thermochromic) optical modulation.

However, this method mixes the electrolyte and photonic crystal material together and cannot be separated. Simple and rapid preparation of structural color patterned electrochromic devices cannot be achieved. Moreover, there are too many defects in the photonic crystal assembly process, the color saturation is low, and the angle dependence is not obvious.

Contents of the invention

The technical problem to be solved by the present invention is to provide a device that can present a variety of optical states under different voltages, viewing angles and environmental background colors, can realize switching of different structural color patterns, and carry more optical information. This is beneficial to its application in the field of advanced anti-counterfeiting and has a simple manufacturing method for an electrochromic device with multiple optical states and its preparation method and use.

The electrochromic device with multiple optical states of the present invention includes a top transparent electrode layer, a multi-colored structural color layer, an electrolyte layer, an electrochromic layer, and a base transparent electrode layer that are combined in sequence from top to bottom.

Preferably, the multi-colored structural color layer is composed of polymer microspheres. Further preferably, the material of the colorful structural color layer is composed of P(St-MMA-AA) nanospheres, and the particle size of the nanospheres is 180-300 nm.

Preferably, the material of the electrochromic layer is polythiophene, polyaniline, polypyrrole, poly3,4-propylenedioxythiophene, triphenylamine, poly(3,4-propylenedioxythiophene), tungsten oxide, One of molybdenum oxide, nickel oxide, vanadium oxide, viologen, metal phthalocyanine and its derivatives; the thickness of the electrochromic layer is 100-1000nm.

Preferably, the electrolyte layer is composed of a solute and a gel polymer; the solute is a lithium salt compound, including LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN(CF ₃ SO ₂ ) ₂ , LiC(CF ₃ SO ₂ ) ₃ , LiFSI, LiBOB and LiTFSI. The gel polymer is one or more of PC, PEGDA, PVDF, PEO, PAN, PMMA and PVA. Mixture; solute concentration is 10 ^-5 -10 ^-4 mol/L.

Preferably, the materials of the top transparent electrode layer and the base transparent electrode layer are any of ITO glass, FTO glass, zinc oxide, tin oxide, carbon nanotube transparent conductive materials, silver metal films, copper metal films, and gold metal films. One or a combination of more.

Preferably, the bottom of the base transparent electrode layer has a preset pattern layer, and the preset pattern layer is formed on the bottom surface of the base transparent electrode by one or more of laser etching, cutting, engraving, and embossing. , or formed by pasting a preset pattern film on the bottom.

The preparation method of the electrochromic device with multiple optical states of the present invention includes the following steps:

a. Fix the electrochromic material on the base transparent electrode layer using any method including magnetron sputtering, thermal evaporation, spin coating, spray coating, coating, screen printing, inkjet printing, and gravure printing. kind;

b. Use encapsulant and insulating strips to regulate the glass gap along the edge of the base transparent electrode layer to form an insulating frame, and a cavity is defined in the insulating frame; the material of the insulating frame can be organic epoxy resin.

c. Cover the gel electrolyte containing lithium salt on the base transparent electrode layer with the electrochromic layer to form an electrolyte layer; the covering method is brushing or spraying.

d. Cover the top transparent electrode layer coated with a multi-colored structural color layer on the electrolyte layer, and cross-link the gel electrolyte under ultraviolet light.

Preferably, before step a, a preset pattern layer is formed on the bottom surface of the base transparent electrode by one or more of laser etching, cutting, engraving, and embossing; or, after step d, by pasting a preset pattern layer on the bottom The patterned film forms a preset pattern layer.

Preferably, the method of coating the multi-colored structural color layer on the top transparent electrode layer is as follows:

a) The P(St-MMA-AA) nanosphere emulsion is spin-coated or coated to form a film on the surface of the top transparent electrode layer to form a colorful structural color film; the spin-coating method is preferably used, the rotation speed is 600-1500prm, and the time is 300s; better range: rotation speed is 800rpm;

b) Anneal the prepared multi-colored structural color film at 100°C for 10 minutes to obtain a photonic crystal structural color film with a film thickness of 6-10 μm; pattern the multi-colored structural color layer through etching or solvent treatment; a better range: use laser engraving For etching, place the prepared structural color film on the UV laser platform and perform direct laser etching at a moving speed of 0.5mm/s to obtain the structural color pattern pre-designed by the computer.

Further preferably, the preparation method of the P(St-MMA-AA) nanosphere emulsion includes the following steps:

1) In a three-necked flask, add styrene (St), methyl methacrylate (MMA), acrylic acid (AA), deionized water, a small amount of surfactant sodium dodecylbenzene sulfonate (SDBS), and buffer in sequence. ammonium bicarbonate (MSDS); the amount of each component is: for every 100ml of deionized water, 182.60mmol of styrene, 10mmol of methyl methacrylate, 13.89mmol of acrylic acid, and 6.3mmol of buffer ammonium bicarbonate are added;

By changing the monomer mass ratio of sodium dodecylbenzenesulfonate in P(St-MMA-AA) nanospheres, the particle size of P(St-MMA-AA)) nanospheres is adjusted; structural color layer The color can be adjusted by changing the particle size of polymer P (St-MMA-AA);

2) Then, magnetic stirring and heating under protective atmosphere;

3) Finally, add ammonium persulfate (APS) to the reaction mixture in the previous step and react at high temperature to obtain P(St-MMA-AA) nanosphere emulsion.

Further preferably, the monomer mass ratio of sodium dodecylbenzene sulfonate in the P(St-MMA-AA) nanospheres is 1:0.025-0.060.

Further preferably, the particle size range of P(St-MMA-AA) nanospheres is 200-300nm.

Further preferably, the protective atmosphere in step 2) is nitrogen.

Further preferably, the heating reaction temperature in step 2) is 75°C and the reaction time is 20 minutes.

Further preferably, the amount of ammonium persulfate added in step 3) is that for every 100 ml of deionized water added in step 1), 2.32 mmol of ammonium persulfate is added in step 3).

Further preferably, the heating reaction temperature in step 3) is 80°C, and the reaction time is 10 h.

The use of the electrochromic device with multiple optical states of the present invention lies in its application in anti-counterfeiting devices.

The positive effects of the present invention are reflected in:

1. The device of the present invention can provide more optical information and provide new strategies for designing advanced multi-dimensional anti-counterfeiting devices.

2. Due to the presence of the electrochromic layer in the device, the present invention can display and hide structural colors by actively adjusting the voltage and passively changing the background.

3. Due to the anisotropy of the photonic crystal structure, the device of the present invention also has obvious angle-dependent iridescence color, so that it can carry more optical information.

4. The device of the present invention can prepare various patterns through mature methods such as engraving or laser etching PC films without affecting its multi-dimensional optical properties.

5. The prepared photonic crystal is more ordered, more saturated, and has more obvious structural color characteristics in electrochromic devices.

6. Utilizing the synergistic effect of background color and electrochromism, the inherent pattern of the device of the present invention can be cleverly changed into different preset background patterns.

Description of drawings

Figure 1 is a schematic structural diagram of an electrochromic device with multiple optical states according to Embodiment 1 of the present invention;

Figure 2 is a schematic structural diagram of an electrochromic device with multiple optical states according to Embodiment 2 of the present invention;

Figure 3 is a state diagram of the electrochromic device under different voltages and observation angles in Embodiment 3 of the present invention;

Figure 4 is a state diagram of the electrochromic device in Embodiment 4 of the present invention under different voltages, background environments and observation angles;

Figure 5 is a diagram of the switching states of the electrochromic device in different patterns under different voltages in Embodiment 5 of the present invention.

Detailed ways

Example 1

An electrochromic device with multiple optical states consists of a top transparent electrode layer 1, a multi-colored structural color layer 2, an electrolyte layer 3, an electrochromic layer 4 and a base transparent electrode layer 5 that are combined in sequence from top to bottom. The material of the colorful structural color layer is composed of P(St-MMA-AA) nanospheres, and the particle size of the nanospheres is 255-275nm. The electrochromic layer is made of poly3,4-propylenedioxythiophene and has a thickness of 100nm. The electrolyte layer contains the solute LiTFSI lithium salt compound, the gel polymer in the electrolyte uses PC and PEGDA, and the concentration of the solute is 10 ^-5 mol/L. The material of the top transparent electrode layer and the base transparent electrode layer is ITO glass.

Example 2

An electrochromic device with multiple optical states consists of a top transparent electrode layer 1, a multi-colored structural color layer 2, an electrolyte layer 3, an electrochromic layer 4 and a base transparent electrode layer 5 that are combined in sequence from top to bottom. The material of the colorful structural color layer is composed of P(St-MMA-AA) nanospheres, and the particle size of the nanospheres is 255-275nm. The electrochromic layer is made of poly3,4-propylenedioxythiophene and has a thickness of 100nm. The electrolyte layer contains the solute LiTFSI lithium salt compound, the gel polymer in the electrolyte uses PC and PEGDA, and the concentration of the solute is 10 ^-5 mol/L. The material of the top transparent electrode layer and the base transparent electrode layer is ITO glass. The preset pattern layer 6 is formed by pasting a preset pattern film on the bottom of the base transparent electrode layer.

Example 3

An electrochromic device with multiple optical states having the structure of Example 1 was prepared.

1. Preparation of P(St-MMA-AA) nanospheres and patterns in colorful structural color layers.

In a three-necked flask, add 182.60mmol of styrene (St), 10mmol of methyl methacrylate (MMA), 13.89mmol of acrylic acid (AA), 100ml of deionized water, and the surfactant sodium dodecylbenzene sulfonate (SDBS). ), buffer ammonium bicarbonate (MSDS) 6.3 mmol, monomer mass ratio of SDBS (1:0.025). Then, magnetic stirring was performed at 75°C under a protective nitrogen atmosphere, and the reaction time was 20 minutes. Finally, 2.32 mmol of ammonium persulfate (APS) was added to the above reaction mixture. React at high temperature of 80℃, reaction time is 10h. A P(St-MMA-AA) nano-microsphere emulsion is obtained, and the particle size of the P(St-MMA-AA) composite nano-microsphere is 255-275 nm. Used directly without further purification.

The P(St-MMA-AA) nanomicrosphere emulsion is spin-coated on the surface of the top transparent electrode layer to form a multi-colored structural color film; the spin coating speed is 800 prm and the time is 300 s; the obtained multi-colored structural color film is After annealing at 100°C for 10 minutes, a photonic crystal structural color film is obtained with a film thickness of 6-10 μm; the prepared structural color film is placed on the ultraviolet laser platform and directly laser etched at a moving speed of 0.5mm/s to obtain " Photonic crystal film composite film with "Jade Rabbit Window Grill" pattern. The color of the photonic crystal composite film pattern is orange-red. Since the interstitial air (n=1) of the photonic crystal is filled with a higher refractive index electrolyte (n=1.45), the color in the structural color electrochromic device is red. .

2. Preparation of electrochromic devices:

a. Fix the electrochromic material poly-3,4-propylenedioxythiophene on the base transparent electrode layer by spin coating; the thickness of the electrochromic layer is 100nm.

b. Use encapsulant and insulating strips to regulate the glass gap along the edge of the base transparent electrode layer to form an insulating frame. A cavity is defined in the insulating frame; the insulating frame is made of organic epoxy resin.

c. Cover the gel electrolyte containing lithium salt on the base transparent electrode layer with the electrochromic layer to form an electrolyte layer; the covering method is spraying; the electrolyte layer contains the solute LiTFSI lithium salt compound and the gel polymer in the electrolyte Using PC and PEGDA, the concentration of solute is 10 ^-5 mol/L.

d. Cover the top transparent electrode layer coated with a multi-colored structural color layer on the electrolyte layer, and cross-link the gel electrolyte under ultraviolet light.

A red structural color electrochromic device with a "jade rabbit window grille" pattern in multiple optical states as shown in Figure 3 was obtained. The device can display and hide structural color patterns through voltage on a white background, and can display different structural color colors at different viewing angles.

Example 4: Prepare an electrochromic device with multiple optical states having the structure of Example 1.

1. Preparation of P(St-MMA-AA) nanospheres and patterns in colorful structural color layers.

In a three-necked flask, add 182.60mmol of styrene (St), 10mmol of methyl methacrylate (MMA), 13.89mmol of acrylic acid (AA), 100ml of deionized water, and the surfactant sodium dodecylbenzene sulfonate (SDBS). ), buffer ammonium bicarbonate (MSDS) 6.3 mmol, monomer mass ratio of SDBS (1:0.040). Then, magnetic stirring was performed at 75°C under a protective nitrogen atmosphere, and the reaction time was 20 minutes. Finally, 2.32 mmol of ammonium persulfate (APS) was added to the above reaction mixture. React at high temperature of 80℃, reaction time is 10h. A P(St-MMA-AA) nano-microsphere emulsion is obtained, and the particle size of the P(St-MMA-AA) composite nano-microsphere is 240-260 nm. Used directly without further purification.

The P(St-MMA-AA) nanomicrosphere emulsion is formed on the surface of the top transparent electrode layer by spin coating to form a multi-colored structural color film; the spin coating speed is 800 prm and the time is 300 s; the obtained multi-colored structural color film is After annealing at 100°C for 10 minutes, a photonic crystal structural color film is obtained with a film thickness of 6-10 μm; the prepared structural color film is placed on the ultraviolet laser platform and directly laser etched at a moving speed of 0.5mm/s to obtain " Photonic crystal film composite film with duck” pattern. The color of the photonic crystal composite film pattern is yellow, and the color in the structural color electrochromic device is orange.

2. Preparation of electrochromic devices:

a. Fix the electrochromic material poly-3,4-propylenedioxythiophene on the base transparent electrode layer by spin coating; the thickness of the electrochromic layer is 100nm.

b. Use encapsulant and insulating strips to regulate the glass gap along the edge of the base transparent electrode layer to form an insulating frame. A cavity is defined in the insulating frame; the insulating frame is made of organic epoxy resin.

c. Cover the gel electrolyte containing lithium salt on the base transparent electrode layer with the electrochromic layer to form an electrolyte layer; the covering method is spraying; the electrolyte layer contains the solute LiTFSI lithium salt compound and the gel polymer in the electrolyte Using PC and PEGDA, the concentration of solute is 10 ^-5 mol/L.

d. Cover the top transparent electrode layer coated with a multi-colored structural color layer on the electrolyte layer, and cross-link the gel electrolyte under ultraviolet light.

An orange-red structural color electrochromic device with a "duck" pattern in multiple optical states as shown in Figure 4 was obtained. As shown in Figure 4, the device can display and hide structural color patterns through voltage on a white background, can display and hide structural color patterns by switching different backgrounds, and can display different structural color colors at different viewing angles. .

Example 5: Prepare an electrochromic device with multiple optical states having the structure of Example 2.

1. Preparation of P(St-MMA-AA) nanospheres and patterns in colorful structural color layers.

In a three-necked flask, add 182.60mmol of styrene (St), 10mmol of methyl methacrylate (MMA), 13.89mmol of acrylic acid (AA), 100ml of deionized water, and the surfactant sodium dodecylbenzene sulfonate (SDBS). ), buffer ammonium bicarbonate (MSDS) 6.3 mmol, monomer mass ratio of SDBS (1:0.025). Then, magnetic stirring was performed at 75°C under a protective nitrogen atmosphere, and the reaction time was 20 minutes. Finally, 2.32 mmol of ammonium persulfate (APS) was added to the above reaction mixture. React at high temperature of 80℃, reaction time is 10h. A P(St-MMA-AA) nano-microsphere emulsion is obtained, and the particle size of the P(St-MMA-AA) composite nano-microsphere is 255-275nmnm. Used directly without further purification.

The P(St-MMA-AA) nanomicrosphere emulsion is spin-coated on the surface of the top transparent electrode layer to form a multi-colored structural color film; the spin coating speed is 800 prm and the time is 300 s; the obtained multi-colored structural color film is After annealing at 100°C for 10 minutes, a photonic crystal structural color film is obtained with a film thickness of 6-10 μm; the prepared structural color film is placed on the ultraviolet laser platform and directly laser etched at a moving speed of 0.5mm/s to obtain " Photonic crystal film composite film with Suzhou University of Science and Technology logo” pattern. The color of the photonic crystal composite film pattern is orange-red, and the color in the structural color electrochromic device is red.

2. Preparation of electrochromic devices:

a. Fix the electrochromic material poly-3,4-propylenedioxythiophene on the base transparent electrode layer by spin coating; the thickness of the electrochromic layer is 100nm.

b. Use encapsulant and insulating strips to regulate the glass gap along the edge of the base transparent electrode layer to form an insulating frame. A cavity is defined in the insulating frame; the insulating frame is made of organic epoxy resin.

c. Cover the gel electrolyte containing lithium salt on the base transparent electrode layer with the electrochromic layer to form an electrolyte layer; the covering method is spraying; the electrolyte layer contains the solute LiTFSI lithium salt compound and the gel polymer in the electrolyte Using PC and PEGDA, the concentration of solute is 10 ^-5 mol/L.

d. Cover the top transparent electrode layer coated with a multi-colored structural color layer on the electrolyte layer, and cross-link the gel electrolyte under ultraviolet light.

e. Paste the preset pattern film on the bottom of the base transparent electrode layer to form the preset pattern layer "flower" pattern.

An orange-red structural color electrochromic device with a "Suzhou University of Science and Technology" pattern in multiple optical states was obtained. As shown in Figure 5, the device can display and switch the "Suzhou University of Science and Technology emblem" and "flower" structural color patterns through voltage.

Claims (14)

1. An electrochromic device having multiple optical states, characterized by: comprises a top transparent electrode layer, a colorful structural color layer, an electrolyte layer, an electrochromic layer and a base transparent electrode layer which are sequentially combined from top to bottom.

2. The electrochromic device with multiple optical states of claim 1, wherein: the colorful structural color layer is composed of polymer microspheres.

3. The electrochromic device with multiple optical states of claim 2, wherein: the material of the colorful structural color layer is composed of P (St-MMA-AA) nanometer microspheres, and the particle size of the nanometer microspheres is 180-300 nm.

4. The electrochromic device with multiple optical states of claim 1, wherein: the electrochromic layer is made of one of polythiophene, polyaniline, polypyrrole, poly 3, 4-propylene dioxythiophene, triphenylamine, poly (3, 4-propylene dioxythiophene), tungsten oxide, molybdenum oxide, nickel oxide, vanadium oxide, viologen, metal phthalocyanine and derivatives thereof; the thickness of the electrochromic layer is 100-1000 a nm a.

5. The electrochromic device with multiple optical states of claim 1, wherein: the electrolyte layer is composed of a solute and a gel polymer; the solute is a lithium salt compound including LiPF ₆ 、LiBF ₄ 、LiClO ₄ 、LiAsF ₆ 、LiCF ₃ SO ₃ 、LiN(CF ₃ SO ₂ ) ₂ 、LiC(CF ₃ SO ₂ ) ₃ One or more of LiFSI, liBOB and LiTFSI, the gel polymer being one or more of PC, PEGDA, PVDF, PEO, PAN, PMMA, PVA; solute concentration at 10 ^-5 -10 ^{- 4} mol/L。

6. The electrochromic device with multiple optical states of claim 1, wherein: the top transparent electrode layer and the base transparent electrode layer are made of any one or a combination of more of ITO glass, FTO glass, zinc oxide, tin oxide, carbon nano tube transparent conductive materials, silver metal films, copper metal films and gold metal films.

7. The electrochromic device with multiple optical states of claim 1, wherein: the bottom of the base transparent electrode layer is provided with a preset pattern layer, and the preset pattern layer is formed on the bottom surface of the base transparent electrode by one or more of laser etching, cutting, carving and embossing, or is formed by sticking a preset pattern film on the bottom.

8. A method of making an electrochromic device having multiple optical states as recited in claim 1, wherein: comprises the following steps of the method,

a. fixing the electrochromic material on the base transparent electrode layer by any one of magnetron sputtering, thermal evaporation, spin coating, spray coating, screen printing, ink-jet printing and gravure printing;

b. packaging the substrate along the edge of the transparent electrode layer of the substrate by using packaging adhesive and an insulating strip for regulating and controlling the glass gap to form an insulating frame, wherein a cavity is defined in the insulating frame;

c. covering a gel electrolyte containing lithium salt on a base transparent electrode layer with an electrochromic layer to form an electrolyte layer;

d. a top transparent electrode layer coated with a multi-color structural color layer was overlaid on the electrolyte layer and the gel electrolyte was crosslinked under uv light.

9. The method for manufacturing an electrochromic device with multiple optical states according to claim 8, characterized in that: forming a preset pattern layer on the bottom surface of the base transparent electrode by one or more of laser etching, cutting, carving and embossing before the step a; or, after the step d, forming a preset pattern layer by sticking a preset pattern film on the bottom.

10. The method for manufacturing an electrochromic device with multiple optical states according to claim 8, characterized in that: the method of coating the multicolor structure color layer on the top transparent electrode layer is as follows,

a) Forming a film on the surface of the top transparent electrode layer by using P (St-MMA-AA) nanometer microsphere emulsion in a spin coating or coating mode to form a colorful structural color film;

b) Annealing the prepared colorful structural color film for 10min at 100 ℃ to obtain a photonic crystal structural color film with the thickness of 6-10 mu m; patterning the multicolor structure color layer by etching or solvent treatment.

11. The method of manufacturing an electrochromic device having multiple optical states according to claim 10, characterized in that: the preparation method of the P (St-MMA-AA) nanometer microsphere emulsion comprises the following steps,

1) Sequentially adding styrene (St), methyl Methacrylate (MMA), acrylic Acid (AA), deionized water, a small amount of surfactant Sodium Dodecyl Benzene Sulfonate (SDBS) and buffer ammonium bicarbonate (MSDS) into a three-neck flask; the addition amount of each component is as follows: every 100ml deionized water is added, 182.60mmol of styrene, 10mmol of methyl methacrylate, 13.89mmol of acrylic acid and 6.3mmol of buffer ammonium bicarbonate are correspondingly added;

the particle size of the P (St-MMA-AA)) nano microsphere is regulated by changing the monomer mass ratio of sodium dodecyl benzene sulfonate in the P (St-MMA-AA) nano microsphere; the color of the structural color layer is regulated by changing the particle size of the polymer P (St-MMA-AA);

2) Then, magnetically stirring and heating under a protective atmosphere;

3) Finally, ammonium Persulfate (APS) is added into the reaction mixture in the last step, and the mixture is reacted at high temperature to obtain the P (St-MMA-AA) nanometer microsphere emulsion.

12. The method for manufacturing an electrochromic device having multiple optical states according to claim 11, characterized in that: the monomer mass ratio of the sodium dodecyl benzene sulfonate in the P (St-MMA-AA) nano-microsphere is 1:0.025-0.060, and the particle size range of the P (St-MMA-AA) nano-microsphere is 200-300nm.

13. The method for manufacturing an electrochromic device having multiple optical states according to claim 11, characterized in that: in the step 2), the protective atmosphere is nitrogen, the heating reaction temperature is 75 ℃, and the reaction time is 20 minutes.

14. The method for manufacturing an electrochromic device having multiple optical states according to claim 11, characterized in that: in the step 3), the addition amount of the ammonium sulfate is 100.32 mmol of the ammonium sulfate which is added in the step 3) every time 100ml deionized water is added in the step 1); the temperature of the heating reaction in the step 3) is 80 ℃ and the reaction time is 10 hours.