Multi-mode color electrochromic device and preparation method thereof

Abstract

The invention relates to a multi-mode color electrochromic device and a preparation method thereof. A working electrode of the multi-mode color electrochromic device is formed by stacking a plurality of optical cavities, a single optical cavity structure comprises a dielectric layer, an optical layer and a dielectric layer which are sequentially arranged from top to bottom, and the optical layer has optical reflection and / or transmissivity; the number N of the optical cavities is greater than or equal to 1, preferably N = 2; the multi-mode color electrochromic device has a transmission mode and a reflection mode; in a static state, reflection / transmission colors can be shown; when voltage is applied, the refractive index of the electrochromic material in the device is changed, and by adjusting the voltage applied to the two sides of the device, the combination of structural color and electrochromism is realized, and meanwhile, the change of two modes of transmission and reflection can be realized, so that the transmission color and the reflection color of the multi-color electrochromic device are regulated and controlled; the reflection color of the multi-mode color electrochromic device is red or green or blue, the transmission color of the multi-mode color electrochromic device is blue or red or green, and full-color-gamut coverage can be achieved through three-primary-color dot matrix arrangement.

Description

Technical Field

[0001] This invention belongs to the field of optical device technology, specifically relating to a multimodal color electrochromic device and its preparation method. Background Technology

[0002] Multi-color electrochromic devices, as an emerging electronic technology, can dynamically adjust the color of objects under the influence of an electric field. Their basic working principle lies in the redox reaction caused by the insertion and extraction of ions or electrons into and out of the electrochromic material, thereby achieving color changes within the visible light range. Multi-color electrochromic technology boasts advantages such as no backlight, low energy consumption, and high contrast. In terms of static display capabilities and eye-protection characteristics, it far surpasses current mature display technologies such as LCD and OLED, and has immense application potential in future display fields, optical information storage, and military camouflage.

[0003] Previous studies primarily focused on multi-color electrochromic technologies using small organic molecules or conjugated polymer electrochromic materials, modifying their functional groups to alter colors—a technique known as chemical coloring. In recent years, researchers, based on thin-film optics principles, have manipulated the structure of electrochromic devices to induce dispersion, scattering, interference, and diffraction of light within the device. This allows the device to exhibit vibrant structural colors even when static. Combining electrochromism with structural coloring overcomes the monotonous colors of some inorganic electrochromic materials (such as WO3), enabling multi-color electrochromic displays.

[0004] Multi-color electrochromic devices and materials can be categorized into two types based on their operating scenarios: transmissive and reflective. Transmissive devices are primarily used in smart windows, smart glasses, and display technologies; reflective devices are mainly applied in displays, optical sensors, military camouflage, and photoelectric converters. However, currently, multi-color electrochromic devices are generally limited to a single mode, and the achievable color gamut, brightness, and saturation are relatively narrow, making it difficult to meet practical application requirements. This undoubtedly restricts the application areas of color electrochromic devices. Therefore, the fabrication of multi-modal color electrochromic devices is beneficial for further expanding their application scenarios and potential in the display field. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a multimodal color electrochromic device and its fabrication method, which is simple in process and can achieve a wide color gamut area, high brightness, and high saturation.

[0006] In a first aspect, the present invention provides a multimodal color electrochromic device, the structure of which includes, from top to bottom, a working electrode, a cathode electrochromic material, an electrolyte, an anode electrochromic material and a transparent electrode; The working electrode is composed of a stack of optical cavities. Each optical cavity structure includes a dielectric layer, an optical layer, and a dielectric layer arranged sequentially from top to bottom. The optical layer has optical reflection and / or transmission properties. The number of optical cavities N≥1, preferably N=2. The multimodal color electrochromic device has both transmission and reflection modes; in a static state, it can display reflected / transmitted colors; when a voltage is applied to both the working electrode and the transparent electrode, the refractive index of the electrochromic material in the device changes; by adjusting the magnitude of the voltage applied to both sides of the device, the combination of structural color and electrochromism can be achieved, and the changes in both transmission and reflection modes can be realized, thereby controlling the transmitted and reflected colors of the multi-color electrochromic device. The multimodal color electrochromic device reflects red, green, or blue colors and transmits blue, red, or green colors. The arrangement of the three primary color dot matrix can achieve full color gamut coverage.

[0007] Preferably, the dielectric layer is selected from transparent conductive inorganic materials or transparent conductive organic materials; more preferably, it is a liquid crystal material or a MOF material. The transparent conductive inorganic material includes at least one of the following: metallic elements, non-metallic elements, oxides, and inorganic salts; preferably, the metallic element is a nanowire structure, the non-metallic element includes at least one of selenium, silicon, graphite, carbon nanotube films, and graphene films, the oxide includes at least one of cadmium oxide, indium oxide, tin oxide, zinc oxide, indium tin oxide, doped zinc oxide, doped tin oxide, and doped indium oxide, and the inorganic salt includes MoS2 and SrSnO3; The transparent conductive organic material includes small organic molecule compounds and / or polymers; preferably, the transparent conductive organic material includes at least one of polyacetylene, polypyrrole, polyaniline, polythiophene, poly(p-phenylenevinylene), polyphenylene sulfide, polyphthalocyanine, and conductive plastics. The thickness of the dielectric layer is ≤2000nm, preferably 26~284nm, and more preferably 30~200nm.

[0008] Preferably, the optical layer is selected from metallic or non-metallic materials; wherein the metallic material includes at least one of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, and palladium, and the non-metallic material includes at least one of monocrystalline silicon, polycrystalline silicon, and diamond; The extinction coefficient of the optical layer is 2-16; The thickness of the optical layer is ≤20nm, preferably 10-20nm, and more preferably 10-15nm.

[0009] Preferably, when incident light is perpendicular to the working electrode, the light component on the upper surface of the first dielectric layer... and The optical component at the lower surface of the m-th dielectric layer and Related to the transfer matrix M: in: I j(j+1) Here is the interface matrix for light reflection and transmission at the interface between layer j and layer j+1 of the working electrode: The light reflectance coefficient r at the interface between layer j and layer j+1 of the working electrode j( j +1) and transmission coefficient t j( j +1) for: in: Let n be the complex refractive index of the j-th layer of the working electrode, n0 be the refractive index of the medium on the upper surface of the first dielectric layer, and θ be the incident angle of the incident light. L j The layer matrix describing the light propagation through the working electrode layer j is as follows: Where: d j The thickness of the j-th layer in the working electrolysis process; When light is incident from the upper surface of the first dielectric layer of the working electrode The complex reflection coefficient r and transmission coefficient t of the optical cavity multilayer structure of the working electrode can be expressed as: Preferably, according to Fresnel's equations, the reflectivity R and transmittance T of the optical cavity multilayer structure are: R = lr1 2 in: n m+1 Let θm be the refractive index of the film material beneath the m-th dielectric layer of the working electrode. +1 The angle of refraction is the angle at which the working electrode exits the m-th dielectric layer.

[0010] Preferably, the cathode electrochromic material includes at least one of cathode electrochromic inorganic material and cathode electrochromic organic material; wherein the cathode electrochromic inorganic material includes at least one of tungsten oxide, molybdenum oxide, vanadium oxide, niobium oxide, titanium oxide, and tantalum oxide, and the cathode electrochromic organic material includes at least one of iologen, polypyrrole, polythiophene, and polyaniline. The thickness of the cathode electrochromic material is ≤2000nm, preferably 100~175nm, and more preferably 100~150nm.

[0011] Preferably, the electrolyte comprises at least one cation; more preferably, the cation in the electrolyte includes H+. + Li + Al 3+ Na + K + 、Rb + Ag + Ni 2+ Ca 2+ Mo 6+ Mn 2+ Ti 4+ V 4+ Zn 2+ W 6+ Ta 5+ Cu 2+ Bi 3+ Sn 4+ Mg 2 + Cs + At least one of them; The electrolyte is in liquid, gel, or solid state; the thickness of the electrolyte is ≤2000nm, preferably 100-200nm.

[0012] Preferably, the anodic electrochromic material includes at least one of anodic electrochromic inorganic material and anodic electrochromic organic material; wherein the anodic electrochromic inorganic material includes at least one of nickel oxide, platinum oxide, iridium oxide, osmium oxide, palladium oxide, ruthenium oxide, rhodium oxide or hydrates of the above oxides, and the anodic electrochromic organic material includes at least one of violetin, polypyrrole, polythiophene, and polyaniline; The thickness of the anodic electrochromic material is ≤2000nm, preferably 50-100nm.

[0013] Preferably, the transparent electrode may include a transparent conductive layer and a transparent substrate; wherein, the transparent conductive layer includes at least one of FTO, ITO, Ag nanowires, Ag nanogrids, carbon nanotubes, and graphene; and the transparent substrate includes at least one of plastic products, fabrics, plexiglass, metal alloys, ceramics, PET, PES, PEN, PC, PMMA, and PDMS. The thickness of the transparent conductive layer is 90-100 nm, and the thickness of the transparent substrate is ≤1 cm.

[0014] Preferably, the voltage applied to the multimodal color electrochromic device is -1.5V to 2.5V.

[0015] Secondly, the present invention provides a method for fabricating the above-mentioned multimodal color electrochromic device, the method comprising the following steps: on a transparent electrode substrate, an anode electrochromic layer, an electrolyte layer, a cathode electrochromic layer, and a working electrode are sequentially deposited by magnetron sputtering to obtain the multimodal color electrochromic device.

[0016] Beneficial effects (1) Based on the principle of thin film optics, this invention utilizes the refractive index n and extinction coefficient k of each specific material layer, and designs a color electrochromic device based on the determined film structure, with the color change state of the electrochromic layer and the thickness of each layer as variables, thus expanding the application field of electrochromic devices. (2) The products obtained by the present invention have diverse colors, high brightness and are adjustable by human, realizing fine control of color, and at the same time have the performance of reversible change in both transmission and reflection states, which is suitable for display applications in different scenarios. (3) The device provided by the present invention is simple to prepare, has excellent all-solid-state performance, and can realize a single device with high purity and high brightness, and the reflective color is red, green or blue (transmitting color is blue, red or green) of the three primary colors. The dot matrix arrangement of the three primary color devices can achieve full color gamut coverage. Attached Figure Description

[0017] Figure 1 A schematic diagram of the structure of the multimodal color electrochromic device prepared in Example 1; Figure 2 The visible light transmittance of the interference layer of the ITO / Ag / ITO structure with an Ag thickness of 10 nm is plotted as a function of the thickness of the bottom and top ITO layers. Figure 3 The visible light reflectance of the interference layer of the ITO / Ag / ITO structure with an Ag thickness of 10 nm is plotted as a function of the thickness of the bottom and top ITO layers. Figure 4 Schematic diagram of reflective color for ITO / Ag / ITO / Ag / ITO with different thicknesses; Figure 5This is a schematic diagram showing the changes in reflected color of devices in Examples 1, 4, and 6 under different voltages; Figure 6 This is a schematic diagram showing the changes in transmitted color of devices 1, 4, and 6 under different voltages; Figure 7 These are high-purity, high-brightness reflective red, green, and blue primary color devices, as described in Examples 1, 4, and 6. Detailed Implementation

[0018] The present invention will be further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0019] First, this invention provides a high-purity, high-brightness multimodal color electrochromic device. The structure of the multimodal color electrochromic device includes, from top to bottom, a working electrode, a cathode electrochromic material, an electrolyte, an anode electrochromic material, and a transparent electrode.

[0020] The working electrode is composed of a stack of optical cavities, and each optical cavity includes a dielectric layer, an optical layer and a dielectric layer arranged sequentially from top to bottom; preferably, the optical layer has optical reflectivity and / or transmissivity; the number of optical cavities N≥1, preferably N=2.

[0021] The working electrode provided by this invention, composed of a stack of optical cavities, enables light interference and diffraction when sunlight enters the device, thus forming the device's structural color. The number of optical cavities, N, is important to ensure light interference and diffraction; however, an excessive number would lead to light loss along the optical path and complicate the fabrication process. Preferably, N=2 ensures a wide color gamut, high brightness, and high saturation for the device's structural color.

[0022] In some embodiments, the dielectric layer may be selected from transparent conductive inorganic materials or transparent conductive organic materials; preferably, liquid crystal materials or MOF materials.

[0023] The transparent conductive inorganic material may include at least one of the following: metallic elements, non-metallic elements, oxides, and inorganic salts. Preferably, the metallic element may be a nanowire structure, the non-metallic element may include at least one of selenium, silicon, graphite, carbon nanotube films, and graphene films, the oxide may include at least one of cadmium oxide, indium oxide, tin oxide, zinc oxide, indium tin oxide, doped zinc oxide (such as aluminum or gallium doped), doped tin oxide (such as antimony doped), and doped indium oxide (such as zinc doped), and the inorganic salt may include MoS2 and SrSnO3.

[0024] The transparent conductive organic material may include small organic molecule compounds and / or polymers; preferably, the transparent conductive organic material may include at least one of polyacetylene (PA), polypyrrole (Ppy), polyaniline (PANI), polythiophene (PT), poly(p-phenylenevinylene) (PPV), polyphenylene sulfide, polyphthalocyanine, and conductive plastics.

[0025] In some embodiments, the thickness of the dielectric layer can be ≤2000nm, preferably 26-284nm, and more preferably 30-200nm. The thickness of the dielectric layer affects the optical path length of light within it, which in turn affects the interference and diffraction of light in the device. By controlling an appropriate dielectric layer thickness, good interference and diffraction effects can be ensured.

[0026] In some embodiments, the optical layer may be selected from metallic or non-metallic materials; wherein the metallic material may include at least one of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, and palladium, and the non-metallic material may include at least one of monocrystalline silicon, polycrystalline silicon, and diamond.

[0027] In some embodiments, the extinction coefficient of the optical layer can be 2-16.

[0028] In some embodiments, the thickness of the optical layer can be ≤20nm, preferably 10-20nm, and more preferably 10-15nm. The thickness of the optical layer also affects the interference and diffraction of light in the device. Excessive thickness will cause the device to be opaque, exhibiting only reflected colors; insufficient thickness will result in insufficient light reflection, preventing the formation of an optical cavity and thus preventing light interference and diffraction.

[0029] In some embodiments, when incident light is perpendicularly incident on the working electrode, the light component on the upper surface of the first dielectric layer... (same as the direction of the incident light) and (Opposite to the direction of incident light) and the light component at the output end of the lower surface of the m-th dielectric layer. (Same as the direction of transmitted light) and (Opposite to the direction of transmitted light) Related to the transmission matrix M: in: I j(j+1) Here is the interface matrix for light reflection and transmission at the interface between layer j and layer j+1 of the working electrode: The light reflectance coefficient r at the interface between layer j and layer j+1 of the working electrode j(j+1) and transmission coefficient tj(j+1) for: in: Let n be the complex refractive index of the j-th layer of the working electrode, n0 be the refractive index of the medium on the upper surface of the first dielectric layer, and θ be the incident angle of the incident light. L j The layer matrix describing the light propagation through the working electrode layer j is as follows: Where: d j Let be the thickness of the j-th layer in the working electrolysis.

[0030] In some embodiments, when light is incident from the upper surface of the first dielectric layer of the working electrode... The complex reflection coefficient r and transmission coefficient t of the optical cavity multilayer structure of the working electrode can be expressed as: Preferably, according to Fresnel's equations, the reflectivity R and transmittance T of the optical cavity multilayer structure are: R = lr1 2 in: n m+1 Let θm be the refractive index of the film material beneath the m-th dielectric layer of the working electrode. +1 The angle of refraction is the angle at which the working electrode exits the m-th dielectric layer.

[0031] Previous technologies for fabricating multi-color electrochromic devices typically generate structural colors using Fabry-Perot resonant cavities, also calculating reflectivity R and transmittance T. However, these formulas are related to the reflectivity of the metal film and the total phase shift accumulated during a single round trip within the cavity. In this invention, the reflectivity R and transmittance T of the working electrode are designed based on formulas related to the light component E, which affects brightness and saturation. Therefore, the working electrode designed based on the matrix and formulas provided in this invention can significantly improve brightness and saturation.

[0032] The cathode electrochromic material is a material that changes color through a cathode reduction reaction under the influence of an electric field. In some embodiments, the cathode electrochromic material may include at least one of cathode electrochromic inorganic materials and cathode electrochromic organic materials; wherein, the cathode electrochromic inorganic material may include at least one of tungsten oxide, molybdenum oxide, vanadium oxide, niobium oxide, titanium oxide, and tantalum oxide, and the cathode electrochromic organic material may include at least one of iridoid, polypyrrole, polythiophene, and polyaniline.

[0033] In some embodiments, the thickness of the cathode electrochromic material can be ≤2000nm, preferably 100-175nm, and more preferably 100-150nm.

[0034] In some embodiments, the electrolyte may contain at least one cation; preferably, the cation in the electrolyte may include H+. + Li + Al 3+ Na + K + 、Rb + Ag + Ni 2+ Ca 2+ Mo 6+ Mn 2+ Ti 4+ V 4+ Zn 2+ W 6+ Ta 5+ Cu 2+ Bi 3+ Sn 4+ Mg 2+ Cs + At least one of them.

[0035] In some embodiments, the electrolyte may be liquid, gel, or solid; the thickness of the electrolyte may be ≤2000 nm, preferably 100–200 nm.

[0036] The anodic electrochromic material is a material that changes color through an anodic oxidation reaction under the action of an electric field. In some embodiments, the anodic electrochromic material may include at least one of anodic electrochromic inorganic materials and anodic electrochromic organic materials; wherein, the anodic electrochromic inorganic material may include at least one of nickel oxide, platinum oxide, iridium oxide, osmium oxide, palladium oxide, ruthenium oxide, rhodium oxide, or hydrates of the above oxides, and the anodic electrochromic organic material may include at least one of iridoid, polypyrrole, polythiophene, and polyaniline.

[0037] In some embodiments, the thickness of the anodic electrochromic material is ≤2000nm, preferably 50-100nm.

[0038] In some embodiments, the transparent electrode may include a transparent conductive layer and a transparent substrate. The transparent conductive layer may include at least one of FTO, ITO, Ag nanowires, Ag nanogrids, carbon nanotubes, and graphene; the transparent substrate may include at least one of plastic products, fabrics, plexiglass, metal alloys, ceramics, PET, PES, PEN, PC, PMMA, and PDMS.

[0039] In some embodiments, the thickness of the transparent conductive layer can be 90-100 nm, and the thickness of the transparent substrate can be ≤1 cm.

[0040] The multimodal color electrochromic device provided by this invention has both transmission and reflection modes. In a static state, it can display a rich variety of reflected / transmitted colors. Simultaneously, when a voltage is applied across the working electrode and the transparent electrode, the refractive index of the electrochromic material in the device changes. By adjusting the magnitude of the voltage applied across the device, the combination of structural color and electrochromism can be achieved, while also realizing the change between the transmission and reflection modes. This allows for the control of the transmitted and reflected colors of the multi-color electrochromic device, making it suitable for various applications.

[0041] In some embodiments, the voltage applied to the multimodal color electrochromic device can be -1.5V to 2.5V.

[0042] In some embodiments, the multimodal color electrochromic device provided by the present invention can be a single device with high purity and high brightness, and the reflective color is red, green or blue (transmitting color is blue, red or green). The dot matrix arrangement of the three primary color devices can achieve full color gamut coverage.

[0043] The multimodal color electrochromic device provided by this invention can achieve both transmission and reflection modes, accompanied by color changes, depending on the viewing angle or the sign and magnitude of the applied voltage. Furthermore, based on thin-film optics principles, and according to the refractive index n and extinction coefficient k of the device's constituent materials, any color can be achieved. By optimizing the film structure and thickness of the multimodal color electrochromic device, a single device with high purity and high brightness, reflecting red, green, or blue (transmitting blue, red, or green) as the three primary colors, can be realized. The dot matrix arrangement of these three primary color devices can achieve full color gamut coverage.

[0044] In some embodiments, the luminance L value of the reflected color of the multimodal electrochromic device provided by the present invention ranges from 20 to 60.

[0045] As an example, the multimodal color electrochromic device may include the following structure: (1) The working electrode is composed of alternating stacks of dielectric layer ITO and optical layer Ag, specifically ITO / Ag / ITO / Ag / ITO; the thickness of dielectric layer ITO is 26-284nm, preferably 30-200nm, and the thickness of optical layer Ag is 10-15nm. (2) The cathode electrochromic material is WO3 with a thickness of 100-175 nm, preferably 100-150 nm; (3) The electrolyte is LiTaO3 with a thickness of 100-200 nm; (4) The anodic electrochromic material is NiO x The thickness is 50–100 nm; (5) The transparent electrode is made of conductive ITO glass with an ITO thickness of 90-100 nm; Modal color electrochromic devices are all solid-state.

[0046] For the multimodal color electrochromic device in the above example, when NiO is fixed... x With a thickness of 50nm, a LiTaO3 thickness of 100nm, and an optical layer Ag thickness of 10nm, by adjusting the thickness of the dielectric layer ITO and the cathode electrochromic layer WO3 in the working electrode, different static colors and single devices with high purity and high brightness reflective colors of red, green, or blue (transmitted colors of blue, red, or green) can be obtained.

[0047] The following exemplarily describes a method for fabricating a multimodal color electrochromic device provided by the present invention. The fabrication method may include the following steps: on a transparent electrode substrate, an anodic electrochromic layer, an electrolyte layer, a cathode electrochromic layer, and a working electrode are sequentially deposited by magnetron sputtering to obtain the multimodal color electrochromic device.

[0048] In some embodiments, the magnetron sputtering deposition uses DC magnetron sputtering. The DC magnetron sputtering system may include: a deposition chamber, a sample inlet chamber, several target heads, a substrate, a DC current source, an RF power source, and several mechanical pumps and vacuum pumps, wherein the target head is at a certain angle to the substrate and is separated by a certain distance, and the DC power source and the RF power source are connected to the target head.

[0049] In some embodiments, the magnetron sputtering deposition process may include: ultrasonically cleaning the substrate with acetone, anhydrous ethanol, and deionized water for 30 minutes each, and then drying it with compressed air; then, covering a portion of the conductive substrate with high-temperature tape as an electrode and fixing it on the substrate tray, placing it in the sample injection chamber, and evacuating it to below 5 Pa using a mechanical pump; finally, opening the baffle valve to introduce a vacuum (baseline vacuum) of 10 Pa.-4 Sputtering deposition is carried out in sputtering chambers at Pa and below.

[0050] This invention employs a convenient magnetron sputtering process to fabricate the thin films of the device. Based on the principles of thin-film optics, and according to the refractive index n and extinction coefficient k of the constituent materials of the device, any color of the device can be achieved. With changes in the observation angle or adjustment of the positive and negative values ​​and magnitudes of the applied voltage, the device can achieve both transmission and reflection modes, accompanied by color changes. Furthermore, by optimizing the film structure and thickness of the multimodal color electrochromic device, a single device with high purity and high brightness, reflecting red, green, or blue (transmitting blue, red, or green) as the three primary colors, can be achieved. The dot matrix arrangement of the three primary color devices can achieve full color gamut coverage.

[0051] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Additionally: For each basic color, the parameters are set to (R,G,B,L), where the (R,G,B) values ​​represent the color coordinates of hue and saturation, and the L value corresponds to the brightness of the reflected color.

[0052] Example 1

[0053] The method for fabricating a multimodal color electrochromic device provided in this embodiment includes the following steps: (1) Fix an ITO transparent conductive glass substrate to the substrate tray with high-temperature tape, place it in the sample injection chamber, turn on the mechanical pump to pump to below 5 Pa, open the baffle valve, and introduce a vacuum (background vacuum) to reach 10. -4 In sputtering chambers below Pa; (2) Using a Ni target as the target material, Ar:O2 = 40:10, a total pressure of 1.0 Pa, a DC power supply of 100 W, and a deposition time of 1500 s, a NiO thin film with a thickness of 50 nm was obtained; using a LiTaO3 target as the target material, Ar:O2 = 48:2, a total pressure of 1.0 Pa, an RF power supply of 200 W, and a deposition time of 8000 s, a NiO thin film with a thickness of 100 nm was obtained. A LiTaO3 thin film was obtained with a thickness of 140 nm using a W target, Ar:O2 = 94:6, a total pressure of 1.0 Pa, a DC power supply of 100 W, and a deposition time of 1298 s. An ITO thin film with a thickness of 161 nm was obtained with an ITO target, Ar:O2 = 80:0, a total pressure of 0.3 Pa, a RF power supply of 90 W, and a deposition time of 1290 s. An Ag target with an Ar:O2 = 60:0 was also obtained with a thickness of 140 nm. With a pressure of 0.3 Pa, a DC power supply of 50 W, and a deposition time of 30 s, an Ag thin film with a thickness of 10 nm is obtained. Then, ITO is sputtered for 463 s to obtain an ITO thin film with a thickness of 58 nm. Ag is sputtered for 30 s to obtain an Ag thin film with a thickness of 10 nm. ITO is sputtered for 1131 s to obtain an ITO thin film with a thickness of 142 nm, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer, thus obtaining the multimodal color electrochromic device.

[0054] In this embodiment, the reflected color of the multimodal color electrochromic device is red (126,78,79,38.6), and the transmitted color is blue.

[0055] Figure 1 This is a schematic diagram of the structure of the multimodal color electrochromic device prepared in Example 1.

[0056] Example 2

[0057] The fabrication method of the multimodal color electrochromic device provided in this embodiment is the same as that in Embodiment 1, the main difference being: in step (2), a W target is used as the target material, Ar:O2 = 94:6, the total pressure is 1.0 Pa, the DC power supply is 100 W, and the deposition time is 1205 s, to obtain an amorphous WO3 thin film layer with a thickness of 130 nm; an ITO target is used as the target material, Ar:O2 = 80:0, the total pressure is 0.3 Pa, the RF power supply is 90 W, and the deposition time is 1184 s, to obtain a film layer with a thickness of 148 nm. An ITO thin film layer was obtained by sputtering an Ag target with an Ar:O2 ratio of 60:0, a total pressure of 0.3 Pa, a DC power supply of 50 W, and a deposition time of 30 s. The Ag thin film layer with a thickness of 10 nm was obtained by sputtering ITO for 1705 s to obtain an ITO thin film layer with a thickness of 213 nm. Ag was sputtered for 30 s to obtain an Ag thin film layer with a thickness of 10 nm. ITO was sputtered for 311 s to obtain an ITO thin film layer with a thickness of 40 nm, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0058] The multimodal color electrochromic device obtained in this embodiment reflects orange (177, 133, 103, 59.2).

[0059] Example 3

[0060] The fabrication method of the multimodal color electrochromic device provided in this embodiment is the same as that in Embodiment 1, the main difference being: in step (2), a W target is used as the target material, Ar:O2 = 94:6, the total pressure is 1.0 Pa, the DC power supply is 100 W, and the deposition time is 1205 s to obtain an amorphous WO3 thin film layer with a thickness of 130 nm; an ITO target is used as the target material, Ar:O2 = 80:0, the total pressure is 0.3 Pa, the RF power supply is 90 W, and the deposition time is 973 s to obtain an ITO thin film layer with a thickness of 121 nm; an Ag target is used as the target material, Ar:O2 = 60:0, the total pressure is 0.3 Pa, the DC power supply is 50 W, and the deposition time is 30 s to obtain an Ag thin film layer with a thickness of 10 nm; then ITO is sputtered for 518 s to obtain an ITO thin film layer with a thickness of 65 nm; Ag is sputtered for 30 s to obtain an Ag thin film layer with a thickness of 10 nm; ITO is sputtered... After 274s, an ITO thin film with a thickness of 35nm was obtained, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0061] The multimodal color electrochromic device prepared in this embodiment reflects yellow (153,138,85,57.8).

[0062] Example 4

[0063] The fabrication method of the multimodal color electrochromic device provided in this embodiment is the same as that in Embodiment 1, the main difference being: in step (2), a W target is used as the target material, Ar:O2 = 94:6, the total pressure is 1.0 Pa, the DC power supply is 100 W, and the deposition time is 1205 s to obtain an amorphous WO3 thin film layer with a thickness of 130 nm; an ITO target is used as the target material, Ar:O2 = 80:0, the total pressure is 0.3 Pa, the RF power supply is 90 W, and the deposition time is 985 s to obtain an ITO thin film layer with a thickness of 123 nm; an Ag target is used as the target material, Ar:O2 = 60:0, the total pressure is 0.3 Pa, the DC power supply is 50 W, and the deposition time is 30 s to obtain an Ag thin film layer with a thickness of 10 nm; and then ITO is sputtered in the same manner. After 931s, an ITO thin film with a thickness of 116nm was obtained; after sputtering Ag for 30s, an Ag thin film with a thickness of 10nm was obtained; after sputtering ITO for 1175s, an ITO thin film with a thickness of 147nm was obtained, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0064] The multimodal color electrochromic device obtained in this embodiment has a reflected color of green (95,152,105,58.0) and a transmitted color of red.

[0065] Example 5

[0066] The fabrication method of the multimodal color electrochromic device provided in this embodiment is the same as that in Embodiment 1, the main difference being: in step (2), a W target is used as the target material, Ar:O2 = 94:6, the total pressure is 1.0 Pa, the DC power supply is 100 W, and the deposition time is 1205 s to obtain an amorphous WO3 thin film layer with a thickness of 130 nm; an ITO target is used as the target material, Ar:O2 = 80:0, the total pressure is 0.3 Pa, the RF power supply is 90 W, and the deposition time is 689 s to obtain an ITO thin film layer with a thickness of 86 nm; an Ag target is used as the target material, Ar:O2 = 60:0, the total pressure is 0.3 Pa, the DC power supply is 50 W, and the deposition time is 30 s to obtain an Ag thin film layer with a thickness of 10 nm; then ITO is sputtered for 2272 s to obtain an ITO thin film layer with a thickness of 284 nm; Ag is sputtered for 30 s to obtain an Ag thin film layer with a thickness of 10 nm; ITO is sputtered... After 480s, a 60nm thick ITO thin film layer was obtained, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0067] The multimodal color electrochromic device prepared in this embodiment reflects cyan (142, 113, 157, 51.8).

[0068] Example 6

[0069] The fabrication method of the multimodal color electrochromic device provided in this embodiment is the same as that in Embodiment 1, the main difference being: in step (2), a W target is used as the target material, Ar:O2 = 94:6, the total pressure is 1.0 Pa, the DC power supply is 100 W, and the deposition time is 1618 s, to obtain an amorphous WO3 thin film layer with a thickness of 175 nm; an ITO target is used as the target material, Ar:O2 = 80:0, the total pressure is 0.3 Pa, the RF power supply is 90 W, and the deposition time is 213 s, to obtain an ITO thin film layer with a thickness of 26 nm; an Ag target is used as the target material, Ar:O2 = 60:0, the total pressure is 0.3 Pa, the DC power supply is 50 W, and the deposition time is 30 s, to obtain an Ag thin film layer with a thickness of 15 nm; then ITO is sputtered for 2143 s to obtain an ITO thin film layer with a thickness of 267 nm; Ag is sputtered for 30 s to obtain an Ag thin film layer with a thickness of 15 nm; ITO is sputtered... After 480s, a 60nm thick ITO thin film layer was obtained, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0070] The multimodal color electrochromic device prepared in this embodiment has a reflected color of blue (97,128,146,52.0) and a transmitted color of green.

[0071] Example 7

[0072] The fabrication method of the multimodal color electrochromic device provided in this embodiment is the same as that in Embodiment 1, the main difference being: in step (2), a W target is used as the target material, Ar:O2 = 94:6, the total pressure is 1.0 Pa, the DC power supply is 100 W, and the deposition time is 1618 s to obtain an amorphous WO3 thin film layer with a thickness of 175 nm; an ITO target is used as the target material, Ar:O2 = 80:0, the total pressure is 0.3 Pa, the RF power supply is 90 W, and the deposition time is 213 s to obtain an ITO thin film layer with a thickness of 26 nm; an Ag target is used as the target material, Ar:O2 = 60:0, the total pressure is 0.3 Pa, the DC power supply is 50 W, and the deposition time is 30 s to obtain an Ag thin film layer with a thickness of 15 nm; then, ITO is sputtered for 1946 s to obtain an ITO thin film layer with a thickness of 243 nm; Ag is sputtered for 30 s to obtain an Ag thin film layer with a thickness of 15 nm; ITO is sputtered for 480 s to obtain an Ag thin film layer with a thickness of 15 nm. s, a 60nm thick ITO thin film layer was obtained, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0073] The multimodal color electrochromic device prepared in this embodiment reflects purple (161,97,176,51.0).

[0074] Comparative Example 1

[0075] The preparation method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1. The main difference is that in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 2318 s to obtain an amorphous WO3 thin film layer with a thickness of 250 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 1400 s to obtain an ITO thin film layer with a thickness of 175 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 60 s to obtain an Ag thin film layer with a thickness of 20 nm; then ITO is sputtered for 800 s to obtain an ITO thin film layer with a thickness of 100 nm; and an ITO / Ag / ITO composite electrode layer is obtained.

[0076] The multimodal color electrochromic device prepared in this comparative example has a reflected color of purplish-red (193, 118, 158, 25.4).

[0077] Comparative Example 2

[0078] The preparation method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1. The main difference is that in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 2318 s to obtain an amorphous WO3 thin film layer with a thickness of 250 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 1200 s to obtain an ITO thin film layer with a thickness of 150 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 60 s to obtain an Ag thin film layer with a thickness of 20 nm; then ITO is sputtered for 800 s to obtain an ITO thin film layer with a thickness of 100 nm; and an ITO / Ag / ITO composite electrode layer is obtained.

[0079] The multimodal color electrochromic device obtained in this comparative example has a reflected color of ochre (210, 178, 104, 28.1).

[0080] Comparative Example 3

[0081] The preparation method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1. The main difference is that in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 2318 s to obtain an amorphous WO3 thin film layer with a thickness of 250 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 1000 s to obtain an ITO thin film layer with a thickness of 125 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 60 s to obtain an Ag thin film layer with a thickness of 20 nm; then ITO is sputtered for 800 s to obtain an ITO thin film layer with a thickness of 100 nm; and an ITO / Ag / ITO composite electrode layer is obtained.

[0082] The multimodal color electrochromic device obtained in this comparative example has a reflected color of yellow-green (207,223,132,29.0).

[0083] Comparative Example 4

[0084] The preparation method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1. The main difference is that in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 2318 s to obtain an amorphous WO3 thin film layer with a thickness of 250 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 800 s to obtain an ITO thin film layer with a thickness of 63 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 60 s to obtain an Ag thin film layer with a thickness of 20 nm; then ITO is sputtered for 800 s to obtain an ITO thin film layer with a thickness of 100 nm; and an ITO / Ag / ITO composite electrode layer is obtained.

[0085] The multimodal color electrochromic device obtained in this comparative example has a reflected color of light green (166,214,187,23.3).

[0086] Comparative Example 5

[0087] The preparation method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1. The main difference is that in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 2318 s to obtain an amorphous WO3 thin film layer with a thickness of 250 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 400 s to obtain an ITO thin film layer with a thickness of 50 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 60 s to obtain an Ag thin film layer with a thickness of 20 nm; then ITO is sputtered for 800 s to obtain an ITO thin film layer with a thickness of 100 nm; and an ITO / Ag / ITO composite electrode layer is obtained.

[0088] The multimodal color electrochromic device obtained in this comparative example has a reflected color of pale blue-purple (159, 163, 189, 20.5).

[0089] Comparative Example 6

[0090] The fabrication method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1, the main difference is that in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 1205 s to obtain an amorphous WO3 thin film layer with a thickness of 130 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 1184 s to obtain an ITO thin film layer with a thickness of 148 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 60 s to obtain an Ag thin film layer with a thickness of 22 nm; then ITO is sputtered for 568 s to obtain an ITO thin film layer with a thickness of 71 nm; Ag is sputtered for 30 s to obtain an Ag thin film layer with a thickness of 22 nm; ITO is sputtered... After 688s, an ITO thin film with a thickness of 86nm was obtained, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0091] The multimodal color electrochromic device proposed in this invention can be obtained, with a reflected color of dark yellow (227,205,87,42.2).

[0092] Comparative Example 7

[0093] The preparation method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1, the main difference is that: in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 1618 s to obtain an amorphous WO3 thin film layer with a thickness of 171 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 213 s to obtain an ITO thin film layer with a thickness of 21 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 30 s to obtain an Ag thin film layer with a thickness of 10 nm; then ITO is sputtered for 2143 s to obtain an ITO thin film layer with a thickness of 267 nm; Ag30 is sputtered. s, to obtain an Ag thin film layer with a thickness of 10 nm; sputter ITO 400 s, to obtain an ITO thin film layer with a thickness of 54 nm, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0094] The multimodal color electrochromic device proposed in this invention can be obtained, with a reflected color of blue (70, 119, 163, 48.4).

[0095] Comparative Example 8

[0096] The preparation method of the multimodal color electrochromic device provided in this comparative example is the same as that in Example 1, the main difference is that: in step (2), W target is used as target material, Ar:O2 = 94:6, total pressure is 1.0 Pa, DC power is 100 W, and deposition time is 1618 s to obtain an amorphous WO3 thin film layer with a thickness of 171 nm; ITO target is used as target material, Ar:O2 = 80:0, total pressure is 0.3 Pa, RF power is 90 W, and deposition time is 40 s to obtain an ITO thin film layer with a thickness of 5 nm; Ag target is used as target material, Ar:O2 = 60:0, total pressure is 0.3 Pa, DC power is 50 W, and deposition time is 30 s to obtain an Ag thin film layer with a thickness of 10 nm; then ITO is sputtered for 1946 s to obtain an ITO thin film layer with a thickness of 248 nm; Ag is sputtered for 30 s to obtain an Ag thin film layer with a thickness of 10 nm; ITO is sputtered... After 480s, an ITO thin film with a thickness of 53nm was obtained, resulting in an ITO / Ag / ITO / Ag / ITO composite electrode layer.

[0097] The multimodal color electrochromic device proposed in this invention can be obtained, with a reflected color of blue-violet (102,114,171,49.3).

[0098] Table 1 below compares the electrochromic devices (R, G, B, L) prepared in Examples 1-7 with those prepared in Comparative Examples 1-8:

[0099] Table 2 shows the changes in RGB color values ​​and L brightness with voltage for Examples 1, 4, and 6:

[0100] Figure 2 This is a contour plot showing the visible light transmittance of an ITO / Ag / ITO interference layer with an Ag thickness of 10 nm as a function of the thickness of the bottom and top ITO layers. The plot shows that the visible light transmittance of the ITO / Ag / ITO interference layer varies from 0.5 to 0.9 nm with the thickness of the two ITO layers.

[0101] Figure 3 This is a contour plot showing the visible light reflectance of an ITO / Ag / ITO interference layer with an Ag thickness of 10 nm as a function of the thickness of the bottom and top ITO layers. The plot shows that the visible light reflectance of the ITO / Ag / ITO interference layer varies from 0.02 to 0.5 nm with the thickness of the two ITO layers.

[0102] Figure 4 This diagram illustrates the reflective colors of ITO / Ag / ITO / Ag / ITO with different thicknesses. As can be seen from the diagram, the saturation and brightness of the reflected colors decrease as the Ag thickness increases. Within the ITO / Ag / ITO / Ag / ITO structure, full color gamut coverage can be achieved.

[0103] Figure 5 The diagram shows the changes in reflected color of devices in Examples 1, 4, and 6 under different voltages. As can be seen from the diagram, as the voltage increases, the reflected color changes, and the brightness decreases.

[0104] Figure 6 The diagram shows the changes in transmitted color of devices in Examples 1, 4, and 6 under different voltages. As can be seen from the diagram, as the voltage increases, the transmitted color of the device changes, the transmittance decreases, and the device changes from a transmission mode to a reflection mode.

[0105] Figure 7 Examples 1, 4, and 6 show high-purity, high-brightness reflective red, green, and blue primary color devices. As can be seen from the figures, these red, green, and blue primary color devices can be combined, showing great potential in future display applications.

[0106] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Various modifications and substitutions to the present invention will be apparent to those skilled in the art after reading the above description. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A multi-modal color electrochromic device, characterized in that, The structure of the multi-modal color electrochromic device comprises, from top to bottom, a working electrode, a cathode electrochromic material, an electrolyte, an anode electrochromic material, and a transparent electrode; The working electrode is stacked by a plurality of optical cavities, and a single optical cavity structure comprises, from top to bottom, a dielectric layer, an optical layer, and a dielectric layer, wherein the optical layer has optical reflection and / or transmission; the number of optical cavities N≥1, preferably N=2; The multi-modal color electrochromic device has two modes of transmission and reflection; in a static state, it can show reflective / transmissive colors; when a voltage is applied to the two sides of the working electrode and the transparent electrode, the refractive index of the electrochromic material in the device changes, and by adjusting the voltage applied to the two sides of the device, the combination of structural color and electrochromism can be achieved, and the change of the two modes of transmission and reflection can be achieved, thereby controlling the transmission color and reflection color of the multi-color electrochromic device; The reflection color of the multi-modal color electrochromic device is red or green or blue, and the transmission color is blue or red or green, and the arrangement of the three primary color dots can achieve full color gamut coverage.

2. The multi-modal color electrochromic device of claim 1, wherein, The dielectric layer is selected from transparent conductive inorganic materials or transparent conductive organic materials; preferably, liquid crystal materials or MOF materials; The transparent conductive inorganic material includes at least one of metal elements, non-metal elements, oxides, and inorganic salts; preferably, the metal element is in a nanowire structure, the non-metal element includes at least one of selenium, silicon, graphite, carbon nanotube film, and graphene film, the oxide includes at least one of cadmium oxide, indium oxide, tin oxide, zinc oxide, indium tin oxide, doped zinc oxide, doped tin oxide, and doped indium oxide, and the inorganic salt includes MoS2 and SrSnO3; The transparent conductive organic material includes organic small molecule compounds and / or polymers; preferably, the transparent conductive organic material includes at least one of polyacetylene, polypyrrole, polyaniline, polythiophene, poly-p-phenylenevinylene, polyphenylene sulfide, polyphthalocyanine acetylene, and conductive plastic; The thickness of the dielectric layer is ≤2000 nm, preferably 26-284 nm, and more preferably 30-200 nm.

3. Multimodal color electrochromic device according to claim 1 or 2, characterized in that, The optical layer is selected from metal materials and non-metal materials; wherein the metal material includes at least one of tungsten, gold, silver, copper, titanium, aluminum, chromium, iron, cobalt, nickel, platinum, germanium, and palladium, and the non-metal material includes at least one of single crystal silicon, polycrystalline silicon, and diamond; The extinction coefficient of the optical layer is 2-16; The thickness of the optical layer is ≤20 nm, preferably 10-20 nm, and more preferably 10-15 nm.

4. The multi-modal color electrochromic device according to any one of claims 1-3, characterized in that, When the incident light is normally incident on the working electrode, the light component on the upper surface of the first dielectric layer and and the light component output from the lower surface of the mth dielectric layer and is related to the transmission matrix M: Preferably, according to the Fresnel equation, the reflectivity R and the transmissivity T of the optical cavity multilayer structure are: I j(j+1) Interface matrix for light reflection and transmission at the interface between j and j+1 layers which are working electrodes: The light reflection coefficient r at the interface of the j layer and the j+1 layer of the working electrode j(j+1) and the transmission coefficient t j(j+1) are: wherein: n0is the refractive index of the medium on the upper surface of the first dielectric layer, and θ is the incident angle of the incident light; L j To describe the layer matrix of the light propagation through the working electrode j layer, it is described as: wherein: d j is the thickness of the jth working electrolyte layer; When light is incident from the upper surface of the first dielectric layer of the working electrode The complex reflection coefficient r and the transmission coefficient t of the optical cavity multilayer structure of the working electrode can be expressed as: wherein: R＝|r| 2 The cathode electrochromic material includes at least one of cathode electrochromic inorganic materials and cathode electrochromic organic materials; wherein the cathode electrochromic inorganic material includes at least one of tungsten oxide, molybdenum oxide, vanadium oxide, niobium oxide, titanium oxide, and tantalum oxide, and the cathode electrochromic organic material includes at least one of viologen, polypyrrole, polythiophene, and polyaniline; n m+1 n is the refractive index of the film material under the mth dielectric layer of the working electrode m+1 is the refracted angle of the light emitted under the mth dielectric layer of the working electrode 5. The multi-modal color electrochromic device according to any one of claims 1-4, wherein, ​ The thickness of the cathode electrochromic material is ≤2000 nm, preferably 100-175 nm, and more preferably 100-150 nm.

6. The multi-modal color electrochromic device according to any one of claims 1-5, wherein, The electrolyte comprises at least one cation; preferably, the cations in the electrolyte include H + , Li + , Al 3+ , Na + , K + , Rb + , Ag + , Ni 2+ , Ca 2+ , Mo 6+ , Mn 2+ , Ti 4+ , V 4+ , Zn 2+ , W 6+ , Ta 5+ , Cu 2+ , Bi 3+ , Sn 4+ , Mg 2+ , Cs + , at least one of The electrolyte is in a liquid, gel or solid state; the thickness of the electrolyte is ≤2000 nm, preferably 100-200 nm.

7. The multi-modal color electrochromic device according to any one of claims 1-6, wherein, The anode electrochromic material comprises at least one of an anode electrochromic inorganic material and an anode electrochromic organic material; the anode electrochromic inorganic material comprises at least one of nickel oxide, platinum oxide, iridium oxide, osmium oxide, palladium oxide, ruthenium oxide, rhodium oxide or a hydrate of each of the above oxides, and the anode electrochromic organic material comprises at least one of violet, polypyrrole, polythiophene and polyaniline; The thickness of the anode electrochromic material is ≤2000 nm, preferably 50-100 nm.

8. The multi-modal color electrochromic device according to any one of claims 1-7, wherein, The transparent electrode can comprise a transparent conductive layer and a transparent substrate; the transparent conductive layer comprises at least one of FTO, ITO, Ag nanowire, Ag nanomesh, carbon nanotube and graphene; and the transparent substrate comprises at least one of plastic product, fabric, organic glass, metal alloy, ceramic, PET, PES, PEN, PC, PMMA, PDMS. The thickness of the transparent conductive layer is 90-100 nm, and the thickness of the transparent substrate is ≤1 cm.

9. The multi-modal color electrochromic device according to any one of claims 1-8, wherein, The voltage applied to the multi-modal color electrochromic device is -1.5 V to 2.5 V.

10. A method of manufacturing a multi-modal color electrochromic device according to any one of claims 1-9, characterized in that, The preparation method comprises the following steps: sequentially depositing an anode electrochromic layer, an electrolyte layer, a cathode electrochromic layer and a working electrode on a transparent electrode substrate by magnetron sputtering to obtain the multi-modal color electrochromic device.

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