CN114563896A - A kind of multi-color inorganic all-solid-state electrochromic device and preparation method thereof - Google Patents

Abstract

The invention discloses a multi-color inorganic all-solid electrochromic device and a preparation method thereof. The device comprises a substrate, a transparent bottom electrode layer, a multi-color ion storage layer, a first electron blocking layer, an electrolyte layer, a second electron blocking layer, an electrochromic layer, and a transparent top electrode layer, which are sequentially stacked; the multi-color ion storage layer The material is A _x O _y , A _x O _y is a bipolar coloring material, wherein A is a metal element with multiple valence states. The invention utilizes the multi-color ion storage layer to exhibit multi-color characteristics when ions and electrons are co-injected/extracted. The multi-color ion storage layer is matched with a transparent electrochromic layer with electrochemical activity and a single color change, so as to realize the device's performance. Multi-color change capability with yellow-green-blue transition. The device prepared by the invention has a large optical modulation amplitude, is easy to be uniformly prepared in a large area, has good stability, and has a simple preparation process, and effectively overcomes the problem of single color of the traditional inorganic all-solid-state electrochromic device.

Description

A kind of multi-color inorganic all-solid-state electrochromic device and preparation method thereof

technical field

The invention relates to the technical field of electrochromic devices, in particular to a multi-color inorganic all-solid-state electrochromic device and a preparation method thereof.

Background technique

Electrochromic technology provides an effective way to controllably adjust the optical properties of materials. Under the action of an electric field, the redox reaction inside the electrochromic material changes its valence or composition, resulting in a stable and reversible optical property (absorptivity, transmittance and reflectance, etc.) of the material in the visible, infrared and even microwave regions. Variety. Electrochromic devices are devices that utilize the electrochromic effect of materials, based on the electrochromic layer, supplemented by other related layers and structures.

Based on the unique advantages of "wide viewing angle, low driving voltage, micro energy consumption, and memory function", the research and development of high-performance electrochromic devices is of great significance to the fields of energy, construction, information and national defense. Especially in the field of military defense technology, because the color of traditional camouflage materials is fixed, it cannot change with the environment and season, and cannot meet the requirements of intelligent defense military camouflage, and electrochromic technology with adjustable optical color can solve this problem. Achieve the purpose of military stealth and camouflage.

At present, electrochromic devices based on organic molecules, polymers and metal-organic frameworks show multicolor properties, but in practical applications, organic materials have poor thermal stability and photostability compared with inorganic electrochromic materials. , poor chemical stability and radiation resistance. Therefore, realizing multicolor properties of inorganic material-based electrochromic devices is a paradigm shift in the field of electrochromic defense. At the same time, all-solid-state electrochromic thin-film devices based on inorganic electrolytes have the advantages of high stability, good durability, and easy large-area fabrication, and are currently a research hotspot. At the same time, the all-solid-state structure also makes the device design more flexible and miniaturized, making it easier to integrate into lightweight, portable smart electronic products.

At present, inorganic all-solid-state electrochromic devices are mainly based on the matched coupling of cathodic tungsten oxide and anodized nickel oxide functional layers, and these two typical electrochromic materials can only be switched between the transparent state and the intrinsic valence state color of the material. Therefore, the final thin-film device can only achieve adjustment between different transparency and single color change.

Therefore, the existing technology still needs to be improved and developed.

SUMMARY OF THE INVENTION

In view of the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a multi-color inorganic all-solid-state electrochromic device and a preparation method thereof, aiming to solve the problem of single color change of the existing inorganic all-solid-state electrochromic device.

The technical scheme of the present invention is as follows:

A first aspect of the present invention provides a multi-color inorganic all-solid-state electrochromic device, which includes a substrate, a transparent bottom electrode layer, a multi-color ion storage layer, a first electron blocking layer, an electrolyte layer, a Two electron blocking layer, electrochromic layer, transparent top electrode layer;

Wherein, the material of the multi-color ion storage layer is A _x O _y , the A _x O _y is a bipolar coloring material, wherein A is a metal element with multiple valence states.

Optionally, the material of the multi-color ion storage layer is selected from any one or more of V ₂ O ₅ , Co ₃ O ₄ , and Rh ₂ O ₃ ;

The thickness of the multi-color ion storage layer is 100-400 nm.

Optionally, the material of the transparent bottom electrode layer is selected from any one or more of indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide, gallium-doped zinc oxide, and indium-doped zinc oxide; Alternatively, the transparent bottom electrode layer is selected from metal transparent films or metal mesh material films;

The material of the transparent top electrode layer is selected from any one or more of indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide, gallium-doped zinc oxide, and indium-doped zinc oxide; or, the The transparent top electrode layer is selected from metal transparent films or metal mesh material films.

Optionally, the sheet resistance value of the transparent bottom electrode layer is 10-20Ω/sq, and the transmittance of the transparent bottom electrode layer is higher than 80% at a wavelength of 550 nm;

The sheet resistance value of the transparent top electrode layer is 20-100Ω/sq, and the transmittance of the transparent top electrode layer is higher than 80% at a wavelength of 550 nm.

Optionally, the thickness of the first electron blocking layer is 20-50 nm, and the thickness of the second electron blocking layer is 20-50 nm.

Optionally, the material of the first electron blocking layer and the material of the second electron blocking layer are independently selected from any of SiO ₂ , Si ₃ N ₄ , Ta ₂ O ₅ , ZrO ₂ , and Nb ₂ O ₅ one or more.

Optionally, the material of the electrolyte layer is selected from any one or more of LiF, LiAlO _x , LiPON, LiNbO ₃ , and LiTaO ₃ , and the thickness of the electrolyte layer is 50-500 nm.

Optionally, the material of the electrochromic layer is selected from any one or more of WO ₃ , TiO ₂ , Li ₄ Ti ₅ O ₁₂ , and MoO ₃ .

Optionally, the thickness of the electrochromic layer is 100-300 nm.

The second aspect of the present invention provides a method for preparing a multi-color inorganic all-solid-state electrochromic device according to the present invention, comprising the steps of:

providing a substrate with a transparent bottom electrode layer on the surface;

forming a multi-color ion storage layer on the transparent bottom electrode layer;

forming a first electron blocking layer on the multicolor ion storage layer;

forming an electrolyte layer on the first electron blocking layer;

forming a second electron blocking layer on the electrolyte layer;

forming an electrochromic layer on the second electron blocking layer;

forming a transparent top electrode layer on the electrochromic layer to obtain the multi-color inorganic all-solid-state electrochromic device;

Wherein, the material of the multi-color ion storage layer is A _x O _y , the A _x O _y is a bipolar coloring material, wherein A is a metal element with multiple valence states.

Beneficial effects: The multi-color inorganic all-solid-state electrochromic device of the present invention mainly includes a transparent electrode layer, a multi-color ion storage layer, an electrolyte layer (also called an ion conduction layer), an electron blocking layer and an electrochromic layer. Utilizing the characteristic that the multi-color ion storage layer exhibits multi-color when ions and electrons are co-injected/extracted, the multi-color ion storage layer is matched with the transparent electrochromic layer which has electrochemical activity and a single color change, and finally realizes the inorganic full-color ion storage layer. Yellow-green-blue transitionable multi-color change performance of solid-state electrochromic devices. The multi-color inorganic all-solid-state electrochromic device prepared by the invention has a large optical modulation amplitude, is easy to be uniformly prepared in a large area, has good stability, and has a simple preparation process. The invention effectively overcomes the technical problem of single color of the traditional inorganic all-solid-state electrochromic device.

Description of drawings

FIG. 1 is a schematic structural diagram of the multi-color inorganic all-solid-state electrochromic device in Example 1. FIG.

FIG. 2 is a full spectrum diagram of the transmittance of the multi-color inorganic all-solid-state electrochromic device in the colored/discolored state in Example 1. FIG.

FIG. 3 is the chromaticity change of the multi-color inorganic all-solid-state electrochromic device in Example 1 under the action of different voltages.

Detailed ways

The present invention provides a multi-color inorganic all-solid-state electrochromic device and a preparation method thereof. In order to make the purpose, technical solution and effect of the present invention clearer and clearer, the present invention is further described below in detail. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

Conventional inorganic solid-state electrochromic devices usually consist of five consecutive layers, which are two transparent current collector layers, an electrochromic active layer, an ion conductor layer, and an ion storage layer. The inorganic solid-state electrochromic device is mainly based on the matching coupling of cathodic tungsten oxide and anodic nickel oxide functional layers, and these two typical electrochromic materials can only be switched between the transparent state and the intrinsic valence state color of the material. Therefore, the final device can only achieve adjustment between different transparency and single color change.

Based on this, the embodiment of the present invention selects an electrochromic material with rich color changes as the ion storage layer to match the transparent electrochromic layer with electrochemical activity and a single color change, thereby realizing the multi-functionality of inorganic all-solid-state electrochromic devices. color characteristics.

Specifically, an embodiment of the present invention provides a multi-color inorganic all-solid-state electrochromic device, which includes a substrate, a transparent bottom electrode layer, a multi-color ion storage layer, a first electron blocking layer, an electrolyte layer, a Two electron blocking layer, electrochromic layer, transparent top electrode layer;

Wherein, the material of the multi-color ion storage layer is A _x O _y , the A _x O _y is a bipolar coloring material, wherein A is a metal element with multiple valence states.

It should be noted that the bipolar coloring material refers to that the material exhibits color changes in the state of ion implantation and extraction. For example, WO ₃ material is a monopolar coloring material, which appears blue when lithium ions are implanted, and is transparent when lithium ions are extracted.

The multi-color inorganic all-solid-state electrochromic device in this embodiment mainly includes a transparent electrode layer, a multi-color ion storage layer, an electrolyte layer, an electron blocking layer, and an electrochromic layer. In the multi-color ion storage layer, the valence state of metal ions is changed due to the injection/extraction of cations driven by the electric field, thereby adjusting the optical refractive index and extinction coefficient of the material, so that the material exhibits color changes. Since the A metal ion in _AxOy has multiple _valence states, the material exhibits multiple color changes. Therefore, the multi-color ion storage layer exhibits the characteristics of different color changes under different voltage regulation.

This embodiment utilizes the multi-color ion storage layer to exhibit multi-color characteristics when ions and electrons are co-injected/extracted. The multi-color ion storage layer is matched with a transparent electrochromic layer that has electrochemical activity and a single color change, and finally realizes the Inorganic all-solid-state electrochromic devices capable of yellow-green-blue transition with multi-color change performance. The multi-color inorganic all-solid-state electrochromic device prepared in this example has a large optical modulation amplitude, is easy to prepare uniformly in a large area, has good stability, and has a simple preparation process. This embodiment effectively overcomes the technical problem of single color of the traditional inorganic all-solid-state electrochromic device.

Specifically, the principle that the inorganic all-solid-state electrochromic device in this embodiment can realize multi-color is that the multi-color ion storage layer presents different colors when lithium ions are implanted/extracted or with different amounts of implantation/extraction, and the electrochromic layer is in the lithium ion. There is only one color change in the process of ion implantation/extraction, and only with the change of the amount of lithium ion implantation, its color changes from a transparent state to a single color and the color continues to deepen. When an electric field is applied to the inorganic all-solid-state electrochromic device, the applied electric field is opposite for the cathode and anode electrodes. In addition, with the change of the applied voltage, the amount of lithium ion implantation/extraction in each color-changing functional layer will increase or decrease correspondingly, so that the multi-color ion storage layer in it will show different colors, while the electrochromic layer is due to the lithium ion storage layer. The color of the ion content changes from the transparent state to the colored state, and the color of the multi-color ion storage layer and the electrochromic layer in the corresponding state is superimposed and the color is the final color of the device. Therefore, the color change of the device can be adjusted accordingly by the magnitude of the applied voltage.

In one embodiment, A in the _AxOy is any one of V, Co and _Rh . That is, the material of the multi-color ion storage layer is selected from any one or more of vanadium pentoxide (V ₂ O ₅ ), cobalt oxide (Co ₃ O ₄ ), and rhodium oxide (Rh ₂ O ₃ ).

In one embodiment, the thickness of the multi-color ion storage layer is 100-400 nm.

The function of the transparent bottom electrode layer in this embodiment is to conduct electrons for device operation.

In one embodiment, the material of the transparent bottom electrode layer is selected from indium tin oxide (In ₂ O ₃ :Sn, abbreviated as ITO), aluminum-doped zinc oxide (ZnO:Al, abbreviated as AZO), fluorine-doped zinc oxide (ZnO:Al, abbreviated as AZO), Any one or more of tin oxide, gallium-doped zinc oxide (ZnO:Ga, abbreviated as GZO), indium-doped zinc oxide (ZnO:In, abbreviated as IZO), etc.; or, the transparent bottom electrode The layers are selected from extremely thin metallic transparent films or metallic mesh material films. That is, in addition to doped transparent conductive oxides, extremely thin metal transparent films or metal mesh material films can also be used as transparent bottom electrodes.

Since the resistance of the transparent bottom electrode layer is too large, the voltage required for the device to work is too large, and the light transmittance of the transparent bottom electrode layer will affect the overall transmittance of the device. The sheet resistance value of the transparent bottom electrode layer is 10-20Ω/sq , the transmittance of the transparent bottom electrode layer is higher than 80% at a wavelength of 550 nm.

In one embodiment, the thickness of the transparent bottom electrode layer is 100-200 nm. When the transparent bottom electrode layer is an extremely thin metal transparent film, the thickness of the transparent bottom electrode layer is 10-20 nm.

The function of the transparent top electrode layer in this embodiment is that it is a transparent thin film layer that conducts electrons in the device, and together with the transparent bottom electrode layer, builds a uniform electric field for the redox reaction of the multicolor ion storage layer and the electrochromic layer in the device.

In one embodiment, the material of the transparent top electrode layer is selected from indium tin oxide (In ₂ O ₃ :Sn, abbreviated as ITO), aluminum-doped zinc oxide (ZnO:Al, abbreviated as AZO), fluorine-doped zinc oxide (ZnO:Al, abbreviated as AZO), Any one or more of tin oxide, gallium-doped zinc oxide (ZnO:Ga, abbreviated as GZO), indium-doped zinc oxide (ZnO:In, abbreviated as IZO), etc.; or, the transparent top electrode The layers are selected from extremely thin metallic transparent films or metallic mesh material films. That is, in addition to doped transparent conductive oxides, extremely thin metal transparent films or metal mesh material films can also be used as transparent top electrodes.

In one embodiment, the sheet resistance of the transparent top electrode layer is 20-100Ω/sq, and the transmittance of the transparent top electrode layer is higher than 80% at a wavelength of 550 nm.

In one embodiment, the thickness of the transparent top electrode layer is 100-200 nm. When the transparent top electrode layer is an extremely thin metal transparent film, the thickness of the transparent top electrode layer is 10-20 nm.

In order to realize the excellent color retention performance of the multi-color inorganic all-solid-state electrochromic device and ensure that it does not require a continuous loading voltage to maintain the color, therefore, in this embodiment, electron blocking layers are added on both sides of the electrolyte layer, and the electron The barrier layer does not affect the efficient transport of ions. That is, in this embodiment, the first electron blocking layer and the second electron blocking layer are added on both sides of the electrolyte layer, so that the reverse electron transfer in the device can be suppressed, the coloring efficiency of the device can be improved, and the color retention performance of the device can be ensured.

Since the thickness of the first electron blocking layer has an influence on the dielectric properties of the electrolyte layer, and at the same time, a certain potential barrier needs to be overcome for lithium ions to enter the multi-color ion storage layer from the electrolyte layer, the thickness of the first electron blocking layer is 20-50 nm .

In one embodiment, the material of the first electron blocking layer is selected from any one or more of SiO ₂ , Si ₃ N ₄ , Ta ₂ O ₅ , ZrO ₂ , and Nb ₂ O ₅ .

In one embodiment, consistent with the principle of determining the thickness of the first electron blocking layer, the thickness of the second electron blocking layer is 20-50 nm.

In one embodiment, the material of the second electron blocking layer is selected from any one or more of SiO ₂ , Si ₃ N ₄ , Ta ₂ O ₅ , ZrO ₂ , and Nb ₂ O ₅ .

The function of the electrolyte layer between the two electron blocking layers in this embodiment is to provide chromogenic cations for the operation of the device, and to provide the required channels for the transport of ions, while isolating the electron transport inside the device. The electrolyte layer in electrochromic devices has high ionic conductivity and low electronic conductivity, and is always transparent. The types of electrolytes include liquid electrolytes, gel electrolytes, and solid ceramic electrolytes, depending on the form in which the electrolyte exists. Although the ionic conductivity of solid-state ceramic electrolytes is relatively low compared to the first two, they have the advantages of a wide electrochemically stable working window and excellent weatherability. Therefore, in this embodiment, a solid ceramic electrolyte is preferred as the electrolyte layer.

In one embodiment, the material of the electrolyte layer is selected from any one or more of LiF, LiAlO _x , LiPON, LiNbO ₃ , and LiTaO ₃ .

Since the thickness of the electrolyte layer is too thick will affect the overall device transmittance and interface performance, while the thickness of the electrolyte layer is too thin to affect its dielectric properties, the thickness of the electrolyte layer is determined to be 50-500nm.

There are many factors that affect the operation of multi-color inorganic all-solid-state electrochromic devices. The amount of charge injected into multi-color inorganic all-solid-state electrochromic devices is often determined by the layer with less charge injection in the two layers of electrochromic materials. decision, and the amount of charge injected into the device will limit the shading depth of the device. At the same time, compared with single-electrode electrochromic devices, the advantage of complementary electrochromic devices is that the charge balance during the discoloration process of bipolar materials makes the device color deeper and can achieve higher color contrast. Therefore, as the counter electrode layer, the electrochromic layer in this embodiment can not only achieve charge balance, but also perform color complementation with the multi-color electrochromic layer to achieve a multi-color state during the color change process of the multi-color electrochromic layer.

In one embodiment, the material of the electrochromic layer is selected from any one or more of WO ₃ , TiO ₂ , Li ₄ Ti ₅ O ₁₂ , and MoO ₃ .

Due to the charge balance of the multi-color ion storage layer and the electrochromic layer and the color coupling matching of the bipolar functional layer, the thickness of the electrochromic layer is 100-300 nm.

The embodiment of the present invention also provides a method for preparing a multi-color inorganic all-solid-state electrochromic device according to the present invention, wherein the method includes the steps:

S1. Provide a substrate with a transparent bottom electrode layer on the surface;

S2, forming a multi-color ion storage layer on the transparent bottom electrode layer;

S3, forming a first electron blocking layer on the multi-color ion storage layer;

S4, forming an electrolyte layer on the first electron blocking layer;

S5, forming a second electron blocking layer on the electrolyte layer;

S6, forming an electrochromic layer on the second electron blocking layer;

S7, forming a transparent top electrode layer on the electrochromic layer to obtain the multi-color inorganic all-solid-state electrochromic device;

Wherein, the material of the multi-color ion storage layer is A _x O _y , the A _x O _y is a bipolar coloring material, wherein A is a metal element with multiple valence states.

In this example, multi-target magnetron sputtering technology is used to carry out continuous and integrated deposition of multilayer films on rigid or flexible substrates, and a multi-color inorganic all-solid-state electrochromic device is obtained in a vacuum environment. The structure of the device is a transparent bottom electrode layer, a multicolor ion storage layer, a first electron blocking layer, an electrolyte layer, a second electron blocking layer, an electrochromic layer, and a transparent top electrode layer.

The invention mainly adopts the easy-to-control magnetron sputtering technology to prepare multi-color inorganic all-solid electrochromic devices with large area, variable colors, high light modulation amplitude and good uniformity.

In step S2, the multi-color electrochromic layer can be obtained by using the magnetron sputtering technology to set the gas pressure and the ratio of oxygen and argon in a vacuum system, and control the thickness of the film by controlling the deposition time.

In step S4, the electrolyte layer may be obtained by using a radio frequency reactive sputtering technology.

The present invention will be further described below through specific embodiments.

Example

A multi-color inorganic all-solid-state electrochromic device with an area of 10 × 10 cm ² was prepared. The structure of the device is shown in Figure 1, where TC 1 represents the transparent bottom electrode layer, EC 1 represents the multi-color ion storage layer, and EB1 represents the first Electron blocking layer, EL denotes electrolyte layer, EB2 denotes second electron blocking layer, EC2 denotes electrochromic layer, TC2 denotes transparent top electrode layer.

The ITO conductive glass is placed in a vacuum chamber, and the multi-layer film is continuously deposited by magnetron sputtering deposition technology.

First, a multi-color ion storage layer was prepared, using a 3-inch metal vanadium as the target, controlling the ratio of oxygen and argon to 5sccm:45sccm, the air pressure to 0.3pa, and the power to 150W. During the deposition process, the substrate was always in a state of uniform rotation. , to obtain a uniform multi-color ion storage layer. The first electron blocking layer was prepared on the multi-color ion storage layer, and the metal tantalum was used as the target. During the sputtering process, the gas pressure was set to 0.3Pa, the power was 150W, and the temperature was O ₂ : Ar=5:45 ( A uniform and dense tantalum oxide film was obtained in a mixed atmosphere with a flow ratio). The preparation of the electrolyte layer is based _on LiNbO3 ceramic material as the target material, the deposition pressure is 0.5pa, the ratio of oxygen and argon is 5sccm:95sccm, and the radio frequency power is 130W, so as to obtain the electrolyte layer with high ionic conductivity. A second electron blocking layer is deposited on the basis of the electrolyte layer, and the preparation parameters of the second electron blocking layer are consistent with those of the first electron blocking layer. The electrochromic layer is still obtained by magnetron reactive sputtering. During the preparation of the film, the air pressure is controlled to 2.0pa, the flow ratio of oxygen to argon is 1:3, the sputtering power is 200W, and the target The distance from the center position to the substrate was 13 cm, and a transparent WO ₃ film was obtained. The resistance of the transparent top electrode layer has a huge influence on the voltage applied to the device. A low and uniform sheet resistance is very important for the uniform color and fading of the device. The air pressure during the deposition process is adjusted to 0.3Pa, and the ratio of oxygen and argon is 0.6sccm:78.4sccm, the sputtering power is 80W, and a transparent ITO film with surface resistance lower than 100Ω/sq is obtained.

The obtained multi-color inorganic all-solid-state electrochromic device is placed in a two-electrode system, and the device is colored and faded by applying positive and negative voltages. Using the simultaneous combination of an electrochemical workstation and a spectrometer, the transmittance spectra in the visible and near-infrared bands were recorded in the faded and colored states of the device, respectively. As shown in Fig. 2, the multi-color inorganic all-solid-state electrochromic device has excellent modulation capability in the entire wavelength band, its light modulation amplitude at 550 nm reaches 58%, and its transparency in the faded state is as high as 72%.

The prepared multi-color inorganic all-solid-state electrochromic device was placed in a colorimeter, and the color change of the device was manipulated by Shanghai Chenhua electrochemical workstation. Under the action of different voltages, the color of the device is recorded by the colorimeter, and the device can switch back and forth between the three color systems of yellow-green-blue, as shown in Figure 3.

In summary, the present invention provides a multi-color inorganic all-solid-state electrochromic device and a preparation method thereof. The multi-color inorganic all-solid-state electrochromic device of the present invention mainly includes a transparent electrode layer, a multi-color electrochromic layer, an electrolyte layer (also called an ion conduction layer), an electron blocking layer and an ion storage layer. The multi-color ion storage layer is matched with a transparent electrochromic layer with electrochemical activity and a single color change by utilizing the multi-color electrochromic layer when ions and electrons are co-injected/extracted. Yellow-green-blue switchable multi-color change performance of all-solid-state electrochromic devices. The multi-color inorganic all-solid-state electrochromic device prepared by the invention has a large optical modulation amplitude, is easy to be uniformly prepared in a large area, has good stability, and has a simple preparation process. The invention effectively overcomes the technical problem of single color of the traditional inorganic all-solid-state electrochromic device.

It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or transformations can be made according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present invention.

Claims (10)

1. A multicolor inorganic all-solid-state electrochromic device is characterized by comprising a substrate, a transparent bottom electrode layer, a multicolor ion storage layer, a first electron barrier layer, an electrolyte layer, a second electron barrier layer, an electrochromic layer and a transparent top electrode layer which are sequentially stacked;

wherein the material of the multicolor ion storage layer is A_xO_ySaid A is_xO_yIs a bipolar coloring material, wherein A is a metal element having multiple valence states.

2. The multi-colored inorganic all-solid-state electrochromic device according to claim 1, wherein the material of the multi-colored ion storage layer is selected from V₂O₅、Co₃O₄、Rh₂O₃Any one or more of;

the thickness of the multicolor ion storage layer is 100-400 nm.

3. The multi-color inorganic all-solid-state electrochromic device according to claim 1, wherein the material of the transparent bottom electrode layer is selected from any one or more of indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide, gallium-doped zinc oxide, indium-doped zinc oxide; or the transparent bottom electrode layer is selected from a metal transparent film or a metal grid material film;

The transparent top electrode layer is made of any one or more of indium tin oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide, gallium-doped zinc oxide and indium-doped zinc oxide; alternatively, the transparent top electrode layer is selected from a metal transparent film or a metal mesh material film.

4. The multicolor inorganic all-solid-state electrochromic device according to claim 1, wherein the transparent bottom electrode layer has a sheet resistance value of 10-20 Ω/sq, and the transmittance of the transparent bottom electrode layer is higher than 80% at a wavelength of 550 nm;

the square resistance value of the transparent top electrode layer is 20-100 omega/sq, and the transmittance of the transparent top electrode layer is higher than 80% at the wavelength of 550 nm.

5. The multi-color inorganic all-solid-state electrochromic device according to claim 1, wherein the thickness of the first electron blocking layer is 20-50nm and the thickness of the second electron blocking layer is 20-50 nm.

6. The multi-color inorganic all-solid-state electrochromic device according to claim 1, wherein the material of the first electron blocking layer and the material of the second electron blocking layer are independently selected from SiO₂、Si₃N₄、Ta₂O₅、ZrO₂、Nb₂O₅Any one or more of them.

7. The multi-color inorganic all solid state electrochromic device according to claim 1, wherein the material of said electrolyte layer is selected from LiF, LiAlO _x、LiPON、LiNbO₃、LiTaO₃And the electrolyte layer has a thickness of 50 to 500 nm.

8. The multi-color inorganic all-solid-state electrochromic device according to claim 1, wherein the material of the electrochromic layer is selected from WO₃、TiO₂、Li₄Ti₅O₁₂、MoO₃Any one or more of them.

9. The multi-color inorganic all-solid-state electrochromic device according to claim 1, wherein the thickness of the electrochromic layer is 100-300 nm.

10. A method of making a multi-colored inorganic all-solid-state electrochromic device according to any one of claims 1 to 9, comprising the steps of:

providing a substrate with a transparent bottom electrode layer on the surface;

forming a multicolor ion storage layer on the transparent bottom electrode layer;

forming a first electron blocking layer on the multicolor ion storage layer;

forming an electrolyte layer on the first electron blocking layer;

forming a second electron blocking layer on the electrolyte layer;

forming an electrochromic layer on the second electron blocking layer;

forming a transparent top electrode layer on the electrochromic layer to obtain the multicolor inorganic all-solid-state electrochromic device;

wherein the material of the multicolor ion storage layer is A_xO_ySaid A is _xO_yThe coloring material is a bipolar coloring material, wherein A is a metal element with multiple valence states.

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