Method for preparing efficient electrochromic device by coupling liquid-phase process with pvd

Abstract

The present invention relates to the technical field of electrochromic devices. Disclosed is a method for preparing an efficient electrochromic device by coupling a liquid-phase process with PVD. The method comprises the following steps: step 1, separately preparing a WO3 electrochromic layer and an ionic electrolyte layer on an ITO-coated substrate by means of a chemical sol-gel method, wherein at this moment, each layer only needs to be dried at a low temperature without a heat treatment; step 2, subjecting the surface of the prepared ITO coating / WO3 layer / ion electrolyte layer film system to spray rinsing with a high-pressure gas, and transferring same into a chamber of PVD equipment; and step 3, evacuating the chamber of the PVD equipment, heating the substrate, and then separately preparing an ion storage layer, i.e., a NiO layer, and an electrode ITO layer in a heating state. In the method of the present invention, a multi-layer thin film in the device is prepared by means of a chemical solution method, an individual liquid-phase heat treatment process, which is the most energy-consuming step, is not needed, and a heat treatment is carried out on the front-end liquid-phase-process thin film by means of heating conditions used in a subsequent PVD film preparation process, thereby achieving two goals with one action.

Description

Method for preparing high-efficiency electrochromic device by coupling liquid phase and PVD TECHNICAL FIELD

[0001] The present application relates to the technical field of all-solid-state inorganic plating devices, in particular to a method for preparing high-efficiency electrochromic devices by coupling liquid phase and PVD. BACKGROUND

[0002] Electrochromism refers to the stable and reversible change of optical properties (transmission, reflection and absorption, etc.) of a material under the action of an applied electric field or current. Electrochromic devices prepared by using electrochromic materials have the advantages of low energy consumption, fast response and human control, and the prepared electrochromic smart glass has been more researched and popularized. An all-solid-state inorganic device includes five layers of films, namely TCO / EC / IC / CE / TCO, wherein TCO is a transparent conductive film, EC is an electrochromic film, IC is an ion-conducting film (also called an electrolyte film), and CE is an ion storage film (some counter electrodes are also electrochromic films). Under the action of an applied electric field, small-radius cations (such as H+ and Li+) and electrons are double-injected or double-extracted in the EC layer, causing changes in the phase or energy level, thereby realizing dynamic adjustment of the transmission and reflection spectrum. At the same time, due to the infrared cutoff characteristics of the electrochromic layer, the electrochromic smart glass can also realize low heat radiation function, and has a huge application market. The industrialization of electrochromic smart devices in China is still in the initial stage of maturity, and there is an urgent need to improve product performance, increase yield, and reduce cost. SUMMARY

[0003] The purpose of the present application is to provide a method for preparing high-efficiency electrochromic devices by coupling liquid phase and PVD, which aims to meet the urgent needs of improving product performance and reducing cost in the current electrochromic industry.

[0004] The purpose of the present application can be achieved by the following technical solutions:

[0005] A method for preparing high-efficiency electrochromic devices by coupling liquid phase and PVD, comprising the following steps:

[0006] Step 1: preparing a color-changing WO3 layer and an ion electrolyte layer on an ITO plating substrate by a chemical sol-gel method, at this time, each layer only needs to be dried at low temperature, and does not need to be heat-treated;

[0007] Step 2: performing surface high-pressure gas spraying on the prepared ITO / WO3 layer / ion electrolyte layer film system and moving it into a PVD equipment chamber;

[0008] Step 3: vacuumizing the PVD equipment and heating the substrate, and then preparing an ion storage layer NiO layer and an electrode ITO layer under the heating state, respectively;

[0009] Step four, the ITO / WO3 layer / ionic electrolyte layer / NiO layer / ITO layer is removed from the PVD chamber to obtain the device.

[0010] As a further scheme of the present application: the ITO coating substrate in step one is ITO / glass substrate or ITO / PC substrate.

[0011] As a further scheme of the present application: the WO3 layer sol in step one is prepared by using tungsten powder and hydrogen peroxide; the electrolyte layer is LiTaO3 or Li+ doped AlPO4: the LiTaO3 sol is prepared by using ethanol or isopropanol as solvent, lithium acetate and ethanol tantalate as precursors; or the Li+ doped AlPO4 is prepared by using isopropanol as solvent, isopropanol aluminum, lithium perchlorate and phosphoric acid as precursors.

[0012] As a further scheme of the present application: the WO3 layer and the ionic electrolyte layer are prepared by using spin coating, blade coating or screen printing method according to the size of the device.

[0013] As a further scheme of the present application: the drying temperature in step one is 100-200℃.

[0014] As a further scheme of the present application: the heating in step three is by using step-by-step heating method, first, the NiO layer is prepared by using low-temperature heating, the heating temperature is 100-200℃, and the metal Ni target is prepared by using reaction sputtering method; the ITO electrode is prepared by using high-temperature heating, the heating temperature is 150-400℃, and the ITO ceramic target is prepared by using direct current sputtering method.

[0015] The present application has the following advantages:

[0016] The multilayer thin film in the device is prepared by using chemical solution method, and there is no need for energy-consuming separate liquid phase heat treatment process, and the heating condition in the subsequent PVD film preparation process is used for heat treatment of the front-end liquid phase method thin film, which is achieved at one time. The preparation cost can be greatly reduced, and the ideas of cost reduction and efficiency increase, energy saving and carbon reduction are provided for industrial production. At the same time, since the color-changing layer and the ionic electrolyte layer are prepared by using liquid phase method, the loose thin film structure is provided, which is more conducive to the transmission of ions and improves the working efficiency and other performances of the device. BRIEF DESCRIPTION OF DRAWINGS

[0017] The present application will be further described below in combination with the drawings.

[0018] Fig. 1 is a sectional view of a typical sample prepared by the embodiment of the present application;

[0019] Fig. 2 is a timing current curve of a typical sample prepared by the embodiment of the present application before and after color change under different driving voltages;

[0020] Fig. 3 is a curve of in-situ transmittance change of a typical sample prepared in the embodiment of the present application before and after color change under different driving voltages;

[0021] Fig. 4 is a full spectrum transmittance pattern of a typical sample prepared in the embodiment of the present application before and after color change. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0023] Please refer to Figs. 1-4, the present application is a method for preparing high-efficiency electrochromic devices by coupling liquid phase and PVD, comprising the following steps:

[0024] (1) First, prepare a plating film sol, including WO3, LiTaO3, AlPO4 sol, etc.

[0025] The preparation method of WO3 sol: take tungsten powder and hydrogen peroxide as raw materials, slowly pour the tungsten powder into the H2O2, move the reaction system into an ice water bath, and fully stir the tungsten powder and hydrogen peroxide to obtain the sol.

[0026] The preparation method of LiTaO3 sol: take ethanol or isopropanol as a solvent, take lithium acetate and ethanoltantalum as precursors, add anhydrous lithium acetate into the above-mentioned solvent, place the system in an oil bath at 100-150℃, stir until the anhydrous lithium acetate is dissolved, add acetic acid to adjust the pH of the solution to 4-6, add ethanoltantalum in a molar ratio of 1:1 to lithium acetate, and stir to obtain the plating film sol.

[0027] The preparation method of AlPO4 sol: take isopropanol as a solvent, and take aluminum isopropanol, lithium perchlorate and phosphoric acid as precursors.

[0028] (2) Prepare a color-changing WO3 layer and an ion electrolyte layer on an ITO plating film substrate by a chemical sol-gel method, and the WO3 layer and the ion electrolyte layer are prepared by spin coating, blade coating, screen printing and other methods according to the size of the device area. At this time, each layer only needs to be dried at a low temperature of 100-200℃.

[0029] (3) Perform surface high-pressure gas spraying on the prepared ITO / WO3 layer / ion electrolyte layer film system and move it into a PVD equipment chamber;

[0030] (4) The PVD device is vacuumed to 10-6 torr and the substrate is heated, then the ion storage layer NiO layer and the electrode ITO layer are prepared respectively under heating. The sputtering power is 1000-2000 W, the sputtering pressure is 0.1-1 Pa, the sputtering thickness is 100-500 nm, the heating temperature of the NiO layer is 100-200 ℃, and the heating temperature of the ITO layer is 150-400 ℃.

[0031] (5) The coated ITO / WO3 layer / ion electrolyte layer / NiO layer / ITO layer is removed from the PVD chamber to obtain the device of the present application.

[0032] As shown in the following Figure 1, the prepared film layer device has a relatively loose structure, Figures 2-3 show that different color changing abilities are exhibited under different voltages, and Figure 4 shows that the device has a large color changing range under visible light, and the colored state has a low visible light transmittance, which achieves the expected effect.

[0033] The above describes one embodiment of the present application in detail, but the content described is only a preferred embodiment of the present application and cannot be considered as limiting the implementation scope of the present application. Any equivalent changes and improvements made according to the scope of the present application should still belong to the patent coverage scope of the present application.

Claims

1. A method for the preparation of high performance electrochromic devices by coupling of liquid phase with PVD, characterized by, The method comprises the following steps: Step 1: preparing a color-changing WO3 layer and an ion electrolyte layer on an ITO-coated substrate by a chemical sol-gel method, wherein each layer only needs to be dried at low temperature and does not need to be heat-treated; Step 2: performing surface high-pressure gas spraying on the prepared ITO / WO3 layer / ion electrolyte layer film system and moving the film system into a PVD equipment chamber; Step 3: performing vacuum pumping on the PVD equipment and heating the substrate, and then preparing an ion storage layer NiO layer and an electrode ITO layer in a heated state; Step 4: moving the ITO / WO3 layer / ion electrolyte layer / NiO layer / ITO layer film system out of the PVD chamber to obtain a device.

2. The method for preparing high-performance electrochromic devices by coupling liquid phase with PVD according to claim 1, characterized in that, The ITO-coated substrate in step 1 is an ITO / glass substrate or an ITO / PC substrate.

3. The method for preparing high-performance electrochromic devices by coupling liquid phase with PVD according to claim 1, characterized in that, The WO3 layer sol in step 1 is prepared from tungsten powder and hydrogen peroxide; the electrolyte layer is LiTaO3 or Li+ doped AlPO4: LiTaO3 sol is prepared by using ethanol or isopropanol as a solvent, lithium acetate and ethanol tantalate as precursors; or Li+ doped AlPO4 is prepared by using isopropanol as a solvent, isopropanol aluminum, lithium perchlorate and phosphoric acid as precursors.

4. The method for preparing high-performance electrochromic devices by coupling liquid phase with PVD according to claim 1, characterized in that, The WO3 layer and the ion electrolyte layer are prepared by spin coating, blade coating or screen printing according to the size of the device area.

5. The method for preparing high-performance electrochromic devices by coupling liquid phase with PVD according to claim 1, characterized in that, The drying temperature in step 1 is 100-200℃.

6. The method for preparing high-performance electrochromic devices by coupling liquid phase with PVD according to claim 1, characterized in that, The heating in step 3 is performed by a step-by-step heating method, wherein the NiO layer is prepared by low-temperature heating at a temperature of 100-200℃ and the electrode ITO is prepared by high-temperature heating at a temperature of 150-400℃.

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