A method for preparing high-efficiency electrochromic device by coupling liquid phase and PVD

Abstract

The application discloses a kind of liquid phase and PVD coupling preparation high-efficiency electrochromic device method, it is related to electrochromic device technical field, comprising the following steps: step one, with chemical sol-gel method in ITO coating film substrate respectively preparation color-changing WO3 layer, ion electrolyte layer, at this time, each layer only needs low-temperature drying, need not be heat treated;Step two, prepared coating film ITO / WO3 layer / ion electrolyte layer is moved into PVD equipment chamber and is washed with high-pressure gas on surface;Step three, PVD equipment is pumped down and is heated to substrate, subsequently respectively in heated state respectively preparation ion storage layer NiO layer and electrode ITO layer.The method of the application is because using chemical solution method preparation multilayer film in device, and without energy consumption biggest separate liquid phase heat treatment process, with the heating condition in subsequent PVD film preparation process as front-end liquid phase method film carries out heat treatment, and achieves.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of all-solid-state inorganic coating devices, and particularly relates to a method for preparing a high-efficiency electrochromic device 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 conduction 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, and realizing dynamic adjustment of the transmission and reflection spectrum. At the same time, due to the infrared cutoff characteristics of the color-changing 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 starting, and there is an urgent need to improve product performance, reduce costs and improve yield. SUMMARY

[0003] The present application relates to the technical field of all-solid-state inorganic coating devices, and particularly relates to a method for preparing a high-efficiency electrochromic device by coupling liquid phase and PVD.

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

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

[0006] Step one, preparing a color-changing WO3 layer and an ion electrolyte layer on an ITO coating 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 two, performing surface high-pressure gas spraying on the prepared coating ITO / WO3 layer / ion electrolyte layer film system and moving into a PVD equipment chamber;

[0008] Step three, vacuumizing 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, respectively;

[0009] Step four, the device is obtained by moving the ITO / WO3 layer / ion electrolyte layer / NiO layer / ITO layer out of the PVD chamber.

[0010] As a further aspect of the present application, the ITO plating substrate in step one is an ITO / glass substrate or an ITO / PC substrate.

[0011] As a further aspect 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: LiTaO3 sol is prepared by using ethanol or isopropanol as a solvent, and lithium acetate and ethanol tantalum as precursors; or isopropanol is used as a solvent, and isopropanol aluminum, lithium perchlorate, and phosphoric acid are used as precursors to prepare Li+ doped AlPO4.

[0012] As a further aspect of the present application, 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.

[0013] As a further aspect of the present application, the drying temperature in step one is 100-200°C.

[0014] As a further aspect of the present application, the heating in step three is a step-by-step heating method, in which low-temperature heating is used to prepare the NiO layer, the heating temperature is 100-200°C, and the metal Ni target is used to prepare by a reaction sputtering method; high-temperature heating is used to prepare the electrode ITO, the heating temperature is 150-400°C, and the ITO ceramic target is used to prepare by a direct current sputtering method.

[0015] The present application has the following advantages:

[0016] The multilayer thin film in the device is prepared by using a chemical solution method, and there is no need for an energy-consuming separate liquid phase heat treatment process. The subsequent heating conditions in the PVD film preparation process are used for heat treatment of the front-end liquid phase method thin film, and both advantages are achieved at once. 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, due to the preparation of the color-changing layer and the ion electrolyte layer by the 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 with reference to the accompanying drawings.

[0018] FIG. 1 is a schematic diagram of a device according to the present application; Figure 1 FIG. 2 is a sectional view of a typical sample prepared according to an embodiment of the present application;

[0019] FIG. 3 is a timing current curve of a typical sample prepared according to an embodiment of the present application before and after color change under different driving voltages; Figure 2 FIG. 4 is a timing current curve of a typical sample prepared according to an embodiment of the present application before and after color change under different driving voltages.

[0020] Figure 2 shows the in-situ transmittance curves of a typical sample prepared in an embodiment of the present application before and after color change at different driving voltages. Figure 3 Figure 3 shows the in-situ transmittance curves of a typical sample prepared in an embodiment of the present application before and after color change at different driving voltages.

[0021] Figure 4 shows the in-situ transmittance curves of a typical sample prepared in an embodiment of the present application before and after color change at different driving voltages. Figure 4 Figure 5 shows the full spectrum transmittance curves of a typical sample prepared in an 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 with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

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

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

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

[0026] The LiTaO3 sol preparation method is as follows: take ethanol or isopropyl alcohol 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°C, stir until the anhydrous lithium acetate is dissolved, add acetic acid to adjust the pH of the solution to 4-6, and then add ethanoltantalum in a molar ratio of 1:1 to the lithium acetate, and stir to obtain the plating film sol.

[0027] The AlPO4 sol preparation method is as follows: take isopropyl alcohol as a solvent, and take aluminum isopropoxide, lithium perchlorate and phosphoric acid as precursors.

[0028] (2) Use the chemical sol-gel method to prepare a color-changing WO3 layer and an ionic electrolyte layer on an ITO plating film substrate, and use a spin coating, a blade coating or a screen printing method to coat the WO3 layer and the ionic electrolyte layer according to the size of the device. At this time, each layer only needs to be dried at a low temperature of 100-200°C.

[0029] (3) Perform surface high-pressure gas spraying on the prepared plating film ITO / WO3 layer / ionic electrolyte layer film system and move it into a PVD device 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 IT0 layer are prepared respectively in the heated state. 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 IT0 layer is 150-400 ℃.

[0031] (5) The device is obtained by moving the coated IT0 / WO3 layer / ion electrolyte layer / NiO layer / IT0 layer out of the PVD chamber.

[0032] The following table shows the color change of the device under different voltages Figure 1 It can be seen that the prepared film layer device has a loose structure, and the Figures 2-3 It shows that the device exhibits different color change abilities under different voltages, and the Figure 4 It shows that the device has a large color change 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 the preferred embodiment of the present application, and cannot be considered as limiting the scope of the present application. Any equivalent changes and improvements made according to the scope of the present application should still belong to the scope of the present application.

Claims

1. A method for preparing a high-efficiency electrochromic device by coupling liquid phase with PVD, characterized in that, Includes the following steps: Step 1: Prepare a color-changing WO3 layer and an ionic electrolyte layer on an ITO coated substrate using a chemical sol-gel method. Each layer only needs to be dried at a low temperature and does not require heat treatment. The drying temperature is 100-200℃. Step 2: The prepared ITO / WO3 / ion electrolyte layer film system is subjected to high-pressure gas spray washing and then transferred into the PVD equipment chamber; Step 3: Vacuum the PVD equipment and heat the substrate. Then, prepare the NiO ion storage layer and the ITO electrode layer separately under heating conditions. The heating conditions during the PVD sputtering process are heat treatment of the color-changing WO3 layer and the ion electrolyte layer. Step 4: Remove the coated ITO / WO3 layer / ionic electrolyte layer / NiO layer / ITO layer from the PVD chamber to obtain the device.

2. The method for preparing a high-efficiency electrochromic device by coupling liquid phase with PVD according to claim 1, characterized in that, The ITO coating substrate mentioned in step one is an ITO / glass substrate or an ITO / PC substrate.

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

4. The method for preparing a high-efficiency electrochromic device by coupling liquid phase with PVD according to claim 1, characterized in that, The WO3 layer and the ion electrolyte layer are coated using spin coating, scraping coating, or screen printing methods, depending on the size of the device.

5. The method for preparing a high-efficiency electrochromic device by coupling liquid phase with PVD according to claim 1, characterized in that, The heating described in step three adopts a stepwise heating method. First, when preparing the NiO layer, low-temperature heating is used, with a heating temperature of 100-200℃, and it is prepared by reactive sputtering using a metallic Ni target. When preparing the ITO electrode, high-temperature heating is used, with a heating temperature of 150-400℃, and it is prepared by DC sputtering using an ITO ceramic target.

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