Preparation method of WO3-CA composite porous electrochromic glass film
By doping cerium acetate in WO3 film to form Ce-O bonds, the performance of WO3 electrochromic materials is improved, the problems of its color discoloration efficiency and light adjustment range are solved, and high-efficiency and low-cost WO3-CA composite porous electrical circuits are achieved. Preparation of discolored glass film.
Patent Information
- Application Number
- CN202411427114.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-14
- Publication Date
- 2025-01-10
AI Technical Summary
WO3 electrochromic materials have defects in discoloration efficiency, photoregulation range and cycle life, which limits its further development in the industrial field.
The WO3-CA composite porous electrochromic glass film was prepared by hydrothermal method and annealing method. By doping different concentrations of cerium acetate in the WO3 film, Ce-O bonds were formed, the ion diffusion rate and ion storage capacity were improved, and the materials were increased. effective contact surface area.
The electrochromic performance of WO3 film is significantly improved, including discoloration efficiency and light adjustment range, reducing costs and achieving a pollution-free preparation process.
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Figure CN119285247A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of material preparation, and specifically relates to a method for preparing a WO3-CA composite porous electrochromic glass film. Background Art
[0002] According to statistics, the energy consumption of the construction industry accounts for 28% of the total energy consumption in the country, second only to industry. Therefore, taking energy-saving measures to improve buildings will significantly reduce energy consumption. Building energy-saving measures mainly focus on environmental control designs such as indoor temperature and brightness. At present, the proportion of glass used in modern building exterior walls is increasing. Statistics show that the heat loss caused by windows in ordinary residences in summer and winter accounts for 71% and 48% of the total energy consumption of buildings, respectively. Therefore, the energy-saving problems that need to be urgently solved in the construction industry are mainly concentrated on the energy-saving performance of glass doors and windows. Under the current situation, a series of energy-saving glasses have emerged on the market, such as heat-absorbing glass, low-emissivity glass, and heat-reflecting glass. However, these glasses have fixed adjustments to sunlight after production, and cannot be adjusted according to environmental changes, so it is difficult to meet all-weather energy-saving needs. This urgently requires the development of a glass with intelligent adjustment function. In this research boom, color-changing materials came into being. The emergence of color-changing materials marks a new step in the utilization of solar energy and provides a new solution for energy saving and environmental protection.
[0003] Since it was first proposed in 1953, electrochromic technology has received widespread attention and has shown great commercial potential. It is widely used in fields such as building smart windows, car sunroofs and aircraft windows. Early research focused on the development of electrochromic materials and devices. In the 1980s, electrochromic technology based on transition metal oxides began to receive attention, and it was generally believed that this technology was of great significance for energy-saving windows. In the early 1990s, the Granquvist team proposed a new smart window based on electrochromic film, aiming to apply electrochromic materials to the field of smart windows. Subsequently, SAGE, an American company, took the lead in commercializing electrochromic smart window products, laying the foundation for the development of this technology. The first International Conference on Electrochromism was successfully held in 1994. The conference mainly discussed the characteristics of electrochromic materials, electrochromic devices, and electrolytes in electrochromic applications. In 2005 and 2008, electrochromic glass was used on the roof and windshield of the sports car produced by the Italian Ferrari company and the cabin windows of the American Boeing 787 aircraft. The French Saint-Gobain Group announced its entry into the smart window industry in 2009. China's first electrochromic website was established in September of the same year. The core technology of electrochromic, especially the research methods of all-solid-state electrochromic devices, is currently mainly in the hands of Europe, Japan and the United States. Relatively speaking, my country started late in the field of electrochromic, but with the unremitting efforts of domestic universities and research institutes, it has also achieved remarkable results.
[0004] Electrochromism refers to the phenomenon that when a certain voltage is applied, the optical properties of the material (transmittance, absorption and reflectivity of light) undergo reversible changes, and its color change can be characterized by different parameters in the color space. From the perspective of the electromagnetic spectrum, reversible changes can occur in the ultraviolet to microwave region, and devices with electrochromic effects are electrochromic devices (ECDs). Electrochromic materials can be divided into three categories according to their structure and chemical properties, namely organic electrochromic materials, inorganic electrochromic materials and composite electrochromic materials. Commonly used inorganic color-changing materials are mainly WO3, TiO2, NiO, etc. Among them, tungsten trioxide (WO3) is considered to be the most promising electrochromic material for large-scale industrialization due to its excellent electrochromic performance and relatively low cost. However, WO3 still has some defects in color change efficiency, light adjustment range and cycle life, which restrict its further development in the industrial field. Therefore, how to improve the color change efficiency of WO3, expand its light adjustment range and increase the cycle life has become the key to improving the electrochromic performance of WO3 film. Summary of the invention
[0005] In order to further improve the electrochromic performance of the WO3 film, the present invention proposes a method for preparing a WO3-CA composite porous electrochromic glass film.
[0006] The technical solution of the present invention is:
[0007] A method for preparing a WO3-CA composite porous electrochromic glass film comprises the following steps:
[0008] The steps are as follows: Preparation of WO3-CA composite porous electrochromic glass film
[0009] (1) Prepare a solution containing a tungsten source precursor; prepare a WO3 thin film by a hydrothermal method and a heat treatment method. Prepare cerium acetate of different concentrations;
[0010] (2) The WO3-CA composite porous electrochromic glass film was prepared by doping different concentrations of cerium acetate into the solution for preparing the WO3 thin film using a hydrothermal method.
[0011] Furthermore, the process parameters of step (1) are as follows: sodium tungstate and potassium oxalate are used as precursors, deionized water is used as solvent, hydrochloric acid is used as pH regulator, stirring is performed at 8°C-40°C for 0.6h-2.2h, and 0.10-0.15mol·L -1 50 mL of a solution in which the molar ratio of hydrochloric acid to sodium tungstate and potassium oxalate is 3:1:1 is prepared to obtain a solution containing a tungsten source precursor.
[0012] Further, the cleaned and dried conductive glass is tilted downward at 45° into the solution containing the tungsten source precursor in the step, heated to 180°C-200°C at 1-2°C / min, kept warm for 6.0h-6.5h, then heated to 530°C-560°C at 2-5°C / min, kept warm for 2.0h-2.2h, and naturally cooled to room temperature to obtain a WO3 rod-shaped film.
[0013] Furthermore, the process parameters of step (1) are as follows: using cerium acetate as a precursor and deionized water as a solvent, ultrasonically dispersing at 8°C-40°C for 0.6h-2.2h, and preparing different concentrations of 0.10-0.60 mol·L -1 of solution.
[0014] Furthermore, the process parameters of step (2) are as follows: the WO3-CA composite porous electrochromic glass film is prepared by hydrothermal method and annealing method, using the precursor solution of tungsten trioxide porous nanorods prepared in step (1), adding different concentrations of cerium acetate to the solution in sequence, and the molar ratio of cerium is 1:3:5. The temperature is raised to 180-200°C at 1-2°C / min, kept at this temperature for 6.0h-6.5h, and then raised to 530-560°C at 2-5°C / min, kept at this temperature for 2.0h-2.2h, and naturally cooled to room temperature to obtain the WO3-CA composite porous electrochromic glass film.
[0015] Compared with the prior art, the present invention has the following beneficial effects:
[0016] (1) After various tests, it was found that the WO3-CA composite porous electrochromic glass film obtained by the present invention exhibited good electrochromic performance.
[0017] (2) The preparation method provided by the present invention is simple and easy to operate, has practical feasibility, and the prepared WO3-CA composite porous electrochromic glass film is low-cost and pollution-free. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 It is a scanning electron microscope image of the WO3 and WO3-CA composite porous electrochromic glass film of the present invention. DETAILED DESCRIPTION
[0019] The following examples can enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way.
[0020] Example 1
[0021] The steps are as follows: Preparation of WO3-CA composite porous electrochromic glass film
[0022] Sodium tungstate and potassium oxalate were used as precursors, deionized water as solvent, and hydrochloric acid as pH regulator. Stirring was performed at 20°C for 0.5 h to prepare 0.10 mol·L -1 50 mL of a solution in which the concentrations of hydrochloric acid, sodium tungstate and potassium oxalate are 3 mol / L, 1 mol / L and 1 mol / L respectively, is prepared to obtain a solution containing a tungsten source precursor.
[0023] The cleaned and dried conductive glass was tilted downward at 45° into the solution containing the tungsten source precursor, and the temperature was raised to 180°C at 1°C / min, kept at this temperature for 6.5h, and dried at 60°C for 2.0h. Then the temperature was raised to 550°C at 2°C / min, kept at this temperature for 2.0h, and naturally cooled to room temperature to obtain a WO3 rod-shaped film. Using cerium acetate solution as the precursor and deionized water as the solvent, ultrasonic dispersion was performed at 20°C for 1.0h, and different concentrations of 0.10-0.60mol·L were prepared in turn. -1 of cerium acetate solution.
[0024] The preparation was carried out by hydrothermal method and annealing method. Using the precursor solution of tungsten trioxide porous nanorods, different concentrations of cerium acetate were added to the solution in sequence, and the molar ratio of cerium was 1:3:5. The temperature was raised to 180℃ at 1℃ / min, kept for 6.5h, and dried at 60℃ for 2.0h. Then the temperature was raised to 550℃ at 2℃ / min, kept for 2.0h, and naturally cooled to room temperature to obtain WO3-CA composite porous electrochromic glass film.
[0025] Example 2
[0026] The steps are as follows: Preparation of WO3 / PEDOT composite porous electrochromic glass film
[0027] Sodium tungstate and potassium oxalate were used as precursors, deionized water as solvent, and hydrochloric acid as pH regulator. Stirring was performed at 10°C for 2.0 h to prepare 0.15 mol·L -1 50 mL of a solution in which the concentrations of hydrochloric acid, sodium tungstate and potassium oxalate are 2.9 mol / L, 0.9 mol / L and 0.9 mol / L respectively, is prepared to obtain a solution containing a tungsten source precursor.
[0028] The cleaned and dried conductive glass was tilted downward at 45° into the solution containing the tungsten source precursor, and the temperature was raised to 200°C at 2°C / min, kept at this temperature for 5.0h, and dried at 70°C for 1.0h. Then the temperature was raised to 560°C at 5°C / min, kept at this temperature for 2.2h, and naturally cooled to room temperature to obtain a WO3 rod-shaped film. Using cerium acetate solution as the precursor and deionized water as the solvent, ultrasonic dispersion was performed at 10°C for 2.0h, and different concentrations of 0.10-0.60mol·L were prepared in turn. -1 of cerium acetate solution.
[0029] The preparation was carried out by hydrothermal method and annealing method. Using the precursor solution of tungsten trioxide porous nanorods, different concentrations of cerium acetate were added to the solution in sequence, and the molar ratio of cerium was 2:4:6. The temperature was raised to 200℃ at 2℃ / min, kept warm for 5.0h, and dried at 70℃ for 1.0h. Then the temperature was raised to 560℃ at 5℃ / min, kept warm for 2.2h, and naturally cooled to room temperature to obtain WO3-CA composite porous electrochromic glass film.
[0030] The mechanism of action of the present invention is that the cerium atoms in cerium acetate will form new Ce-O bonds with oxygen atoms in tungsten oxide, which will increase the ion diffusion rate when the film is working and increase the ion storage capacity of the film. New chemical bonds are introduced into WO3 by doping with rare earth element Ce. In addition, the tungsten oxide film doped with cerium will adsorb acetate ions, increase the effective contact surface area of the material, thereby affecting the optical and electrochemical properties of the material and improving the coloring efficiency of the WO3 electrochromic film.
[0031] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.
Claims
1. A method for preparing a WO3-CA composite porous electrochromic glass film, comprising the following steps: The steps are as follows: Preparation of WO3-CA composite porous electrochromic glass film (1) Prepare a solution containing a tungsten source precursor; prepare a WO3 thin film by a hydrothermal method and a heat treatment method. Prepare cerium acetate with different concentrations; (2) The WO3-CA composite porous electrochromic glass film was prepared by doping different concentrations of cerium acetate into the solution for preparing the WO3 thin film using a hydrothermal method.
2. The method for preparing a WO3-CA composite porous electrochromic glass film according to claim 1, characterized in that: The process parameters of step (1) are as follows: sodium tungstate and potassium oxalate are used as precursors, deionized water is used as solvent, hydrochloric acid is used as pH regulator, stirring is performed at 8°C-40°C for 0.6h-2.2h, and 0.10-0.15mol·L -1 50mL of solution, in which the molar ratio of hydrochloric acid, sodium tungstate and potassium oxalate is 3:1:1, to obtain a solution containing a tungsten source precursor. The clean and dried conductive glass is tilted downward at 45° into the solution containing a tungsten source precursor, and the temperature is raised to 180℃-200℃ at 1-2℃ / min, kept warm for 6.0h-6.5h, and then raised to 530℃-560℃ at 2-4℃ / min, kept warm for 2.0h-2.2h, and naturally cooled to room temperature to obtain a WO3 rod-shaped film. Using cerium acetate solution as a precursor and deionized water as a solvent, ultrasonic dispersion is performed at 8℃-40℃ for 0.6h-2.2h to prepare different concentrations of 0.10-0.60mol·L -1 of solution.
3. The method for preparing a WO3-CA composite porous electrochromic glass film according to claim 1, characterized in that: The process parameters of step (2) are as follows: the WO3-CA composite porous electrochromic glass film is prepared by hydrothermal method and annealing method, using the precursor solution of tungsten trioxide porous nanorods prepared in step (1), adding different concentrations of cerium acetate to the solution in sequence, and the molar ratio of cerium is 1:3:
5. The temperature is raised to 180-200°C at 1-2°C / min, kept at this temperature for 6.0h-6.5h, and then raised to 530-560°C at 2-5°C / min, kept at this temperature for 2.0h-2.2h, and naturally cooled to room temperature to obtain the WO3-CA composite porous electrochromic glass film.