阅读说明：本技术 一种多维wo3复合电致变色薄膜的制备方法 (Multi-dimensional WO3Preparation method of composite electrochromic film ) 是由 刘志锋 韩建华 宋庆功 严慧羽 康建海 郭艳蕊 于 2020-05-28 设计创作，主要内容包括：一种多维WO<Sub>3</Sub>复合电致变色薄膜的制备方法。该方法首先采用草酸钾和钨酸钠制备混合溶液,通过加入稀盐酸调控溶液pH值,配制一维WO<Sub>3</Sub>纳米棒前驱体反应液,随后利用水热反应和热处理制得一维WO<Sub>3</Sub>纳米棒薄膜；然后采用钨酸钠、稀盐酸和草酸铵制备二维WO<Sub>3</Sub>纳米片前驱体反应液,再利用水热反应和热处理制备一维WO<Sub>3</Sub>纳米棒和二维WO<Sub>3</Sub>纳米片复合的电致变色薄膜。利用本发明方法制备的WO<Sub>3</Sub>复合电致变色薄膜电致变色性能好,制备方法操作简单,成本低廉,节能环保,应用范围广。(Multi-dimensional WO 3 A preparation method of a composite electrochromic film. The method comprises the steps of firstly preparing a mixed solution by adopting potassium oxalate and sodium tungstate, regulating and controlling the pH value of the solution by adding dilute hydrochloric acid, and preparing one-dimensional WO 3 The nanorod precursor reaction solution is subjected to hydrothermal reaction and heat treatment to obtain one-dimensional WO 3 A nanorod film; then preparing two-dimensional WO by adopting sodium tungstate, dilute hydrochloric acid and ammonium oxalate 3 One-dimensional WO is prepared by using nanosheet precursor reaction solution and then by using hydrothermal reaction and thermal treatment 3 Nanorods and two-dimensional WO 3 An electrochromic film compounded by nano-sheets. WO prepared by the Process of the invention 3 The composite electrochromic film has good electrochromic performance and a preparation methodThe method has the advantages of simple operation, low cost, energy conservation, environmental protection and wide application range.)

1. Multi-dimensional WO₃The preparation method of the composite electrochromic film is characterized by comprising the following steps: said WO₃Composite electroproductionThe preparation method of the color-changing film comprises the following steps which are carried out in sequence:

1) dissolving potassium oxalate in deionized water to obtain potassium oxalate solution, dissolving sodium tungstate in the potassium oxalate solution, and dropwise adding dilute hydrochloric acid while stirring to adjust the pH value of the solution to acidity, thereby preparing one-dimensional WO₃Reaction liquid of a nanorod precursor;

2) putting clean FTO conductive glass into a hydrothermal kettle inner container, and adding the one-dimensional WO₃Carrying out hydrothermal reaction on the nanorod precursor reaction solution, and carrying out heat treatment on the FTO conductive glass after the reaction, thereby forming one-dimensional WO on the surface of the FTO conductive glass₃A nanorod film;

3) dissolving sodium tungstate in deionized water to prepare sodium tungstate solution, then dropwise adding dilute hydrochloric acid into the sodium tungstate solution while stirring to form turbid solution, then adding ammonium oxalate into the turbid solution, stirring to clarify, and preparing into two-dimensional WO₃Nanosheet precursor reaction liquid;

4) forming the surface with one-dimensional WO₃FTO conductive glass of the nanorod film is put into the inner container of the hydrothermal kettle, and the two-dimensional WO is added₃Performing hydrothermal reaction on the nanosheet precursor reaction solution, performing heat treatment on the FTO conductive glass after the reaction, and finally forming one-dimensional WO on the surface of the FTO conductive glass₃Nanorods and two-dimensional WO₃An electrochromic film compounded by nano-sheets.

2. Multidimensional WO according to claim 1₃The preparation method of the composite electrochromic film is characterized by comprising the following steps: in the step 1), the concentrations of the potassium oxalate and the sodium tungstate are respectively 0.010-0.014M and 0.080-0.084M, and one-dimensional WO₃The pH value of the nanorod precursor reaction liquid is 0.98-1.02.

3. Multidimensional WO according to claim 1₃The preparation method of the composite electrochromic film is characterized by comprising the following steps: in the step 2), the temperature and the time of the hydrothermal reaction are respectively 175-185 ℃ and 22-26 h, and the heat treatment temperature is 500-550 ℃.

4. Multidimensional WO according to claim 1₃The preparation method of the composite electrochromic film is characterized by comprising the following steps: in the step 3), the concentrations of the sodium tungstate and the ammonium oxalate are 0.022-0.024M and 0.035-0.045M respectively.

5. Multidimensional WO according to claim 1₃The preparation method of the composite electrochromic film is characterized by comprising the following steps: in the step 4), the temperature and the time of the hydrothermal reaction are respectively 115-125 ℃ and 11-13 h, and the heat treatment temperature is 350-400 ℃.

Technical Field

The invention belongs to the technical field of electrochromic film material preparation, and particularly relates to a multi-dimensional WO₃A preparation method of a composite electrochromic film.

Background

Technological advances have led to unprecedented advances in the ability of mankind to transform and utilize nature, with tremendous advances in productivity, accompanied by rapid human resource utilization and energy consumption rates. The electrochromic glass utilizes an external electric field to change the color of the material, so that the active dynamic control of visible light is achieved, partial dynamic adjustment of the transmittance of solar radiation energy is realized, and the electrochromic glass is energy-saving intelligent glass which is most hopeful to realize large-scale commercial production at present. The electrochromic material has the advantages of low driving voltage, bistable state, high contrast, low cost, no visual blind angle, wide working temperature range and the like, so the electrochromic material has wide application potential in many fields. Electrochromic devices have been extensively studied since 1980, and Granqvist et al proposed the concept of Smart Window; in 1999, Stadt Sparkasse savings bank, dereston, germany, used an electrochromic glass outer wall for the first time; in 2004, the glass curtain wall of the switzerland reinsurance building in london, england used electrochromic technology; in 2008, the cabin window glass of the passenger plane dream of Boeing 787 eliminates a mechanical porthole sun shield and adopts electrochromic glass. Electrochromic technology is also becoming more mature and beginning to be widely used.

The electrochromic glass system mainly comprises a power supply, a conductive layer, an electrochromic layer, an electrolyte layer and an ion storage layer. The electrochromic layer is the most important core function part in the whole electrochromic glass device, and the performance of the electrochromic layer directly influences the performance of the electrochromic glass device. The basic requirements of the electrochromic material are that the material has high light transmittance in a fading state, has good absorption or reflection characteristics in a coloring state, i.e. has high light modulation amplitude, and in addition, has good cycle stability, high color change efficiency and high electrochromic response speed. The electrochromic material mainly comprises an inorganic electrochromic materialMaterials (transition metal oxides and prussian blue) and organic electrochromic materials. Inorganic electrochromic materials can be further classified into reduced-state colored electrochromic materials (e.g., oxides of W, Mo, V, Nb, and Ti) and oxidized-state colored electrochromic materials (e.g., oxides of Ir, Rh, Ni, and Co). Some materials (e.g., V, Co and Rh oxides) may exhibit different colors in both the oxidized and reduced states. Prussian blue is also an inorganic electrochromic material with various color-changing characteristics, and can be converted between dark blue, transparent colorless (reduction state) and light green (oxidation state). Organic electrochromic materials include redox compounds (e.g., viologen), conductive polymers (e.g., polyaniline polythiophene), and metal organic chelates (e.g., phthalocyanine). Among them, tungsten oxide (WO)₃) The material has attracted extensive attention because of its advantages of high coloring efficiency, good reversibility and wide visible light adjusting range, and is the most potential electrochromic material. In recent years, for WO₃The research mainly focuses on the aspects of doping modification, micro-morphology regulation and the like of the material, and the research progress is well achieved. But still face a series of problems of low coloring efficiency, slow response time, low cycle life and the like.

Disclosure of Invention

In order to solve the above problems, it is an object of the present invention to provide a multidimensional WO₃Preparation method of composite electrochromic film by using one-dimensional WO₃Nanorods and two-dimensional WO₃The respective advantages of the nano sheets are utilized to synthesize WO with a composite structure₃An electrochromic film.

In order to achieve the above object, the present invention provides WO₃The preparation method of the composite electrochromic film comprises the following steps which are sequentially carried out:

1) dissolving potassium oxalate in deionized water to obtain potassium oxalate solution, dissolving sodium tungstate in the potassium oxalate solution, and dropwise adding dilute hydrochloric acid while stirring to adjust the pH value of the solution to acidity, thereby preparing one-dimensional WO₃Reaction liquid of a nanorod precursor;

2) clean FTO conductive glass (the FTO conductive glass is SnO doped with fluorine)₂Transparent conductive glass) is put into the inner container of the hydrothermal kettle, andadding the above one-dimensional WO₃Carrying out hydrothermal reaction on the nanorod precursor reaction solution, and carrying out heat treatment on the FTO conductive glass after the reaction, thereby forming one-dimensional WO on the surface of the FTO conductive glass₃A nanorod film;

3) dissolving sodium tungstate in deionized water to prepare sodium tungstate solution, then dropwise adding dilute hydrochloric acid into the sodium tungstate solution while stirring to form turbid solution, then adding ammonium oxalate into the turbid solution, stirring to clarify, and preparing into two-dimensional WO₃Nanosheet precursor reaction liquid;

4) forming the surface with one-dimensional WO₃FTO conductive glass of the nanorod film is put into the inner container of the hydrothermal kettle, and the two-dimensional WO is added₃Performing hydrothermal reaction on the nanosheet precursor reaction solution, performing heat treatment on the FTO conductive glass after the reaction, and finally forming one-dimensional WO on the surface of the FTO conductive glass₃Nanorods and two-dimensional WO₃An electrochromic film compounded by nano-sheets.

In the step 1), the concentrations of the potassium oxalate and the sodium tungstate are respectively 0.010-0.014M and 0.080-0.084M, and one-dimensional WO₃The pH value of the nanorod precursor reaction liquid is 0.98-1.02.

In the step 2), the temperature and the time of the hydrothermal reaction are respectively 175-185 ℃ and 22-26 h, and the heat treatment temperature is 500-550 ℃.

In the step 3), the concentrations of the sodium tungstate and the ammonium oxalate are 0.022-0.024M and 0.035-0.045M respectively.

In the step 4), the temperature and the time of the hydrothermal reaction are respectively 115-125 ℃ and 11-13 h, and the heat treatment temperature is 350-400 ℃.

The invention provides a multi-dimensional WO₃The preparation method of the composite electrochromic film has the following beneficial effects: incorporating one-dimensional WO₃Nanorods and two-dimensional WO₃The respective advantages of the nano-sheets are utilized, the faster electron transport, the high specific surface area, the porous channel and the provision of more active sites for the reaction are utilized, so that WO is enabled to be obtained₃The composite electrochromic film has extremely fast electrochromic response and high coloring efficiency, and the coloring time and the fading time are respectively 4.5sAnd 3.7s, coloring efficiency of 63.1cm²·C^-1. In addition, the preparation method is simple to operate and low in cost.

Drawings

FIG. 1 is a multi-dimensional WO provided by the present invention₃Scanning electron microscopy of the composite electrochromic film.

Detailed Description

The present invention will be described in detail with reference to the following specific examples: