阅读说明：本技术 一种高效变色丝网印刷钼掺杂氧化钨纳米结构电致变色薄膜的制备方法 (Preparation method of high-efficiency color-changing silk-screen printing molybdenum-doped tungsten oxide nanostructure electrochromic film ) 是由 王宏志 辜为民 刘学龙 张青红 李耀刚 侯成义 林改 于 2017-04-24 设计创作，主要内容包括：本发明公开了一种高效变色丝网印刷钼掺杂氧化钨纳米结构电致变色薄膜的制备方法,其技术方案要点是包括以下步骤：将钨酸溶于过氧化氢中,油浴加热搅拌至得到澄清溶液,在所得澄清溶液中加入氧化钼、乙二醇和去离子水后,将油浴锅升温,冷凝回流后得到钼掺杂氧化钨纳米溶胶,离心、洗涤备用；在室温下,将乙基纤维素溶解在乙醇中,搅拌得到澄清透明的溶胶,在溶胶中加入松油醇和前述步骤中制备的钼掺杂氧化钨纳米溶胶,旋转蒸发有机溶剂后,得到钼掺杂氧化钨纳米浆料；采用丝网印刷或刮涂法将钼掺杂氧化钨纳米浆料均匀地附着在ITO或FTO导电玻璃基底上,然后用马弗炉煅烧,自然冷却得到钼掺杂氧化钨纳米结构电致变色薄膜。(The invention discloses a preparation method of a high-efficiency electrochromic screen printing molybdenum-doped tungsten oxide nanostructure electrochromic film, which adopts the technical scheme that the method comprises the following steps: dissolving tungstic acid in hydrogen peroxide, heating and stirring in an oil bath until a clear solution is obtained, adding molybdenum oxide, ethylene glycol and deionized water into the clear solution, heating an oil bath, condensing and refluxing to obtain molybdenum-doped tungsten oxide nano sol, centrifuging and washing for later use; dissolving ethyl cellulose in ethanol at room temperature, stirring to obtain clear and transparent sol, adding terpineol and the molybdenum-doped tungsten oxide nano sol prepared in the previous step into the sol, and performing rotary evaporation on an organic solvent to obtain molybdenum-doped tungsten oxide nano slurry; uniformly attaching the molybdenum-doped tungsten oxide nano slurry to an ITO (indium tin oxide) or FTO (fluorine-doped tin oxide) conductive glass substrate by adopting a screen printing or blade coating method, calcining by using a muffle furnace, and naturally cooling to obtain the molybdenum-doped tungsten oxide nano structural electrochromic film.)

1. A preparation method of an electrochromic film with a high-efficiency color-changing screen printing molybdenum-doped tungsten oxide nano structure is characterized by comprising the following steps:

a. dissolving tungstic acid in hydrogen peroxide, heating and stirring in an oil bath until a clear solution is obtained, adding molybdenum oxide, ethylene glycol and deionized water into the clear solution, heating an oil bath, condensing and refluxing to obtain molybdenum-doped tungsten oxide nano sol, centrifuging and washing for later use; the initial heating temperature of the oil bath is 85-95 ℃, the temperature of an oil bath pot after molybdenum oxide, ethylene glycol and deionized water are added is 100-130 ℃, the centrifugal speed is 8000-12000 rpm, the centrifugal time is 15-25 min, and deionized water and ethanol are adopted for washing

b. At room temperature, dissolving ethyl cellulose in ethanol, stirring to obtain clear and transparent sol, adding terpineol and the molybdenum-doped tungsten oxide nano sol prepared in the step a into the sol, and rotationally evaporating an organic solvent to obtain molybdenum-doped tungsten oxide nano slurry; in the ethyl cellulose sol, the mass ratio of ethyl cellulose to ethanol is 1: 8-1: 12; the mass ratio of the molybdenum-doped tungsten oxide to the ethyl cellulose sol to the terpineol is 1: 4: 5-1: 6: 3;

c. uniformly attaching the molybdenum-doped tungsten oxide nano slurry to an ITO (indium tin oxide) or FTO (fluorine-doped tin oxide) conductive glass substrate by adopting a screen printing or blade coating method, calcining by using a muffle furnace, and naturally cooling to obtain the molybdenum-doped tungsten oxide nano structural electrochromic film; the ITO or FTO conductive glass is subjected to ultrasonic cleaning treatment and surface activity treatment, wherein the ultrasonic cleaning treatment is to perform ultrasonic treatment on the ITO or FTO conductive glass for 10-15 minutes by using a detergent, deionized water, acetone and ethanol respectively, and dry the ITO or FTO conductive glass in an oven at the temperature of 60-80 ℃.

2. The preparation method of the high-efficiency electrochromic screen printing molybdenum-doped tungsten oxide nanostructure electrochromic film according to claim 1, which is characterized in that the surface active treatment is to carry out surface active treatment on ITO or FTO conductive glass by using a plasma instrument, the working power is 150-250 w, the time is 5-10 min, and the pressure change sequence of oxygen is controlled to be 120Pa, 40Pa, 90Pa and 68Pa during working.

3. The preparation method of the high-efficiency electrochromic screen-printed molybdenum-doped tungsten oxide nanostructure electrochromic film according to claim 1, wherein the heat treatment temperature of the muffle furnace in the step c is 350-480 ℃, and the heat preservation time is 1-3 h.

[ technical field ] A method for producing a semiconductor device

The invention belongs to the field of electrochromism, and particularly relates to a preparation method of an electrochromic film with a high-efficiency color-changing screen printing molybdenum-doped tungsten oxide nanostructure.

[ background of the invention ]

A phenomenon that a material exhibits a reversible color change when a voltage is applied to the material is called electrochromism, and electrochromic materials include organic materials and inorganic materials, which are receiving attention due to their good cycle stability, and tungsten oxide is a representative substance among inorganic materials.

At present, magnetron sputtering is mostly adopted for preparing large-area tungsten oxide electrochromic films, but a plurality of problems exist: the cost is expensive and the energy consumption is large. One continuous magnetron sputtering instrument is tens of millions in movement and has large power consumption. And secondly, the tungsten oxide film prepared by magnetron sputtering is too compact, is not beneficial to the insertion and the extraction of lithium ions in the color changing process, and has the problems of overlong response time, poor energy utilization rate and the like. How to prepare the electrochromic film with large area and loose and porous microstructure by a simple and cheap process is a problem to be solved urgently in the engineering process.

[ summary of the invention ]

The invention provides a preparation method of a high-efficiency color-changing silk-screen printing molybdenum-doped tungsten oxide nanostructure electrochromic film, the prepared film has a loose and porous structure, is beneficial to embedding and removing electrolyte ions in an electrochromic process, has the advantages of short response time, high color-changing speed and the like, and is hopeful to be applied and popularized in an electrochromic industrialization process.

The invention is realized by the following technical scheme:

a preparation method of an electrochromic film with a high-efficiency color-changing screen printing molybdenum-doped tungsten oxide nano structure comprises the following steps:

a. dissolving tungstic acid in hydrogen peroxide, heating and stirring in an oil bath until a clear solution is obtained, adding molybdenum oxide, ethylene glycol and deionized water into the clear solution, heating an oil bath, condensing and refluxing to obtain molybdenum-doped tungsten oxide nano sol, centrifuging and washing for later use;

b. at room temperature, dissolving ethyl cellulose in ethanol, stirring to obtain clear and transparent sol, adding terpineol and the molybdenum-doped tungsten oxide nano sol prepared in the step a into the sol, and rotationally evaporating an organic solvent to obtain molybdenum-doped tungsten oxide nano slurry;

c. uniformly attaching the molybdenum-doped tungsten oxide nano slurry to an ITO (indium tin oxide) or FTO (fluorine-doped tin oxide) conductive glass substrate by adopting a screen printing or blade coating method, calcining by using a muffle furnace, and naturally cooling to obtain the molybdenum-doped tungsten oxide nano structural electrochromic film.

Preferably, the initial heating temperature of the oil bath in the step a is 85-95 ℃, the temperature of an oil bath pot after adding molybdenum oxide, ethylene glycol and deionized water is 100-130 ℃, the centrifugation speed is 8000-12000 rpm, the centrifugation time is 15-25 min, and deionized water and ethanol are adopted for washing.

Preferably, in the ethylcellulose sol in the step b, the mass ratio of the ethylcellulose to the ethanol is 1: 8-1: 12. the ethyl cellulose is generally insoluble in water, and the proportion of the ethyl cellulose and the ethanol is selected to be proper, so that the dissolving and volatilization of organic matters can be facilitated, and the porosity of the film is improved.

Preferably, the mass ratio of the molybdenum-doped tungsten oxide, the ethyl cellulose sol and the terpineol in the step b is 1: 4: 5-1: 6: 3. the tungsten oxide nano particles have small size, and after redundant organic matters are volatilized, a main body structure of the porous film is formed.

Preferably, the ITO or FTO conductive glass in the step c is subjected to ultrasonic cleaning treatment and surface activity treatment, wherein the ultrasonic cleaning treatment is to perform ultrasonic treatment on the ITO or FTO conductive glass for 10-15 minutes by using a detergent, deionized water, acetone and ethanol respectively, and dry the ITO or FTO conductive glass in an oven at the temperature of 60-80 ℃. The glass is ultrasonically cleaned by using a mixed solution of a detergent, deionized water, acetone and ethanol, so that foreign matters on the surface are effectively removed, and the glass can be removed by ultrasonic oscillation even though insoluble chemical substances are adsorbed.

Preferably, the surface active treatment is to carry out surface active treatment on the ITO or FTO conductive glass by using a plasma instrument, the working power is 150-250 w, the time is 5-10 min, and the pressure change sequence of oxygen is controlled to be 120Pa, 40Pa, 90Pa and 68Pa during working. The surface of the conductive glass is subjected to surface active treatment, particularly the pressure of oxygen is controlled, the nanoscale material adhesion rate is favorably controlled, and the service life of the electrochromic layer is prolonged.

Preferably, the heat treatment temperature of the muffle furnace in the step c is 350-480 ℃, and the heat preservation time is 1-3 h. The muffle furnace has stable high-temperature condition, is beneficial to the full volatilization of organic matters, and is suitable for the mass production of large-area porous structure films.

Compared with the prior art, the invention has the following advantages:

(1) according to the preparation method of the high-efficiency color-changing silk-screen printing molybdenum-doped tungsten oxide nanostructure electrochromic film, the silk-screen printing molybdenum-doped tungsten oxide film is adopted, the thickness of the film layer can be controlled to be 50-400 nm, the size of tungsten oxide nanoparticles is small, electron transmission is facilitated, the transmission efficiency is improved, and therefore the color-changing efficiency is improved;

(2) according to the preparation method of the electrochromic film with the high-efficiency color-changing screen printing molybdenum-doped tungsten oxide nanostructure, the molybdenum-doped tungsten oxide nano sol prepared based on the condensation reflux method is a simple and convenient method for preparing a large-area electrochromic layer, after the molybdenum-doped tungsten oxide film is subjected to heat treatment, a loose and porous microstructure is generated due to volatilization of organic matters, so that the ion embedding and the ion releasing in the color-changing process are facilitated, the molybdenum-doped tungsten oxide film is prepared by screen printing, and the key problem encountered in the industrialization of an electrochromic intelligent window is facilitated to be solved;

(2) the preparation method of the high-efficiency electrochromic screen printing molybdenum-doped tungsten oxide nanostructure electrochromic film has the advantages of low process energy consumption and low cost, is beneficial to greatly reducing the production cost of enterprises, and is expected to be popularized in the engineering of electrochromic intelligent windows.

[ description of the drawings ]

FIG. 1 is an electron micrograph of a cross section of a screen printed molybdenum doped tungsten oxide film of example 1;

FIG. 2 is a digital photograph of the assembled device of example 1 before discoloration;

FIG. 3 is a digital photograph of the assembled device of example 1 after discoloration;

FIG. 4 is a graph of the transmittance of the assembled device of example 1;

FIG. 5 is a current-potential diagram of the assembled device in example 2;

fig. 6 is a cyclic voltammogram of the assembled device of example 2.

[ detailed description ] embodiments

The preparation method of the electrochromic film with the high-efficiency color-changing screen printing molybdenum-doped tungsten oxide nano structure is described by combining specific embodiments