阅读说明：本技术 一种柔性基底上纳米晶多孔二氧化钛薄膜的制备方法 (Preparation method of nanocrystalline porous titanium dioxide film on flexible substrate ) 是由 林琳 吴晓燕 王敬锋 徐少洪 陈超 于 2019-10-15 设计创作，主要内容包括：本发明公开一种柔性基底上纳米晶多孔二氧化钛薄膜的制备方法,采用水热/丝网印刷复合法制备,包括如下步骤：(1)二氧化钛胶体的制备：在150℃水热反应24h,生成纳米TiO<Sub>2</Sub>胶体溶液；(2)丝网印刷胶体的制备：将水热生成的纳米TiO<Sub>2</Sub>胶体溶液取出,超声分散后,加入质量分数为10-30%的工业粘稠剂,恒温80℃加热,搅拌至适当的黏度,采用丝网印刷法在柔性基底上溅射直接获得二氧化钛纳米晶多孔薄膜。本发明方法是一种新兴的微纳结构制备技术,产物性质稳定,成膜均匀,膜厚可控；且具有成本低、可大面积制备、可用于柔性衬底等优点,特别适用于产业化生产。(The invention discloses a preparation method of a nanocrystalline porous titanium dioxide film on a flexible substrate, which is prepared by adopting a hydrothermal/silk-screen printing composite method and comprises the following steps: (1) preparing titanium dioxide colloid: hydrothermal reaction at 150 deg.c for 24 hr to produce nanometer TiO 2 A colloidal solution; (2) preparing a screen printing colloid: hydrothermally generating nano TiO 2 Taking out the colloidal solution, ultrasonically dispersing, adding 10-30% by mass of industrial viscous agent, heating at a constant temperature of 80 ℃, stirring to a proper viscosity, and directly sputtering on a flexible substrate by adopting a screen printing method to obtain the titanium dioxide nanocrystalline porous film. The method is a novel micro-nano structure preparation technology, the product is stable in property, uniform in film forming and controllable in film thickness; and has the advantages of low cost, large-area preparation, flexible substrate application, etcHas the advantages of being particularly suitable for industrialized production.)

1. A preparation method of a nanocrystalline porous titanium dioxide film on a flexible substrate is characterized in that the preparation method is a hydrothermal/silk-screen printing composite method, and comprises the following steps:

(1) preparing titanium dioxide colloid: respectively taking 20ml of butyl titanate and glacial acetic acid, uniformly mixing in a beaker, and standing; adding 120ml of distilled water into a beaker, adding 6ml of diethanolamine under vigorous stirring, and continuing stirring for 4 hours until a milky semitransparent hydrothermal precursor solution is obtained; adding the precursor solution into a hydrothermal high-pressure reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 24h to generate nano TiO₂A colloidal solution;

(2) preparing a screen printing colloid: hydrothermally generating nano TiO₂Taking out the colloidal solution, performing ultrasonic dispersion, adding 10-30% by mass of industrial viscous agent, heating at constant temperature of 80 ℃, stirring to proper viscosity, and directly sputtering on a flexible substrate (PET) by adopting a screen printing method to obtain the titanium dioxide nanocrystalline porous film.

2. The method for preparing the nanocrystalline porous titanium dioxide film on the flexible substrate according to claim 1, wherein in the step (2), the industrial thickening agent is one or a mixture of more of PEG20000, carboxymethyl cellulose and carboxyethyl cellulose.

3. The method for preparing a nanocrystalline porous titanium dioxide film on a flexible substrate according to claim 1, wherein before the film coating in the step (2), the flexible substrate material is subjected to pretreatment: respectively cleaning the flexible substrate material in ethanol and water for no less than 30min by ultrasonic waves; or respectively cleaning the flexible substrate material in ethanol and water by ultrasonic wave for no less than 30min, and soaking the material after ultrasonic wave in ethanol solution.

Technical Field

The invention relates to preparation of a nanocrystalline porous titanium dioxide layer, in particular to a preparation method of a nanocrystalline porous titanium dioxide film on a flexible substrate.

Background

The nano material has the special performances of small-size effect, surface effect, quantum size effect, macroscopic quantum tunneling effect, dielectric confinement effect and the like, and shows various superior performances which are not possessed by the conventional material. In the field of nano material research, nano titanium dioxide as a functional semiconductor material has extremely wide application in the fields of environmental protection, photoelectric conversion, coating industry, industrial catalysis and the like. The nano titanium dioxide material has the advantages of low price, no toxicity, small particle size, less particle agglomeration, uniform and stable appearance, capability of recycling and the like, and is favored in the aspects of sewage treatment and air purification.

The flexible substrate has the advantages of being bendable, light in weight, good in flexibility, impact-resistant, low in cost, capable of being designed in various shapes or surfaces and the like, can be produced in a coiled continuous mode, can be coated quickly and the like, is convenient for large-area production, reduces production cost, has stronger competitiveness, and becomes a new research hotspot. For example, the application of the double-sided DSSC can be effectively expanded by adopting a light, flexible and cheap conductive plastic substrate such as PEN/FTO and PET/FTO. Because the titanium dioxide nanoparticle film is prepared on a PEN/FTO or PET/FTO substrate in the existing flexible dye-sensitized solar cell, the crystal form is converted into anatase form by calcining at 450 ℃ for 30min so as to improve the activity and the adhesiveness of the titanium dioxide film, but neither PEN nor PET can bear the high-temperature long-term calcining, the existing preparation process generally adopts low-temperature calcining, so that the crystal form conversion of the titanium dioxide is incomplete, and the photoelectric activity is lower. For example, the invention patent with Chinese patent publication No. CN102086045A includes the following steps: 1) mixing tetrabutyl titanate, diethanolamine and ethanol, adding dropwise added liquid, stirring and mixing uniformly, and aging to obtain a glue throwing liquid; the dropping liquid consists of water, ethanol and concentrated hydrochloric acid; 2) coating the whirl coating solution obtained in the step 1) on a substrate, drying and carrying out heat treatment to obtain rutile TiO on the surface of the substrate₂A film; 3) the rutile TiO obtained in the step 2) is₂Mixing the film with the precursor I, reacting at 190 ℃ to obtain TiO after the reaction is finished₂A first-order nanorod array; the precursor I is TiCl₃The pH value of the precursor I is 0.25; 4) subjecting the TiO obtained in the step 3) to₂Mixing the primary nanorod array with the precursor II, reacting at 190 ℃, and obtaining the TiO after the reaction is finished₂A second-level nanorod array; the precursor II is TiCl₃The pH value of the precursor II is 0.25-1.20. According to the invention, a coating method is utilized to obtain a layer of titanium film, then a hydrothermal method is adopted to grow the nanorod array, the process is complex, and in the invention, a screen printing method is utilized to directly sputter the porous nanocrystalline titanium dioxide layer, so that the method has the advantages of simple equipment, low price, uniform film forming, capability of being used for film preparation in large batch and the like.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method of a nanocrystalline porous titanium dioxide film on a flexible substrate.

The purpose of the invention is realized by the following scheme: a preparation method of a nanocrystalline porous titanium dioxide film on a flexible substrate is characterized in that the preparation method is a hydrothermal/silk-screen printing composite method, and comprises the following steps: (1) preparing titanium dioxide colloid: respectively taking 20ml of butyl titanate and glacial acetic acid, uniformly mixing in a beaker, and standing; adding 120ml of distilled water into a beaker, adding about 6ml of diethanolamine under vigorous stirring, and continuing stirring for 4 hours until a milky semitransparent hydrothermal precursor solution is obtained; adding the precursor solution into a hydrothermal high-pressure reaction kettle, and carrying out hydrothermal reaction at 150 ℃ for 24h to generate nano TiO₂A colloidal solution;

(2) preparing a screen printing colloid: hydrothermally generating nano TiO₂Taking out the colloidal solution, performing ultrasonic dispersion, adding 10-30% by mass of industrial viscous agent, heating at constant temperature of 80 ℃, stirring to proper viscosity, and directly sputtering on a flexible substrate (PET) by adopting a screen printing method to obtain the titanium dioxide nanocrystalline porous film.

In the step (2), the industrial viscous agent is one or a mixture of more of PEG20000, carboxymethyl cellulose and carboxyethyl cellulose.

Before the film coating in the step (2), pretreating the flexible substrate material: respectively cleaning the flexible substrate material in ethanol and water for no less than 30min by ultrasonic waves; or respectively cleaning the flexible substrate material in ethanol and water by ultrasonic wave for no less than 30min, and soaking the material after ultrasonic wave in ethanol solution.

Compared with the prior art, the method has the advantages of simple and convenient operation, low price, mild reaction conditions, uniform film formation and suitability for large-area film preparation, and the thickness of the nano film layer can be controlled by sputtering time and temperature, and the method is suitable for industrial production. The prepared nano film has application prospects in photoluminescence, photocatalysis and other aspects.

Drawings

FIG. 1 is an SEM image of example 1 of the present invention;

figure 2 is an XRD pattern of example 1 of the present invention.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.