CN102774885B - Porous submicron sphere, porous film electrode and preparation method and application in dye sensitized solar cells thereof - Google Patents
Porous submicron sphere, porous film electrode and preparation method and application in dye sensitized solar cells thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
本发明公开了一种多孔亚微米球、多孔薄膜电极及其制备方法和在染料敏化太阳电池中的应用，亚微米球是由纳米TiO2颗粒构成的多孔结构，孔径在5～50nm，纳米TiO2颗粒的粒径在10～100nm，亚微米球的直径在150～1000nm之间，BET比表面积调控在80～200m2/g。本发明制备的由二氧化钛纳米颗粒构成的多孔亚微米球，此球成单分散、宽直径分布，该结构同时具有大的比表面积、对可见光具有较高散射能力和在球内部较快的电子传输性能，使得多孔薄膜具有较大的光散射能力和染料吸附能力。在光催化、光电转换领域应用时，提高光的利用率、电子的收集率，染料敏化太阳电池能获得较高的光电转换效率以及节省TiO2用量。
The invention discloses a porous submicron sphere, a porous thin film electrode and its preparation method and application in dye-sensitized solar cells. The particle size of the TiO 2 particles is 10-100 nm, the diameter of the submicron sphere is 150-1000 nm, and the BET specific surface area is regulated at 80-200 m 2 /g. The porous submicron spheres made of titanium dioxide nanoparticles prepared by the present invention are monodisperse and have a wide diameter distribution. The structure has a large specific surface area, high scattering ability for visible light and fast electron transmission inside the sphere. performance, so that the porous film has greater light scattering ability and dye adsorption ability. When applied in the fields of photocatalysis and photoelectric conversion, the utilization rate of light and the collection rate of electrons can be improved, and the dye-sensitized solar cells can obtain higher photoelectric conversion efficiency and save the amount of TiO 2 .
Description
技术领域 technical field
本发明属于化学化工和纳米材料的交叉领域，确切地说是一种由二氧化钛纳米颗粒构成的多孔亚微米球及染料敏化太阳电池的分级多孔亚微米球的多孔薄膜电极的制备方法。The invention belongs to the interdisciplinary fields of chemistry and nanomaterials, and specifically relates to a method for preparing porous submicron spheres composed of titanium dioxide nanoparticles and a porous film electrode of hierarchical porous submicron spheres for dye-sensitized solar cells.
背景技术 Background technique
近年来，纳米材料发展快速，由于纳米粒子具有表面效应、量子效应、小尺寸效应、宏观量子隧道效应等特性，从而在电学、光学、力学、磁学等方面表现出不同于一般宏观材料的显著特征。In recent years, nanomaterials have developed rapidly. Due to the characteristics of nanoparticles such as surface effects, quantum effects, small size effects, and macroscopic quantum tunneling effects, they exhibit significant differences from general macroscopic materials in terms of electricity, optics, mechanics, and magnetism. feature.
二氧化钛主要的晶型：锐钛矿型、金红石型和板钛矿型。金红石型比锐钛矿型稳定而致密，有较高的硬度、密度、介电常数及折射率，其遮盖力和着色力也较高。而锐钛矿型在可见光短波部分的反射率比金红石型高，带蓝色色调，并且对紫外线的吸收能力比金红石型低，光催化活性比金红石型高。The main crystal forms of titanium dioxide are anatase, rutile and brookite. The rutile type is more stable and dense than the anatase type, and has higher hardness, density, dielectric constant and refractive index, and its hiding power and tinting power are also higher. The reflectance of anatase in the short-wave part of visible light is higher than that of rutile, with a blue hue, and its absorption ability to ultraviolet rays is lower than that of rutile, and its photocatalytic activity is higher than that of rutile.
目前报道的纳米二氧化钛的制备方法主要有溶胶凝胶法、水热法、微乳液法、溶剂热法、化学气相沉积法、模板法、阳极氧化法等等。二氧化钛大部分为单独的纳米颗粒、纳米片、一维纳米结构（纳米棒、纳米管、纳米带等）和由纳米材料组成的三维分级结构。二氧化钛由于有特殊光电性能（较好的能带、化学稳定性等等），在光催化、光电领域有着广泛的应用，但这些结构很难同时具有大比表面积、高光散射和较快的电子传输路径，限制了器件性能的提高。而由纳米颗粒、纳米棒或者纳米管构成多级结构就有可能同时具有大比表面积、高光散射和较快的电子传输路径等特性。本发明采用溶胶凝胶法合成由纳米颗粒构成的分级多孔亚微米球，具有较大比表面积、对可见光具有较高散射和在球内部较快的电子传输路径，使得此多孔亚微米球在光催化、光电领域有较大的应用前景。The preparation methods of nano-titanium dioxide reported so far mainly include sol-gel method, hydrothermal method, microemulsion method, solvothermal method, chemical vapor deposition method, template method, anodic oxidation method and so on. Titanium dioxide is mostly individual nanoparticles, nanosheets, one-dimensional nanostructures (nanorods, nanotubes, nanobelts, etc.) and three-dimensional hierarchical structures composed of nanomaterials. Due to its special photoelectric properties (better energy band, chemical stability, etc.), titanium dioxide has been widely used in photocatalysis and photoelectric fields, but it is difficult for these structures to have large specific surface area, high light scattering and fast electron transport at the same time. path, which limits the improvement of device performance. However, the hierarchical structure composed of nanoparticles, nanorods or nanotubes may have the characteristics of large specific surface area, high light scattering and fast electron transport path at the same time. The present invention adopts the sol-gel method to synthesize hierarchical porous submicron spheres composed of nanoparticles, which have a larger specific surface area, higher scattering of visible light and faster electron transmission paths inside the spheres, so that the porous submicron spheres can withstand light Catalysis and optoelectronics have great application prospects.
而二氧化钛多孔薄膜电极是染料敏化太阳电池的重要组成部分，其利用有机光敏功能分子与半导体纳米材料结合的复合体系对太阳光进行光电转换，它综合了有机和无机光电功能材料的特点：利用有机光敏染料高效采集可见光的性能，半导体材料的快速电荷转移与分离优势，结合纳晶半导体薄膜的多孔性和高比表面积，充分利用有机分子的设计灵活性以及半导体纳米材料不同于体材料的一些新特性。The titanium dioxide porous film electrode is an important part of the dye-sensitized solar cell, which uses a composite system combining organic photosensitive functional molecules and semiconductor nanomaterials to photoelectrically convert sunlight. It combines the characteristics of organic and inorganic photoelectric functional materials: using The performance of organic photosensitive dyes in efficiently collecting visible light, the advantages of fast charge transfer and separation of semiconductor materials, combined with the porosity and high specific surface area of nanocrystalline semiconductor films, fully utilize the design flexibility of organic molecules and some of the differences between semiconductor nanomaterials and bulk materials. new features.
在染料敏化太阳电池中应用较好的染料敏化剂是Ru的联吡啶类配合物，这种染料有很宽的可见光谱吸收范围，其中400 nm～600 nm可见光范围的单色光量子效率超过80%。而传统的纳米多孔薄膜由纳米颗粒构成，在可见光谱范围的光散射很弱，光在薄膜中为直线传播，光程短，导致在染料敏化太阳电池中对光的利用较低。因此，染料敏化太阳电池对太阳光的有限利用制约了其光电转化效率的进一步提高。The better dye sensitizer used in dye-sensitized solar cells is the bipyridine complex of Ru. This dye has a wide range of visible spectrum absorption, and the monochromatic light quantum efficiency in the visible range of 400 nm to 600 nm exceeds 80%. However, the traditional nanoporous film is composed of nanoparticles, and the light scattering in the visible spectrum range is very weak. The light travels in a straight line in the film, and the optical path is short, resulting in low utilization of light in dye-sensitized solar cells. Therefore, the limited utilization of sunlight by dye-sensitized solar cells restricts the further improvement of its photoelectric conversion efficiency.
利用亚微米球有效地提高光散射，在薄膜中提高光程，更有效激发染料产生光电子，提高光的利用率，从而提高电池的光电性能。亚微米球在可见光谱区能有效地散射光，例如4μm厚的由亚微米球组成的多孔薄膜在400～800nm间的反射率为50%左右。根据Mie原理计算和实验证明，直径为250～400nm的纳米大颗粒在薄膜中作为散射中心提高光的利用率；直径300～400nm的纳米大颗粒在约20nm纳米颗粒薄膜表面形成散射层，将透过损失的光部分散射回染料敏化层从而提高电池对光的利用率。然而这些大颗粒表面平滑，比表面积低，吸附染料的量非常少，作为光散射中心的大颗粒在薄膜中的含量越高散射效率越好，染料吸附就越少，这严重影响光的利用率。同时这样的大颗粒的加入使得薄膜TiO2的用量明显提高，电池的成本相应上升。为了克服这个问题，近年来，分级亚微米球在染料敏化太阳电池的性能研究逐渐成为了焦点，已观察到了优异的光学新颖特征。例如，陈一兵等利用直径为830nm左右亚微米多孔球构成单层薄膜在染料敏化太阳电池中取得了10.7%的光电转换效率，该薄膜不仅能吸附大量的染料，而且能有效地散射光和有利于电解液的传输。The use of submicron spheres effectively increases light scattering, increases the optical path in the film, more effectively excites the dye to generate photoelectrons, and improves the utilization rate of light, thereby improving the photoelectric performance of the battery. Submicron spheres can effectively scatter light in the visible spectrum region. For example, a 4μm thick porous film composed of submicron spheres has a reflectivity of about 50% between 400 and 800nm. Calculations and experiments based on the Mie principle have proved that large nanoparticles with a diameter of 250-400nm act as scattering centers in the film to improve light utilization; large nanoparticles with a diameter of 300-400nm form a scattering layer on the surface of a nanoparticle film with a diameter of about 20nm. Part of the lost light is scattered back to the dye-sensitized layer to improve the utilization of light by the cell. However, the surface of these large particles is smooth, the specific surface area is low, and the amount of dye adsorption is very small. The higher the content of large particles as light scattering centers in the film, the better the scattering efficiency and the less dye adsorption, which seriously affects the light utilization. . At the same time, the addition of such large particles significantly increases the amount of thin film TiO 2 , and the cost of the battery increases accordingly. To overcome this problem, in recent years, the research on the performance of hierarchical submicron spheres in dye-sensitized solar cells has gradually become the focus, and excellent optical novel features have been observed. For example, Chen Yibing and others have achieved a photoelectric conversion efficiency of 10.7% in a dye-sensitized solar cell by using submicron porous spheres with a diameter of about 830nm to form a single-layer film. The film can not only absorb a large amount of dyes, but also effectively scatter light and effectively Facilitate the transport of electrolyte.
综上所述，传统的纳米颗粒多孔薄膜由于光散射很弱，影响了电池的光电转化效率。TiO2纳米颗粒构成的宽直径分布亚微米多孔球拥有较大的比表面积来吸附染料，有效的散射光提高光的利用，则提高电池的光电流；在薄膜中亚微米球之间存在较大的空隙有利于电解质的扩散，从而提高染料敏化太阳电池的光电转换效率。因此，开发性能优良的光阳极材料，提高染料敏化太阳电池的光电性能具有重要的实用价值。To sum up, the traditional nanoparticle porous film has weak light scattering, which affects the photoelectric conversion efficiency of the battery. The wide-diameter distribution submicron porous spheres composed of TiO 2 nanoparticles have a large specific surface area to adsorb dyes, effectively scatter light to improve light utilization, and increase the photocurrent of the battery; there is a large gap between the submicron spheres in the film. The voids are conducive to the diffusion of electrolyte, thereby improving the photoelectric conversion efficiency of dye-sensitized solar cells. Therefore, it is of great practical value to develop photoanode materials with excellent performance and improve the photoelectric performance of dye-sensitized solar cells.
发明内容 Contents of the invention
本发明的目的在于提供一种由二氧化钛纳米颗粒构成的多孔亚微米球以及高效便捷且可以获得由二氧化钛纳米颗粒构成的多孔亚微米球的制备方法，使得这结构同时具有大的比表面积、对可见光具有较高散射和在球内部较快的电子传输路径；以及提供一种该分级多孔亚微米球组成的薄膜电极的制备方法，它既解决了在染料敏化太阳电池中大颗粒比表面积低造成染料吸附量少的问题，又可以有效地散射光延长光程提高光的利用率，还有利于电解质的扩散，使电池最大程度地利用太阳光，提高电池的光电转换效率。The object of the present invention is to provide a porous submicron sphere composed of titanium dioxide nanoparticles and an efficient and convenient method for preparing porous submicron spheres composed of titanium dioxide nanoparticles, so that the structure has a large specific surface area and is sensitive to visible light. Has higher scattering and faster electron transport path inside the sphere; and provides a method for preparing a film electrode composed of the hierarchical porous submicron sphere, which not only solves the problem of low specific surface area of large particles in dye-sensitized solar cells The problem of less dye adsorption can effectively scatter light and extend the optical path to improve the utilization rate of light, and it is also conducive to the diffusion of electrolyte, so that the battery can maximize the use of sunlight and improve the photoelectric conversion efficiency of the battery.
上述目的通过以下方案实现：The above purpose is achieved through the following schemes:
多孔亚微米球是由纳米TiO2颗粒构成的，具有多孔结构，孔径在5～50 nm，纳米TiO2颗粒的粒径在10～100 nm，亚微米球的直径在150～1000 nm之间，BET比表面积在80～200 m2/g之间。Porous submicron spheres are composed of nano- TiO2 particles with a porous structure, the pore size is 5-50 nm, the particle size of nano- TiO2 particles is 10-100 nm, and the diameter of sub-micron spheres is between 150-1000 nm. The BET specific surface area is between 80 and 200 m 2 /g.
所述的多孔亚微米球制备方法，包括以下步骤：The method for preparing porous submicron spheres comprises the following steps:
(1)、在保护气体氛围中将钛酸四异丙酯或其他钛酸酯类溶于含有少量水和氯化钾的乙醇溶液中，在搅拌条件下缓慢水解生长成无定型亚微米球，此球没有结晶相，内部密实，表面平滑，得无定型亚微米球悬浮液；(1) Dissolve tetraisopropyl titanate or other titanates in an ethanol solution containing a small amount of water and potassium chloride in a protective gas atmosphere, and slowly hydrolyze and grow into amorphous submicron spheres under stirring conditions, The ball has no crystalline phase, the interior is dense, the surface is smooth, and the suspension of amorphous submicron balls is obtained;
(2)、将所得无定型亚微米球悬浮液离心或真空抽虑，收集白色沉淀，再用水和酒精多次洗涤，去除氯化钾，得无定型的亚微米球；(2), centrifuging or vacuum filtering the obtained amorphous submicron sphere suspension, collecting the white precipitate, then washing with water and alcohol multiple times, removing potassium chloride, and obtaining amorphous submicron spheres;
(3)、将所得无定型的亚微米球择下列方法之一进行热处理：(3), heat-treat the resulting amorphous submicron spheres by one of the following methods:
(a)将无定型亚微米球分散在含氨的水和酒精的混合溶液中，调节PH＞2，其体积比为（2～7）∶1，不断搅拌形成溶胶，将此溶胶在120～180℃热处理10～30小时，在这条件下，热处理后得到亚微米球为锐钛矿型；(a) Disperse the amorphous submicron spheres in the mixed solution of ammonia-containing water and alcohol, adjust the pH>2, and the volume ratio is (2-7):1, and continuously stir to form a sol. Heat treatment at 180°C for 10 to 30 hours. Under this condition, the submicron spheres obtained after heat treatment are anatase;
(b)将无定型亚微米球分散在硝酸的水溶液中，不断搅拌直至成为溶胶，将溶胶在200～250℃热处理20～40小时，其中CHNO3≥0.5mol/L，在这条件下，热处理后得到亚微米球为金红石型；(b) Disperse the amorphous submicron spheres in the aqueous solution of nitric acid, stir continuously until it becomes a sol, and heat-treat the sol at 200-250°C for 20-40 hours, wherein CHNO3 ≥ 0.5mol/L, under this condition, heat-treat The obtained submicron spheres are rutile type;
(c)将无定型亚微米球分散在硝酸的水溶液中，不断搅拌直至成为溶胶，将溶胶在180～220℃热处理10～20小时，其中0.01mol/L≤CHNO3＜0.5mol/L在这条件下，热处理后得到亚微米球为金红石和锐钛矿型的复合相；(c) Disperse the amorphous submicron spheres in an aqueous solution of nitric acid, stir continuously until it becomes a sol, and heat-treat the sol at 180-220°C for 10-20 hours, wherein 0.01mol/ L≤CHNO3 <0.5mol/L Under the same conditions, the submicron spheres obtained after heat treatment are composite phases of rutile and anatase;
将得到的亚微米球再通过离心、真空抽虑除去溶剂、以去离子水和无水酒精反复洗涤多次，在60℃左右的温度下干燥后通过研磨得到白色粉体产品，或者直接分散在无水酒精等溶剂中。The obtained submicron spheres are then centrifuged and vacuum filtered to remove the solvent, washed repeatedly with deionized water and absolute alcohol, dried at a temperature of about 60°C, and then ground to obtain a white powder product, or directly dispersed in In solvents such as absolute alcohol.
步骤(1)所述的水是去离子水或蒸馏水，乙醇为无水乙醇，水和乙醇加入量的体积比为1∶（100～500），氯化钾的含量为1×10-1～8×10-1 mol/L，保护气体为氮气等惰性气体，反应温度在0～100℃之间，搅拌速度200～700rpm，反应时间为2～24小时。The water in step (1) is deionized water or distilled water, the ethanol is absolute ethanol, the volume ratio of water and ethanol is 1: (100-500), and the content of potassium chloride is 1×10 -1 -1 8×10 -1 mol/L, the protective gas is an inert gas such as nitrogen, the reaction temperature is between 0-100°C, the stirring speed is 200-700rpm, and the reaction time is 2-24 hours.
步骤（2）所述的洗涤去除氯化钾，通过用ρ(AgNO3) = 0.8～1.2g/L的酸性硝酸银溶液进行卤素检查，当无卤素离子反应时即可结束洗涤。Potassium chloride is removed by washing in step (2), and halogen inspection is carried out by using an acidic silver nitrate solution of ρ(AgNO 3 ) = 0.8-1.2g/L, and the washing can be ended when no halogen ion reacts.
一种利用多孔亚微米球制备多孔薄膜电极的方法，包括以下步骤：A method for preparing a porous film electrode by using porous submicron spheres, comprising the following steps:
（1）、多孔亚微米球的浆料制备：将一定量的多孔亚微米球分散在酒精、松油醇和乙基纤维素形成的混合溶液中，酒精、松油醇和乙基纤维素质量比为1:（1～8）:（1～10），经过充分分散，通过24小时左右的搅拌和2小时左右的超声处理，使得多孔纳米球均匀的分散在混合溶液中，再经过真空旋蒸处理，除去酒精，形成粘稠的适合丝网印刷、刮涂或旋涂的浆料；(1) Slurry preparation of porous submicron spheres: Disperse a certain amount of porous submicron spheres in a mixed solution of alcohol, terpineol and ethyl cellulose, the mass ratio of alcohol, terpineol and ethyl cellulose is 1: (1~8): (1~10), after fully dispersed, through stirring for about 24 hours and ultrasonic treatment for about 2 hours, the porous nanospheres are evenly dispersed in the mixed solution, and then vacuum rotary evaporation treatment , remove the alcohol to form a viscous slurry suitable for screen printing, scrape coating or spin coating;
（2）、多孔薄膜电极的制备：将步骤（1）所得的浆料通过丝网印刷、刮涂或旋涂等方式在导电玻璃基底上制备一层膜厚均匀的薄膜，将薄膜在400～550℃烧结30分钟左右，自然冷却形成多孔薄膜，即得产品。(2) Preparation of porous thin film electrodes: Prepare a thin film with uniform film thickness on the conductive glass substrate by screen printing, scraping or spin coating the slurry obtained in step (1), and place the film at 400- Sinter at 550°C for about 30 minutes, and cool naturally to form a porous film to obtain the product.
步骤（1）所述的酒精、松油醇和乙基纤维素的质量比更优选为1：（1～4）：（1～5）。The mass ratio of alcohol, terpineol and ethyl cellulose in step (1) is more preferably 1:(1-4):(1-5).
该多孔薄膜电极由全部或部分由分级多孔亚微米球组成。The porous thin film electrode is composed entirely or partly of hierarchically porous submicron spheres.
本发明的原理为：Principle of the present invention is:
采用溶胶凝胶法，以钛酸四异丙酯或其他钛酸酯类作为钛源，在乙醇溶液中，用氯化钾控制水解速度，用氨水和硝酸控制水热处理时溶液的PH值；在室温、搅拌的条件下同时在氮气气氛中，将钛酸四异丙酯或其他钛酸酯类滴加到含有少量水和氯化钾的乙醇溶液中，缓慢水解，乙醇作为一种抑制剂，能与钛酸四异丙酯发生醇解，延缓水解的过程；氯化钾等盐类控制水解后纳米颗粒的聚集及控制亚微米球的直径，同时阴离子外层容易形成水的外壳结构使得与钛酸四异丙酯水解的水含量减少，经过一段时间的反应，无定型的亚微米球成型。将该无定型的实心的亚微米球分散在一定PH值的水溶液中，经过热处理，得到高结晶度的氧化钛纳米颗粒构成的多孔亚微米球。Using sol-gel method, using tetraisopropyl titanate or other titanate as titanium source, in ethanol solution, using potassium chloride to control the hydrolysis rate, and using ammonia and nitric acid to control the pH value of the solution during hydrothermal treatment; Add tetraisopropyl titanate or other titanate esters dropwise to an ethanol solution containing a small amount of water and potassium chloride in a nitrogen atmosphere under room temperature and stirring, and slowly hydrolyze. Ethanol acts as an inhibitor. It can undergo alcoholysis with tetraisopropyl titanate to delay the process of hydrolysis; salts such as potassium chloride can control the aggregation of nanoparticles after hydrolysis and control the diameter of submicron spheres, and the outer layer of anions can easily form a water shell structure, making it compatible with The water content of the hydrolysis of tetraisopropyl titanate is reduced, and after a period of reaction, amorphous submicron spheres are formed. Disperse the amorphous solid submicron spheres in an aqueous solution with a certain pH value, and undergo heat treatment to obtain porous submicron spheres composed of titanium oxide nanoparticles with high crystallinity.
本发明的有益效果为：The beneficial effects of the present invention are:
1、本发明制备的由二氧化钛纳米颗粒构成的多孔亚微米球，此球成单分散、宽直径分布，该结构同时具有大的比表面积、对可见光具有较高散射和在球内部较快的电子传输路径。在光催化、光电领域应用时，提高光的利用率、电子的收集率；该方法不需要模板，不需要特殊设备，操作简单，成本低，制备过程温和，生产周期短。1. The porous submicron spheres made of titanium dioxide nanoparticles prepared by the present invention are monodisperse and have a wide diameter distribution. The structure has a large specific surface area, high scattering of visible light and faster electrons inside the sphere. transfer path. When applied in the field of photocatalysis and photoelectricity, the utilization rate of light and the collection rate of electrons are improved; the method does not require a template, does not require special equipment, is simple to operate, low in cost, mild in the preparation process, and short in production cycle.
2、本发明TiO2锐钛矿纳米颗粒构成的宽直径分布亚微米多孔球浆料，制备成光阳极，用于染料敏化太阳电池中，在不牺牲染料吸附量的情况下，有效的散射光提高光的利用率，且有利于电解质在薄膜中的传输，提高光电流，从而提高电池的光电转换效率，使得电池的效率超过10%。2. The wide-diameter distribution submicron porous spherical slurry composed of TiO2 anatase nanoparticles of the present invention is prepared as a photoanode for use in dye-sensitized solar cells, and can effectively scatter without sacrificing the amount of dye adsorption Light improves the utilization rate of light, facilitates the transmission of electrolyte in the film, increases the photocurrent, and thus improves the photoelectric conversion efficiency of the battery, making the efficiency of the battery exceed 10%.
3、本发明制得的薄膜具有较高的光反射率和很低的光透过率，具有较大的比表面积，如4μm厚的薄膜，在400～800nm的可见光区，反射率超过50%，而透过率小于5%。3. The film prepared by the present invention has high light reflectance and very low light transmittance, and has a large specific surface area, such as a 4 μm thick film, in the visible light region of 400-800nm, the reflectance exceeds 50% , while the transmittance is less than 5%.
附图说明： Description of drawings:
图1为本发明实施例1的由锐钛矿纳米颗粒构成的宽直径分布TiO2多孔亚微米球的FE-SEM图；Fig. 1 is the wide diameter distribution TiO that is made of anatase nanoparticle of the embodiment of the present invention 1 The FE-SEM figure of porous submicron sphere;
图2为本发明实施例1的由锐钛矿纳米颗粒构成的宽直径分布TiO2多孔亚微米球的TEM图；Fig. 2 is the wide diameter distribution TiO that is made of anatase nanoparticle according to the embodiment of the present invention 1 The TEM figure of porous submicron sphere;
图3为本发明实施例1的由锐钛矿纳米颗粒构成的宽直径分布TiO2多孔亚微米球的XRD图。Fig. 3 is an XRD pattern of the wide diameter distribution TiO 2 porous submicron spheres composed of anatase nanoparticles in Example 1 of the present invention.
图4为本发明实施例1的由丝网印刷制备的TiO2多孔亚微米球薄膜的FE-SEM图；Fig. 4 is the FE-SEM figure of the TiO2 porous submicron spherical film prepared by screen printing of the embodiment of the present invention 1;
图5为本发明实施例1的由丝网印刷制备的TiO2多孔亚微米球薄膜和传统的纳米颗粒薄膜的透过率；Fig. 5 is the TiO prepared by screen printing according to the embodiment of the present invention 2 The transmittance of the porous submicron spherical film and the traditional nanoparticle film;
图6为本发明实施例1的由丝网印刷制备的TiO2多孔亚微米球薄膜和传统的纳米颗粒薄膜的反射率。FIG. 6 shows the reflectance of the TiO 2 porous submicron spherical film and the traditional nanoparticle film prepared by screen printing in Example 1 of the present invention.
具体实施方式 Detailed ways
实施例1：Example 1:
参见图1、图2、图3、图4、图5、图6，在室温和氮气的气氛保护下，250ml的无水乙醇中加入2ml 0.1mol/L 的KCl溶液和2ml的去离子水，500rpm搅拌10分钟，然后将5ml的钛酸四异丙酯滴加在这混合溶液中，不断搅拌持续反应6小时，有白色沉淀产生，通过抽虑收集白色沉淀。然后用去离子水和酒精反复洗涤各5次，再将白色固体分散到含有3ml氨水的10ml乙醇和30ml水的混合溶液中，不断搅拌直至成为溶胶。再将此溶胶转移进高压釜中，在160℃条件下热处理25小时；通过洗涤和真空旋蒸除去水和氨，干燥研磨后收集到由二氧化钛纳米颗粒构成的宽直径分布多孔亚微米球粉末。See Figure 1, Figure 2, Figure 3, Figure 4, Figure 5, and Figure 6, at room temperature and under the protection of a nitrogen atmosphere, add 2ml of 0.1mol/L KCl solution and 2ml of deionized water to 250ml of absolute ethanol, Stir at 500rpm for 10 minutes, then add 5ml of tetraisopropyl titanate dropwise into the mixed solution, stir continuously and continue to react for 6 hours, a white precipitate is formed, and the white precipitate is collected by filtration. Then wash with deionized water and alcohol repeatedly 5 times each, then disperse the white solid into a mixed solution of 10ml ethanol and 30ml water containing 3ml ammonia water, and keep stirring until it becomes a sol. The sol was then transferred into an autoclave and heat-treated at 160°C for 25 hours; water and ammonia were removed by washing and vacuum rotary evaporation, and a porous submicron spherical powder with a wide diameter distribution composed of titanium dioxide nanoparticles was collected after drying and grinding.
将5g分级TiO2多孔亚微米球粉体分散到15ml无水酒精中，按一定的质量比加入松油醇和乙基纤维素，其与TiO2多孔亚微米球的质量比为WTiO2：W松油醇：W乙基纤维素=1：2：4，经过超声处理2小时，搅拌24小时，使原料分散均匀。再将均匀的混合溶液真空旋蒸，除去酒精，形成粘稠的适合丝网印刷的浆料。用丝网印刷制备不同膜厚的薄膜，在450℃烧结30分钟，随炉自然冷却，形成多孔薄膜，将薄膜和电极质、铂反电极用沙淋膜组装成电池器件。Disperse 5g of graded TiO 2 porous submicron sphere powder into 15ml of absolute alcohol, add terpineol and ethyl cellulose in a certain mass ratio, and its mass ratio to TiO 2 porous submicron spheres is W TiO 2 : W pine Oleyl alcohol : W ethyl cellulose = 1:2:4, ultrasonic treatment for 2 hours, stirring for 24 hours to make the raw materials evenly dispersed. Then the homogeneous mixed solution is vacuum-spun to remove alcohol to form a viscous slurry suitable for screen printing. Films with different film thicknesses were prepared by screen printing, sintered at 450°C for 30 minutes, and cooled naturally with the furnace to form a porous film. The film, electrode material, and platinum counter electrode were assembled into battery devices.
实施例2：Example 2:
在室温和氮气的气氛保护下，250ml的无水乙醇中加入2ml 0.1mol/L的KCl溶液和2ml的去离子水，500rpm搅拌10分钟，然后将5ml的钛酸四异丙酯滴加在这混合溶液中，不断搅拌持续反应6小时。白色沉淀生产，通过抽虑收集白色沉淀。然后用去离子水和酒精反复洗涤各5次，再将白色固体分散到PH值为0.1的HNO3水溶液中，不断搅拌直至成为溶胶。再将此溶胶转移进高压釜中，在180 ℃条件下热处理30小时。通过洗涤和真空旋蒸除去水和HNO3，将收集到的宽直径分布二氧化钛多孔亚微米球均匀分散到无水酒精中，待应用到其他领域。At room temperature and under the protection of a nitrogen atmosphere, 2ml of 0.1mol/L KCl solution and 2ml of deionized water were added to 250ml of absolute ethanol, stirred at 500rpm for 10 minutes, and then 5ml of tetraisopropyl titanate was added dropwise to the In the mixed solution, the reaction was continued for 6 hours with constant stirring. A white precipitate produced which was collected by suction filtration. Then wash with deionized water and alcohol repeatedly 5 times each, and then disperse the white solid into HNO 3 aqueous solution with a pH value of 0.1, and keep stirring until it becomes a sol. The sol was then transferred into an autoclave and heat-treated at 180°C for 30 hours. Water and HNO 3 are removed by washing and vacuum rotary evaporation, and the collected titanium dioxide porous submicron spheres with wide diameter distribution are evenly dispersed in absolute alcohol, to be applied to other fields.
将5g分级TiO2多孔亚微米球粉体分散到50ml无水酒精中，按一定的质量比加入松油醇和乙基纤维素，其与TiO2多孔亚微米球的质量比为WTiO2：W松油醇：W乙基纤维素=1：5：2，经过超声处理2小时，搅拌24小时，使原料分散均匀，形成粘稠的适合旋涂的浆料。用旋涂制备不同膜厚的薄膜，在450℃烧结30分钟，随炉自然冷却，形成多孔薄膜，将薄膜和电极质、铂反电极用沙淋膜组装成电池器件。Disperse 5g of graded TiO 2 porous submicron sphere powder into 50ml of absolute alcohol, add terpineol and ethyl cellulose in a certain mass ratio, and its mass ratio to TiO 2 porous submicron spheres is W TiO 2 : W pine Oleyl alcohol : W ethyl cellulose = 1:5:2, after ultrasonic treatment for 2 hours and stirring for 24 hours, the raw materials are dispersed evenly to form a viscous slurry suitable for spin coating. Films with different film thicknesses were prepared by spin coating, sintered at 450°C for 30 minutes, and cooled naturally with the furnace to form a porous film. The film, electrode material, and sand shower film for platinum counter electrode were assembled into a battery device.
实施例3：Example 3:
在室温和氮气的气氛保护下，250ml的无水乙醇中加入2ml 0.1mol/L的KCl溶液和2ml的去离子水，500rpm搅拌10分钟，然后将5ml的钛酸四异丙酯滴加在这混合溶液中，不断搅拌持续反应6小时。白色沉淀生产，通过抽虑收集白色沉淀。然后用去离子水和酒精反复洗涤各5次，再将白色固体分散到0.1mol/L的HNO3水溶液中，不断搅拌直至成为溶胶。再将此溶胶转移进高压釜中，在200℃条件下热处理15小时。通过洗涤和真空旋蒸除去水和HNO3，干燥研磨后收集到由二氧化钛纳米颗粒构成的宽直径分布多孔亚微米球粉末。At room temperature and under the protection of a nitrogen atmosphere, 2ml of 0.1mol/L KCl solution and 2ml of deionized water were added to 250ml of absolute ethanol, stirred at 500rpm for 10 minutes, and then 5ml of tetraisopropyl titanate was added dropwise to the In the mixed solution, the reaction was continued for 6 hours with constant stirring. A white precipitate produced which was collected by suction filtration. Then wash with deionized water and alcohol repeatedly 5 times each, and then disperse the white solid into 0.1mol/L HNO 3 aqueous solution, and keep stirring until it becomes a sol. The sol was then transferred into an autoclave and heat-treated at 200° C. for 15 hours. Water and HNO 3 were removed by washing and vacuum rotary evaporation, and porous submicron spherical powder with wide diameter distribution composed of titanium dioxide nanoparticles was collected after drying and grinding.
将5g分级TiO2多孔亚微米球粉体分散到20ml无水酒精中，按一定的质量比加入松油醇和乙基纤维素，其与TiO2多孔亚微米球的质量比为WTiO2：W松油醇：W乙基纤维素=1：1：3，经过超声处理2小时，搅拌24小时，使原料分散均匀。再将均匀的混合溶液真空旋蒸，除去酒精，形成粘稠的适合刮涂的浆料。用手术刀刮涂制备不同膜厚的薄膜，在450℃烧结30分钟，随炉自然冷却，形成多孔薄膜，将薄膜和电极质、铂反电极用沙淋膜组装成电池器件。Disperse 5g of graded TiO2 porous submicron sphere powder into 20ml of absolute alcohol, add terpineol and ethyl cellulose in a certain mass ratio, and its mass ratio to TiO2 porous submicron sphere is W TiO2 :W pine Oleyl alcohol : W ethyl cellulose = 1:1:3, ultrasonic treatment for 2 hours and stirring for 24 hours to make the raw materials evenly dispersed. Then the uniform mixed solution is vacuum-spun to remove alcohol to form a thick slurry suitable for scraping. Films with different thicknesses were prepared by scraping with a scalpel, sintered at 450°C for 30 minutes, and cooled naturally with the furnace to form a porous film. The film, electrode material, and platinum counter electrode were assembled into a battery device.
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