CN113736445B - Porous crystalline/amorphous titanium dioxide electrochromic material and preparation method and application thereof - Google Patents
Porous crystalline/amorphous titanium dioxide electrochromic material and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 226
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 32
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 17
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- -1 titanium alkoxide Chemical class 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 11
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Abstract
Description
技术领域technical field
本发明属于电致变色薄膜材料领域，具体涉及一种多孔晶态/非晶二氧化钛电致变色材料及其制备方法和应用。The invention belongs to the field of electrochromic thin film materials, in particular to a porous crystalline/amorphous titanium dioxide electrochromic material and a preparation method and application thereof.
背景技术Background technique
电致变色现象指的是材料的颜色在外界电场下发生可逆变化的现象。由于电致变色材料在隐身材料、智能变色薄膜等领域应用前景巨大，近年来越来越受到人们的重视。过渡金属氧化物是一种研究最广泛的电致变色材料，其中晶态二氧化钛被认为是一种很有前途的电致变色材料，具有化学稳定性、无毒性、环境友好和储量丰富等优点。然而，二氧化钛在光调制幅度、着色效率、阈值电压和响应时间等方面存在一些缺陷，因此，在电致变色应用中，二氧化钛经常作为“惰性模板”与其他电致变色材料结合使用。但在实际应用时，复合电极不能利用二氧化钛的光调制特性，包括波长和着色状态的调制；而且复合电极的合成意味着操作方法复杂，在商业使用上受到限制。因此，如何提高晶态二氧化钛的电致变色性能是领域内广泛关注的问题。Electrochromic phenomenon refers to the phenomenon that the color of a material changes reversibly under an external electric field. Due to the huge application prospects of electrochromic materials in stealth materials, smart color-changing films and other fields, people have paid more and more attention in recent years. Transition metal oxides are one of the most widely studied electrochromic materials, among which crystalline titanium dioxide is considered to be a promising electrochromic material with advantages such as chemical stability, non-toxicity, environmental friendliness, and abundant reserves. However, TiO2 has some drawbacks in terms of light modulation amplitude, coloring efficiency, threshold voltage, and response time. Therefore, in electrochromic applications, TiO2 is often used as an "inert template" in combination with other electrochromic materials. However, in practical application, composite electrodes cannot utilize the light modulation properties of TiO2, including modulation of wavelength and coloring state; and the synthesis of composite electrodes means complicated operation methods, which are limited in commercial use. Therefore, how to improve the electrochromic properties of crystalline titanium dioxide is a widely concerned issue in the field.
微观结构以及电极的结构和形态是决定电致变色材料性能的关键因素。从微观结构的角度来看，非晶态二氧化钛除了开放空间通道和自由空间外，还有更多的锂离子***点。因此，当锂离子***非晶态二氧化钛时，会导致钛原子周围的配位环境发生变化，这与晶态二氧化钛的配位环境不同。钛原子周围的配位环境的变化将导致二氧化钛的光吸收发生变化，从而产生不同的颜色(如白色、蓝色、绿色、黑色等)。然而，由于非晶态二氧化钛的结构不容易合成、化学稳定性不好且着色效率较低，因此对其电致变色特性的研究较少。而晶态氧化钛具有稳定的晶体结构，可以减小锂离子***引起的晶格畸变和膨胀，提高电致变色过程中的循环稳定性。但是只有非晶态和晶态氧化钛形成良好的界面接触才可以降低界面处锂离子的***势垒，从而提高电致变色性能。但是目前还没有人合成出界面接触良好的非晶/晶态复合氧化钛薄膜材料。从电极的结构和形态来看，多孔结构的薄膜具有较大的比表面积，增加了电极与电解质的接触面积，缩短了离子传输路径，缓解因锂离子***引起的晶格膨胀，从而改善了电极的电致变色性能。但多孔薄膜的制备普遍涉及到模板的制备与去除过程，方法复杂且成本较高。申请号为201910844815.0的发明专利通过二氧化硅微球为模板制备多孔二氧化钛材料，但是该专利涉及高温煅烧和氢氟酸刻蚀去除模板，方法复杂、不环保且不宜大面积推广。因此如何无模板制备出界面接触良好的具有多孔形貌的晶态/非晶二氧化钛复合材料来提高电致变色性能成为了目前国内外的研究重点。The microstructure as well as the structure and morphology of the electrodes are key factors that determine the performance of electrochromic materials. From the microstructural point of view, amorphous TiO2 has more Li-ion insertion points in addition to open space channels and free spaces. Therefore, when lithium ions are inserted into amorphous TiO2, it leads to a change in the coordination environment around the titanium atoms, which is different from that of crystalline TiO2. Changes in the coordination environment around the titanium atoms will lead to changes in the light absorption of titanium dioxide, resulting in different colors (such as white, blue, green, black, etc.). However, due to the structure of amorphous titania is not easy to synthesize, its chemical stability is not good, and its coloring efficiency is low, so its electrochromic properties are less studied. The crystalline titanium oxide has a stable crystal structure, which can reduce the lattice distortion and expansion caused by the insertion of lithium ions, and improve the cycle stability during the electrochromic process. However, only the formation of good interfacial contact between amorphous and crystalline titanium oxide can reduce the insertion barrier of lithium ions at the interface, thereby improving the electrochromic performance. However, no one has yet synthesized amorphous/crystalline composite titanium oxide thin film materials with good interfacial contact. From the structure and morphology of the electrode, the porous structure film has a larger specific surface area, which increases the contact area between the electrode and the electrolyte, shortens the ion transmission path, and relieves the lattice expansion caused by the insertion of lithium ions, thereby improving the electrode. electrochromic properties. However, the preparation of porous films generally involves the preparation and removal of templates, and the methods are complex and costly. The invention patent with the application number of 201910844815.0 uses silica microspheres as a template to prepare porous titania materials, but this patent involves high temperature calcination and hydrofluoric acid etching to remove the template, and the method is complex, not environmentally friendly, and not suitable for large-scale promotion. Therefore, how to prepare crystalline/amorphous titania composites with good interfacial contact and porous morphology without template to improve the electrochromic performance has become the current research focus at home and abroad.
发明内容SUMMARY OF THE INVENTION
本发明的目的是提供一种多孔晶态/非晶二氧化钛电致变色材料及其制备方法和应用。The purpose of the present invention is to provide a porous crystalline/amorphous titanium dioxide electrochromic material and its preparation method and application.
首先，根据本发明的一方面，本发明提供了一种多孔晶态/非晶二氧化钛电致变色材料，所述多孔晶态/非晶二氧化钛电致变色材料是通过配制钛源前驱体溶液并采用溶剂热法使晶态二氧化钛和非晶二氧化钛形成多孔混晶结构并沉积在FTO导电玻璃基底上制得。First, according to an aspect of the present invention, the present invention provides a porous crystalline/amorphous titanium dioxide electrochromic material, the porous crystalline/amorphous titanium dioxide electrochromic material is prepared by preparing a titanium source precursor solution and using The solvothermal method makes crystalline titania and amorphous titania form porous mixed crystal structure and deposit them on FTO conductive glass substrate.
优选地，本发明的多孔晶态/非晶二氧化钛电致变色材料，其中，钛源为氟钛酸铵、钛酸四丁酯、异丙醇钛的混合物；环己醇的含量为50ml，氟钛酸铵、钛酸四丁酯、异丙醇钛和去离子水的含量范围分别为0.198-0.99g、0.85-3.4g、0.71-2.84g、25-100μL，得到的非晶二氧化钛和晶态二氧化钛相互之间具有良好的界面接触，形成混晶结构，在FTO导电玻璃基底上得到致密、均匀、透明的多孔晶态/非晶二氧化钛电致变色材料。Preferably, in the porous crystalline/amorphous titanium dioxide electrochromic material of the present invention, the titanium source is a mixture of ammonium fluorotitanate, tetrabutyl titanate and titanium isopropoxide; the content of cyclohexanol is 50ml, and the fluorine The content ranges of ammonium titanate, tetrabutyl titanate, titanium isopropoxide and deionized water are 0.198-0.99g, 0.85-3.4g, 0.71-2.84g, 25-100μL, respectively, and the obtained amorphous titanium dioxide and crystalline Titanium dioxide has good interfacial contact with each other to form a mixed crystal structure, and a dense, uniform and transparent porous crystalline/amorphous titanium dioxide electrochromic material is obtained on the FTO conductive glass substrate.
优选地，上述多孔晶态/非晶二氧化钛电致变色材料经下述步骤制备而成：Preferably, the above-mentioned porous crystalline/amorphous titanium dioxide electrochromic material is prepared through the following steps:
(1)FTO导电玻璃基底表面清洗：将FTO导电玻璃基底依次置于丙酮、乙醇、去离子水中，分别进行超声清洗8-12min，超声清洗后的FTO导电玻璃基底置于滤纸上，采用红外灯烤干；(1) Surface cleaning of the FTO conductive glass substrate: Place the FTO conductive glass substrate in acetone, ethanol, and deionized water in sequence, and carry out ultrasonic cleaning for 8-12 minutes respectively. The ultrasonically cleaned FTO conductive glass substrate is placed on filter paper, and an infrared lamp is used. dry;
(2)配制钛源前驱体溶液：按配比将钛源和去离子水加入到环己醇中，搅拌溶解后得到钛源前驱体溶液；其中，钛源为氟钛酸铵、钛酸四丁酯、异丙醇钛的混合物；环己醇的含量为50ml，氟钛酸铵、钛酸四丁酯、异丙醇钛和去离子水的含量分别为0.198-0.99g、0.85-3.4g、0.71-2.84g、25-100μL；(2) Preparation of titanium source precursor solution: adding titanium source and deionized water into cyclohexanol according to the ratio, stirring and dissolving to obtain a titanium source precursor solution; wherein, the titanium source is ammonium fluorotitanate, tetrabutyl titanate The mixture of ester and titanium isopropoxide; the content of cyclohexanol is 50ml, the content of ammonium fluorotitanate, tetrabutyl titanate, titanium isopropoxide and deionized water are 0.198-0.99g, 0.85-3.4g, 0.71-2.84g, 25-100μL;
(3)溶剂热反应：将步骤(2)配制的钛源前驱体溶液加入到高压反应釜中，将FTO导电玻璃基底的导电面朝下45°固定于钛源前驱体溶液中进行反应，反应温度为140-190℃，反应时间为120-420min，得到溶剂热反应产物；(3) Solvothermal reaction: adding the titanium source precursor solution prepared in step (2) into the autoclave, fixing the conductive surface of the FTO conductive glass substrate downward at 45° in the titanium source precursor solution for reaction, and reacting The temperature is 140-190°C, and the reaction time is 120-420min to obtain a solvothermal reaction product;
(4)干燥处理：采用去离子水对步骤(3)得到的溶剂热反应产物反复冲洗，冲洗后的溶剂热反应产物在鼓风干燥箱中干燥，干燥时温度为50-100℃，干燥时间为200-1000min，得到干燥处理产物；(4) Drying treatment: the solvothermal reaction product obtained in step (3) is repeatedly rinsed with deionized water, and the rinsed solvothermal reaction product is dried in a blast drying oven, and the temperature during drying is 50-100 ° C, and the drying time For 200-1000min, the dried product is obtained;
(5)热处理：将步骤(4)得到的干燥处理产物在空气中进行退火处理，其中，退火温度为200-450℃，退火时间为30-120min，升温速率为1-10℃/min，在FTO导电玻璃基底上得到致密均匀的透明薄膜，即为多孔晶态/非晶二氧化钛电致变色材料。(5) Heat treatment: the dried product obtained in step (4) is annealed in air, wherein the annealing temperature is 200-450° C., the annealing time is 30-120 min, and the heating rate is 1-10° C./min. A dense and uniform transparent film is obtained on the FTO conductive glass substrate, which is a porous crystalline/amorphous titanium dioxide electrochromic material.
进一步地，本发明多孔晶态/非晶二氧化钛电致变色材料具有优异的电致变色性能，可以在不同电压下实现透明和深绿色的迅速可逆转变。Further, the porous crystalline/amorphous titanium dioxide electrochromic material of the present invention has excellent electrochromic properties, and can achieve rapid and reversible transitions from transparent to dark green at different voltages.
进一步地，本发明涉及上述多孔晶态/非晶二氧化钛电致变色材料作为的应用。Further, the present invention relates to the application of the above-mentioned porous crystalline/amorphous titanium dioxide electrochromic material.
另一方面，本发明还提供了一种多孔晶态/非晶二氧化钛电致变色材料的制备方法，包括下述步骤：On the other hand, the present invention also provides a preparation method of porous crystalline/amorphous titanium dioxide electrochromic material, comprising the following steps:
(1)FTO导电玻璃基底表面清洗：将FTO导电玻璃基底依次置于丙酮、乙醇、去离子水中，分别进行超声清洗8-12min，超声清洗后的FTO导电玻璃基底置于滤纸上，采用红外灯烤干；(1) Surface cleaning of the FTO conductive glass substrate: Place the FTO conductive glass substrate in acetone, ethanol, and deionized water in sequence, and carry out ultrasonic cleaning for 8-12 minutes respectively. The ultrasonically cleaned FTO conductive glass substrate is placed on filter paper, and an infrared lamp is used. dry;
(2)配制前驱体溶液：按配比将钛源和去离子水加入到环己醇中，搅拌溶解后得到钛源前驱体溶液；其中，钛源为氟钛酸铵、钛酸四丁酯、异丙醇钛的混合物；环己醇的含量为50ml，加入的氟钛酸铵、钛酸四丁酯、异丙醇钛和去离子水的含量范围分别为0.198-0.99g、0.85-3.4g、0.71-2.84g、25-100μL；(2) Preparation of precursor solution: adding titanium source and deionized water into cyclohexanol according to the proportion, stirring and dissolving to obtain a titanium source precursor solution; wherein, the titanium source is ammonium fluorotitanate, tetrabutyl titanate, The mixture of titanium isopropoxide; the content of cyclohexanol is 50ml, and the content ranges of added ammonium fluorotitanate, tetrabutyl titanate, titanium isopropoxide and deionized water are 0.198-0.99g, 0.85-3.4g respectively , 0.71-2.84g, 25-100μL;
(3)溶剂热反应：将步骤(2)配制的钛源前驱体溶液加入到高压反应釜中，将FTO导电玻璃基底的导电面朝下45°固定于钛源前驱体溶液中进行反应，反应温度为140-190℃，反应时间为120-420min，得到溶剂热反应产物；(3) Solvothermal reaction: adding the titanium source precursor solution prepared in step (2) into the autoclave, fixing the conductive surface of the FTO conductive glass substrate downward at 45° in the titanium source precursor solution for reaction, and reacting The temperature is 140-190°C, and the reaction time is 120-420min to obtain a solvothermal reaction product;
(4)干燥处理：采用去离子水对步骤(3)得到的溶剂热反应产物反复冲洗，冲洗后的溶剂热反应产物在鼓风干燥箱中干燥，干燥时温度为50-100℃，干燥时间为200-1000min，得到干燥处理产物；(4) Drying treatment: the solvothermal reaction product obtained in step (3) is repeatedly rinsed with deionized water, and the rinsed solvothermal reaction product is dried in a blast drying oven, and the temperature during drying is 50-100 ° C, and the drying time For 200-1000min, the dried product is obtained;
(5)热处理：将步骤(4)得到的干燥处理产物在空气中进行退火处理，其中，退火温度为200-450℃，退火时间为30-120min，升温速率为1-10℃/min，在FTO导电玻璃基底上得到致密均匀的透明薄膜，即为多孔晶态/非晶二氧化钛电致变色材料。(5) Heat treatment: the dried product obtained in step (4) is annealed in air, wherein the annealing temperature is 200-450° C., the annealing time is 30-120 min, and the heating rate is 1-10° C./min. A dense and uniform transparent film is obtained on the FTO conductive glass substrate, which is a porous crystalline/amorphous titanium dioxide electrochromic material.
最后，本发明还涉及上述多孔晶态/非晶二氧化钛电致变色材料的制备方法在的应用。Finally, the present invention also relates to the application of the above-mentioned preparation method of the porous crystalline/amorphous titanium dioxide electrochromic material.
与现有技术相比，本发明的有益效果：Compared with the prior art, the beneficial effects of the present invention:
1、本发明在无模板的情况下制备出的氧化钛薄膜具有多孔结构，可有效提高电子传输速度和粒子扩散速率，加快反应动力学过程，大幅提高电致变色材料的响应速度和循环稳定性；1. The titanium oxide film prepared by the present invention without a template has a porous structure, which can effectively improve the electron transmission speed and particle diffusion rate, accelerate the reaction kinetic process, and greatly improve the response speed and cycle stability of the electrochromic material. ;
2、一步制备出的晶态/非晶二氧化钛的非晶/晶态界面具有良好的界面接触，有利于锂离子的传输。；2. The amorphous/crystalline interface of the crystalline/amorphous titanium dioxide prepared in one step has good interfacial contact, which is beneficial to the transport of lithium ions. ;
3、在粘度较大的环己醇添加微量水的溶剂环境下，多种钛源(氟钛酸铵、钛酸四丁酯、异丙醇钛)在反应过程中的联合作用对形成多孔非晶/晶态混晶氧化钛结构具有关键影响。3. In the solvent environment of cyclohexanol with high viscosity and a small amount of water added, the combined action of various titanium sources (ammonium fluorotitanate, tetrabutyl titanate, titanium isopropoxide) in the reaction process has a negative effect on the formation of porous non-porous The crystalline/crystalline mixed crystal titanium oxide structure has a key influence.
4、本发明多孔晶态/非晶二氧化钛电致变色材料制备方法简单、设备易操作、重复性好且生产周期短，工艺成本低，有利于大规模工业化生产。4. The porous crystalline/amorphous titanium dioxide electrochromic material of the present invention has the advantages of simple preparation method, easy operation of equipment, good repeatability, short production cycle and low process cost, which is favorable for large-scale industrial production.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明作进一步详细地说明。The present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments.
图1为实施例1所得多孔晶态/非晶二氧化钛电致变色材料的Raman表征图。1 is a Raman characterization diagram of the porous crystalline/amorphous titanium dioxide electrochromic material obtained in Example 1.
图2为实施例1所得多孔晶态/非晶二氧化钛电致变色材料的xps表征图。FIG. 2 is an xps characterization diagram of the porous crystalline/amorphous titanium dioxide electrochromic material obtained in Example 1. FIG.
图3为本发明中实施例2所制备的多孔晶态/非晶二氧化钛电致变色材料的电镜扫描图；3 is a scanning electron microscope view of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 of the present invention;
图4为本发明中实施例2所制备的多孔晶态/非晶二氧化钛电致变色材料的高放大倍数下的电镜扫描图；Fig. 4 is the electron microscope scanning figure under the high magnification of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 of the present invention;
图5为本发明中实施例2所制备的多孔晶态/非晶二氧化钛电致变色材料多孔特征透射电镜形貌图；FIG. 5 is a TEM morphology diagram of porous features of porous crystalline/amorphous titanium dioxide electrochromic materials prepared in Example 2 of the present invention;
图6为本发明中实施例3所制备的多孔晶态/非晶二氧化钛电致变色材料透射电镜高分辨图；6 is a high-resolution TEM image of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 3 of the present invention;
图7为本发明中实施例3所制备的多孔晶态/非晶二氧化钛电致变色材料透射电镜高分辨图；7 is a high-resolution TEM image of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 3 of the present invention;
图8(a)、8(b)、8(c)分别为本发明中实施例3所制备的多孔晶态/非晶二氧化钛电致变色材料透射电镜暗场像、Ti原子和O原子的电子能谱图；Figures 8(a), 8(b), and 8(c) are the TEM images of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 3 of the present invention, the electrons of Ti atoms and O atoms, respectively. energy spectrum;
图9为本发明中实施例4所制备的多孔晶态/非晶二氧化钛电致变色材料动力学电致变色性能示意图。9 is a schematic diagram of kinetic electrochromic performance of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 4 of the present invention.
图10为本发明中实施例4所制备的多孔晶态/非晶二氧化钛电致变色材料不同外加电压下的可见和近红外透射光谱性能示意图。10 is a schematic diagram showing the visible and near-infrared transmission spectral properties of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 4 of the present invention under different applied voltages.
图11为本发明中实施例4所制备的多孔晶态/非晶二氧化钛电致变色材料不同外加电压下的吸收光谱示意图。11 is a schematic diagram of the absorption spectrum of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 4 of the present invention under different applied voltages.
图12为本发明中实施例4所制备的多孔晶态/非晶二氧化钛电致变色材料的着色效率示意图。12 is a schematic diagram of the coloring efficiency of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 4 of the present invention.
图13为本发明中实施例1所制备的多孔晶态/非晶二氧化钛电致变色材料动力学电致变色性能示意图。13 is a schematic diagram of the kinetic electrochromic performance of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 1 of the present invention.
图14为本发明中实施例1所制备的多孔晶态/非晶二氧化钛电致变色材料的着色效率示意图。14 is a schematic diagram of the coloring efficiency of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 1 of the present invention.
图15为本发明中实施例2所制备的多孔晶态/非晶二氧化钛电致变色材料动力学电致变色性能示意图。15 is a schematic diagram of kinetic electrochromic performance of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 of the present invention.
图16为本发明中实施例2所制备的多孔晶态/非晶二氧化钛电致变色材料的着色效率示意图。16 is a schematic diagram of the coloring efficiency of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 of the present invention.
具体实施方式Detailed ways
以下通过特定的具体实例详细描述本发明的实施方式，但是以下具体实施方式本质上仅是示例，本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。The embodiments of the present invention are described in detail below through specific specific examples, but the following specific embodiments are merely examples in nature, and the present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be Based on different viewpoints and applications, various modifications or changes can be made without departing from the spirit of the present invention.
除非另有指明，本发明中使用的所有技术和科学术语与本领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本领域技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the mastery of the prior art by those skilled in the art and the description of the present invention, methods, equipment, and materials similar to those described in the embodiments of the present invention can also be used or Any methods, devices and materials that are equivalent to the prior art to practice the present invention.
在本发明中，若非特指，所有的份、百分比均为重量单位；若无特别说明，所有的设备和原料均可从商业途径得到或是本行业常用的；下述实施例中的方法，如无特别说明，均为本领域的常规方法。In the present invention, unless otherwise specified, all parts and percentages are units by weight; unless otherwise specified, all equipment and raw materials can be obtained from commercial sources or commonly used in the industry; the methods in the following examples, Unless otherwise specified, it is a conventional method in the art.
实施例1Example 1
一种多孔晶态/非晶二氧化钛电致变色材料的制备方法，具体步骤如下：A preparation method of porous crystalline/amorphous titanium dioxide electrochromic material, the specific steps are as follows:
(1)FTO导电玻璃基底表面清洗：将FTO导电玻璃基底依次置于丙酮、乙醇、去离子水中，分别进行超声清洗8min，超声清洗后的FTO导电玻璃基底置于滤纸上，采用红外灯烤干；(1) Surface cleaning of the FTO conductive glass substrate: The FTO conductive glass substrate was placed in acetone, ethanol, and deionized water in sequence, and ultrasonically cleaned for 8 minutes, respectively. The ultrasonically cleaned FTO conductive glass substrate was placed on filter paper, and dried with an infrared lamp. ;
(2)配制前驱体溶液：将0.99g氟钛酸铵、0.85g钛酸四丁酯、0.71g异丙醇钛和25μL的去离子水加入到50ml环己醇中，搅拌溶解后得到钛源前驱体溶液；(2) Preparation of precursor solution: add 0.99 g of ammonium fluorotitanate, 0.85 g of tetrabutyl titanate, 0.71 g of titanium isopropoxide and 25 μL of deionized water to 50 ml of cyclohexanol, stir and dissolve to obtain a titanium source precursor solution;
(3)溶剂热反应：将步骤(2)配制的钛源前驱体溶液加入到高压反应釜中，将FTO导电玻璃基底的导电面朝下45°固定于钛源前驱体溶液中进行反应，反应温度为140℃，反应时间为120min，得到溶剂热反应产物；(3) Solvothermal reaction: adding the titanium source precursor solution prepared in step (2) into the autoclave, fixing the conductive surface of the FTO conductive glass substrate downward at 45° in the titanium source precursor solution for reaction, and reacting The temperature is 140°C, and the reaction time is 120min to obtain a solvothermal reaction product;
(4)干燥处理：采用去离子水对步骤(3)得到的溶剂热反应产物反复冲洗，冲洗后的溶剂热反应产物在鼓风干燥箱中干燥，干燥时温度为50℃，干燥时间为200min，得到干燥处理产物；(4) Drying treatment: the solvothermal reaction product obtained in step (3) is repeatedly rinsed with deionized water, and the rinsed solvothermal reaction product is dried in a blast drying oven, the temperature during drying is 50°C, and the drying time is 200min , to obtain the dried product;
(5)热处理：将步骤(4)得到的干燥处理产物在空气中进行退火处理，其中，退火温度为200℃，退火时间为30min，升温速率为1℃/min，在FTO导电玻璃基底上得到致密均匀的透明薄膜，即为多孔晶态/非晶二氧化钛电致变色材料。(5) Heat treatment: the dried product obtained in step (4) is annealed in air, wherein the annealing temperature is 200° C., the annealing time is 30 min, and the heating rate is 1° C./min, obtained on the FTO conductive glass substrate. The dense and uniform transparent film is a porous crystalline/amorphous titanium dioxide electrochromic material.
实施例2Example 2
一种多孔晶态/非晶二氧化钛电致变色材料的制备方法，具体步骤如下：A preparation method of porous crystalline/amorphous titanium dioxide electrochromic material, the specific steps are as follows:
(1)FTO导电玻璃基底表面清洗：将FTO导电玻璃基底依次置于丙酮、乙醇、去离子水中，分别进行超声清洗10min，超声清洗后的FTO导电玻璃基底置于滤纸上，采用红外灯烤干；(1) Surface cleaning of the FTO conductive glass substrate: The FTO conductive glass substrate was placed in acetone, ethanol and deionized water in sequence, and ultrasonically cleaned for 10 minutes respectively. The ultrasonically cleaned FTO conductive glass substrate was placed on filter paper, and baked with an infrared lamp. ;
(2)配制前驱体溶液：将0.78g氟钛酸铵、2.42g钛酸四丁酯、1.78g异丙醇钛和50μL的去离子水加入到50ml环己醇中，搅拌溶解后得到钛源前驱体溶液；(2) Preparation of precursor solution: 0.78g of ammonium fluorotitanate, 2.42g of tetrabutyl titanate, 1.78g of titanium isopropoxide and 50μL of deionized water were added to 50ml of cyclohexanol, and the titanium source was obtained after stirring and dissolving precursor solution;
(3)溶剂热反应：将步骤(2)配制的钛源前驱体溶液加入到高压反应釜中，将FTO导电玻璃基底的导电面朝下45°固定于钛源前驱体溶液中进行反应，反应温度为150℃，反应时间为280min，得到溶剂热反应产物；(3) Solvothermal reaction: adding the titanium source precursor solution prepared in step (2) into the autoclave, fixing the conductive surface of the FTO conductive glass substrate downward at 45° in the titanium source precursor solution for reaction, and reacting The temperature is 150°C, and the reaction time is 280min to obtain a solvothermal reaction product;
(4)干燥处理：采用去离子水对步骤(3)得到的溶剂热反应产物反复冲洗，冲洗后的溶剂热反应产物在鼓风干燥箱中干燥，干燥时温度为70℃，干燥时间为500min，得到干燥处理产物；(4) Drying treatment: the solvothermal reaction product obtained in step (3) was repeatedly rinsed with deionized water, and the rinsed solvothermal reaction product was dried in a blast drying oven, the temperature during drying was 70°C, and the drying time was 500min , to obtain the dried product;
(5)热处理：将步骤(4)得到的干燥处理产物在空气中进行退火处理，其中，退火温度为300℃，退火时间为60min，升温速率为5℃/min，在FTO导电玻璃基底上得到致密均匀的透明薄膜，即为多孔晶态/非晶二氧化钛电致变色材料。(5) Heat treatment: the dried product obtained in step (4) is annealed in air, wherein the annealing temperature is 300° C., the annealing time is 60 min, and the heating rate is 5° C./min, and obtained on the FTO conductive glass substrate The dense and uniform transparent film is a porous crystalline/amorphous titanium dioxide electrochromic material.
实施例3Example 3
一种多孔晶态/非晶二氧化钛电致变色材料的制备方法，具体步骤如下：A preparation method of porous crystalline/amorphous titanium dioxide electrochromic material, the specific steps are as follows:
(1)FTO导电玻璃基底表面清洗：将FTO导电玻璃基底依次置于丙酮、乙醇、去离子水中，分别进行超声清洗10min，超声清洗后的FTO导电玻璃基底置于滤纸上，采用红外灯烤干；(1) Surface cleaning of the FTO conductive glass substrate: The FTO conductive glass substrate was placed in acetone, ethanol and deionized water in sequence, and ultrasonically cleaned for 10 minutes respectively. The ultrasonically cleaned FTO conductive glass substrate was placed on filter paper, and baked with an infrared lamp. ;
(2)配制前驱体溶液：将0.23g氟钛酸铵、3.12g钛酸四丁酯、2.64g异丙醇钛和80μL的去离子水加入到50ml环己醇中，搅拌溶解后得到钛源前驱体溶液；(2) Preparation of precursor solution: 0.23g of ammonium fluorotitanate, 3.12g of tetrabutyl titanate, 2.64g of titanium isopropoxide and 80μL of deionized water were added to 50ml of cyclohexanol, and the titanium source was obtained after stirring and dissolving precursor solution;
(3)溶剂热反应：将步骤(2)配制的钛源前驱体溶液加入到高压反应釜中，将FTO导电玻璃基底的导电面朝下45°固定于钛源前驱体溶液中进行反应，反应温度为170℃，反应时间为400min，得到溶剂热反应产物；(3) Solvothermal reaction: adding the titanium source precursor solution prepared in step (2) into the autoclave, fixing the conductive surface of the FTO conductive glass substrate downward at 45° in the titanium source precursor solution for reaction, and reacting The temperature is 170°C, and the reaction time is 400min to obtain a solvothermal reaction product;
(4)干燥处理：采用去离子水对步骤(3)得到的溶剂热反应产物反复冲洗，冲洗后的溶剂热反应产物在鼓风干燥箱中干燥，干燥时温度为85℃，干燥时间为800min，得到干燥处理产物；(4) Drying treatment: the solvothermal reaction product obtained in step (3) is repeatedly rinsed with deionized water, and the rinsed solvothermal reaction product is dried in a blast drying oven, the temperature during drying is 85°C, and the drying time is 800min , to obtain the dried product;
(5)热处理：将步骤(4)得到的干燥处理产物在空气中进行退火处理，其中，退火温度为400℃，退火时间为100min，升温速率为8℃/min，在FTO导电玻璃基底上得到致密均匀的透明薄膜，即为多孔晶态/非晶二氧化钛电致变色材料。(5) Heat treatment: the dried product obtained in step (4) is annealed in air, wherein the annealing temperature is 400° C., the annealing time is 100 min, and the heating rate is 8° C./min, and obtained on the FTO conductive glass substrate The dense and uniform transparent film is a porous crystalline/amorphous titanium dioxide electrochromic material.
实施例4Example 4
一种多孔晶态/非晶二氧化钛电致变色材料的制备方法，具体步骤如下：A preparation method of porous crystalline/amorphous titanium dioxide electrochromic material, the specific steps are as follows:
(1)FTO导电玻璃基底表面清洗：将FTO导电玻璃基底依次置于丙酮、乙醇、去离子水中，分别进行超声清洗12min，超声清洗后的FTO导电玻璃基底置于滤纸上，采用红外灯烤干；(1) Surface cleaning of the FTO conductive glass substrate: The FTO conductive glass substrate was placed in acetone, ethanol, and deionized water in turn, and ultrasonically cleaned for 12 minutes, respectively. The ultrasonically cleaned FTO conductive glass substrate was placed on filter paper, and dried by infrared light. ;
(2)配制前驱体溶液：将0.198g氟钛酸铵、3.4g钛酸四丁酯、2.84g异丙醇钛和100μL的去离子水加入到50ml环己醇中，搅拌溶解后得到钛源前驱体溶液；(2) Preparation of precursor solution: 0.198g of ammonium fluorotitanate, 3.4g of tetrabutyl titanate, 2.84g of titanium isopropoxide and 100μL of deionized water were added to 50ml of cyclohexanol, stirred and dissolved to obtain a titanium source precursor solution;
(3)溶剂热反应：将步骤(2)配制的钛源前驱体溶液加入到高压反应釜中，将FTO导电玻璃基底的导电面朝下45°固定于钛源前驱体溶液中进行反应，反应温度为190℃，反应时间为420min，得到溶剂热反应产物；(3) Solvothermal reaction: adding the titanium source precursor solution prepared in step (2) into the autoclave, fixing the conductive surface of the FTO conductive glass substrate downward at 45° in the titanium source precursor solution for reaction, and reacting The temperature was 190°C and the reaction time was 420min to obtain a solvothermal reaction product;
(4)干燥处理：采用去离子水对步骤(3)得到的溶剂热反应产物反复冲洗，冲洗后的溶剂热反应产物在鼓风干燥箱中干燥，干燥时温度为100℃，干燥时间为1000min，得到干燥处理产物；(4) Drying treatment: the solvothermal reaction product obtained in step (3) was repeatedly rinsed with deionized water, and the rinsed solvothermal reaction product was dried in a blast drying oven, the temperature during drying was 100° C., and the drying time was 1000 min , to obtain the dried product;
(5)热处理：将步骤(4)得到的干燥处理产物在空气中进行退火处理，其中，退火温度为450℃，退火时间为120min，升温速率为10℃/min，在FTO导电玻璃基底上得到致密均匀的透明薄膜，即为多孔晶态/非晶二氧化钛电致变色材料。(5) Heat treatment: the dried product obtained in step (4) is annealed in air, wherein the annealing temperature is 450° C., the annealing time is 120 min, and the heating rate is 10° C./min, and obtained on the FTO conductive glass substrate The dense and uniform transparent film is a porous crystalline/amorphous titanium dioxide electrochromic material.
实施例5Example 5
采用显微共焦激光拉曼光谱仪(LabRAM HR Evolution)对实施例1制备的多孔晶态/非晶二氧化钛电致变色材料的多孔晶态/非晶二氧化钛的结构观察，如图1所示，实施例1制备的多孔晶态/非晶二氧化钛电致变色材料，拉曼光谱分别在大约150cm-1、400cm-1、515cm-1和638cm-1处表现出振动模式，代表锐钛矿结构的Eg、B1g、A1g+B1g和Eg模式。表明制备的二氧化钛薄膜的结构主要是锐钛矿结构，并且振动模式不明显代表了非晶氧化钛的存在。The structure of the porous crystalline/amorphous titanium dioxide of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 1 was observed by using a micro confocal laser Raman spectrometer (LabRAM HR Evolution). The porous crystalline/amorphous titania electrochromic material prepared in Example 1 exhibits vibrational modes at about 150 cm -1 , 400 cm -1 , 515 cm -1 and 638 cm -1 in Raman spectra, representing the E of the anatase structure. g , B 1g , A 1g +B 1g and E g modes. It is shown that the structure of the prepared TiO2 film is mainly anatase structure, and the vibration mode does not clearly represent the existence of amorphous TiO2.
采用X射线光电子能谱仪(ESCALAB250Xi)对实施例1制备的多孔晶态/非晶二氧化钛电致变色材料的多孔晶态/非晶二氧化钛薄膜的表面原子状态进行观察，如图2所示，实施例1制备的多孔晶态/非晶二氧化钛电致变色材料，在531eV处存在代表Ti-OH基团或水的峰，证明了薄膜存在非晶态氧化钛。The surface atomic state of the porous crystalline/amorphous titanium dioxide film of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 1 was observed by X-ray photoelectron spectroscopy (ESCALAB250Xi). The porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 1 has a peak representing Ti-OH group or water at 531 eV, which proves the existence of amorphous titanium oxide in the film.
采用SU-8200扫描电镜对实施例2制备的多孔晶态/非晶二氧化钛电致变色材料的多孔晶态/非晶二氧化钛的形貌进行观察，如图3和图4所示，实施例2制备的多孔晶态/非晶二氧化钛电致变色材料，氧化钛薄膜表面存在着不规则的多孔结构，促进了电解液的渗入，增加了电解液与薄膜的接触面积，可有效提高电子传输速度和粒子扩散速率，加快反应动力学过程，降低薄膜褪色电压，大幅提高电致变色材料的响应速度和循环稳定性。The morphology of porous crystalline/amorphous titanium dioxide of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 was observed by SU-8200 scanning electron microscope, as shown in Figures 3 and 4, prepared in Example 2 The porous crystalline/amorphous titanium dioxide electrochromic material has an irregular porous structure on the surface of the titanium oxide film, which promotes the infiltration of the electrolyte, increases the contact area between the electrolyte and the film, and can effectively improve the electron transport speed and particle size. The diffusion rate can be accelerated, the reaction kinetics can be accelerated, the film fading voltage can be reduced, and the response speed and cycle stability of electrochromic materials can be greatly improved.
采用场发射透射电子显微镜(JEM-2100F)对实施例2和实施例3制备的多孔晶态/非晶二氧化钛电致变色材料的多孔晶态/非晶二氧化钛薄膜的组织和晶格结构进行观察。如图5所示，实施例2制备的多孔晶态/非晶二氧化钛电致变色材料，呈明显的多孔结构，有利于其电致变色性能。The microstructure and lattice structure of the porous crystalline/amorphous titania thin films of the porous crystalline/amorphous titania electrochromic materials prepared in Examples 2 and 3 were observed by field emission transmission electron microscopy (JEM-2100F). As shown in FIG. 5 , the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 has an obvious porous structure, which is beneficial to its electrochromic performance.
如图6和图7所示，实施例3制备的多孔晶态/非晶二氧化钛电致变色材料，存在明显的晶态氧化钛和非晶态的区域，并且二者具有良好的界面接触。良好的界面接触作为离子通道，促进离子传输。这些界面区域也为电致变色反应的发生提供了一个活性部位，并降低了界面相界的活化能。低活化能导致锂离子在界面上的***率很高，使界面在某种程度上充当了"着色/漂白中心"。As shown in Figure 6 and Figure 7, the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 3 has obvious crystalline titanium oxide and amorphous regions, and the two have good interfacial contact. Good interfacial contacts act as ion channels, facilitating ion transport. These interfacial regions also provide an active site for the electrochromic reaction to take place and reduce the activation energy of the interfacial phase boundary. The low activation energy results in a high rate of lithium ion insertion at the interface, making the interface act as a "coloring/bleaching center" to some extent.
图8为实施例3制备的多孔晶态/非晶二氧化钛电致变色材料的能谱图。其中，透射电镜暗场像如图8(a)所示，Ti原子核O原子的电子能谱图分别如图8(b)和8(c)所示。可以观察到钛、氧原子均匀分布，无其它杂质存在。FIG. 8 is an energy spectrum diagram of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 3. FIG. Among them, the dark field image of transmission electron microscope is shown in Fig. 8(a), and the electron energy spectrum of O atom of Ti nucleus is shown in Fig. 8(b) and 8(c), respectively. It can be observed that titanium and oxygen atoms are uniformly distributed, and no other impurities exist.
按如下方式测试实施例1、实施例2和实施例4所得多孔晶态/非晶二氧化钛电致变色材料的动力学、可见和近红外透射(吸收)光谱、着色效率：通过使用电化学工作站(CHI760E)和紫外-可见-近红外分光光度计(UV-3600，日本)，在三电极***(FTO基底上的电致变色膜为工作电极，Ag/AgCl为参比电极，铂丝为对电极，1.0M LiClO4/PC溶液为电解质)中记录了样品的电化学和电致变色性能。为了确保光路畅通，参比电极和对电极被放置在工作电极的一侧。参考电极和对电极被放置在一侧。在-1.5V和+0.2V的电压下，在250至1650nm的波长范围内记录透射光谱。通过在700纳米处施加-1.5V(30秒)和+0.2V(30秒)的方波电压，记录动态光学透射率变化。并计算薄膜的着色效率。The kinetics, visible and near-infrared transmission (absorption) spectra, coloring efficiency of the porous crystalline/amorphous titanium dioxide electrochromic materials obtained in Example 1, Example 2, and Example 4 were tested as follows: by using an electrochemical workstation ( CHI760E) and UV-Vis-NIR spectrophotometer (UV-3600, Japan) in a three-electrode system (electrochromic film on FTO substrate as working electrode, Ag/AgCl as reference electrode, and platinum wire as counter electrode , 1.0 M LiClO 4 /PC solution as electrolyte), the electrochemical and electrochromic properties of the samples were recorded. To ensure an unobstructed optical path, the reference and counter electrodes were placed on one side of the working electrode. The reference and counter electrodes are placed on one side. Transmission spectra were recorded in the wavelength range from 250 to 1650 nm at voltages of -1.5V and +0.2V. Dynamic optical transmittance changes were recorded by applying square wave voltages of -1.5 V (30 sec) and +0.2 V (30 sec) at 700 nm. And calculate the tinting efficiency of the film.
如图9和图10所示，实施例4制备的多孔晶态/非晶二氧化钛电致变色材料材料的着褪色时间分别为15.2s和3.5s，700nm下的对比度为65.2％。As shown in Fig. 9 and Fig. 10 , the color-fading times of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 4 were 15.2s and 3.5s, respectively, and the contrast ratio at 700 nm was 65.2%.
如图11所示，实施例4制备的多孔晶态/非晶二氧化钛电致变色材料，彩色状态下的材料的吸收峰存在于可见光区的453nm和700nm处，因此材料的着色态呈绿色。非晶二氧化钛具有开放空间通道和自由空间和更多的锂离子***位点。因此，当锂离子***非晶态二氧化钛时，会导致钛原子周围的配位环境发生变化，从而导致二氧化钛的光吸收发生变化，从而产生深绿色区别于着色下的晶态氧化钛(蓝色)。而晶态氧化钛的存在可以减小离子***脱出引起的晶格畸变和膨胀，提高了电致变色过程中的循环稳定性。As shown in FIG. 11 , for the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 4, the absorption peaks of the material in the colored state exist at 453 nm and 700 nm in the visible light region, so the colored state of the material is green. Amorphous titania has open space channels and free spaces and more sites for Li ion insertion. Therefore, when lithium ions are inserted into amorphous titanium dioxide, it causes a change in the coordination environment around the titanium atoms, which results in a change in the light absorption of titanium dioxide, resulting in a dark green color that distinguishes it from crystalline titanium oxide (blue) in coloration . The existence of crystalline titanium oxide can reduce the lattice distortion and expansion caused by ion insertion and extraction, and improve the cycle stability during the electrochromic process.
如图12所示，实施例4制备的多孔晶态/非晶二氧化钛电致变色材料，着色效率为30.1cm2/C。As shown in FIG. 12 , the coloring efficiency of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 4 was 30.1 cm 2 /C.
如图13所示，实施例1制备的多孔晶态/非晶二氧化钛电致变色材料材料的着褪色时间分别为12.9s和2.4s，700nm下的对比度为55.6％。As shown in FIG. 13 , the coloring and fading times of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 1 were 12.9s and 2.4s, respectively, and the contrast ratio at 700 nm was 55.6%.
如图14所示，实施例1制备的多孔晶态/非晶二氧化钛电致变色材料，着色效率为28.3cm2/C。As shown in FIG. 14 , the coloring efficiency of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 1 was 28.3 cm 2 /C.
如图15所示，实施例2制备的多孔晶态/非晶二氧化钛电致变色材料材料的着褪色时间分别为18.3s和13.8s，700nm下的对比度为36.1％。As shown in FIG. 15 , the coloring and fading times of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 were 18.3s and 13.8s, respectively, and the contrast ratio at 700 nm was 36.1%.
如图16所示，实施例2制备的多孔晶态/非晶二氧化钛电致变色材料，着色效率为17.4cm2/C。As shown in FIG. 16 , the coloring efficiency of the porous crystalline/amorphous titanium dioxide electrochromic material prepared in Example 2 is 17.4 cm 2 /C.
以上所述的本发明实施方式，并不构成对本发明保护范围的限定。任何在本发明的精神和原则之内所作的修改、等同替换和改进等，均应包含在本发明的权利要求保护范围之内。The embodiments of the present invention described above do not limit the protection scope of the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.
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