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CN103172273A - Method for preparing nickel oxide electrochromic film by hydrothermal method - Google Patents

Method for preparing nickel oxide electrochromic film by hydrothermal method Download PDF

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CN103172273A
CN103172273A CN2013101282284A CN201310128228A CN103172273A CN 103172273 A CN103172273 A CN 103172273A CN 2013101282284 A CN2013101282284 A CN 2013101282284A CN 201310128228 A CN201310128228 A CN 201310128228A CN 103172273 A CN103172273 A CN 103172273A
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nickel oxide
film
hydrothermal
conductive glass
acetate tetrahydrate
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CN103172273B (en
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王宏志
马董云
李耀刚
张青红
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Donghua University
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Abstract

本发明涉及一种水热法制备氧化镍电致变色薄膜的方法,包括:将四水乙酸镍溶于乙醇和正丁醇的混合溶液中,溶解后滴加氨水,得到溶胶;将上述溶胶旋涂于FTO导电玻璃表面,干燥,得到带有晶种层的FTO导电玻璃;四水乙酸镍、尿素和溶剂混合,得反应溶液,然后将上述带有晶种层的FTO导电玻璃浸入反应溶液中,进行水热反应,在160-180℃条件下,保持6-12h,冷却至室温,清洗、烘干、煅烧,即得。本发明的制备方法简单,成本低,具有在玻璃表面制膜的产业应用可能性;本发明的纳米结构氧化镍薄膜是通过水热法直接生长在FTO导电玻璃的表面,氧化镍与基底有着较好的结合力,有利于电子传导,同时也提高了薄膜的电化学稳定性。

Figure 201310128228

The invention relates to a method for preparing a nickel oxide electrochromic film by a hydrothermal method, comprising: dissolving nickel acetate tetrahydrate in a mixed solution of ethanol and n-butanol, and adding ammonia water dropwise after dissolving to obtain a sol; spin coating the above sol On the surface of the FTO conductive glass, dry to obtain the FTO conductive glass with the seed layer; nickel acetate tetrahydrate, urea and solvent are mixed to obtain the reaction solution, and then the above-mentioned FTO conductive glass with the seed layer is immersed in the reaction solution, Carry out hydrothermal reaction, keep at 160-180°C for 6-12h, cool to room temperature, wash, dry and calcinate to obtain the product. The preparation method of the present invention is simple, and cost is low, has the industrial application possibility of forming film on glass surface; The nanostructure nickel oxide thin film of the present invention is directly grown on the surface of FTO conductive glass by hydrothermal method, and nickel oxide has relatively close contact with the substrate. Good binding force is conducive to electron conduction, and also improves the electrochemical stability of the film.

Figure 201310128228

Description

一种水热法制备氧化镍电致变色薄膜的方法A method for preparing nickel oxide electrochromic thin film by hydrothermal method

技术领域technical field

本发明属于电致变色薄膜的制备领域,特别涉及一种水热法制备氧化镍电致变色薄膜的方法。The invention belongs to the field of preparation of electrochromic thin films, in particular to a method for preparing nickel oxide electrochromic thin films by a hydrothermal method.

背景技术Background technique

电致变色是指材料在电场作用下产生稳定可逆变化的现象。当材料在电化学作用下发生电子与离子的注入与抽出,使其价态和化学组分发生变化,从而使材料的反射与透射性能改变,实现对外界热辐射和可见光的选择性透过或反射,亦可阻止内部能量(如热)的扩散,从而使建筑物、交通工具等设施在夏季保持凉爽和冬季保持温暖,减少能源的大量消耗。因此,电致变色玻璃或器件可以广泛地应用于建筑、航天、交通等各方面,对于节能、环保等方面具有重要意义。Electrochromism refers to the phenomenon that materials produce stable and reversible changes under the action of electric field. When the material is electrochemically injected and extracted with electrons and ions, its valence state and chemical composition change, so that the reflection and transmission properties of the material are changed, and the selective transmission or transmission of external thermal radiation and visible light is realized. Reflection can also prevent the diffusion of internal energy (such as heat), thereby keeping buildings, vehicles and other facilities cool in summer and warm in winter, reducing a large amount of energy consumption. Therefore, the electrochromic glass or device can be widely used in various aspects such as construction, aerospace, transportation, etc., and is of great significance for energy saving, environmental protection, and the like.

电致变色材料一般可分为阳极着色和阴极着色两类。NiO是极具代表性的阳极致色的电致变色材料,NiO薄膜透过率的可调范围主要在可见光区,可调范围较大,具有稳定的电致变色性能和长的使用寿命,而且能与WO3等阴极致色材料配合使用,组成互补式电致变色器件,是目前电致变色材料研究的热点。NiO电致变色薄膜最常用的制备方法有溅射、真空蒸镀、脉冲激光沉积、溶胶-凝胶技术、化学以及电化学沉积等。但上述方法或依赖于复杂的设备和工艺技术,难以制得大面积均匀的NiO薄膜;或制得的薄膜与基底的粘附力弱,循环稳定性差,难以满足实际应用需求。采用晶种辅助的水热法直接在导电玻璃基底上生长纳米结构的氧化镍电致变色薄膜不仅可以提高薄膜与基底之间的结合力,而且可以通过调节水热工艺参数实现对氧化镍微观结构的可控制备,此方法制备工艺简单,成本低,具有在玻璃表面制膜的产业应用可能性,有望突破现有电致变色薄膜材料的技术瓶颈,解决上述提到的问题,为实现电致变色玻璃的大规模产业化打下坚实的基础。Electrochromic materials can generally be divided into two categories: anodic coloring and cathodic coloring. NiO is a very representative anodic electrochromic material. The adjustable range of NiO film transmittance is mainly in the visible light region, and the adjustable range is large. It has stable electrochromic performance and long service life, and It can be used in conjunction with WO 3 and other cathochromic materials to form a complementary electrochromic device, which is a hot spot in the research of electrochromic materials at present. The most commonly used preparation methods of NiO electrochromic thin films are sputtering, vacuum evaporation, pulsed laser deposition, sol-gel technology, chemical and electrochemical deposition, etc. However, the above methods rely on complex equipment and process technology, making it difficult to produce large-area uniform NiO films; or the prepared films have weak adhesion to the substrate and poor cycle stability, making it difficult to meet the needs of practical applications. Direct growth of nanostructured nickel oxide electrochromic films on conductive glass substrates by the seed-assisted hydrothermal method can not only improve the bonding force between the film and the substrate, but also realize the modification of the nickel oxide microstructure by adjusting the hydrothermal process parameters. The controllable preparation of this method, the preparation process is simple, the cost is low, and it has the possibility of industrial application to form a film on the glass surface. The large-scale industrialization of color-changing glass has laid a solid foundation.

发明内容Contents of the invention

本发明所要解决的技术问题是提供一种水热法制备氧化镍电致变色薄膜的方法,该方法制备方法简单,成本低具有在玻璃表面制膜的产业应用可能性;本发明通过晶种辅助的水热法实现了氧化镍纳米结构薄膜在导电基底上可控制备,并通过调节水热工艺参数实现了对薄膜表面形貌的调控,从而有效地提高了薄膜的响应速度、着色效率;本发明的纳米结构氧化镍薄膜是通过水热法直接生长在FTO导电玻璃的表面,氧化镍与基底有着较好的结合力,有利于电子传导,同时也提高了薄膜的电化学稳定性。The technical problem to be solved by the present invention is to provide a method for preparing nickel oxide electrochromic thin film by hydrothermal method, which has simple preparation method, low cost and industrial application possibility of film formation on glass surface; The hydrothermal method realizes the controllable preparation of nickel oxide nanostructure film on the conductive substrate, and realizes the control of the surface morphology of the film by adjusting the hydrothermal process parameters, thereby effectively improving the response speed and coloring efficiency of the film; The invented nano-structured nickel oxide film is directly grown on the surface of FTO conductive glass by hydrothermal method. The nickel oxide has a good bonding force with the substrate, which is conducive to electron conduction and also improves the electrochemical stability of the film.

本发明的一种水热法制备氧化镍电致变色薄膜的方法,包括:A method for preparing a nickel oxide electrochromic film by a hydrothermal method of the present invention comprises:

(1)将四水乙酸镍溶于乙醇和正丁醇的混合溶液中,溶解后滴加氨水,得到溶胶;其中四水乙酸镍和氨水的摩尔比为1:1;(1) Dissolve nickel acetate tetrahydrate in a mixed solution of ethanol and n-butanol, and then add ammonia water dropwise after dissolving to obtain a sol; the molar ratio between nickel acetate tetrahydrate and ammonia water is 1:1;

(2)将上述溶胶旋涂于FTO导电玻璃表面,干燥,得到带有晶种层的FTO导电玻璃;(2) Spin-coat the above-mentioned sol on the surface of FTO conductive glass and dry to obtain FTO conductive glass with a seed layer;

(3)四水乙酸镍、尿素和溶剂混合,得反应溶液,然后将上述带有晶种层的FTO导电玻璃浸入反应溶液中,进行水热反应,在160-180℃条件下,保持6-12h,冷却至室温,清洗、烘干、煅烧,即得氧化镍纳米结构电致变色薄膜,其中四水乙酸镍和尿素的摩尔比为1:2.1-4.2。(3) Nickel acetate tetrahydrate, urea and solvent are mixed to obtain a reaction solution, and then the above-mentioned FTO conductive glass with a seed layer is immersed in the reaction solution for hydrothermal reaction. After 12 hours, cool to room temperature, wash, dry, and calcinate to obtain a nickel oxide nanostructure electrochromic film, wherein the molar ratio of nickel acetate tetrahydrate to urea is 1:2.1-4.2.

所述步骤(1)中四水乙酸镍的浓度为0.2~0.4mol/L,所用氨水浓度为14.8mol/L(补充)。The concentration of nickel acetate tetrahydrate in the step (1) is 0.2-0.4 mol/L, and the concentration of ammonia water used is 14.8 mol/L (supplement).

所述步骤(1)中的正丁醇和乙醇的体积比为1:2-5。The volume ratio of n-butanol and ethanol in the step (1) is 1:2-5.

所述步骤(2)中FTO导电玻璃经超声洗涤。In the step (2), the FTO conductive glass is ultrasonically washed.

所述超声洗涤为依次经去离子水、丙酮和乙醇超声洗涤,超声洗涤时间为20~30分钟。The ultrasonic washing is followed by ultrasonic washing with deionized water, acetone and ethanol, and the ultrasonic washing time is 20-30 minutes.

所述步骤(2)中干燥为真空干燥,干燥温度为40-60℃,干燥时间为6-12h。The drying in the step (2) is vacuum drying, the drying temperature is 40-60° C., and the drying time is 6-12 hours.

所述步骤(3)中四水乙酸镍的浓度为0.02~0.04mol/L,溶剂为水、乙醇或体积比为1:1的水和乙醇混合液。In the step (3), the concentration of nickel acetate tetrahydrate is 0.02-0.04 mol/L, and the solvent is water, ethanol or a mixed solution of water and ethanol with a volume ratio of 1:1.

所述步骤(3)中水热反应在反应釜中进行,反应溶液量占反应釜体积的80%。The hydrothermal reaction in the step (3) is carried out in a reactor, and the amount of the reaction solution accounts for 80% of the volume of the reactor.

所述步骤(3)中煅烧温度为400-600℃,煅烧时间为2-6h。In the step (3), the calcination temperature is 400-600°C, and the calcination time is 2-6h.

所述步骤(3)氧化镍纳米结构为纳米线、纳米片或纳米片状花结构。The nickel oxide nanostructure in the step (3) is a nanowire, nanosheet or nanosheet flower structure.

本发明中,首先在清洗过的FTO玻璃片上通过晶种辅助水热法生长前驱物Ni(OH)2纳米结构薄膜,然后通过煅烧得到NiO纳米结构薄膜。通过调节反应溶液中尿素的添加量以及溶剂的组成,可以实现氧化镍纳米结构的可控制备。In the present invention, a precursor Ni(OH) 2 nanostructure film is first grown on a cleaned FTO glass sheet by a seed-assisted hydrothermal method, and then a NiO nanostructure film is obtained by calcining. The controllable preparation of nickel oxide nanostructures can be achieved by adjusting the amount of urea added in the reaction solution and the composition of the solvent.

本发明的氧化镍纳米结构薄膜具有较大的比表面积,且纳米结构之间的孔隙是完全开放的,可减小离子和电子注入/抽出电极材料的路径长度,缩短离子和电子在电极材料内部的迁移时间。因此,本发明的NiO纳米结构电致变色薄膜具有变色速度快、着色效率高和循环稳定性优良等优点,可以组装成各类电致变色器件,在智能窗、大屏幕显示等领域有广泛的应用前景。The nickel oxide nanostructure film of the present invention has a relatively large specific surface area, and the pores between the nanostructures are completely open, which can reduce the path length of ions and electrons injected into/extracted from the electrode material, and shorten the flow of ions and electrons inside the electrode material. migration time. Therefore, the NiO nanostructured electrochromic film of the present invention has the advantages of fast discoloration speed, high coloring efficiency and excellent cycle stability, and can be assembled into various electrochromic devices, and has wide application in fields such as smart windows and large-screen displays. Application prospect.

有益效果Beneficial effect

(1)本发明的制备方法简单,成本低,具有在玻璃表面制膜的产业应用可能性;(1) The preparation method of the present invention is simple, low in cost, and has the possibility of industrial application for forming a film on the surface of glass;

(2)本发明通过晶种辅助的水热法实现了氧化镍纳米结构薄膜在导电基底上可控制备,并通过调节水热工艺参数实现了对薄膜表面形貌的调控,从而有效地提高了薄膜的响应速度、着色效率;(2) The present invention realizes the controllable preparation of the nickel oxide nanostructure film on the conductive substrate through the hydrothermal method assisted by the seed crystal, and realizes the control of the surface morphology of the film by adjusting the hydrothermal process parameters, thereby effectively improving the Thin film response speed, coloring efficiency;

(3)本发明的纳米结构氧化镍薄膜是通过水热法直接生长在FTO导电玻璃的表面,氧化镍与基底有着较好的结合力,有利于电子传导,同时也提高了薄膜的电化学稳定性。(3) The nano-structured nickel oxide film of the present invention is directly grown on the surface of the FTO conductive glass by the hydrothermal method. The nickel oxide has a good bonding force with the substrate, which is beneficial to electron conduction and also improves the electrochemical stability of the film. sex.

附图说明Description of drawings

图1实施例1制备的氧化镍纳米结构电致变色薄膜的X射线衍射图;The X-ray diffraction pattern of the nickel oxide nanostructure electrochromic thin film prepared in Fig. 1 embodiment 1;

图2实施例1制备的氧化镍纳米结构电致变色薄膜的扫描电镜照片;The scanning electron micrograph of the nickel oxide nanostructure electrochromic thin film prepared in Fig. 2 embodiment 1;

图3实施例2制备的氧化镍纳米结构电致变色薄膜的扫描电镜照片;The scanning electron micrograph of the nickel oxide nanostructure electrochromic thin film prepared in Fig. 3 embodiment 2;

图4实施例3制备的氧化镍纳米结构电致变色薄膜的扫描电镜照片;The scanning electron micrograph of the nickel oxide nanostructure electrochromic thin film prepared in Fig. 4 embodiment 3;

图5实施例4制备的氧化镍纳米结构电致变色薄膜的扫描电镜照片。Fig. 5 is a scanning electron micrograph of the nickel oxide nanostructured electrochromic film prepared in Example 4.

具体实施方式Detailed ways

下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

实施例1Example 1

将FTO导电玻璃依次浸入去离子水、丙酮和乙醇中各自超声洗涤后烘干备用。称取0.45g四水乙酸镍溶于6mL乙醇和3mL正丁醇的混合溶液中,待四水乙酸镍完全溶解后滴加0.12mL浓氨水得到透明溶胶;然后将透明溶胶旋涂于超声清洗过的FTO导电玻璃表面,在40℃下真空干燥12小时得到氢氧化镍晶种层。配制含有0.6g四水乙酸镍、0.6g尿素、56mL水的反应溶液,然后将上述得到的带有晶种层的FTO导电玻璃侵入盛有反应溶液的水热釜中,于180℃保温6小时,最后自然冷却至室温,取出FTO导电玻璃,用水和乙醇依次清洗、烘干后,在500℃下煅烧3小时即可。The FTO conductive glass was sequentially immersed in deionized water, acetone and ethanol, respectively, ultrasonically washed and dried for later use. Weigh 0.45g of nickel acetate tetrahydrate and dissolve it in a mixed solution of 6mL of ethanol and 3mL of n-butanol. After the nickel acetate tetrahydrate is completely dissolved, add 0.12mL of concentrated ammonia water dropwise to obtain a transparent sol; then spin-coat the transparent sol on an ultrasonically cleaned The FTO conductive glass surface was vacuum-dried at 40° C. for 12 hours to obtain a nickel hydroxide seed layer. Prepare a reaction solution containing 0.6g of nickel acetate tetrahydrate, 0.6g of urea, and 56mL of water, then intrude the above-obtained FTO conductive glass with a seed layer into a hydrothermal kettle containing the reaction solution, and keep it warm at 180°C for 6 hours , and finally cooled naturally to room temperature, took out the FTO conductive glass, washed with water and ethanol in sequence, dried, and calcined at 500°C for 3 hours.

图1为所制得薄膜的X射线衍射图,对照标准X射线衍射图谱可以看出:该薄膜为立方相的氧化镍,与标准卡片JCPDS 04-0835对应。图2为所制得氧化镍薄膜的扫描电镜照片,可以看出该薄膜是由NiO纳米线网络结构组成。Figure 1 is the X-ray diffraction pattern of the prepared film, and it can be seen from the standard X-ray diffraction pattern that the film is nickel oxide in the cubic phase, which corresponds to the standard card JCPDS 04-0835. FIG. 2 is a scanning electron micrograph of the prepared nickel oxide film, and it can be seen that the film is composed of NiO nanowire network structure.

实施例2Example 2

将FTO导电玻璃依次浸入去离子水、丙酮和乙醇中各自超声洗涤后烘干备用。称取0.9g四水乙酸镍溶于7.5mL乙醇和2.5mL正丁醇的混合溶液中,待四水乙酸镍完全溶解后滴加0.24mL浓氨水得到透明溶胶;然后将透明溶胶旋涂于超声清洗过的FTO导电玻璃表面,在60℃下真空干燥6小时得到氢氧化镍晶种层。配制含有0.6g四水乙酸镍、0.3g尿素、56mL水的反应溶液,然后将上述得到的带有晶种层的FTO导电玻璃侵入盛有反应溶液的水热釜中,于160℃保温12小时,最后自然冷却至室温,取出FTO导电玻璃,用水和乙醇依次清洗、烘干后,在400℃下煅烧6小时即可。The FTO conductive glass was sequentially immersed in deionized water, acetone and ethanol, respectively, ultrasonically washed and dried for later use. Weigh 0.9g of nickel acetate tetrahydrate and dissolve it in a mixed solution of 7.5mL of ethanol and 2.5mL of n-butanol. After nickel acetate tetrahydrate is completely dissolved, add 0.24mL of concentrated ammonia water dropwise to obtain a transparent sol; then spin coat the transparent sol on an ultrasonic The cleaned FTO conductive glass surface was vacuum-dried at 60° C. for 6 hours to obtain a nickel hydroxide seed layer. Prepare a reaction solution containing 0.6g of nickel acetate tetrahydrate, 0.3g of urea, and 56mL of water, then intrude the above-obtained FTO conductive glass with a seed layer into a hydrothermal kettle containing the reaction solution, and keep it warm at 160°C for 12 hours , and finally cooled naturally to room temperature, took out the FTO conductive glass, washed with water and ethanol in sequence, dried, and calcined at 400°C for 6 hours.

图3为所制得的氧化镍薄膜的扫描电镜照片,可以看出该薄膜是由NiO纳米线组成。FIG. 3 is a scanning electron micrograph of the prepared nickel oxide film, and it can be seen that the film is composed of NiO nanowires.

实施例3Example 3

将FTO导电玻璃依次浸入去离子水、丙酮和乙醇中各自超声洗涤后烘干备用。称取0.6g四水乙酸镍溶于7mL乙醇和2mL正丁醇的混合溶液中,待四水乙酸镍完全溶解后滴加0.16mL浓氨水得到透明溶胶;然后将透明溶胶旋涂于超声清洗过的FTO导电玻璃表面,在50℃下真空干燥8小时得到氢氧化镍晶种层。配制含有0.3g四水乙酸镍、0.3g尿素、56mL乙醇的反应溶液,然后将上述得到的带有晶种层的FTO导电玻璃侵入盛有反应溶液的水热釜中,于170℃保温8小时,最后自然冷却至室温,取出FTO导电玻璃,用水和乙醇依次清洗、烘干后,在600℃下煅烧2小时即可。The FTO conductive glass was sequentially immersed in deionized water, acetone and ethanol, respectively, ultrasonically washed and dried for later use. Weigh 0.6g of nickel acetate tetrahydrate and dissolve it in a mixed solution of 7mL of ethanol and 2mL of n-butanol. After the nickel acetate tetrahydrate is completely dissolved, add 0.16mL of concentrated ammonia water dropwise to obtain a transparent sol; then spin-coat the transparent sol on an ultrasonically cleaned The FTO conductive glass surface was vacuum-dried at 50° C. for 8 hours to obtain a nickel hydroxide seed layer. Prepare a reaction solution containing 0.3g of nickel acetate tetrahydrate, 0.3g of urea, and 56mL of ethanol, then intrude the above-obtained FTO conductive glass with a seed layer into a hydrothermal kettle containing the reaction solution, and keep it warm at 170°C for 8 hours , and finally cooled naturally to room temperature, took out the FTO conductive glass, washed with water and ethanol in sequence, dried, and calcined at 600°C for 2 hours.

图4为所制得的氧化镍薄膜的扫描电镜照片,可以看出该薄膜是由NiO纳米片组成,这些纳米片形成了一个多孔的结构,这种结构不仅增大了电化学反应的活性比表面积,而且有利于离子和电子的注入/抽出。Figure 4 is a scanning electron micrograph of the prepared nickel oxide film. It can be seen that the film is composed of NiO nanosheets, and these nanosheets form a porous structure, which not only increases the activity ratio of the electrochemical reaction surface area, and facilitates the injection/extraction of ions and electrons.

实施例4Example 4

将FTO导电玻璃依次浸入去离子水、丙酮和乙醇中各自超声洗涤后烘干备用。称取0.6g四水乙酸镍溶于7mL乙醇和2mL正丁醇的混合溶液中,待四水乙酸镍完全溶解后滴加0.16mL浓氨水得到透明溶胶;然后将透明溶胶旋涂于超声清洗过的FTO导电玻璃表面,在50℃下真空干燥8小时得到氢氧化镍晶种层。配制含有0.3g四水乙酸镍、0.3g尿素、28mL乙醇和28mL水的反应溶液,然后将上述得到的带有晶种层的FTO导电玻璃侵入盛有反应溶液的水热釜中,于170℃保温8小时,最后自然冷却至室温,取出FTO导电玻璃,用水和乙醇依次清洗、烘干后,在600℃下煅烧2小时即可。图5为所制得的氧化镍薄膜的扫描电镜照片,可以看出该薄膜的表面形貌是由NiO纳米片组成的花状结构。The FTO conductive glass was sequentially immersed in deionized water, acetone and ethanol, respectively, ultrasonically washed and dried for later use. Weigh 0.6g of nickel acetate tetrahydrate and dissolve it in a mixed solution of 7mL of ethanol and 2mL of n-butanol. After the nickel acetate tetrahydrate is completely dissolved, add 0.16mL of concentrated ammonia water dropwise to obtain a transparent sol; then spin-coat the transparent sol on an ultrasonically cleaned The FTO conductive glass surface was vacuum-dried at 50° C. for 8 hours to obtain a nickel hydroxide seed layer. Prepare a reaction solution containing 0.3g nickel acetate tetrahydrate, 0.3g urea, 28mL ethanol and 28mL water, then intrude the above-obtained FTO conductive glass with a seed layer into a hydrothermal kettle containing the reaction solution, and heat it at 170°C Keep it warm for 8 hours, and finally cool down to room temperature naturally, take out the FTO conductive glass, wash it with water and ethanol in sequence, dry it, and then calcinate it at 600°C for 2 hours. FIG. 5 is a scanning electron micrograph of the prepared nickel oxide film. It can be seen that the surface morphology of the film is a flower-like structure composed of NiO nanosheets.

为了了解上述各实施例所制得的氧化镍纳米结构薄膜的电致变色性能,我们用三电极系统结合电化学工作站和固体紫外可见分光光度计来测定制得的氧化镍纳米结构薄膜的光透过率变化和电致变色响应速度,并计算着色效率。其中三电极系统为:以制备的氧化镍纳米结构薄膜电极作为工作电极,以Ag/AgCl为参比电极,以铂丝为对电极,以1mol/L的高氯酸锂的聚碳酸酯溶液为电解质。In order to understand the electrochromic properties of the nickel oxide nanostructure films prepared in the above examples, we used a three-electrode system in combination with an electrochemical workstation and a solid ultraviolet-visible spectrophotometer to measure the light transmittance of the nickel oxide nanostructure films. Rate change and electrochromic response speed, and calculate coloring efficiency. The three-electrode system is as follows: the prepared nickel oxide nanostructure film electrode is used as the working electrode, the Ag/AgCl is used as the reference electrode, the platinum wire is used as the counter electrode, and the polycarbonate solution of 1mol/L lithium perchlorate is used as the electrolyte.

结果表明:当施加-1V和1V的方压时,氧化镍纳米结构薄膜在透明和棕色之间可逆变化;该薄膜的透光率在400~900nm波段有着明显的变化,在λ=550nm处达到了最大值;因此,记录氧化镍纳米结构薄膜在λ=550nm处的透光率变化值,同时以λ=550nm处的透光率响应变化来检测其电致变色效应速度,并计算其着色效率,测试及计算结果如表1所示。由以上结果可知,实施例1和实施例3所制得的氧化镍纳米结构薄膜具有良好的电致变色性能。The results show that: when the square pressure of -1V and 1V is applied, the nickel oxide nanostructure film changes reversibly between transparent and brown; Therefore, record the light transmittance change value of the nickel oxide nanostructure film at λ=550nm, and at the same time use the light transmittance response change at λ=550nm to detect its electrochromic effect speed, and calculate its coloring efficiency , the test and calculation results are shown in Table 1. From the above results, it can be seen that the nickel oxide nanostructure films prepared in Example 1 and Example 3 have good electrochromic properties.

表1Table 1

薄膜film 透光率变化值Transmittance change value 着色时间coloring time 褪色时间fade time 着色效率Coloring efficiency

实施例1Example 1 60%60% 6s6s 8s8s 69.6cm2/C69.6cm 2 /C 实施例2Example 2 53%53% 9s9s 12s12s 56.4cm2/C56.4cm 2 /C 实施例3Example 3 66%66% 4s4s 8s8s 73.2cm2/C73.2cm 2 /C 实施例4Example 4 52%52% 18s18s 16s16s 46.2cm2/C46.2cm 2 /C

Claims (10)

1.一种水热法制备氧化镍电致变色薄膜的方法,包括:1. A method for preparing nickel oxide electrochromic thin film by hydrothermal method, comprising: (1)将四水乙酸镍溶于乙醇和正丁醇的混合溶液中,溶解后滴加氨水,得到溶胶;其中四水乙酸镍和氨水的摩尔比为1:1;(1) Dissolve nickel acetate tetrahydrate in a mixed solution of ethanol and n-butanol, and then add ammonia water dropwise after dissolving to obtain a sol; the molar ratio between nickel acetate tetrahydrate and ammonia water is 1:1; (2)将上述溶胶旋涂于FTO导电玻璃表面,干燥,得到带有晶种层的FTO导电玻璃;(2) Spin-coat the above-mentioned sol on the surface of FTO conductive glass and dry to obtain FTO conductive glass with a seed layer; (3)四水乙酸镍、尿素和溶剂混合,得反应溶液,然后将上述带有晶种层的FTO导电玻璃浸入反应溶液中,进行水热反应,在160-180℃条件下,保持6-12h,冷却至室温,清洗、烘干、煅烧,即得氧化镍纳米结构电致变色薄膜,其中四水乙酸镍和尿素的摩尔比为1:2.1-4.2。(3) Nickel acetate tetrahydrate, urea and solvent are mixed to obtain a reaction solution, and then the above-mentioned FTO conductive glass with a seed layer is immersed in the reaction solution for hydrothermal reaction. After 12 hours, cool to room temperature, wash, dry, and calcinate to obtain a nickel oxide nanostructure electrochromic film, wherein the molar ratio of nickel acetate tetrahydrate to urea is 1:2.1-4.2. 2.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(1)中四水乙酸镍的浓度为0.2~0.4mol/L,所用氨水浓度为14.8mol/L(补充)。2. A method for preparing nickel oxide electrochromic film by hydrothermal method according to claim 1, characterized in that: the concentration of nickel acetate tetrahydrate in the step (1) is 0.2-0.4mol/L, and the used The concentration of ammonia water is 14.8mol/L (supplement). 3.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(1)中的正丁醇和乙醇的体积比为1:2-5。3 . The method for preparing nickel oxide electrochromic thin film by hydrothermal method according to claim 1 , characterized in that: the volume ratio of n-butanol and ethanol in the step (1) is 1:2-5. 4.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(2)中FTO导电玻璃经超声洗涤。4. A method for preparing a nickel oxide electrochromic film by a hydrothermal method according to claim 1, characterized in that: in the step (2), the FTO conductive glass is ultrasonically washed. 5.根据权利要求4所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述超声洗涤为依次经去离子水、丙酮和乙醇超声洗涤,超声洗涤时间为20~30分钟。5. a kind of hydrothermal method according to claim 4 prepares the method for nickel oxide electrochromic thin film, it is characterized in that: described ultrasonic washing is through deionized water, acetone and ethanol ultrasonic washing successively, and ultrasonic washing time is 20 ~30 minutes. 6.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(2)中干燥为真空干燥,干燥温度为40-60℃,干燥时间为6-12h。6. A method for preparing nickel oxide electrochromic thin film by hydrothermal method according to claim 1, characterized in that: the drying in the step (2) is vacuum drying, the drying temperature is 40-60°C, and the drying time is 6-12h. 7.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(3)中四水乙酸镍的浓度为0.02~0.04mol/L,溶剂为水、乙醇或体积比为1:1的水和乙醇混合液。7. A method for preparing nickel oxide electrochromic film by hydrothermal method according to claim 1, characterized in that: the concentration of nickel acetate tetrahydrate in the step (3) is 0.02-0.04mol/L, and the solvent It is water, ethanol or a mixture of water and ethanol with a volume ratio of 1:1. 8.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(3)中水热反应在反应釜中进行,反应溶液量占反应釜体积的80%。8. A method for preparing a nickel oxide electrochromic film by a hydrothermal method according to claim 1, characterized in that: the hydrothermal reaction in the step (3) is carried out in a reactor, and the amount of the reaction solution accounts for 80% of the volume. 9.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(3)中煅烧温度为400-600℃,煅烧时间为2-6h。9 . The method for preparing nickel oxide electrochromic thin film by hydrothermal method according to claim 1 , characterized in that: in the step (3), the calcination temperature is 400-600° C., and the calcination time is 2-6 hours. 10.根据权利要求1所述的一种水热法制备氧化镍电致变色薄膜的方法,其特征在于:所述步骤(3)氧化镍纳米结构为纳米线、纳米片或纳米片状花结构。10. A method for preparing nickel oxide electrochromic film by hydrothermal method according to claim 1, characterized in that: the step (3) nickel oxide nanostructure is a nanowire, nanosheet or nanosheet flower structure .
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