Ti2Nb10O29薄膜的制备及其电致变色性能

doi:10.15541/jim20230154

无机材料学报 ›› 2023, Vol. 38 ›› Issue (12): 1434-1440.DOI: 10.15541/jim20230154 CSTR: 32189.14.10.15541/jim20230154

所属专题：【信息功能】敏感陶瓷（202409）；【信息功能】电致变色与热致变色材料(202312)

Ti₂Nb₁₀O₂₉薄膜的制备及其电致变色性能

孙佳伟(), 宛心怡, 杨婷, 马董云(), 王金敏()

上海理工大学材料与化学学院, 上海 200093

收稿日期:2023-03-27 修回日期:2023-04-07 出版日期:2023-09-12 网络出版日期:2023-09-12
通讯作者: 王金敏, 教授. E-mail: jmwang@usst.edu.cn;
马董云, 讲师. E-mail: dyma@usst.edu.cn
作者简介:孙佳伟(1997-), 男, 硕士研究生. E-mail: 203612300@st.usst.edu.cn
基金资助:
国家自然科学基金(62275154)

Preparation and Electrochromic Properties of Ti₂Nb₁₀O₂₉Films

SUN Jiawei(), WAN Xinyi, YANG Ting, MA Dongyun(), WANG Jinmin()

School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China

Received:2023-03-27 Revised:2023-04-07 Published:2023-09-12 Online:2023-09-12
Contact: WANG Jinmin, professor. E-mail: jmwang@usst.edu.cn;
MA Dongyun, lecturer. E-mail: dyma@usst.edu.cn
About author:SUN Jiawei (1997-), male, Master candidate. E-mail: 203612300@st.usst.edu.cn
Supported by:
National Natural Science Foundation of China(62275154)

摘要/Abstract

摘要：

电致变色材料是一类可以通过调节光和热而减少能源使用的节能环保材料, 特别是化学性质稳定的过渡金属氧化物, 作为电致变色材料得到广泛研究。近年来, 双金属氧化物由于存在两种可变价态的金属离子, 具有更好的电化学活性而逐渐受到关注。本研究采用水热法成功在透明导电基底上直接生长了Ti₂Nb₁₀O₂₉薄膜, 并探究了前驱体中铌钛原子比对薄膜电致变色性能的影响。结果表明, 由铌钛原子比为3 : 1的前驱体制备的薄膜具有较好的电致变色性能。Ti₂Nb₁₀O₂₉薄膜在−1.6 V呈蓝灰色, 在0.4 V呈无色透明状; 在300~1100 nm的宽波长范围内, 均有较高的光调制幅度, 其褪色态的透过率接近90%; 在波长750 nm处的最大光调制幅度达69.4%; 对薄膜施加-1.6 V、60 s和0.4 V、15 s的方波电位, 测得其着色时间和褪色时间分别为29.8和5.9 s; 薄膜的着色效率为68.3 cm²·C^-1。本研究制备的Ti₂Nb₁₀O₂₉薄膜拓展了双金属氧化物电致变色材料的种类, 具有良好的应用前景。

关键词: 电致变色, 双金属氧化物, Ti₂Nb₁₀O₂₉, 中性色, 光调制幅度

Abstract:

Electrochromic materials are energy-saving and environmentally friendly materials that can reduce energy use by adjusting sunlight and solar-heat. In particular, transition metal oxides with stable chemical properties have been widely studied as electrochromic materials. Recently, bimetallic oxides with two variable valence states of metal ions have received increasing attention due to their better electrochemical activity. In this study, Ti₂Nb₁₀O₂₉ films were successfully prepared on conductive glasses, and the effect of the atomic ratio of niobium to titanium in the precursor on the electrochromic properties of the thin films was investigated. The results show that the thin film prepared from precursors with an atomic ratio of niobium to titanium of 3 : 1 possesses the best electrochromic properties. It is worth noting that the thin film achieves a large optical modulation in the wavelength range of 300-1100 nm, and the transmittance in the bleached state is nearly 90%, appearing grayish blue under the action of −1.6 V, colorless state under the action of 0.4 V, and achieving a maximum optical modulation of 69.4% at the wavelength of 750 nm. After a square-wave potential of -1.6 V for 60 s and 0.4 V for 15 s, the film shows response time of 29.8 s for coloring and 5.9 s for bleaching. Coloration efficiency of the as-prepared film is 68.3 cm²·C^-1. The above results indicate that the successfully prepared Ti₂Nb₁₀O₂₉ thin film enriches variety of bimetallic oxide electrochromic materials and has widely application prospect.

Key words: electrochromic, bimetallic oxide, Ti₂Nb₁₀O₂₉, neutral color, optical modulation

中图分类号:

TQ174

孙佳伟, 宛心怡, 杨婷, 马董云, 王金敏. Ti₂Nb₁₀O₂₉薄膜的制备及其电致变色性能[J]. 无机材料学报, 2023, 38(12): 1434-1440.

SUN Jiawei, WAN Xinyi, YANG Ting, MA Dongyun, WANG Jinmin. Preparation and Electrochromic Properties of Ti₂Nb₁₀O₂₉Films[J]. Journal of Inorganic Materials, 2023, 38(12): 1434-1440.

图/表 10

表1 前驱体中铌源和钛源的浓度

Table 1 Concentrations of niobium and titanium sources in precursors

Sample	[C₄H₄NNbO₉]/(mol·L^-1)	[C₁₆H₃₆O₄Ti]/(mol·L^-1)
TNO-1	0.0360	0.0360
TNO-2	0.0360	0.0180
TNO-3	0.0360	0.0120
TNO-4	0.0360	0.0090

图1 不同铌钛原子比的前驱体得到的薄膜的XRD谱图

Fig. 1 XRD patterns of the films obtained from precursors with different atomic ratios of niobium to titanium (a) TNO-1; (b) TNO-2; TNO-3; (d) TNO-4

图2 不同铌钛原子比前驱体制备的薄膜的SEM照片

Fig. 2 SEM images of the films obtained from precursors with different atomic ratios of niobium to titanium (a) TNO-1; (b) TNO-2; (c) TNO-3; (d) TNO-4

图3 薄膜样品在不同扫描速率下的CV曲线

Fig. 3 CV curves of the films at different scan rates (a) TNO-1; (b) TNO-2; (c) TNO-3; (d) TNO-4

图4 薄膜样品的阳极峰值电流密度与扫描速率的关系

Fig. 4 Relationship between anodic peak current density and scan rate of the films (a) TNO-1; (b) TNO-2; (c) TNO-3; (d) TNO-4

图5 TNO-3薄膜在不同状态下的照片

Fig. 5 Photos of different states of the TNO-3 film (a) Bleached state; (b) Colored state

图6 薄膜的着色态和褪色态的透射光谱

Fig. 6 Transmittance spectra of the films in the colored and bleached states (a) TNO-1; (b) TNO-2; (c) TNO-3; (d) TNO-4

图7 TNO-3薄膜的原位透射光谱

Fig. 7 In-situ transmittance spectrum of the TNO-3 film

图8 TNO-3薄膜的光密度随电荷密度变化曲线

Fig. 8 Optical density variation with respect to the charge density of the TNO-3 film

图9 TNO-3薄膜在5000 s内的原位透射光谱

Fig. 9 In-situ transmittance spectrum of the TNO-3 film within 5000 s

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Ti₂Nb₁₀O₂₉薄膜的制备及其电致变色性能

Preparation and Electrochromic Properties of Ti₂Nb₁₀O₂₉Films

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