基于聚苯胺和银纳米线基局部表面等离子体共振的电致变色电极

doi:10.6023/A24020062

摘要/Abstract

电致变色是指在外加电压下发生可逆颜色变化的现象, 在信息显示器和光学调制设备中具有广泛应用潜力. 导电聚合物聚苯胺作为一类重要的电致变色材料, 其制备工艺简单、成本低廉、响应速度快, 进而备受关注. 此外, 基于金属沉积的局部表面等离子体共振电致变色器件能通过控制金属阳离子的还原来实现金属颗粒或薄膜的沉积, 从而控制器件的颜色或反射状态, 引起广泛兴趣. 本工作通过自组装法制备了基于银纳米线和聚苯胺的纳米复合材料, 得到了既具有导电聚合物电致变色效应又具有银金属局部表面等离子体共振效应的多色电致变色薄膜电极. 该电极在正电位下呈现出深色着色态(透过率25.4%), 施加反向电位时, 电极会先褪色呈现出透明态(透过率83.3%), 然后在更大反向电位下变成深色着色态(透过率10.7%), 具有普通电致变色器件无法实现的双重着色态. 此外, 由于聚苯胺表面胺基与银纳离子的配位, 减少了银离子被氧化后向电解液中的迁移耗散, 改善了电极的多次循环稳定性, 为信息显示和光学调制领域带来新的可能性.

关键词: 电致变色, 导电聚合物, 局部表面等离子体共振, 银纳米线

Electrochromism refers to the reversible color change phenomenon under an applied voltage, which demonstrates wide application potential in information displays and optical modulation devices. Conductive polymers, an important type of electrochromic materials, have gained wide attention for their simple preparation process, cost-effectiveness, fast response speed, and good cycling stability. Electrochromic devices utilizing local surface plasmon resonance based on metallic deposition have also attracted great interest. By controlling the reduction of metal cations, the deposition of metal particles or films can be achieved for controlling the device's color or reflection state. Herein, electrochromic nanocomposites combining silver nanowires and polyaniline were synthesized using a self-assembly method to create composite thin film electrodes exhibiting both the electrochromic and local surface plasmon resonance effects. The obtained electrode can satisfy the inherent electrochromic effect of polyaniline itself, which means the reversible variation from light green to deep purple. Meanwhile, under further negative potential, the lower transmittance of nearly 0% of the black state can be achieved. This is because silver nanowires are oxidized into silver ions at a positive potential, and then reduced to elemental silver under the negative potential, absorbing a large amount of light. In addition, different from traditional electrochromic devices based on the single silver ion, the as-prepared electrodes demonstrate reversible modulation due to the adsorption of silver ions by amine groups on aniline, which can effectively reduce the diffusion of silver ions into the electrolyte and thus improving the stability of this combined electrochromic effect. The electrode displays a dark-colored state with the transmittance of 25.4% at a positive potential. Upon application of a reverse potential, the electrode transitions to a faded state (83.3%), and then returning to a dark-colored state (10.7%) at a higher reverse potential. This electrochromic device with dual-colored state, which can not be achieved by conventional strategy, opens up new possibilities in the fields of information display and optical modulation.

Key words: electrochromic, conductive polymer, local surface plasmon resonance, silver nanowires

引用此文

彭红超, 陈胜, 阎斌. 基于聚苯胺和银纳米线基局部表面等离子体共振的电致变色电极[J]. 化学学报, 2024, 82(7): 797-804.

Hongchao Peng, Sheng Chen, Bin Yan. Electrochromic Electrode Based on Polyaniline and Silver Nanowires Based Localized Surface Plasmon Resonance[J]. Acta Chimica Sinica, 2024, 82(7): 797-804.

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图/表 5

图1. (a) 聚苯胺/银纳米线复合物的制备流程图; (b) 银纳米线的SEM图; (c) 纯的聚苯胺的SEM图; (d) 聚苯胺/银纳米线复合物的SEM图

Figure 1. (a) Schematic diagram of the preparation process of polyaniline/silver nanowires composites; (b) SEM image of silver nanowires; (c) SEM image of pure polyaniline; (d) SEM image of polyaniline/silver nanowires composites

图2. (a) 不同质量比例的聚苯胺/银纳米线复合物的CV曲线; (b) 不同质量比例的聚苯胺/银纳米线复合物的交流阻抗曲线(插图为其等效电路); (c) 多色电极的韦伯系数; (d) 多色电极的离子扩散系数; (e) 10P/1A多色电极的扫描速率响应循环伏安曲线; (f) 10P/1A多色电极的峰值电流对扫描速率的平方根曲线

Figure 2. (a) CV curves of polyaniline/silver nanowire composites with different mass ratios; (b) AC impedance curves of polyaniline/silver nanowire composites with different mass ratios (insert figure shows their equivalent circuits); (c) Weber's coefficient of multi-color electrodes; (d) the ion diffusion coefficient of multi-color electrodes; (e) cyclic voltammetry curve of 10P/1A multi-color electrode at different scanning rates; (f) square root curve of peak current of 10P/1A multi-color electrode versus scanning rate

图3. (a) 10P/1A多色电极在不同电压下的吸光度曲线; (b) 10P/1A多色电极在不同电压下的透过率曲线; (c) 10P/1A多色电极在不同电压下的积分平均透过率; (d) 10P/1A多色电极在循环伏安测试条件下的透过率响应曲线(波长510 nm处); (e) 10P/1A多色电极在510 nm波长处的循环稳定性测试

Figure 3. (a) Absorbance curves of 10P/1A multi-color electrode; (b) transmittance curves of 10P/1A multi-color electrode at different voltages; (c) integral average transmittance of 10P/1A multi-color electrode at different voltages; (d) transmittance-response curves of 10P/1A multi-color electrode under cyclic voltammetry testing conditions at the wavelength of 510 nm; (e) cycle stability of 10P/1A multi-color electrode at the wavelength of 510 nm

图4. (a) 10P/1A多色电极在＋1.0 V电压下的SEM图; (b) 10P/1A多色电极在-0.6 V电压下的SEM图; (c) 10P/1A多色电极在氧化还原过程中的机理示意图

Figure 4. (a) SEM image of 10P/1A multi-color electrode at ＋1.0 V voltage; (b) SEM image of 10P/1A multi-color electrode at -0.6 V voltage; (c) schematic diagram of the mechanism of the redox process of the 10P/1A multi-color electrode

图5. (a) 10P/1A多色电极在不同电压下的数码照片及其图案化显示; (b) 10P/1A多色电极的“L a b”值随电压的变化曲线; (c) 10P/1A多色电极的“L a b”值随电压的空间变化趋势曲线; (d) 10P/1A多色电极在不同电压下的色差变化(初始状态作为标准)

Figure 5. (a) Digital photos and patterned display of 10P/1A multi-color electrode at different voltages; (b) curve showing the "L a b" values of the 10P/1A multi-color electrode as a function of voltage; (c) spatial variation trend curve of "L a b" values of the 10P/1A multi-color electrode concerning voltage; (d) color difference changes of 10P/1A multi-color electrode at different voltages with the initial state as the standard

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