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基于快速响应f-La2O3/PANI电致变色薄膜的制备与性能表征

戴彦 徐子芳 傅宇豪 张翔

戴彦, 徐子芳, 傅宇豪, 等. 基于快速响应f-La2O3/PANI电致变色薄膜的制备与性能表征[J]. 复合材料学报, 2022, 40(0): 1-10
引用本文: 戴彦, 徐子芳, 傅宇豪, 等. 基于快速响应f-La2O3/PANI电致变色薄膜的制备与性能表征[J]. 复合材料学报, 2022, 40(0): 1-10
Yan DAI, Zifang XU, Yuhao FU, Xiang ZHANG. Preparation and characterization of electrochromic thin films based on fast response f-La2O3/PANI[J]. Acta Materiae Compositae Sinica.
Citation: Yan DAI, Zifang XU, Yuhao FU, Xiang ZHANG. Preparation and characterization of electrochromic thin films based on fast response f-La2O3/PANI[J]. Acta Materiae Compositae Sinica.

基于快速响应f-La2O3/PANI电致变色薄膜的制备与性能表征

基金项目: 安徽理工大学2021年研究生创新基金项目(2021 CX2086); 安徽理工大学2021年大学生科普创新及科研育人示范项目(KYX202116)
详细信息
    通讯作者:

    徐子芳,博士,教授,硕士生导师,研究方向为电致变色材料 E-mail:zhfxubao@163.com

  • 中图分类号: (TB332/O646)

Preparation and characterization of electrochromic thin films based on fast response f-La2O3/PANI

  • 摘要: 基于电致变色薄膜在军事伪装、建筑节能、汽车等工业领域具有重要研发前景,研究通过硅烷偶联剂KH-550对氧化镧(La2O3)表面进行修饰,并与导电聚合物聚苯胺(PANI)复合制备f-La2O3/PANI电致变色材料。利用XRD、FTIR、SEM-EDS、UV-vis、电化学工作站对f-La2O3/PANI电极与纯PANI电极进行对比分析,重点研究La2O3掺入量对PANI结构形貌、电化学性能及电致变色性能的影响。结果表明:La2O3的掺入使PANI纤维有向细小化方向变化的趋势,其复合材料较纯PANI具有更高的结晶度和分子链取向;La2O3会打破PANI的网络交联结构导致复合材料的电化学性能有所降低,但可以加快PANI质子化和脱质子化的转变进程,并有效抑制薄膜电致变色过程中PANI的氧化降解;当镧胺比1∶3.5时,f-La2O3/PANI复合材料的电致变色性能达到最佳,波长570 nm处的着色效率(CE)为22.81 cm2·C−1,褪色、着色响应时间(τb/τc)分别为1.29 s、1.33 s,经320次着褪色循环后薄膜电化学活性保持在初始的50%左右。

     

  • 图  1  La2O3改性机制[19]

    Figure  1.  La2O3 modification mechanism

    图  2  f-La2O3/PANI薄膜电极制备流程

    Figure  2.  Preparation process of f-La2O3/PANI thin film electrode

    图  3  PANI与f-La2O3/PANI复合材料的XRD图谱(插图:f-La2O3的XRD图谱)

    Figure  3.  XRD patterns of PANI and f-La2O3/PANI composite (Inset: XRD curves of La2O3 and f- La2O3)

    图  4  PANI与f-La2O3/PANI复合材料的红外图谱(插图:La2O3与f-La2O3的红外谱图)

    Figure  4.  FTIR spectra of PANI and f- La2O3/PANI composite (Inset: Infrared spectra of La2O3 and f- La2O3)

    图  5  PANI与f-La2O3/PANI薄膜表面和截面的SEM图:(a)功能化前后的La2O3;(b)Pure;(c)1:4;(d)1:3.5(含局部Mapping图);(e)1:3

    Figure  5.  SEM images of the surface and cross-section of PANI and f-La2O3/PANI films: (a)La2O3 before and after functionalization; (b)pure;(c)1:4;(d)1:3.5(with Mapping images);(e)1:3

    图  6  PANI与f-La2O3/PANI复合材料的电导率

    Figure  6.  Conductivity of PANI and f-La2O3/PANI composites

    图  7  PANI和f-La2O3/PANI薄膜(n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)的循环伏安曲线

    Figure  7.  Cyclic voltammetry curves of PANI and f-La2O3/PANI films (n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)

    图  8  PANI与f-La2O3/PANI薄膜电极(n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)的能奎斯特曲线和等效电路图

    Figure  8.  Nyquist curve and Equivalent circuit diagram of PANI and f-La2O3/PANI film electrode (n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)

    图  9  PANI和f-La2O3/ PANI薄膜(n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)的计时电流曲线

    Figure  9.  Chronoamperometric curves of PANI and f-La2O3/PANI films (n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)

    图  10  PANI和f-La2O3/PANI薄膜(n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)的紫外-可见光吸收光谱

    Figure  10.  UV-vis absorption spectra of PANI and f-La2O3/PANI films (n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)

    图  11  PANI和f-La2O3/ PANI薄膜(n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)的循环稳定性

    Figure  11.  Cycling stability of PANI and f-La2O3/PANI films (n(La2O3)∶n(An)=1∶4; 1∶3.5; 1∶3)

    表  1  La2O3/聚苯胺(PANI)复合材料的原料配比设计

    Table  1.   Raw material ratio design of f-La2O3 /polyaniline (PANI) composite material

    Sample
    n(La2O3):n(An)
    An/
    g
    fLa2O3/gDBSA/gHCl/gAPS/g
    Pure4.6601.415.711.4
    1:44.664.01.415.711.4
    1:3.54.664.651.415.711.4
    1:34.665.431.415.711.4
    下载: 导出CSV

    表  2  570 nm处PANI和f-La2O3/PANI薄膜的着色效率相关参数表

    Table  2.   Parameters related to coloring efficiency of PANI and f-La2O3/PANI films at 570 nm

    SampleTb/%Tc/%τb/τc/sΔODQin/(C·cm−2)CE(λ)
    /(cm2·C−1)
    Typen(La2O3):n(An)
    PANI83.048.46.29/6.010.230.18201.29
    f-La2O3/PANI1∶473.147.52.13/3.010.190.04384.27
    1∶3.562.835.81.29/1.330.240.010722.81
    1∶360.939.91.94/2.420.180.02756.68
    Note: (1) Tb/Tc: Faded/Colored state film transmittance; τb/τc: Faded/Colored state film response time; ΔOD: Optical density change; Qin: Charge injection rate; CE(λ): Coloration efficiency. (2) When the voltage is −0.4 V, it is in the faded state, and +0.6 V is in the colored state;S=2.52 cm2
    下载: 导出CSV
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  • 收稿日期:  2022-04-27
  • 录用日期:  2022-06-17
  • 修回日期:  2022-06-06
  • 网络出版日期:  2022-06-27

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