基于快速响应f-La<sub>2</sub>O<sub>3</sub>/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

doi:10.13801/j.cnki.fhclxb.20220623.007

基于快速响应f-La₂O₃/PANI电致变色薄膜的制备与性能表征

doi: 10.13801/j.cnki.fhclxb.20220623.007

安徽理工大学　材料科学与工程学院，淮南 232001

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
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出版历程
- 收稿日期: 2022-04-27
- 修回日期: 2022-06-06
- 录用日期: 2022-06-17
- 网络出版日期: 2022-06-24
- 刊出日期: 2023-04-15

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

School of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China

Funds: 2021 Graduate Innovation Fund Project of Anhui University of Science and Technology (2021 CX2086); 2021 College Students Science Innovation and Scientific Research Education Demonstration Project of Anhui University of Science and Technology (KYX202116)

摘要

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(f-La₂O₃)，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f-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。研究结果表明：f-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；f-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(τ_b/τ_c)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。
- 氧化镧 /
- 聚苯胺 /
- 电致变色 /
- 响应时间 /
- 循环稳定性
Abstract: Based on the fact that electrochromic films have important research and development prospects in military camouflage, building energy saving, automobiles and other industrial fields, the surface of La₂O₃ was modified by silane coupling agent KH-550 and compounded with conductive polymer polyaniline (PANI) to prepare f-La₂O₃/PANI electrochromic material. Comparative analysis of composite electrode and pure PANI electrode by XRD, FTIR, SEM-EDS, UV-vis, and electrochemical workstation. The effect of f-La₂O₃ addition on the structure, morphology, electrochemical properties and electrochromic properties of PANI was investigated. The results show that the incorporation of f-La₂O₃ makes the PANI fibers tend to be smaller, and the composite material has higher crystallinity and molecular chain orientation than pure PANI; f-La₂O₃ will break the network cross-linking structure of PANI, resulting in a decrease in the electrochemical performance of the composite, but it can accelerate the transition process of PANI protonation and deprotonation, and effectively inhibit the oxidative degradation of PANI during the electrochromic process of the film; When f-La₂O₃/aniline molar ratio is 1∶3.5, the electrochromic performance of f-La₂O₃/PANI composite reaches the best, the coloration efficiency (CE) at 570 nm is 22.81 cm²·C⁻¹, and the fading and coloring response time (τ_b, τ_c) are 1.29 s and 1.33 s, respectively. After 320 cycles of fading, the electrochemical activity of the thin films remains about 50% of the initial value.
- lanthanum oxide /
- polyaniline /
- electrochromic /
- response time /
- cycling stability

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图 1 La₂O₃改性机制^[19]

Figure 1. La₂O₃ modification mechanism^[19]

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图 2 f-La₂O₃/PANI薄膜电极制备流程

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

ITO—Indium tin oxide

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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 pattern of f-La₂O₃)

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

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

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

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 PANI ; f-La₂O₃/An molar ratio1∶4 (c), 1∶3.5 (with local Mapping images) (d), 1∶3 (e)

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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

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图 7 PANI和f-La₂O₃/PANI薄膜(f-La₂O₃/An摩尔比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 (f-La₂O₃/An molar ratio 1∶4, 1∶3.5, 1∶3)

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图 8 PANI和f-La₂O₃/PANI薄膜电极(f-La₂O₃/An摩尔比1∶4、1∶3.5、1∶3)的能奎斯特曲线和等效电路图

Figure 8. Nyquist curves and equivalent circuit diagram of PANI and f-La₂O₃/PANI films electrode (f-La₂O₃/An molar ratio 1∶4, 1∶3.5, 1∶3)

Z'—Real part of impedance; Z''—Imaginary part of impedance; R_s—Solution resistance; R_ct—Charge transfer resistance; CPE—Nonideal capacitance; W—Warburg Impendance

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图 9 PANI和f-La₂O₃/PANI薄膜电极(f-La₂O₃/An摩尔比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 electrode (f-La₂O₃/An molar ratio 1∶4, 1∶3.5, 1∶3)

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图 10 PANI和f-La₂O₃/PANI薄膜(f-La₂O₃/An摩尔比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 (f-La₂O₃/An molar ratio 1∶4, 1∶3.5, 1∶3)

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图 11 PANI和f-La₂O₃/PANI薄膜(f-La₂O₃/An摩尔比1∶4、1∶3.5、1∶3)的循环稳定性

Figure 11. Cycling stability of PANI and f-La₂O₃/PANI films (f-La₂O₃/An molar ratio 1∶4, 1∶3.5, 1∶3)

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表 1 功能化La₂O₃(f-La₂O₃)/聚苯胺(PANI)复合材料的原料配比设计

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

Molar ratio f-La₂O₃∶An	An/g	f-La₂O₃/g	DBSA/g	HCl/g	APS/g
Pure	4.66	0.00	1.41	5.7	11.4
1∶4	4.66	4.00	1.41	5.7	11.4
1∶3.5	4.66	4.65	1.41	5.7	11.4
1∶3	4.66	5.43	1.41	5.7	11.4
Notes: An—Aniline; DBSA—Dodecylbenzenesulphonic acid; APS—Ammonium persulphate.

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

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

Sample		T_b/%	T_c/%	τ_b/τ_c/s	ΔOD	Q_in/(C·cm⁻²)	CE(λ)/(cm²·C⁻¹)
Type	Molar ratio La₂O₃∶An	T_b/%	T_c/%	τ_b/τ_c/s	ΔOD	Q_in/(C·cm⁻²)	CE(λ)/(cm²·C⁻¹)
PANI	—	83.0	48.4	6.29/6.01	0.23	0.1820	1.29
f-La₂O₃/PANI	1∶4	73.1	47.5	2.13/3.01	0.19	0.0438	4.27
	1∶3.5	62.8	35.8	1.29/1.33	0.24	0.0107	22.81
	1∶3	60.9	39.9	1.94/2.42	0.18	0.0275	6.68
Notes: T_b/T_c—Faded/colored state film transmittance; τ_b/τ_c—Faded/colored state film response time; ΔOD—Optical density change; Q_in—Charge injection rate; CE(λ)—Coloration efficiency; λ—Wavelength; 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.

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