新型多功能无机/有机复合薄膜的制备及电化学性能研究

doi:10.15541/jim20190157

摘要/Abstract

摘要：

将铈钛氧簇[Ti₈O₇(HOEt)(OEt)₂₁Ce]和PEDOT低聚物的混合溶液通过滴涂-二次聚合成膜制得一种表面具有特殊纳米沟壑结构的无机/有机复合薄膜PEDOT:Ce@TiO₂。PEDOT:Ce@TiO₂具有很强的疏水性和对乙腈溶液较好的润湿性, 能用作阴极电致变色材料和超级电容器电极材料。PEDOT:Ce@TiO₂展现出较PEDOT薄膜更优良的电化学性能, 在电流密度为1 A/g时, PEDOT:Ce@TiO₂的质量比电容为71.2 F/g, 是相同条件下PEDOT薄膜的质量比电容的1.7倍。采用PEDOT:Ce@TiO₂进一步组装了全固态电致变色超级电容器原型器件, 当充电完成时器件的变色区域呈现墨绿色, 当放电完成时器件的变色区域呈现亮黄色。

关键词: 聚3, 4-乙烯二氧噻吩, 钛氧簇, 疏水性, 电致变色薄膜, 超级电容器

Abstract:

A new inorganic/organic composite film PEDOT:Ce@TiO₂ was prepared through drop casting-secondary polymerization method using the mixture solution of PEDOT oligomer and cerium-containing polyoxotitanate cage [Ti₈O₇(HOEt)(OEt)₂₁Ce]. PEDOT:Ce@TiO₂ exhibits a special nanostructure with gully-like rough surface, which shows strong hydrophobicity while good wettability to acetonitrile solution. PEDOT:Ce@TiO₂ can be used as cathodically electrochromic film and supercapacitor electrode material. The mass specific capacitance of PEDOT:Ce@TiO₂ is 71.2 F/g at a current density of 1 A/g, which is 1.7 times higher than that of the PEDOT film. An all-solid-state electrochromic supercapacitor prototype device was further assembled using PEDOT:Ce@TiO₂. With charging completed the electrochromic area of this device shows dark green, and it turns bright yellow with discharging completed.

Key words: poly 3, 4-ethylenedioxythiophene, polyoxotitanate, hydrophobicity, electrochromic film, supercapacitor

中图分类号:

O614

陈钧,马培华,张诚,劳伦·鲁尔曼,吕耀康. 新型多功能无机/有机复合薄膜的制备及电化学性能研究[J]. 无机材料学报, 2020, 35(2): 217-223.

CHEN Jun,MA Pei-Hua,ZHANG Cheng,Laurent RUHLMANN,LYU Yao-Kang. Preparation and Electrochemical Property of New Multifunctional Inorganic/Organic Composite Film[J]. Journal of Inorganic Materials, 2020, 35(2): 217-223.

图/表 21

图1 PEDOT:Ce@TiO2薄膜的实验制备流程图

Fig. 1 Schematic illustration of preparation of PEDOT:Ce@TiO2 film

图2 PEDOT薄膜的(a)SEM照片、(b)AFM二维高度图、(c)AFM二维相图和PEDOT:Ce@TiO2薄膜的(d)SEM照片、(e)AFM二维高度图、(f)AFM二维相图

Fig. 2 (a) SEM image, (b) AFM height sensor image (2D), (c) AFM tapping phase image (2D) of PEDOT film, and (d) SEM image, (e) AFM height sensor image (2D), (f) AFM tapping phase image (2D) of PEDOT:Ce@TiO2 film

图3 PEDOT:Ce@TiO2薄膜的SEM-mapping照片

Fig. 3 SEM-mapping images of PEDOT:Ce@TiO2 film

图4 PEDOT薄膜(a)和PEDOT:Ce@TiO2薄膜(c)的水滴接触角照片; PEDOT薄膜(b)和PEDOT:Ce@TiO2薄膜(d)的乙腈液滴接触角照片

Fig. 4 Images of water droplets on the surfaces of PEDOT film (a) and PEDOT:Ce@TiO2 film (c), and images of ACN droplets on the surfaces of PEDOT film (b) and PEDOT: Ce@TiO2 film (d)

图5 (a) PEDOT和(b) PEDOT:Ce@TiO2的循环伏安曲线; (c) PEDOT和(d) PEDOT:Ce@TiO2的恒流充放电曲线

Fig. 5 CV curves of (a) PEDOT and (b) PEDOT:Ce@TiO2; Galvanostatic charge/discharge curves of (c) PEDOT and (d) PEDOT:Ce@TiO2

图6 (a)电致变色超级电容器的结构示意图, (b) 恒流充放电曲线以及充电完成时和放电完成时的照片

Fig. 6 (a) Schematic, (b) galvanostatic charge/discharge curves of electrochromic supercapacitor, and optical photos under the completing of charging and discharging.

图S1 流出时间为12.0~28.0 min内相对分子质量分布

Fig. S1 Relative molecular mass distribution with run time from 12.0 to 28 min

图S2 (a) PEDOT低聚物, (b) 铈钛氧簇[Ti8O7(HOEt)(OEt)21Ce], (c) 铈钛氧簇[Ti8O7(HOEt)(OEt)21Ce]和PEDOT的DCM溶液, (d) PEDOT薄膜(e) PEDOT: Ce@TiO2薄膜的照片

Fig. S2 Photographs of solution of PEDOT oligomer in DCM, (b) solution of polyoxotitanate cluster [Ti8O7(HOEt)(OEt)21Ce] in DCM, (c) mixture solution of PEDOT and polyoxotitanate cluster [Ti8O7(HOEt)(OEt)21Ce] in DCM, (d) PEDOT film (e) PEDOT: Ce@TiO2 film.

图S3 PEDOT和PEDOT:Ce@TiO2的FT-IR光谱图

Fig. S3 FT-IR spectra of PEDOT and PEDOT:Ce@TiO2

图S4 (a) PEDOT:Ce@TiO2粉末; (b) Ce@TiO2粉末和 (c) PEDOT粉末的XRD图谱

Fig. S4 XRD patterns of (a) PEDOT:Ce@TiO2 powder; (b) Ce@TiO2 powder and (c) PEDOT powder

图S5 PEDOT薄膜的EDS能谱图

Fig. S5 EDS spectrum of film PEDOT

图S6 PEDOT:Ce@TiO2薄膜的EDS能谱图

Fig. S6 EDS spectrum of film PEDOT:Ce@TiO2

表S1 PEDOT和PEDOT:Ce@TiO2薄膜中碳, 氧, 硫, 钛和铈原子的元素质量百分比

Table S1 Mass percentages of the carbon, oxygen, sulfur, titanium and cerium atoms in PEDOT and PEDOT: Ce@TiO2 film

Film	C/wt%	O/wt%	S/wt%	Ti/wt%	Ce/wt%
PEDOT	62.38	20.13	17.49	—	—
PEDOT: Ce@TiO₂	60.01	18.26	15.91	3.18	2.01

图S7 (a) PEDOT薄膜的AFM二维高度图, (b) AFM三维高度图; (c) PEDOT:Ce@TiO2薄膜的AFM二维高度图, (d) AFM三维高度图

Fig. S7 (a) AFM height sensor image (2D), (b) AFM height sensor image (3D) of PEDOT film; (c) AFM height sensor image (2D), (d) AFM height sensor image (3D) of PEDOT:Ce@TiO2 film

图S8 在扫描速率100 mV/s下PEDOT和PEDOT:Ce@TiO2薄膜在0.1 mol·L-1 LiClO4/ACN溶液中的循环伏安曲线

Fig. S8 Cyclic voltammetry curves of PEDOT and PEDOT:Ce@TiO2 films in 0.1 mol/L LiClO4/ACN at scan rate of 100 mV/s

图S9 (a) PEDOT和(b) PEDOT:Ce@TiO2薄膜在不同电压下的紫外-可见光谱图和光学照片(插图)

Fig. S9 UV-Vis spectra and optical photos (inserts) of films under different potentialaption (a) PEDOT; (b) PEDOT:Ce@TiO2

图S10 (a) PEDOT和PEDOT:Ce@TiO2的交流阻抗曲线; (b) 不同充放电电流密度下PEDOT和PEDOT:Ce@TiO2薄膜的质量比容量

Fig. S10 (a) Nyquist plots of the impedance spectra of PEDOT and PEDOT: Ce@TiO2; (b) Specific capacitance calculated from discharge curves of PEDOT and PEDOT: Ce@TiO2 films

图S11 (a) PEDOT和(b) PEDOT:Ce@TiO2薄膜在电流密度为1 A/g时的充放电循环稳定性

Fig. S11 Cycling performance of PEDOT (a) and PEDOT:Ce@TiO2 (b) film measured by charging and discharging it at 1 A/g

图S12 PTBPTA薄膜的电聚合路线

Fig. S12 Electro-polymerization route for PTBPTA

图S13 电致变色超级电容器的循环伏安曲线

Fig. S13 CV curves of electrochromic supercapacitor

图S14 不同电流密度下, 电致变色超级电容器的面积比容量

Fig. S14 Specific capacitance calculated from discharge curves of electrochromic supercapacitor

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