Preparation and Electrochemical Property of New Multifunctional Inorganic/Organic Composite Film

doi:10.15541/jim20190157

Abstract

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

CLC Number:

O614

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.

Figures/Tables 21

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

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

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

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)

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

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

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

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.

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

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

Fig. S5 EDS spectrum of film PEDOT

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

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

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

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

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

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

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

Fig. S12 Electro-polymerization route for PTBPTA

Fig. S13 CV curves of electrochromic supercapacitor

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

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