Cu3(HHTP)2 Film-based Ionic-liquid Electrochromic Electrode

doi:10.15541/jim20220097

Abstract

Abstract:

Room temperature ionic liquid shows wide electrochemical windows and good environmental stability, which is expected as an ideal electrolyte for electrochromic devices. However, the small crystal spacing of traditional electrochromic materials limits the diffusion of large ions in ionic liquid. Repeated deintercalation/ intercalation of large ions could also destroy the structure of traditional electrochromic materials, resulting in performance degradation. Metal-organic frameworks (MOFs) are topologically porous materials with a large intrinsic nano to microporous structure in crystalline, which are expected to provide channels for transporting large-sized ions in ionic liquids. In present work, triphenylene-based MOFs Cu₃(HHTP)₂ films were prepared on the surface of the conductive glass. Electrochemical and electrochromic behavior of Cu₃(HHTP)₂ films were studied in traditional propylene carbonate (PC)-based electrolyte and ionic liquid-based electrolytes. The results show that, compared with the traditional LiClO₄/PC or NaClO₄/PC electrolyte, Cu₃(HHTP)₂ film displays low contact resistance and high ion diffusion efficiency in the ionic liquid [EMIm]BF₄electrolyte. Switch speed of the electrochromic electrode is significantly improved with coloring time being reduced from 10.3 s to 8.0 s, and bleaching time being reduced from 23.6 s to 5.2 s. Meanwhile, Cu₃(HHTP)₂/[EMIm]BF₄ electrochromic system also shows a larger light modulation range and coloring efficiency. This work demonstrates the potential of MOFs/ionic liquid electrochemical system in the field of electrochromic device.

Key words: MOFs, film, ionic liquid, electrochromism

CLC Number:

TN303
TB389

ZHANG Xiaoyu, LIU Yongsheng, LI Ran, LI Yaogang, ZHANG Qinghong, HOU Chengyi, LI Kerui, WANG Hongzhi. Cu₃(HHTP)₂ Film-based Ionic-liquid Electrochromic Electrode[J]. Journal of Inorganic Materials, 2022, 37(8): 883-890.

Figures/Tables 6

Fig. 1 Characterization of Cu3(HHTP)2 films (a) Change of absorbance at 800 nm wavelength with film thickness, inset showing the pictures of Cu3(HHTP)2 films obtained in different growth-cycles; (b) Surface SEM image of the Cu3(HHTP)2 film obtained from 20 cycles; (c) XRD patterns of Cu3(HHTP)2; (d) Raman spectra of Cu3(HHTP)2 and HHTP ligand

Fig. 2 XPS spectrum and poresize distribution of Cu3(HHTP)2 (a) XPS full spectrum; (b) High resolution XPS spectrum of Cu2p3/2; (c) Pore size distribution diagram with inset showing N2 adsorption isotherm curves for Cu3(HHTP)2 powders measured at 77 K

Fig. 3 (a) Transmittance at 800 nm wavelength for Cu3(HHTP)2 films with different thicknesses at constant voltages of -0.9 and 0.4 V in [EMIm]BF4 with inset photos showing 20C film at -0.9 V and 0.4 V ; (b) UV-Vis transmission spectra of 20C films measured in various electrolytes at wavelength from 300 to 800 nm; (c) Temporal response of the transmittance of 20C films measured in various electrolytes; (d) Coloring efficiencies of 20C films in various electrolytes, respectively

Fig. 4 Cyclic voltammetry curves of 20C films at scan rates from 10 to 70 mV∙s-1 in (a) LiClO4/PC, (b) NaClO4/PC solution, (c) [EMIm]BF4, and (d) [BMIm]BF4 with inset showing peak current at different scan rates (ip) as a function of square root of the scan rate (V1/2)); (e) Nyquist impedance data (dots) and corresponding fitting results (lines) of 20C films in various electrolytes, respectively with inset showing corresponding equivalent circuit; (f) Calculated diffusion coefficients of 20C films in various electrolytes from electrochemical impedance spectroscopy and cyclic voltammetry, respectively

Fig. 5 Photos of (a) bleaching state and (b) coloring state of Cu3(HHTP)2 EC device, and (c) UV-Vis transmission spectra of Cu3(HHTP)2 EC devices at voltages of +3 and -3 V

Fig. 6 (a) Structure diagram of Cu3(HHTP)2 and poly (3,4-ethylene dioxythiophene) (PEDOT) electrochromic multiple device, and (b) UV-Vis transmission spectra of multiple devices at voltages of +3 and -3 V

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Cu₃(HHTP)₂ Film-based Ionic-liquid Electrochromic Electrode

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