Dynamic Process of Ions Transport and Cyclic Stability of WO3 Electrochromic Film

doi:10.15541/jim20200144

Abstract

Abstract:

The dynamic process of ions transport in electrochromic WO₃ film is usually studied by electrochemical impedance spectroscopy. However, the detailed features are hidden since the ions insertion into WO₃ is a very complex process including structural deformation and phase transformations. Chronopotentiometry is an electrochemical characterization method that measures the response potential of a system under an imposed current. Compared to other dynamic characterization methods (impedance spectroscopy and CV), it allows direct access to the voltage contributions in different states of the solution-electrode system and has frequently been used to investigate kinetic effects such as adsorption and transport phenomena near electrode surface. In this study, chronopotentiometry is creatively applied to study ion transport kinetics and control ions insertion behavior in electrochromic WO₃ film. The results suggest that a large ions insertion flux at the interface of WO₃/electrolyte could broaden ions transport channels due to the fierce lattice expansion during Li⁺ions insertion process, which further improves the ions transportation kinetics and gifts a fast switching speed of optical performance. However, the repeating ions insertion/extraction behaviors at the interface of WO₃/electrolyte for the long-term cycle process can reduce the size of WO₃ grains as a “ball mill effect”. Especially, a large ions transport flux can aggravate the “ball mill effect”. Consequently, the structure of the WO₃ film becomes very dense, which is unfavorable for ions transport and electrolyte permeation. This dense structure also leads to an irreversible accumulation of Li⁺ ions and Li_xWO₃ in the WO₃ host structure, resulting in a decay of optical modulation ability and electrochromic activity. This work offers an efficient method to analyze ion transport kinetics in intercalation materials and a new understanding of the relationship between ion transport behavior and cyclic stability of electrochromic materials.

Key words: WO₃ electrochromic materials, chronopotentiometry, Li ⁺ insertion flux, ions transport dynamic process

CLC Number:

TQ174

ZHOU Kailing, WANG Hao, ZHANG Qianqian, LIU Jingbing, YAN Hui. Dynamic Process of Ions Transport and Cyclic Stability of WO₃ Electrochromic Film[J]. Journal of Inorganic Materials, 2021, 36(2): 152-160.

Figures/Tables 7

Fig. 1 Charge-time curves (a), response current-time curves (b), response potential-time curves (c), and in-situ transmittance curves (d) of WO3 films under different ions insertion flux with 2, 10 and 20 mC·cm-2·s-1

Fig. 2 Evolution of current-time curves of WO3 film by fixing at 20.00 mC·cm-2 under different ions insertion flux with (a) 2, (b) 10, and (c) 20 mC·cm-2·s-1, and contrast of current density evolution (d)

Fig. 3 Evolution of the extracted charge density of WO3 film under different ions insertion flux with (a) 2,(b) 10 and (c) 20 mC·cm-2·s-1, and evolution of trapped ions density upon cycling (d)

Fig. 4 Evolution of potential-time curves of WO3 film under different ions insertion flux with (a) 2, (b) 10 and (c) 20 mC·cm-2·s-1, and contrast of potentials decay (d)

Fig. 5 In situ record of the transmittance of WO3 film at λ=550 nm during the electrochemical test (a) and the transmittance evolution of WO3 film under different ions insertion flux with (b) 2, (c) 10, and (d) 20 mC·cm-2·s-1

Fig. 6 SEM images of WO3 film with different conditions (a) WO3 film at the initial state; (b) WO3-2 film after 5000 cycles; (c) WO3-10 film after 5000 cycles; (d) WO3-20 film after 5000 cycles. The corresponding photographs are inserted

Fig. 7 Schematic diagram of the structural evolution of WO3 film under repeating ions insertion/extraction process

References 37

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Dynamic Process of Ions Transport and Cyclic Stability of WO₃ Electrochromic Film

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