Colorless/Black Switching Electrochromic Device Based on WO3·xH2O and Reversible Metal Electrodeposition

doi:10.15541/jim20250017

Abstract

Abstract:

Electrochromic (EC) smart windows utilizing a reversible metal electrodeposition device (RMED) offer a compelling alternative for dynamically regulating transmissions of optical and thermal energy. An EC device (ECD) is constructed by reversible metal electrodeposition (RME) of Bi/Cu on WO₃·xH₂O film electrodeposited onto fluorine-doped tin oxide (FTO) transparent conductive glass. The electrolyte consists of CuCl₂, BiCl₃, KCl and HCl aqueous solution, supplying necessary components for both electrochemical and electrodeposition processes. The ECD shows ability to rapidly transition between colorless and black states, which achieves a large optical modulation of 77.0% at 570 nm. In the black state, the ECD exhibits a near-zero transmittance in the wavelength range of 400-1100 nm while maintaining 96.6% of its initial optical modulation after coloration/bleaching cycling of 60000 s, exhibiting good cyclic stability. This RMED has relatively high stability under open-circuit voltage and also possesses excellent heat insulation performance. The results offer a solution to overcome the poor cyclic stability of RMEDs and improve the optical modulation of ECDs.

Key words: reversible metal electrodeposition, electrochromic, WO₃·xH₂O

CLC Number:

TQ174

WAN Xinyi, WANG Wenqi, LI Jiacheng, ZHAO Junliang, MA Dongyun, WANG Jinmin. Colorless/Black Switching Electrochromic Device Based on WO₃·xH₂O and Reversible Metal Electrodeposition[J]. Journal of Inorganic Materials, 2025, 40(10): 1163-1174.

Figures/Tables 11

Fig. 1 Schematic illustration and photos of the RMED (a, b) Schematic diagrams of the RMED in the (a) bleached state and (b) colored state; (c, d) Photos of the RMED (c) after 40 s of metal stripping at 1.0 V and (d) after 30 s of metal electrodeposition at -3.0 V

Fig. 2 Mechanism of stripping reactions in the Bi/Cu halide electrolyte

Fig. 3 Mechanisms of chemical and electrochemical reactions in the RMED during operation (a) Colored state (metal electrodeposition); (b) Bleached state (metal stripping)

Fig. 4 GIXRD patterns of the Bi/Cu electrodeposited on the WO3·xH2O film

Fig. 5 SEM images and EDS mappings (a, b) SEM images of (a) WO3·xH2O film and (b) Bi/Cu nanoparticles; (c-f) EDS mappings of Bi/Cu nanoparticles

Fig. 6 Electrochemical behavior of the WO3·xH2O film (a) CV curve at a scan rate of 10 mV·s-1; (b) CV curves at different scan rates; (c) Linear relationship between lgi and lgv; (c, d) Contribution of surface capacitance to total charge storage (shaded area) in CV curves at scan rates of (d) 10 and (e)100 mV·s-1; (f) Proportion of charge storage attributed to diffusion-controlled and surface capacitance characteristics at various scan rates. Colorful figures are available on website

Fig. 7 Optical characteristics of the RMED (a) Transmission spectra at the colored and bleached states measured at -3.0 and 1.0 V, respectively; (b) Solar irradiance spectra of the colored and bleached states measured at -3.0 and 1.0 V, respectively. Colorful figures are available on website

Fig. 8 Electrochemical and EC properties of the RMED (a) Duration needed for the RMED to go from coloration to bleaching at a wavelength of 570 nm when operating at open circuit voltage; (b) Real-time transmittance curve of the RMED recorded at 570 nm by applying a square wave potential of -3.0 V for 30 s and 1.0 V for 40 s; (c) Optical density variations with respect to charge density; (d) Cyclic performance of the RMED measured by applying -3.0 V for 30 s and 1.0 V for 40 s

Fig. 9 Infrared blocking performance of the RMED smart window in a model house (a) Schematic diagram of the indoor temperature change experiment using the model house; (b) Indoor temperature change curves of each mode during heating process of the house; (c) Physical pictures of the house during heating and heating-stopping simulation; (d) Indoor temperature change curves of each mode during the heating-stopping process

Fig. S1 Real-time transmittance curves at 570 nm for RMEDs with different metal atomic ratios under coloration (-3.0 V) and bleaching (1.0 V) conditions (a) Cu:Bi = 5 : 1; (b) Cu:Bi = 4 : 1; (c) Cu:Bi = 2 : 1; (d) Cu:Bi = 1 : 1; (e) Cu:Bi = 1 : 2; (f) Cu:Bi = 1 : 3

Fig. S2 Electrochromic properties of the RMED without WO3·xH2O film (a) Transmission spectra in the colored (-3.0 V for 30 s) and bleached (1.0 V for 40 s) states; (b) Real-time transmittance curve at 570 nm

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Colorless/Black Switching Electrochromic Device Based on WO₃·xH₂O and Reversible Metal Electrodeposition

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