Electrochromic WO3 Thin Films: Preparation by Nanocrystalloid Liquid Phase Coating and Performance Optimization

doi:10.15541/jim20230118

Abstract

Abstract:

Electrochromic materials have been applied in energy-saving buildings, intelligent displays, and other fields, recognized as one of the most promising intelligent materials for research. Liquid phase method for preparation of WO₃ electrochromic thin filmscan construct complex polychromies structures, showing great potential in modulation amplitude and short response time, especially in large area and low cost preparation. This study aims to develop a low-cost, easy-to-scale WO₃nanocrystalline liquid phase coating process, and improve cycle stability and preparation process. WO₃ electrochromic films with high modulation amplitude, rapid response and fatigue resistance were prepared. Optimized the annealing process, WO₃ nanopowders were synthesized with low aggregation and high crystallinity, and then WO₃ nanocrystalline coating solution was prepared by ball milling dispersion. Thin film microstructure and coating solution crystallinity were optimized. The obtained thin electrochromic films of WO₃ show high tuning amplitude (82%), short response time (t_c/t_b: 8 s/4.2 s), high colouring efficiency (81.5 cm²·C^-1), and high cycling stability (> 1000 times). In this work, the crystallization and dispersion properties of WO₃ nano-powder were modified to comprehensively improve the performance of WO₃ electrochromic films prepared by nanocrystalline liquid phase coating technology. All results above demonstrate that the WO₃ electrochromic film prepared by the liquid phase method is expected to be used in the future with high color-changing performance and cycle stability.

Key words: electrochromic, WO₃, nano dispersion, liquid phase coating

CLC Number:

TQ174

CHEN Zhang, ZHAO Ruoyi, HAN Shaojie, WANG Huanran, YANG Qun, GAO Yanfeng. Electrochromic WO₃ Thin Films: Preparation by Nanocrystalloid Liquid Phase Coating and Performance Optimization[J]. Journal of Inorganic Materials, 2023, 38(11): 1355-1363.

Figures/Tables 11

Fig. 1 Thermogravimetric analyses of different samples (a) Thermogravimetric analysis curves of samples; (b) DSC curve of WO3 precursors

Fig. 2 Morphology analyses and XRD patterns of WO3 powders after annealed at different temperatures (a-d) Digital photographs; (e) XRD patterns and (g-j) SEM images of WO3 powders; (f) SEM image of WO3 powders without CTAB

Fig. 3 FT-IR spectra of WO3 at different stages

Fig. 4 XRD patterns of WO3 powders after drying

Fig. 5 Pictures of WO3 annealed at different temperatures (a-d) Digital photographs of WO3 dispersions and (e-g) TEM images at (a, g) 500, (b, f) 600, (c, e) 700, and (d) 800 ℃

Fig. 6 UV-Vis absorbance spectrum of the WO3 dispersion held in a quartz cell Inset: plot of (ahv)1/2 against hv to achieve the bandgap

Fig. 7 Measured digital photos of three electrode system films

Table 1 Electrochromic properties of tungsten oxide films annealed at different temperatures

WO₃ thin film	ΔT/%	(t_c/t_b)/s	CE/(cm²·C^-1)
W500	72.8	11/12	52.6
W600	75.3	8/10	54.3
W700	78.6	7/6	64.8
W800	75.2	13/12	61.2

Fig. 8 Electrochemical performances of thin film W700 (a) Transmittance spectra; (b) Coloring efficiency plot; (c) Cyclic transmittance curves; (d) Chronograph current curve

Fig. 9 Dynamic scattering results of dispersions before (a) and after (b) hydrothermal treatment

Fig. 10 Optical performance of thin films made from dispersions before (a, b) and after (c, d) hydrothermal treatment (a, c) Cyclic transmittance curves ; (b, d) Coloring efficiency plots

References 26

[1]	GRANQVIST C G. Solar energy materials. Advanced Materials, 2003, 15(21): 1248.
[2]	BEAUJUGE P M, REYNOLD J R. Color control in pi-conjugated organic polymers for use in electrochromic devices. Chemical Reviews, 2010, 110(1): 268. DOI PMID
[3]	MCEVOY T M, STEVENSON K J, HUPP J T, et al. Electrochemical preparation of molybdenum trioxide thin films: effect of sintering on electrochromic and electroinsertion properties. Langmuir, 2016, 19(10): 4316. DOI URL
[4]	GRANQVIST C G. Progress in electrochromics: tungsten oxide revisited. Electrochimica Acta, 1999, 44(18): 3005. DOI URL
[5]	GRANQVIST C G. Electrochromic materials: out of a niche. Nature Materials, 2006, 5(2): 89. DOI
[6]	GRANQVIST C G. Oxide electrochromics: an introduction to devices and materials. Solar Energy Materials & Solar Cells, 2012, 99(4): 1. DOI URL
[7]	WEN R T, GRANQVIST C G, NIKLASSON G A. Eliminating degradation and uncovering ion-trapping dynamics in electrochromic WO₃ thin films. Nature Materials, 2015, 14(10): 996. DOI
[8]	XIA X, CHAO D, QI X, et al. Controllable growth of conducting polymers shell for constructing high-quality organic/inorganic core/shell nanostructures and their optical-electrochemical properties. Nano Letters, 2013, 13(9): 4562. DOI PMID
[9]	MORTIMER R J, DYER A L, REYNOLDS J R. Electrochromic organic and polymeric materials for display applications. Displays, 2006, 27(1): 2. DOI URL
[10]	MA D, WANG J, ENGINEERING E M, et al. Inorganic electrochromic materials based on tungsten oxide and nickel oxide nanostructures. Science China (Chemistry), 2017, 60(1): 9.
[11]	GILLASPIE D T, TENENT R C, DILLON A C. Metal-oxide films for electrochromic applications: present technology and future directions. Journal of Materials Chemistry, 2010, 20(1): 168.
[12]	CHEN G X, MIYAUCHI M, SHIMIZU H. UV-induced surface electrical conductivity jump of polymer nanocomposites. Applied Physics Letters, 2008, 92(20): 787.
[13]	ZHU W, LIU J, YU S, et al. Ag loaded WO₃ nanoplates for efficient photocatalytic degradation of sulfanilamide and their bactericidal effect under visible light irradiation. Journal of Hazardous Materials, 2016, 2016(1): 407.
[14]	LI Y, LI X, YANG C, et al. Controlled synthesis of CdS nanorods and hexagonal nanocrystals. Journal of Materials Chemistry, 2003, 13(10): 2641. DOI URL
[15]	DEEPA M, SINGH D P, SHIVAPRASAD S M, et al. A comparison of electrochromic properties of Sol-Gel derived amorphous and nanocrystalline tungsten oxide films. Current Applied Physics, 2007, 7(2): 220. DOI URL
[16]	CHEN X C, LI Y G, WANG H Z, et al. Morphology regulation and photoelectric performance of hole transport layer WO₃ for QLED. Journal of the Chinese Ceramic Society, 2014, 33(5): 1141.
[17]	GUO Y, MURATA N, ONO K, et al. Production of ultrafine particles of high-temperature tetragonal WO₃ by dc arc discharge in Ar-O₂ gases. Journal of Nanoparticle Research, 2005, 7(1): 101. DOI URL
[18]	JIAO Z H, SUN X W. Hydrothermally grown nanostructured tungsten trioxide (hydrate) films and their photocatalytic properties. MRS Proceedings, 2012, 1406: mrsf11-1406-z18-16.
[19]	CAI W L, SU X T, WANG J D. Surfactant-assisted ultrasonic synthesis of nano-tungsten oxide powder. China Tungsten Industry, 2008, 14(6): 26.
[20]	ZHOU D, SHI F, XIE D, et al. Bi-functional Mo-doped WO₃ nanowire array electrochromism-plus electrochemical energy storage. Journal of Colloid and Interface Science, 2016, 465(112): 120.
[21]	CAI G F, TU J P, ZHOU D, et al. The direct growth of a WO₃ nanosheet array on a transparent conducting substrate for highly efficient electrochromic and electrocatalytic applications. CrystEngComm, 2014, 16(30): 6866. DOI URL
[22]	MORALES A E, MORA E S, PAL U. Use of diffuse reflectance spectroscopy for optical characterization of un-supported nanostructures. Sociedad Mexicana de Física A.C, 2007, 53(5): 18.
[23]	LEE Y, LEE T, JANG W, et al. Unraveling the intercalation chemistry of hexagonal tungsten bronze and its optical responses. Chemistry of Materials, 2016, 28(13): 286.
[24]	YAO Y, ZHAO Q, WEI W, et al. WO₃ quantum-dots electrochromism. Nano Energy, 2019, 68(10): 43.
[25]	ZHAO Q, FANG Y, QIAO K, et al. Printing of WO₃/ITO nanocomposite electrochromic smart windows. Solar Energy Materials & Solar Cells, 2019, 2(2): 95.
[26]	PAIK T, CARGNELLO M, GORDON T R, et al. Photocatalytic hydrogen evolution from substoichiometric colloidal WO_3-_x nanowires. ACS Energy Letters, 2018, 3(8): 19.

Electrochromic WO₃ Thin Films: Preparation by Nanocrystalloid Liquid Phase Coating and Performance Optimization

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