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A Diffusional Study of Electrochromical Effect and Electrointercalation of Li+ Ions in WO3 Thin Films

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Abstract

This paper presents a study of physical and electrochemical properties relevant to the lithium ion diffusion process governing WO3 thin films electrochromic phenomenon. The films were prepared from a solution obtained by the sol–gel process and deposited via dip-coating. They were characterized by chronocoulometry, chronoamperometry and in and ex situ ultraviolet–visible spectroscopy during coloring/bleaching of the films. To analyze the experimental data, a mathematical model was applied considering a reaction kinetics controlled by the diffusion of ion pairs. The effects of the intercalation of Li+, Na+ and K+ ions was compared. Theoretical and experimental results for the current, charge density and absorbance profiles in function of time are included in this paper. The highest values obtained were \( \eta = 29.98\,{\text{C/cm}}^{2} \) for electrochromic efficiency, ΔT = 61.6% for optical modulation, \( Q_{i} = 81.78\,{\text{mC/cm}}^{2} \) for charge density, and reversibility of coloring/bleaching in the range of 75–90%. X-Ray diffractometry measurements confirmed the amorphous structure of the films. Fourier transform infrared spectroscopy was employed to analyze the functional groups present in the films structure, while their topology was studied via atomic force microscopy. The collected results confirmed a relationship between the electrochromic and electrochemical reactions, definitively associating color change with cations injection and the reduction of W6+ to W5+.

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Acknowledgments

The authors acknowledge Fundação de Amparo à Pesquisa do Estado de Rio Grande do Sul (FAPERGS, Grant 19/2551-00011856-8), The Brazilian National Council for Scientific and Technological Development (CNPq, Grants 308752/2017-1 and 307429/2017-2), and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brazil (Capes, Grants 1780078 and 88887.481413/2020-00) for the financial support given to this research.

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Authors and Affiliations

  1. Centro de Desenvolvimento Tecnológico, Universidade Federal de Pelotas, Rua Gomes Carneiro 1, Centro, 96010-610, Pelotas, RS, Brazil

    Marco P. Rodrigues, Camila M. Cholant, Luana U. Krüger, Lourenzo M. Rodrigues & César O. Avellaneda

  2. Instituto de Física e Matemática, Universidade Federal de Pelotas, Campus Capão de Leão, Pelotas, RS, 96001-970, Brazil

    Javier A. Gomez

  3. Instituto de Matemática, Estatística e Física, Universidade Federal do Rio Grande, Campus Carreiros, Av. Itália km 8, Rio Grande, RS, 96203-900, Brazil

    João F. Prolo Filho

  4. Campus Bagé, Universidade Federal de Pampa, Rua Maria A.G. de Godoy 1650, Bagé, RS, 96413-170, Brazil

    Wladimir H. Flores & André Gündel

  5. IQSC-Universidade de São Paulo, Av. Trabalhador Sãocarlense 400, São Carlos, SP, 13566-590, Brazil

    Agnieszka Pawlicka

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  1. Marco P. Rodrigues
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Rodrigues, M.P., Cholant, C.M., Krüger, L.U. et al. A Diffusional Study of Electrochromical Effect and Electrointercalation of Li+ Ions in WO3 Thin Films. J. Electron. Mater. 50, 1207–1220 (2021). https://doi.org/10.1007/s11664-020-08648-z

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