Abstract
The interactions of various types of cations with the tungsten trioxide lattice have been investigated to evaluate possible intercalation of these cations and the occurrence of lattice polarization leading to the near-surface structural lattice damage. The interactions of cations, such as the large monovalent cations (K+, Et4N+, CtMe3N+ cations), transition metal dications (Ni2+), heavy metal ions (Cd2+), and representative lanthanides (La3+) and actinides (Th4+), in competition with intercalation of H+ ions have been investigated using pulse-nanogravimetric technique. The effects of these cations in electrochromic processes of WO3 proceeding during cathodic reduction have been assessed. For all of the metal ions studied, a large increase in the apparent mass uptake (up to eightfold) in comparison to pure H+ ion ingress was observed upon the film coloration induced by a cathodic potential pulse. The experiments indicate that the apparent mass gains, although large, are insufficient to confirm predominant contribution of metal ions in the ion transport along the channels in WO3 lattice. The lower decoloration rate in the case of Ni2+ ions, in comparison to H+ and other transition metal cations (Cd2+), has been attributed to a slow dissociation of Ni2+ ions from lattice-bound oxygen atoms. For et4N+ cation, which is too large to enter channels in WO3, a dissociative reduction of the WO3 and severe lattice damage was observed. Among the metal ions investigated, only K+ ions have been found to cause a dissociative reduction of WO3 and near-surface lattice damage. Strong lattice polarization effects and irreversible binding have been found for La3+ and Th4+ cations.
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This work was supported by the National Science Foundation grants no. CCLI-0126402 and 0941364.
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Dedicated to the memory of Professor Vladimir Sergeevich Bagotsky
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Hepel, M., Dela-Moss, L.I. & Redmond, H. Lattice polarization effects in electrochromic switching in WO3−x films studied by pulse-nanogravimetric technique. J Solid State Electrochem 18, 1251–1260 (2014). https://doi.org/10.1007/s10008-013-2219-8
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DOI: https://doi.org/10.1007/s10008-013-2219-8