Nanogravimetric studies of tungsten oxide thin films obtained by the polymeric precursor method

Fernandes, V. C.; Santos, Mauro C.; Bulhões, L.O.S.

doi:10.1016/j.tsf.2007.03.040

Cited by 3 publications

(7 citation statements)

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“…These improvements are often attributed to (i) a facilitated transfer and short diffusion length for ions transport, (ii) a high electrode/electrolyte contact area, and (iii) a better stress/strain management of the material during ion intercalation/extraction. 37 A similar study by Vondrak et al investigated the electrochemical insertion of H + , Li + , Na + ions into thin layers of WO 3 by EQCM in propylene carbonate. 5,36 However, none of these methods alone provide the information on the exact identification of the intercalated ionic species, their dynamics of transfer at the interfaces, as well as the role of electrolyte composition and the effect of ions solvation on the intercalation/extraction phenomena.…”

Section: Introductionmentioning

confidence: 97%

“…The equivalent weight values, higher than that of Li + (7 g mol À1 ) were simply attributed to the acetonitrile molecules, accompanying the Li + ions. 37 A similar study by Vondrak et al investigated the electrochemical insertion of H + , Li + , Na + ions into thin layers of WO 3 by EQCM in propylene carbonate. EQCM data of their work also detected molar mass values higher than that would correspond to the cation present in the electrolyte.…”

Section: Introductionmentioning

confidence: 97%

“…After deposition, surfactants can be easily removed from the pores by washing with a suitable alcohol, leading to the porous inorganic replicas of the surfactant phases. [37][38][39][40][41][42] Conducting electrodes coated on the QCM resonator surface are used as working electrodes in an electrochemical cell, and thus, the electrodeposition process can be monitored. These improvements are often attributed to (i) a facilitated transfer and short diffusion length for ions transport, (ii) a high electrode/electrolyte contact area, and (iii) a better stress/strain management of the material during ion intercalation/extraction.…”

Section: Introductionmentioning

confidence: 99%

“…There have been studies using quartz crystal microbalance (QCM) as an in situ gravimetric probe to study the insertion and/or electroadsorption of ions in metal oxide or carbon based electrodes. [37][38][39][40][41][42] Conducting electrodes coated on the QCM resonator surface are used as working electrodes in an electrochemical cell, and thus, the electrodeposition process can be monitored. Materials of interest deposited are studied in terms of mass changes during the electrochemical processes. )…”

Section: Introductionmentioning

confidence: 99%

“…films in acetonitrile solution containing LiClO 4 by QCM measurements during cyclic voltammetry (EQCM) 37. The mass-to-charge ratios…”

mentioning

confidence: 99%

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Ion intercalation dynamics of electrosynthesized mesoporous WO₃ thin films studied by multi-scale coupled electrogravimetric methods

Razzaghi

Debiemme‐Chouvy

Pillier

et al. 2015

Phys. Chem. Chem. Phys.

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Mesoporous WO3 thin films were prepared electrochemically by using an ionic surfactant during the synthesis, and the electrochemical properties are investigated in comparison with their dense analogues. This report specifically highlights the suitability of a time resolved coupled electrogravimetric method to follow meticulously the ion intercalation/extraction phenomena which revealed the enhanced ion intercalation/extraction behavior of electrodeposited mesoporous WO3 thin films for diverse applications in energy storage and electrochromism. This methodology (electrochemical impedance spectroscopy (EIS) and its coupling with a fast quartz crystal microbalance (QCM)) has the ability to detect the contribution of the charged or uncharged species during the electrochemical processes, and to deconvolute the global EQCM responses into the anionic, cationic, and the free solvent contributions. Our study identifies the involvement of several charged species (Li(+), Li(+)·H2O) in the compensation of charge, and H2O molecules indirectly contribute to the process in both dense and mesoporous WO3 thin films. Even a slight contribution of ClO4(-) ions was detected in the case of mesoporous analogues. The results of the study indicate that the transfer resistances of Li(+) and Li(+)·H2O are decreased when the WO3 films are mesoporous. A more significant difference is observed for the larger and partially dehydrated Li(+)·H2O ions, suggesting that increased surface area and pore volume created by mesoporous morphology facilitate the transfer of larger charged species. The relative concentration changes of cations are also magnified in the mesoporous films. The final concentration variations are higher in mesoporous films than that in the dense analogues; ∼4 times and ∼10 times higher for Li(+) and for Li(+)·H2O, respectively. To the best of our knowledge, an unambiguous identification of species other than desolvated cations (e.g. Li(+) ions), the information on their transfer dynamics and quantification of the transferred species have never been reported in the literature to describe the charge compensation process in WO3 based electrodes.

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…films in acetonitrile solution containing LiClO 4 by QCM measurements during cyclic voltammetry (EQCM) 37. The mass-to-charge ratios…”

mentioning

confidence: 99%

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Ion intercalation dynamics of electrosynthesized mesoporous WO₃ thin films studied by multi-scale coupled electrogravimetric methods

Razzaghi

Debiemme‐Chouvy

Pillier

et al. 2015

Phys. Chem. Chem. Phys.

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Real‐Time Mass Change: An Intrinsic Indicator to Dynamically Probe the Electrochemical Degradation Evolution in WO₃

Wang

Zhang

et al. 2022

Adv Materials Inter

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Although tungsten trioxide (WO3) films are considered as the most popular inorganic electrochromic cathode, the irreversible accumulation of lithium ion in it leads to the degradation of cycling stability. In situ monitoring of mass change is critical to intrinsically probe the dynamical degradation evolution of the WO3 films. Based on electrochemical quartz crystal microbalance analysis, a transfer model based on the migration of three mass carriers (lithium ion, perchlorate ion and propylene carbonate) is proposed. Higher potential can boost the migration of mass carriers, benefiting from the intensive driving force. Due to moderate intercalation of mass carriers and smallest difference in molar mass, the excellent electrochemical reversibility at 40 mV s−1 is observed. As the migration of mass carriers progresses, continuous corrosion of the WO3 films results in electrochemical degradation. It is demonstrated that electrochemical quartz crystal microbalance‐based analyses provide a valuable insight for the intercalation and extraction of mass carriers, in favor of further revealing degradation evolution induced by the irreversible intercalation of conductive ions in electrochemical devices.

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Effect of citric acid on photoelectrochemical properties of tungsten trioxide films prepared by the polymeric precursor method

Wang

et al. 2010

Applied Surface Science

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Nanogravimetric studies of tungsten oxide thin films obtained by the polymeric precursor method

Cited by 3 publications

References 28 publications

Ion intercalation dynamics of electrosynthesized mesoporous WO₃ thin films studied by multi-scale coupled electrogravimetric methods

Ion intercalation dynamics of electrosynthesized mesoporous WO₃ thin films studied by multi-scale coupled electrogravimetric methods

Real‐Time Mass Change: An Intrinsic Indicator to Dynamically Probe the Electrochemical Degradation Evolution in WO₃

Effect of citric acid on photoelectrochemical properties of tungsten trioxide films prepared by the polymeric precursor method

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Nanogravimetric studies of tungsten oxide thin films obtained by the polymeric precursor method

Cited by 3 publications

References 28 publications

Ion intercalation dynamics of electrosynthesized mesoporous WO3 thin films studied by multi-scale coupled electrogravimetric methods

Ion intercalation dynamics of electrosynthesized mesoporous WO3 thin films studied by multi-scale coupled electrogravimetric methods

Real‐Time Mass Change: An Intrinsic Indicator to Dynamically Probe the Electrochemical Degradation Evolution in WO3

Effect of citric acid on photoelectrochemical properties of tungsten trioxide films prepared by the polymeric precursor method

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Ion intercalation dynamics of electrosynthesized mesoporous WO₃ thin films studied by multi-scale coupled electrogravimetric methods

Ion intercalation dynamics of electrosynthesized mesoporous WO₃ thin films studied by multi-scale coupled electrogravimetric methods

Real‐Time Mass Change: An Intrinsic Indicator to Dynamically Probe the Electrochemical Degradation Evolution in WO₃