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Communication Dans Un Congrès Année : 2018

Fast electrogravimetric methods for investigating electrode/electrolyte interfaces in electrochemical storage devices : application to nanostructured metal oxide thin films

Résumé

The need for new materials with improved ion transfer properties continues to be one of the main pressing concerns in energy storage/conversion materials research. In accompanying this search for optimal materials, appropriate characterization tools to assess key parameters of newly developed materials are required. Particularly, the morphology dependent performance, and kinetic or dynamic aspects of ion transfer behaviour of metal oxide electrodes is not very well understood. In the literature, the insertion of ions in metal oxide electrodes was investigated by in situ and ex situ characterization techniques, including electrochemical and gravimetric methods [1-3]. However, none of these methods alone provides the information on the exact identification of the inserted 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 charge compensation phenomena. Therefore, in this work, an alternative characterization tool was proposed which couples fast quartz crystal microbalance (QCM) and electrochemical impedance spectroscopy (EIS) (ac-electrogravimetry) [4-8]. This method has recently been employed for studying transfer and transport phenomena in materials for (pseudo)capacitive charge storage [5-8]. This coupled method, so called ac-electrogravimetry differs from classical EQCM and measures the usual electrochemical impedance, ΔE/ΔI (ω), and the mass variations of the film under a sinusoidal potential perturbation, Δm/ΔE (ω), simultaneously. This coupling has the ability to detect the contribution of the charged or uncharged species and to separate the anionic, cationic, and the free solvent contributions during the various (pseudo)capacitive processes. These features make the ac-electrogravimetry as an attractive and appropriate tool to investigate transfer/transport phenomena of charged and uncharged species in ion insertion materials. As pertinent examples, the adaptation of ac-electrogravimetry to evaluate the ion (Li+, Na+…) transfer in nanostructured metal oxide (MnO2 etc.) based thin films will be discussed in detail. Metal oxide thin films were synthesized by electrodeposition methods and the ion transfer properties (Li+ and Na+ in aqueous and acetonitrile solutions) were investigated by electrochemical quartz crystal microbalance (EQCM) and ac-electrogravimetry. Our study identifies the involvement of several charged species (Li+, Na+ and their solvated counterparts) in the charge compensation, and solvent molecules indirectly contribute to the process. The results of the study indicate that the transfer resistances of the cations, especially that of larger solvated cations are much lower when the metal oxide films are mesoporous, probably due to the increased surface area and pore volume created by mesoporous morphology facilitating the larger charged species transfer. This qualitative and quantitative study of ionic and nonionic species contribution in the charge compensation process, together with dynamic information of their interfacial transfer further proves the advantageous nature of nanostructuration of metal oxide films for potential applications. References [1] Toupin, M.; Brousse, T.; Belanger, D. Chem. Mater. 2004, 16, 3184. [2] Kanoh, H.; Tang, W.; Makita, Y.; Ooi, K. Langmuir 1997, 13, 6845. [3] Kuo, S-L.; Wu, N-L. J. Electrochem. Soc. 2006, 153, A1317. [4] Gabrielli, C; García-Jareño, J. J.; Keddam, M.; Perrot, H.; Vicente, F. J. Phys. Chem. B 2002 106, 3182. [5] Ridruejo Arias, C.; Debiemme-Chouvy, C.; Gabrielli, C.; Laberty-Robert, C.; Pailleret, A.; Perrot, H.; Sel, O. J. Phys. Chem. C 2014, 118, 26551. [6] Razzaghi, F.; Deviemme-Chouvy, C.; Pillier, F.; Perrot, H.; Sel, O. Phys. Chem. Chem. Phys. 2015, 17 (22), 14773. [7] Escobar-Teran, F.; Arnau, A.; Garcia, J.V.; Jiménez, Y.; Perrot, H.; Sel; O. Electrochem. Comm. 2016, 70, 73. [8] Goubaa, H.; Escobar-Teran, F.; Ressam, I.; Gao, W.; El Kadib, A.; Lucas, I. T.; Raihane, M.; Lahcini, M. Perrot, H.; Sel, O. J. Phys. Chem C 2017, 121, 9370.

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hal-03976545 , version 1 (07-02-2023)

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  • HAL Id : hal-03976545 , version 1

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Hubert Perrot, Ozlëm Sel. Fast electrogravimetric methods for investigating electrode/electrolyte interfaces in electrochemical storage devices : application to nanostructured metal oxide thin films. 22nd ISE Topical Meeting, ISE, Apr 2018, Tokyo, Japan. ⟨hal-03976545⟩
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