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New Insights into Pseudocapacitive Charge-Storage Mechanisms inLi-Birnessite Type MnO2 Monitored by Fast Quartz CrystalMicrobalance Methods

Abstract : Fast ionic transfer and transport properties continue to be one of the main pressing research concerns regarding energy storage materials (batteries, supercapacitors). Accompanying this search for optimal materials, appropriate characterization tools to assess key parameters of newly developed materials are required. In spite of its great relevance, fast electrogravimetric methods, i.e., coupling fast quartz crystal microbalance (QCM) and electrochemical impedance spectroscopy(EIS) (ac-electrogravimetry), have not yet been used for studying transfer and transport phenomena in materials for charge storage (except for the use of QCM along with cyclic voltammetry experiments (EQCM)). This coupled method, socalledac-electrogravimetry, differs from classical EQCM and measures the usual electrochemical impedance, ΔE/ΔI (ω), andthe mass variations of the film under a sinusoidal potential perturbation, Δm/ΔE (ω), simultaneously. This coupling has theability to detect the contribution of the charged or uncharged species and to separate the anionic, cationic, and free solventcontributions during the various (pseudo)capacitive processes. The Li-birnessite type MnO2 thin films were studied in twodifferent media, LiClO4 and NaClO4, by ac-electrogravimetry. The Li+ ions, Na+ ions, and their respective hydrated ionic speciesare detected to be involved in the pseudocapacitive charge storage of Li-birnessite type MnO2 thin films. The kinetics (fci) andresistance (Rti) of charged and noncharged species transferred at the electrode/electrolyte interfaces and the number of watermolecules in the hydration shell of the ions are estimated considering integer values. The opposite flux direction of free watermolecules was also detected by ac-electrogravimetry. This indicates that there is a population of hydrated Li+ or hydrated Na+ions losing their hydration shell before being transferred at the electrode/electrolyte interfaces. Therefore, the effect ofdesolvation is clearly and experimentally demonstrated. The ac-electrogravimetry responses of the electrodeposited Li-birnessitetype MnO2 thin films can serve as a gravimetric probe for studying the charge-storage mechanisms and extracting subtletiesunreachable with classical tools.
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Submitted on : Friday, December 12, 2014 - 11:43:06 AM
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Carlota Ridruejo Arias, Catherine Debiemme-Chouvy, Claude Gabrielli, Christel Laberty-Robert, Alain Pailleret, et al.. New Insights into Pseudocapacitive Charge-Storage Mechanisms inLi-Birnessite Type MnO2 Monitored by Fast Quartz CrystalMicrobalance Methods. Journal of Physical Chemistry C, American Chemical Society, 2014, pp.26551-26559. ⟨10.1021/jp508543h⟩. ⟨hal-01094410⟩



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