Making advanced electrogravimetry as an affordable analytical tool for the battery interface characterization
Résumé
Numerous sophisticated diagnostic techniques have been designed to monitor Electrode-Electrolyte
Interfaces that mainly govern the lifetime and reliability of batteries. Among them, is the
electrochemical quartz crystal microbalance that offers valuable insights of the interfaces once the
required conditions of the deposited film in terms of viscoelastic and hydrodynamic properties are
fulfilled. Herein, we propose a friendly protocol that enlists the elaboration of a homogeneous deposit
by spray coating followed by QCM measurements at multiharmonic frequencies to ensure the film
flatness and rigidity for collecting meaningful data. Moreover, for easiness of the measurements, we
report the design of a versatile and airtight EQCM cell setup that can be used either with aqueous or
non-aqueous electrolytes. We also present, using a model battery material, LiFePO4, how dual
frequency and motional resistance monitoring during electrochemical cycling can been used as a wellsuitable
indicator for achieving reliable and reproducible electrogravimetric measurements. We
demonstrate through this study the essential role of the solvent assisting the lithium ion insertion at
the LiFePO4 interface with a major outcome being the solvent dependent interfacial behavior. Namely
in aqueous media, we prove a near surface desolvation of lithium ions from its water solvation shell as
compared with organic molecules. This spatial dissimilarity leads to a smoother Li-ion transport across
the LFP-H2O interface, hence accounting for the difference in rate capability of LFP in the respective
electrolytes. Overall, we hope our analytical insights on interface mechanisms will help in a wider
acceptance of EQCM-based methods by the battery community.
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