Investigating the abnormal conductivity behaviour of divalent cations in low dielectric constant tetraglyme-based electrolytes
Résumé
Solutions made of tetraglyme (G4) containing Ca(TFSI)2 have been studied as models to understand the
solvation structure and the conductivity properties of multivalent ions in low dielectric constant ethereal
electrolytes. These solutions have been characterised using electrochemical impedance spectroscopy,
rheological measurement, and Raman spectroscopy. The ionic conductivity of these electrolytes shows
an intriguing non-monotonic behaviour with temperature which deviates from the semi-empirical
Vogel–Tammann–Fulcher equation at a critical temperature. This behaviour is observed for both
Mg(TFSI) 2 and Ca(TFSI)2, but not LiTFSI, indicating a difference in the solvation structure and the
thermodynamic properties of divalent ions compared to Li +
. The origin of this peculiar behaviour is
demystified using temperature-controlled Raman spectroscopy and first-principles calculations
combined with a thermodynamic analysis of the chemical equilibrium of Ca2+ ion-pairing versus
solvation. As long-range electrostatic interactions are critical in solutions based on low dielectric
ethereal solvents, a periodic approach is here proposed to capture their impact on the solvation
structure of the electrolyte at different salt concentrations. The obtained results reveal that the
thermodynamic and transport properties of Ca(TFSI)2/G4 solutions stem from a competition between
enthalpic (ionic strength) and entropic factors that are directly controlled by the solution concentration
and temperature, respectively. At high salt concentrations, the ionic strength of the solution favours the
existence of free ions thanks to the strong solvation energy of the polydentate G4 solvent conjugated
with the weak complexation ability of TFSI. At elevated temperatures, the configurational entropy
associated with the release of a coordinated G4 favours the formation of contact ion-pairs due to its flat
potential energy surface (weak strain energy), offering a large configuration space. Such a balance
between ion-pair association and dissociation not only rationalises the ionic conductivity behaviour
observed for Ca(TFSI)2/G4 solutions, but also provides valuable information to extrapolate the ionic
transport properties of other electrolytes with different M(TFSI)n salts dissolved in longer-chain glymes
or even poly(ethylene oxide). These findings are essential for the understanding of solvation structures
and ionic transport in low-dielectric media, which can further be used to design new electrolytes for
Li-ion and post Li-ion batteries as well as electrocatalysts.
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