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Numerical simulations are a powerful tool for the development and improvementof Li-ion batteries. Modeling the mass transport of the involved electrolyticsolutions requires precise determination of the corresponding electrolyteparameters. In this work, we attempt to measure the conductivity, the diffusioncoefficient, the transference number and the thermodynamic factor for a systemof 0.5$\,$M LiPF$_6$ dissolved in a blend of ethylene carbonate and ethylmethyl carbonate (EC:EMC, 3:7 weight) at 20$\,${\deg}C and 50$\,${\deg}C.Applying galvanostatic polarization experiments to symmetrical metal Li |electrolyte + separator | Li metal cells reveals, however, a potential responsequalitatively deviating from theoretical expectations. Impeded diffusionprocesses indicate the presence of additional, undesired porous structures onthe Li electrodes, preventing a reliable evaluation of the electrolyteparameters. To spectrally resolve the diffusive processes, we conductvery-low-frequency impedance spectroscopy. The impedance in fact exhibitsmultiple interfering diffusive features. In our measurements, an explicitidentification of the impedance for the sole diffusion through the separator ishowever not feasible. Therefore, the authors doubt that polarizing experimentsusing Li metal electrodes yield accurate parameters for electrolytes.

Challenges in Measuring Transport Parameters of Carbonate-based Electrolytes