Elucidation of Mass Transport Phenomena in Highly Concentrated Electrolytes during Current Cycling Using In-Situ Interferometry and Finite Difference Method

Understanding electrolyte mass transfer during charge-discharge reactions is essential for developing next-generation storage batteries with high energy densities. In this study, we investigated Li+ transport in a highly concentrated electrolyte (HCE) consisting of an equimolar mixture of lithium bis(fluorosulfonyl)amide (LiFSA) and tetraglyme (G4) under current reversal and re-reversal. Concentration profiles of the electrolyte at a distance of 0-600 mu m from the Li electrodes were obtained using in situ laser interferometry. The Li+ transference numbers and LiFSA diffusion coefficients were calculated from these profiles. Raman spectroscopy suggested that the coordination structure surrounding Li+ ions in the electrolytes mainly contributed to the transference number. A one-dimensional unsteady diffusion equation and the finite difference method were employed to simulate the concentration profiles. The maximum error percentage between the measured and simulated values was only 3%, confirming the accuracy and validity of the interferometric measurements. Our findings on Li-ion transfer in HCEs could promote the rational design of high-energy-density Li-ion batteries with higher cation transference numbers of electrolytes and charge-discharge rates.