Electrochimica Acta, Vol.263, 127-133, 2018
Improving salt-to-solvent ratio to enable high-voltage electrolyte stability for advanced Li-ion batteries
High-voltage stability of LiBF4 -propylene carbonate solutions in intermediate concentration range is studied by means of cyclic voltammetry, galvanostatic cycling and X-ray photoelectron spectroscopy using LiCoPO4 and LiNi0.5Mn1.5O4 cathode materials. Coulombic efficiency improves with increasing salt-to- solvent molar ratio from 1:12 to 1:4 (similar to 0.8 m-2.5 m solutions), reaching 98% at 1C charge/discharge rate for 1:4 electrolyte upon cycling of LiNi0.5Mn1.5O4 up to 5 V vs. Li/ Li+. The same positive trend is observed for discharge capacities, cycling stability and capacity scattering for both high-voltage cathode materials. X-ray photoelectron spectroscopy of the electrodes studied after cycling in solutions of different concentrations does not reveal any drastic difference in surface composition. Interface preformation experiment shows that the presence of the interface layer formed at semi-concentrated 1:4 electrolyte does not have a major impact on the electrochemical properties of the dilute solution. We assume that the enhanced oxidation stability of the concentrated solutions itself is a reason of improving the electrochemical performance rather than the cathode-electrolyte interface properties. (C) 2018 Elsevier Ltd. All rights reserved.
Keywords:Li-ion batteries;Concentrated electrolyte;High-voltage electrolyte;LiBF4;Propylene carbonate