Small dissymmetry, yet large effects on the transport properties of electrolytes based on imide salts: Consequences on performance in Li-ion batteries

Autor: Joseph Chidiac, Mérièm Anouti, Laure Timperman
Rok vydání: 2022
Předmět:
Zdroj: Journal of Energy Chemistry. 65:352-366
ISSN: 2095-4956
DOI: 10.1016/j.jechem.2021.05.054
Popis: To gain better insight into the influence of the anion size and symmetry on the transport properties and thermal stability of an electrolyte based on lithium (fluorosulfonyl)(trifluoromethanesulfonyl)-imide (FTFSI) salt, we performed the physical and electrochemical characterization of an electrolyte based on FTFSI incorporated in standard binary (3EC/7EMC) and ternary (EC/PC/3DMC) alkylcarbonate mixtures. By applying the Jones-Dole-Kaminsky (JDK), Eyring and Arrhenius empirical models to the electrolyte viscosity we show that the activation enthalpy and entropy energy barriers ( Δ H ≠ , Δ S ≠ ) for viscous flow are between 12 and 15 kJ·mol−1. They are strongly dependent on the solvent nature and are significantly lower than their symmetric anions LiFSI and LiTFSI (19–20 kJ·mol−1) in the binary mixture. Furthermore, the hydrodynamic radius, rs, calculated by JDK, and the ionicity behavior illustrated by the Walden role, showed that the FTFSI anion is outside the solvation sphere (rs > 0.6 nm) which is smaller in the case of an EC/EMC solvent base. In the 3EC/7EMC solvent mixture, LiFTFSI is less conductive than in the ternary mixture i.e., σmax = 8.9 mS cm−1 at Cmax = 1.1 mol L−1 for 3EC/7EMC and, σmax = 10.5 mS cm−1 at max = 0.7 mol L−1 for EC/PC/3DMC, due to a strong solvation and a greater association of FTFSI ions in the binary solvent mixture. The thermal stability of FTFSI based electrolytes was determined by the shift of the evaporation temperature of the volatile solvents (DMC, EMC) in the presence of salt, towards the higher temperatures. This feature is visible on the thermograms obtained by DSC both with the liquid electrolyte and with charged LMO cathodes in presence of electrolytes. The consequences of these properties on the electrochemical behavior of a graphite (Gr) half-cell, a lithium metal (Li) anode and a manganese lithium oxide (LMO) cathode demonstrated on the one hand the formation of a thick solid electrolyte interphase (SEI) on graphite that consumed a significant amount of lithium i.e., 18% of total capacity of the first charge. Furthermore, LiFTFSI delivered 95% of the initial capacity C = 360 mAh g−1 at C/10 with EC/PC/3DMC versus 91% when it was combined with 3EC/7EMC C = 348 mAh g−1, while the capacities obtained for LiTFSI in EC/PC/3DMC were the lowest (C = 275 mAh g−1) compared to those of the other salts. After 10 cycles, the capacity loss at C/20 is
Databáze: OpenAIRE
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