Rate Performance of LiCoO₂ Half-cells Using Highly Concentrated Lithium Bis(fluorosulfonyl)amide Electrolytes and Their Relevance to Transport Properties

抄録

For the rapid charge-discharge performance of Li-ion batteries (LIBs), ionic conductivity (σ) and Li ion transference number (t+) are important parameters of electrolytes. Electrolytes with high t+ alleviate the concentration polarization upon fast charge-discharge, and prevent the diffusion-limited mass transfer of Li+ ions. Recent studies have suggested that certain highly concentrated electrolytes exhibit better rate performances than conventional organic electrolytes despite their lower σ. However, the relationship between the transport properties (t+ and σ) of highly concentrated electrolytes and the enhanced rate performance of LIBs is yet to be elucidated. To evaluate the rate performance of LIBs with highly concentrated electrolytes in terms of transport properties, we investigated the discharge rate capability of LiCoO2 (LCO) half-cells using highly concentrated lithium bis(fluorosulfonyl)amide (Li[FSA]) electrolyte in γ-butyrolactone (GBL), acetonitrile (AN), dimethyl carbonate (DMC), and 1,2-dimethoxyethane (DME) solvents. There was a remarkable solvent dependence of t+, and the highest tLi+current of 0.67 was observed for GBL-based electrolyte measured using the very-low-frequency impedance spectroscopy (VLF–IS) method. The LCO half-cell with GBL-based electrolyte delivered higher discharge capacities than the cells with DMC- and DME-based electrolytes at high current densities. The improved rate performance in GBL-based electrolytes was attributable to enhanced Li+ ion mass transfer derived from the high tLi+current. We demonstrated the importance of tLi+current on the rate capability of LCO half-cells with highly concentrated electrolytes for high-rate battery performance.