Properties of Thin Lithium Metal Electrodes in Carbonate Electrolytes with Realistic Parameters

To understand the baseline performance of lithium (Li) anode in liquid electrolytes, the electrochemical and physical properties of the Li anode are studied with realistic parameters, including thin thickness (50 μm), practical areal capacity (1-4 mA h cm^-2), practical areal current (0.5-2 mA cm^-2), and low electrolyte/capacity ratio. Two different Li salts, lithium hexafluorophosphate (LiPF₆) and lithium bis(fluorosulfonyl)imide (LiFSI), are used to probe the effects of the electrolyte chemistry and concentration. The cycling of Li/Li symmetric cells, combined with the scanning electron microscopic investigation, demonstrates that the soft-short of Li/Li cells is induced by the continuous volume expansion of Li electrodes during cycling instead of dendrites. The volume change of a Li electrode is dictated by the depth of deposition and stripping (i.e., areal capacity) and the electrolyte/capacity ratio, with no strong correlation with the type of Li salt and concentration. On the other hand, the average Coulombic efficiency (CE) measurement demonstrates inherent correlation with the type of Li salt and its concentration in the electrolyte. Li electrode surface chemical analysis indicates that the fluoride-rich surface layer formed in the LiPF₆ electrolyte can be detrimental to both CE and Li deposition-stripping overpotential.