Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System

Although localized high-concentration electrolytes (LHCEs) have been shown to improve the calendar lifetime of silicon anodes, the roles of the electrolyte constituents in calendar aging are not well understood. Here, in this work, we utilize a voltage hold protocol and an LHCE with varying molar ratios of lithium bis(fluorosulfonyl)imide (LiFSI), tetramethylene sulfone (TMS), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to probe the component roles during aging. Interestingly, the estimated calendar lifetime and irreversible lithium losses from the V-hold experiments are independent of the electrolyte formulations. Contrarily, the solid electrolyte interphase (SEI) composition depends on the electrolyte formulation. X-ray photoelectron spectroscopy shows that TMS-coordinated species decompose to form insoluble alkanes and lithium hydroxide (LiOH), while lithium fluoride (LiF) originates from the anion-coordination complex. The SEI composition does not appear to play a significant role in the silicon anode passivity, as measured by parasitic current, suggesting that the SEI-electrolyte interactions dictate the calendar aging mechanisms.. Authors: Lam, Steven [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)] (ORCID:0000000156429939); Verma, Ankit [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000276108574); Schulze, Maxwell C. [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000183684054); Sacci, Robert L. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000200735221); Meyer III, Harry M. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000349941664). DOE Contract: AC02-06CH11357; AC05-00OR22725; AC36-08GO28308. Subjects: Si anode; calendar aging; localized high concentration electrolytes; parasitic reactions; solid electrolyte interphase