Long cycle and calendar life of Si-based Li-ion batteries enabled by localized high-concentration electrolytes and their surprising water tolerance

Silicon-based anodes promise an increase in energy density for Li-ion batteries, yet they suffer from a poor calendar life. Researchers have posited that fluorinated lithium salt forms reactive side products that destroy the solid electrolyte interphase (SEI), even without cycling. HF is one such reactive side product formed from trace water contamination in the electrolyte. Some electrolytes, such as localized high concentration electrolytes (LHCEs) may improve cell stability in highly reactive systems, such as Li metal and Si. In the present study, LHCEs containing 200–300 ppm of water retained up to 8% greater capacity (1200–1300 mAh/g Si) in calendar life tests over 200 days compared to dried electrolytes ( < 20 ppm water). Calendar aging took place at 100% state of charge. Cells with 200–300 ppm water performed comparably to cells with 20 ppm water in cycle life tests (900–1000 mAh/g Si) . Even adding 1000 ppm water did not lead to rapid capacity fade in cells undergoing cycle life tests. Nano-FTIR spectroscopy revealed chemical and structural differences in the SEI for cells with 1000 ppm water compared to 200–300 ppm water. The SEI differences, including increased Li 2 O concentration, may have contributed to improved calendar life. This research reveals the capabilities of LHCEs to improve the calendar and cycle life of Si-based Li-ion batteries, despite the presence of a highly reactive contaminant. • Localized high concentration electrolytes enable capacity retention for Si anodes. • High water concentration (200 ppm) does not negatively impact calendar aging. • Lithium oxide in the solid electrolyte interphase may contribute to cell stability.