With its impressive specific capacity of 3579 mAh/g (when alloyed into Li15Si4 at room temperature), Silicon (Si) anode is widely regarded as an ideal alternative to graphite anodes. However, its commercial viability is still hampered by rapid capacity degradation. Liquid electrolytes based on ethereal solvents such as dimethoxyethane (DME) and diglyme (DG) have demonstrated excellent long-term cycling performance in Li||Si half cells. However, their utilization in full cells like LiNi0.8Mn0.1Co0.1O2 (NMC811)||Si remains limited due to their relatively low oxidation stability at the NMC811 side.In this investigation, innovative electrolyte systems employing Lithium bis(fluorosulfonyl)imide (LiFSI) salt were developed. Various ethereal solvents including DME, DG, 2,2-dimethyl-3,6,9,12-tetraoxa-2-silatridecane (1NM3), and self-synthesized 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG) were methodically examined. Initially, density functional theory (DFT) calculations were utilized to compare the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of these solvents, revealing that 1NM3 and FDG exhibited lowered HOMO levels, suggesting enhanced oxidative stability on the NMC811 cathode side compared to DME and DG. Subsequently, the solvation structure of the prepared electrolyte systems was investigated via Fourier Transform Infrared Spectroscopy (FTIR). The addition of a -CF3 functional group and the weaker dissociation capacity of FDG resulted in significant cation-anion aggregates (AGGs) within the FDG-based electrolytes, while no such AGGs were observed in the DME, DG, and 1NM3-based electrolytes. Electrochemical properties and performances were further evaluated through systematic tests on Li||Al, Li||Si half cells, and LiNi0.8Mn0.1Co0.1O2 (NMC811)||Si full cells. Differential capacity (dQ/dv) profiles from Si||Li half cells revealed their distinct reduction behavior on the Si anode. Potentiostatic hold tests on NMC811||Li half cells demonstrated the superior oxidative stability of FDG-based electrolytes up to 4.5 V vs. Li/Li+. Long-term cycling results confirmed significant improvements with 1NM3 and FDG solvents in NMC811||Si full cells, maintaining a high specific capacity of 900 mAh/g after 500 cycles for the FDG-based electrolytes. Further analysis of the interphases formed on electrodes via depth-profiling X-ray photoelectron spectroscopy (XPS) indicated enhanced oxidative stability on the NMC811 cathode and improved solid electrolyte interphase (SEI) on Si anodes, leading to enhanced electrochemical performance. Thus, our exploration of these ethereal electrolytes has paved the way for strategic advancements in crafting novel electrolytes specifically designed for Si anodes, highlighting their remarkable long-term cycling capabilities within NMC811||Si full cells.
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