Designing Fluorine-Free Electrolytes for Lithium Metal Batteries.

Fluorination of electrolytes has been a widely used strategy to enable stable cycling in lithium metal batteries. However, a move toward fluorine-free electrolytes is desirable given the safety and environmental concerns surrounding fluorinated materials. Designing these electrolytes requires a comprehensive understanding of bulk electrolyte and interfacial properties in the absence of fluorine, particularly the solvation structures surrounding Li+ and the solid electrolyte interface (SEI) composition. Among fluorine-free Li salts, lithium nitrate (LiNO3) is often used to obtain highly ion-conductive SEI components. However, its poor ion dissociation and rapid consumption upon freshly plated lithium currently hinder its use as the main electrolyte salt. Herein, we show that the modification of Li+ inner solvation structures by employing lithium bis(oxalato)borate (LiBOB) as the secondary salt in LiNO3/diglyme electrolytes synergistically improves both bulk Li+ transport and SEI properties. It significantly enhances ion dissociation, which increases the ionic conductivity of the electrolyte despite an increase in its viscosity. Furthermore, the presence of LiBOB-derived outer SEI components over the LiNO3-derived ion-conductive inner SEI layer results in low-surface-area Li deposits and lower Li+/anion consumption during cycling. The dual-salt fluorine-free electrolyte enables stable, long-term cycling in Li/Cu cells for >700 cycles and shows promising capacity retention in Li/LFP full cells at ambient temperature. Our work highlights the importance of tuning the Li+ solvation structures for optimizing bulk and interface properties in fluorine-free electrolytes and presents a viable pathway toward the development of greener electrolytes for lithium metal batteries.