Thermally stable electrolyte for lithium‑oxygen battery and its metal-free version

Journal article, 2026

Polyethylene glycol dimethyl ether with molecular weight of 250 (PEGDME 250) is considered a solvent of choice to achieve electrolytes with low volatility and high thermal stability for application in lithium oxygen (Li-O2) cells. The study focuses on the concomitant effect of the conducting salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the sacrificial film-forming salt lithium nitrate (LiNO3) both on chemical and electrochemical features. The electrolytes reveal conductivity ranging from ∼10 ⁻³ S cm⁻¹ at 85 °C to ∼10 ⁻⁴ S cm⁻¹ at −7 °C, and Li⁺ transference number (t+) approaching 0.6. The concomitant incorporation of LiTFSI and LiNO3 significantly modifies the thermal characteristics of the electrolyte due to specific salt-solvent interactions. Furthermore, LiNO3 actually enhances the solid electrolyte interphase (SEI), stabilizes the Li, and improves the conductivity below 61 °C without significantly altering the t+ value. Despite the Li-O2 cell can operate suitably even without LiNO3 addition where a capacity limit of 0.5 mAh cm⁻² (500 mAh g⁻¹) is exploited, the one added by LiNO3 can reversibly deliver a higher capacity (4500 mAh g⁻¹, 5.4 mAh cm⁻²) than the bare solution (2000 mAh g⁻¹, 2.2 mAh cm⁻²) if the voltage cutoff is used. On the other hand, the solution added by LiNO3 enhances the performance of the metal-free (Li-ion) version of the cell using O2 and LixSn@C alloying anode, with capacity ranging from 50 to 450 mAh g⁻¹ delivered at currents from 0.1 to 3 mA cm⁻². These findings may favor the achievement of high-energy storage systems with low cost and environmental sustainability.