Fluorine-Rich Electrolyte Additive for Achieving Dendrite-Free Lithium Anodes at Low Temperatures

The practical application of lithium metal anodes is significantly impeded by poor interfacial stability and uncontrolled dendrite growth. Herein, we introduce methyl trifluoroacetate (MTFA), a low-melting-point small molecule, as an electrolyte additive in an ether-based electrolyte. This additive facilitates the formation of an in situ composite solid electrolyte interphase (SEI) layer that is rich in LiF and features an ester-based flexible matrix. The resulting composite layer exhibits high ionic conductivity and mechanical stability, effectively regulating the lithium deposition behavior over a broad temperature range and inhibiting dendrite formation. Based on MTFA, the Li||Li symmetrical cell achieves a lifespan exceeding 5000 h at room temperature and 800 h at −20 °C, both with ultralow overpotential and exceptional cycling stability. In Li||LiFePO4 full cells with a high-area loading (10.52 mg cm–2) and an N/P ratio of 1.68, an average capacity decay of merely 0.096% per cycle is observed over 200 cycles. Even at −20 °C, the Li||LiFePO4 cell shows a CE of over 99% and maintains stable cycling performance. This work provides an innovative approach for optimizing lithium metal anode interfaces and enhancing low-temperature operation capabilities through the use of electrolyte additives.