Molecular Design of Mono-Fluorinated Ether-Based Electrolyte for All-Climate Lithium-Ion Batteries and Lithium-Metal Batteries.

Fluorinated-ethers are promising electrolyte solvents in lithium metal batteries, for their high antioxidant and excellent reductive stability on Li anode. However, fluorinated-ethers with high fluorination degree suffer from low ionic conductivity and narrow temperature adaptibility. Herein, we synthesize a mono-fluorinated linear ether of bis(2-fluoroethoxy) methane (BFME) with enhanced solvated ability. The -OCH2O- structure and fluoride substitution on the ß-C position endows the BFME electrolyte with moderate affinity to Li+, thereby improving the ionic conductivity and decreasing the Li+-desolvation energy barrier at a wide temperature range of -60-60 °C. Additionally, the electrolyte with anion-participated solvation structure demonstrates high film-forming ability by forming LiF-rich interfacial film on the electrode surfaces, rendering the graphite anode with an initial Coulombic efficiency (CE) of 94.9 % and a Li plating/stripping CE of 99.8 % by Aurbach method. Consequently, the Graphite||LiFePO4 pouch cells delivered 83.2 %, 92.5 % and 81.2 % capacity retention after 1250, 200 and 300 cycles at 25, -20 °C and 60 °C, respectively. Moreover, the Li||LFP pouch cell with 3 Ah capacity can operate for 65 cycles with 99 % capacity retention, verifying the effectiveness of the BFME electrolyte in stabilizing the interfaces and broadening the temperature adaptibility of lithium-ion and lithium metal batteries.

A Fully Methylated Cyclic Ether Solvent Enables Graphite Anode Cycling at Low Temperatures.

Graphite anode suffers from great capacity loss and larger cell polarization under low-temperature conditions in lithium-ion batteries (LIBs), which are mainly caused by the high energy barrier for the Li+ desolvation process and sluggish Li+ transfer rate across the solid electrolyte interface (SEI). Regulating an electrolyte with an anion-dominated solvation structure could synchronously stabilize the interface and boost the reaction kinetics of the graphite anode. Herein, a highly ionic conductive electrolyte consisting of a fully methylated cyclic ether solvent of 2,2,4,4,5,5-hexamethyl-1,3-dioxolane (HMD) and fluoroethylene carbonate (FEC) cosolvent was designed. The high electron-donating effect and steric hindrance of -(CH3)2 in HMD endow the HMD-based electrolyte with high ionic conductivity but lower coordination numbers with Li+, and an anion-dominated solvation structure was formed. Such configuration can accelerate the desolvation process and induce the forming of a LiF-rich SEI film on the anode, avoiding the solvent coembedding into graphite and enhancing the ion migration rate under low temperatures. The assembled Li||graphite cell with the tame electrolyte outperformed the conventional carbonates-based cell, showing 93.8% capacity retention after 227 cycles for the DF-based cell compared to 64.7% after 150 cycles. It also exhibited a prolonged cycle life for 200 rounds with 81% capacity retention under -20 °C. Therefore, this work offers a valuable thought for solvent design and provides approaches to electrolyte design for low-temperature LIBs.