Highly fluorinated electrolytes are appealing to directly improve the evolution of Li⁺ solvation sheath and arouse high-quality solid-electrolyte interphases (SEIs) for Li metal batteries (LMBs) with stable cycling. Herein, the effect of fluorinated engineering-based electrolytes on Li⁺ solvation structure and the relevant electrochemical performance were systematically investigated. By a selective combination of the ethylene carbonate (EC), diethyl carbonate (DEC), fluoroethylene carbonate (FEC), and ethyl (2,2,2-trifluoroethyl) carbonate (ETFEC), it is found that all-fluorinated electrolyte containing FEC and ETFEC directly optimizes the Li⁺ solvation environments where coordination numbers of Li⁺ decreases from 3.75 in none-fluorinated electrolyte to 3.02 in all-fluorinated electrolyte according to molecular dynamic (MD) simulations. Impressively, fast Li⁺ desolvation in all-fluorinated electrolyte induced stable LiF-rich interface accompanied by the inhibition of Li dendrites, and thus Li||Cu asymmetrical cells achieved high CE of average 98.3% at 0.5 mA cm^–2 as well as superior cycling stability. Encouragingly, the Li||NCM811 cells even retained the initial capacity of 72.3% with an average CE of 99.8% at high voltage (up to 4.6 V) after 225 cycles. This work offers a Li⁺ solvation sheath-directly tuned strategy to construct the ideal interface chemistry for high-performance LMBs.

^{高度氟化的电解质有吸引力直接改善 Li +}溶剂化鞘的演变，并为具有稳定循环的锂金属电池 (LMB) 产生高质量的固体电解质界面 (SEI)。^{在此，系统地研究了氟化工程基电解质对 Li +}溶剂化结构和相关电化学性能的影响。通过选择性组合碳酸亚乙酯（EC）、碳酸二乙酯（DEC）、氟代碳酸亚乙酯（FEC）和（2,2,2-三氟乙基）碳酸乙酯（ETFEC），发现含FEC的全氟电解液ETFEC 直接优化了 Li ⁺的配位数的 Li ^{+溶剂化环境}根据分子动力学 (MD) 模拟，从非氟化电解质中的 3.75 降低到全氟化电解质中的 3.02。令人印象深刻的是，全氟电解质中的快速 Li ⁺去溶剂化诱导了稳定的富含 LiF 的界面，同时抑制了 Li 枝晶，因此 Li||Cu 不对称电池在 0.5 mA cm –2 下实现了平均 98.3% 的高 CE 以及^优异的循环稳定性。令人鼓舞的是，Li||NCM811 电池在 225 次循环后在高电压（高达 4.6 V）下甚至保持了 72.3% 的初始容量和 99.8% 的平均 CE。这项工作提供了一种 Li ⁺溶剂化鞘层直接调谐策略来构建高性能 LMB 的理想界面化学。