Fine‐Tuning Li‐Ion Solvation Structure by Enhanced Solvent‐Diluent Interactions for Long‐Cycling Lithium Metal Batteries

Enhanced dipole–dipole interaction between solvent DME and non-Li-ion-coordinating diluent TFTHF is achieved and found to fine-tune the Li-ion solvation structure in a binary salt electrolyte. This leads to weakened Li-ion-solvent coordination and strengthened Li-ion-anion interactions, facilitating the formation of a stable bilayered SEI for significantly stabilizing Li metal anode.

Abstract

Achieving durable lithium (Li) metal anodes in liquid electrolytes remains challenging, primarily due to the instability of the formed solid-electrolyte interphases (SEIs). Modulating the Li-ion solvation structures is pivotal in forming a stable SEI for stabilizing Li metal anodes. Here a strategy is developed to fine-tune the Li-ion solvation structures through enhanced dipole–dipole interactions between the Li-ion-coordinated solvent and the non-Li-ion-coordinating diluent, for creating a stable SEI in the developed binary salt electrolyte. The enhanced dipole–dipole interactions weaken the coordination between Li-ions and the solvents while strengthening the interaction between Li-ions and dual anions, thereby facilitating the Li-ion transport and a robust anion-derived SEI with a distinct bilayer structure. Consequently, the developed electrolyte exhibited exceptional electrochemical performance in high energy-density Li||LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) cells, with long calendar life, stable cyclability at 1 C, and reliable operation between 25 and −20 °C, and it also demonstrat remarkable cycling stability for a Li||NMC811 pouch cell with projected energy density of 402 Wh kg⁻¹, maintaining 80% capacity retention over 606 cycles under practical conditions.