Abstract

AbstractUnstable solid electrolyte interface (SEI) and dendrite growth hinder the development of rechargeable lithium‐metal batteries (LMBs) at low temperature (≤−20 °C). In this work, regulating the concentration of Li salt increases the proportion of anions in Li+ solvation structure, thereby forming a denser SEI on Li anode. The optimized solvation structure exhibits fast charge transfer kinetics and high‐voltage (dis)charge performance. As a result, Li||Cu cells with modified electrolyte work over 400 h and maintaining an average coulombic efficiency of 98.05%, the Li||LiNi0.8Co0.1Mn0.1O2 cells (N/P = 3) are capable of one hundred stable cycles with a capacity retention of 93.7% even at −40 °C. These findings confirm the effect of ion‐pairing and anion‐derived SEI on the long‐term cycling of LMBs, contributing a promising solution to the development of low‐temperature LMBs.

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