Asymmetric Trihalogenated Aromatic Lithium Salt Induced Lithium Halide Rich Interface for Stable Cycling of All-Solid-State Lithium Batteries

Solid polymer electrolytes (SPEs) are the key components for all-solid-state lithium metal batteries with high energy density and intrinsic safety. However, the low lithium ion transference number (t₊) of a conventional SPE and its unstable electrolyte/electrode interface cannot guarantee long-term stable operation. Herein, asymmetric trihalogenated aromatic lithium salts, i.e., lithium (3,4,5-trifluorobenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiFFF) and lithium (4-bromo-3,5-difluorobenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiFBF), are synthesized for polymer electrolytes. They exhibit higher t₊ values and better compatibility with Li metal than conventional lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). Due to the trihalogenated aromatic anions, LiFFF- and LiFBF-based electrolytes are prone to generate an LiF- and LiBr-rich solid electrolyte interphase (SEI), therefore increasing the stability of the solid electrolyte/anode interface. Particularly, LiFBF could induce a LiF/LiBr hybrid SEI, where LiF shows a high Young's modulus and high surface energy for homogenizing Li ion flux and LiBr exhibits an extremely low Li ion diffusion barrier in the SEI layer. As a result, the Li/Li symmetric cells could remain stable for more than 1200 h without a short circuit and the LiFePO₄/Li batteries showed superb electrochemical performance over 1200 cycles at 1 C. This work provides valuable insights from the perspective of lithium salt molecular structures for high-performance all-solid-state lithium metal batteries.