Multifunctional Additive Enables a “5H” PEO Solid Electrolyte for High-Performance Lithium Metal Batteries

The solid-state battery with a lithium metal anode is a promising candidate for next-generation batteries with improved energy density and safety. However, the current polymer electrolytes still cannot fulfill the demands of solid-state batteries. In this work, we propose a “5H” poly(ethylene oxide) (PEO) electrolyte via introducing a multifunctional additive of tris(pentafluorophenyl)borane (TPFPB) for high-performance lithium metal batteries. The addition of TPFPB improves the ionic conductivity from 6.08 × 10 –5 to 1.54 × 10 –4 S cm –1 via reducing the crystallinity of the PEO electrolyte and enhances the lithium-ion transference number from 0.19 to 0.53 via anion trapping due to its Lewis acid nature. Furthermore, the fluorine and boron segments from TPFPB can optimize the composition of the solid–electrolyte interphase and cathode–electrolyte interphase, providing a high electrochemical stability window over 4.6 V of the PEO electrolyte along with significantly improved interface stability. At last, TPFPB can ensure improved safety through a self-extinguishing effect. As a result, the “5H” electrolyte enables the Li/Li symmetric cells to achieve a stable cycle over 2200 h at the current density of 0.2 mA cm –2 with a capacity of 0.2 mA h cm –2; the LiFePO 4 /Li full cells with a high LFP loading of 8 mg cm –2 exhibits decay-free capacity of 140 mA h g –1 (99% capacity retention) after 100 cycles; and the NCM811/Li cells exhibit a high capacity of 160 mA h g –1 after 50 cycles at 0.5 C. This work presents an innovative approach to utilizing a “5H” electrolyte for high-performance solid-state lithium batteries.