Long‐Life Lithium‐Metal All‐Solid‐State Batteries and Stable Li Plating Enabled by In Situ Formation of Li3PS4 in the SEI Layer

An ultrastable and kinetically favorable interface is constructed between sulfide-poly(ethylene oxide) (PEO) composite solid electrolytes (CSEs) and lithium metal, via in situ formation of a solid electrolyte interphase (SEI) layer containing Li₃ PS₄ . A specially designed sulfide, lithium polysulfidophosphate (LPS), can distribute uniformly in the PEO matrix via a simple stirring process because of its complete solubility in acetonitrile solvent, which is advantageous for creating a homogeneous SEI layer. The CSE/Li interface with high Li⁺ transportation capability is stabilized quickly through in situ formation of a Li₃ PS₄ /Li₂ S/LiF layer via the reaction between LPS and lithium metal to inhibit lithium dendrite growth. A Li/Li symmetric cell with the LPS-integrated CSE exhibits constant and small CSE/Li resistance of 10 Ω cm² during cycling, delivering stable cycling for 3475 h at a current density of 0.2 mA cm^-2 and a high critical current density of 0.9 mA cm^-2 at 60 °C. Impressive electrochemical performance is also demonstrated for LiFePO₄ /CSE/Li all-solid-state batteries with capacity of 127.6 mAh g^-1 after 1000 cycles at 1 C.