Metastability‐Induced Atom Coordination and Electron Relocalization Toward Dendrite Free All‐Solid‐State Lithium Batteries

Abstract Li‐argyrodite electrolytes have attracted special attention as the promising candidate for all‐solid‐state batteries considering its high ionic conductivity and relative stability. However, the interfacial compatibility issues associated with PS 4 3− tetrahedra decomposition led to dendrite growth and rapid battery failure in integrating the lithium metal anode. Herein, in situ electrochemical (de)lithiation of Li 6 PS 5 Cl coated with Mg(ClO 4 ) 2 (LPSC‐MCO) induced by metastable decomposition is proposed to mitigate undesirable reactions at lithium anode through atomic coordination and electron relocalization. The inhibition of electrochemical decomposition for PS₄ 3 ⁻ tetrahedra is due to the formation of PS 3 O 3− and the components regulation from Li 2 S and Li 3 P to Li 2 O, LiCl in solid electrolyte interphase. Additionally, the ab initio molecular dynamics (AIMD) and density functional theory (DFT) analysis are utilized to uncover the fundamental mechanism behind the interactions of Li‐O and Li‐Cl and electron redistribution around O, Cl, and Mg. A high critical current density of 1.9 mA cm −2 and stable lithium plating/stripping behaviors over 2300 h are presented to verify the suppression for lithium dendrite and the NCM/LPSC‐MCO/Li cell consequently exhibits excellent performance. It inspires new pathways of probing into atom coordination and electron relocalization to address (electro)chemical decomposition and dendrite issues in all‐solid‐state batteries.