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

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 PS43- tetrahedra decomposition led to dendrite growth and rapid battery failure in integrating the lithium metal anode. Herein, in situ electrochemical (de)lithiation of Li6PS5Cl coated with Mg(ClO4)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 PS(4)3(-) tetrahedra is due to the formation of PS3O3- and the components regulation from Li2S and Li3P to Li2O, 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.