Robust and Adhesive Laminar Solid Electrolyte with Homogenous and Fast Li-Ion Conduction for High-Performance All-Solid-State Lithium Metal Battery

Constructing composite solid electrolytes (CSEs) integrating the merits of inorganic and organic components is a promising approach to developing high-performance all-solid-state lithium metal batteries (ASSLMBs). CSEs are now capable of achieving homogeneous and fast Li-ion flux, but how to escape the trade-off between mechanical modulus and adhesion is still a challenge. Herein, a strategy to address this issue is proposed, that is, intercalating highly conductive, homogeneous, and viscous-fluid ionic conductors into robust coordination laminar framework to construct laminar solid electrolyte with homogeneous and fast Li-ion conduction (LSE-HFC). A 9 µm-thick LSH-HFC, in which poly(ethylene oxide)/succinonitrile is adsorbed by coordination laminar framework with metal–organic framework nanosheets as building blocks, is used here as an example to determine the validity. The Li-ion transfer mechanism is verified and works across the entire LSE-HFC, which facilitates homogeneous Li-ion flux and low migration energy barriers, endowing LSE-HFC with high ionic conductivity of 5.62 × 10⁻⁴ S cm⁻¹ and Li-ion transference number of 0.78 at 25 °C. Combining the outstanding mechanical strength against punctures and the enhanced adhesion force with electrodes, LSE-HFC harvests uniform Li plating/stripping behavior. These enable the realization of high-energy-density ASSLMBs with excellent cycling stability when being assembled as LiFePO₄/Li and LiNi_0.6Mn_0.2Co_0.2O₂/Li cells.