Self‐Assembled Cluster Topology Enabled Composite Solid Electrolytes for High‐Performance Lithium Metal Batteries

Abstract To facilitate the practical application of solid‐state lithium metal batteries (SSLMBs), using composite solid electrolytes (CSEs) with both inorganic and polymer components that can overcome the disadvantages of any single component is an effective design method. However, the poor compatibility between inorganic and polymer phase often leads to discontinuous channels for ion transport and insufficient strength for suppressing lithium dendrites. Herein, a class of porous topological design strategy−established by self‐assembly of wheel‐like titanium‐oxo clusters modified with polyethylene glycol (TOC@PEG) − that resolves the compatibility with the poly(ethylene oxide) (PEO) matrix is described. The self‐assembled cluster topology enabled composite electrolyte (PEO/TOC@PEG) exhibits not only high Li‐ion conductivity (2.32 × 10 −3 S cm −1 at 60 °C), but also superb resistance to lithium dendrites. The Li|| PEO/TOC@PEG||Li battery can operate for 6000 h at 0.1 mA cm −2 . The Li metal batteries demonstrate using LiFePO 4 (LFP) cathodes exhibits excellent cycle stability under 0.5 C at 60 °C and 0.2 C at 35 °C, with a capacity retention of 85.5% after 800 cycles and 95.4% after 300 cycles, respectively, showing promising prospects for solid‐state battery applications. This work provides a rational design strategy to address interfacial and ionic transport challenges in SSLMBs.