SiO₂ Hollow Nanosphere‐Based Composite Solid Electrolyte for Lithium Metal Batteries to Suppress Lithium Dendrite Growth and Enhance Cycle Life

The low Coulombic efficiency and serious security issues of lithium (Li) metal anode caused by uncontrollable Li dendrite growth have permanently prevented its practical application. A novel SiO₂ hollow nanosphere‐based composite solid electrolyte (SiSE) for Li metal batteries is reported. This hierarchical electrolyte is fabricated via in situ polymerizing the tripropylene gycol diacrylate (TPGDA) monomer in the presence of liquid electrolyte, which is absorbed in a SiO₂ hollow nanosphere layer. The polymerized TPGDA framework keeps the prepared SiSE in a quasi‐solid state without safety risks caused by electrolyte leakage, meanwhile the SiO₂ layer not only acts as a mechanics‐strong separator but also provides the SiSE with high room‐temperature ionic conductivity (1.74 × 10⁻³ S cm⁻¹) due to the high pore volume (1.49 cm³ g⁻¹) and large liquid electrolyte uptake of SiO₂ hollow nanospheres. When the SiSE is in situ fabricated on the cathode and applied to LiFePO₄/SiSE/Li batteries, the obtained cells show a significant improvement in cycling stability, mainly attributed to the stable electrode/electrolyte interface and remarkable suppression for Li dendrite growth by the SiSE. This work can extend the application of hollow nanooxide and enable a safe, efficient operation of Li anode in next generation energy storage systems.