Utilizing Ultra‐homogeneous SiOx and Defects to Achieve Interlayer Protection for Lithium Metal Anodes

The uncontrollable growth and uneven nucleation of lithium metal can be addressed by utilizing spatial confinement structures in conjunction with lithiophilic sites. However, their complex fabrication technique and the inhomogeneous dispersion of lithiophilic sites make the application ineffective. In this work, ultra‐uniformly dispersed SiOx seeds and defects are produced in situ to achieve the spatially restricted protection within the reduced graphene oxide (rGO) layer. The in situ formed SiOx and defects during annealing double constrain lithium nucleation and growth behaviors thanks to the superlithiophilic characteristic, while both provide the fast Li+ transport channel to utilize the interlayer protection of rGO in limiting lithium dendrite growth. Furthermore, XANES and XPS analyze the SiOx seeds that are dominated by various valence states, and theoretical calculations further verify the control on the nucleation of lithium atoms. Benefiting from the optimum average valence of three for the “control site”, the host realizes steady circulation. In asymmetric cells, the host demonstrates excellent coulombic efficiency of 99.1% and stable lifespans over 1250 h at 1 mA cm−2. When assembled in LiFePO4 full cells, it retains a favorable capacity of 116.2 mA h g−1 after 170 cycles. In situ formed uniform SiOx and defects are dispersed on rGO, achieving the interlayer restricted protection due to the superlithiophilic characteristic and the fast Li+ transport channel provided by SiOx and defects, and SiOx seeds that are dominated by Si3+ demonstrate the most excellent coulombic efficiency and the most stable cycling.