A Protection Route Based on the Dual‐Mode Transfer of Lithium Ions for Lithiophilic Site during the Nucleation Period

Abstract Lithiophilic sites with high binding energy to lithium have a positive effect on the induction of Li deposition. However, saturation deposition of Li‐ions on lithiophilic sites causes a loss of lithiophilicity. Herein, a protection route of lithiophilic sites during the nucleation period is proposed for the first time. The designed heterointerface provides a directional built‐in electric field and a lithiophilic potential well. Li‐ions in the space field can nucleate on the semiconductor side by crossing metal‐based lithiophilic sites through the electric field‐driven mode and the chemical field‐driven mode. Based on a high‐efficiency dual‐mode transfer pathway for Li‐ions, which ensures continuous exposure of lithiophilic sites to the electric field and maximizes its positive effect during the nucleation period. A full cell utilizing the LiFePO 4 cathode exhibits a stable voltage profile with low polarization for over 200 cycles at 1 C, demonstrating the importance of the continued role of the lithiophilic sites. This work provides a new direction to design lithiophilic sites in Li metal batteries, which can be extended to other alkali metal batteries.