A protection route based on the dual-mode transfer of lithium ions for lithiophilic site during the nucleation period

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. (© 2023 Wiley‐VCH GmbH)