High Young′s Modulus LixTiO2 Layer Suppressing the Pulverization and Deactivation of Lithiophilic Ag Nanoparticles

Anode‐free Lithium metal batteries, with their high energy density (>500 Wh/kg), are emerging as a promising solution for high‐energy‐density rechargeable batteries. However, the Coulombic Efficiency and capacity often decline due to interface side reactions. To address this, a lithiophilic layer is introduced, promoting stable and uniform Li deposition. Despite its effectiveness, this layer often undergoes electrochemical deactivation over time. This work investigates lithiophilic silver (Ag), prepared via magnetron sputtering on a copper (Cu) current collector. Finite element simulations identify stress changes from alloying reactions as a key cause of Ag particle pulverization and deactivation. A high Young′s modulus coating layer is proposed to mitigate this. The Ag2TiO3@Ag@TiO2@Cu composite electrode, designed with multi‐layer structures, demonstrates a slower deactivation process through galvanostatic electrochemical cycling. Characterization methods such as SEM, AFM, and TEM confirm the suppression of Ag particle pulverization, while uncoated Ag fractures and deactivates. This work uncovers a potential failure mechanism of lithiophilic metallic nanoparticles and proposes a strategy for deactivation suppression using an artificial coating layer. This work investigates the stress‐induced failure mechanism of lithiophilic Ag particles. During battery cycling, the volume changes of Ag lead to the pulverization of Ag particles, while coating the Ag particles with a high Young′s modulus LixTiO2 layer can suppress their deactivation process. This work provides insights for extending the activity of other lithiophilic materials.