Nickel‐Catalyzed <scp>LiF</scp> ‐Rich Interface for Silicon Anodes

The silicon anodes are fundamentally constrained by interfacial failure caused by severe volume fluctuations during cycling. Herein, this work proposes a Ni‐catalyzed surface engineering strategy to explore the structural evolution behavior and SEI growth properties. By encapsulating silicon particles with Ni‐containing carbon precursors, the composite structure is regulated during high‐temperature carbonization. More importantly, the catalytic function of nickel is used to modulate the decomposition pathway of fluorine‐containing species, enabling the construction of dense LiF‐rich SEI. Specifically, nickel promoted the cleavage of PF bonds in , benefiting from inducing the production of more LiF components during SEI formation. By synergistically enhancing the mechanical strength of the electrode and accelerating Li + diffusion kinetics, the robust LiF‐rich SEI provides an effective way to alleviate the volume expansion and improve Li + transport at high rates. As a result, the Si‐Ni@C anode achieves a reversible capacity of 560 mAh g −1 at 6 A g −1 and retains 570 mAh g −1 after 700 cycles at 3 A g −1 (74.41% retention). This work demonstrates a dual‐function catalytic strategy for synchronously modifying carbon matrices and SEI formation, providing a viable pathway toward high‐performance silicon anodes.