Pulverization of Silicon Upon Lithiation: Problem or Opportunity?

Abstract Silicon's high capacity makes it a promising anode for lithium‐ion batteries. Nevertheless, its application is hindered by pulverization‐induced electrical isolation and solid electrolyte interphase permeation. Herein, a paradigm shift for addressing this issue is proposed by harnessing pulverization. Bulk Si and graphite flakes are integrated and co‐encapsulated within an amorphous carbon matrix, forming a porous spherical Si/G/C composite. The dual‐phase carbon enables controlled pulverization, with the amorphous carbon acting as the self‐adaptive and flexible protective barrier, while the graphite flakes serve as the rigid backbone. This transforms pulverization into a beneficial downsizing process, ensuring pulverized Si maintains electrical contact and electrolyte isolation. The Si/G/C composite delivers a high capacity of 1722 mAh g ⁻¹ at 0.2 A g ⁻¹ , and retains 94.2% capacity after 100 cycles. This work demonstrates that the pulverization of Si is not a problem to be solved, but an opportunity to be seized.