Rapid Release of Silicon by Ultrafast Joule Heating Generates Mechanically Stable Shell–Shell Si/C Anodes with Dominant Inward Deformation

As a promising anode material, silicon–carbon composites encounter great challenges related to internal stress release and contact between the composites during lithiation. These issues lead to material degradation and concomitantly rapid capacity decline. Here, we report a type of shell–shell silicon–carbon (SS-Si/C) composite, which consists of a carbon shell tightly coated with a silicon shell. The mechanical analysis unveils that the dominant inward expansion of the Si shell is achieved through the synergistic effect of the outer carbon shell and the inner hollow structure. Benefiting from the well-tailored shell–shell structure, the SS-Si/C anode exhibits exceptional performance, boasting a high specific capacity (1690.3 mA h g–1 after 550 cycles at 0.5 A g–1), a high areal capacity (2.05 mA h cm–2 after more than 400 cycles at 0.5 mA cm–2), and an extended cycling life (1055.6 mA h g–1 after 1000 cycles at 8 A g–1), far exceeding commercially available Si/C anodes. Using the well-designed SS-Si/C anode, full cells assembled with LiCoO2 (LCO) or LiFePO4 (LFP) cathodes achieve favorable rate capability and cyclic stability. Notably, at a high rate of 6 C (1 C = 170 and 270 mA g–1 for LFP and LCO, respectively), these full cells deliver high specific capacities of 79.5 mA h g–1 and 64.9 mA h g–1 when using LCO and LFP, respectively, demonstrating the potential of SS-Si/C anodes for practical applications. The straightforward and safe synthesis method in this work enables the rational design of hollow structures with distinct properties.