Germanium (Ge) is an attractive anode material for advanced lithium‐ion batteries (LIBs) due to its high theoretical capacity, excellent Li + diffusivity, and high electronic conductivity. However, its substantial volume variation and unstable solid electrolyte interphase (SEI) during cycling lead to rapid capacity decay. Here, a p‐Ge/SiO 2 /NC‐2 composite with a dual‐armor architecture is developed through a rational pore‐filling and interface engineering strategy. This unique structure features a porous Ge skeleton with embedded SiO 2 microspheres and an outer N‐doped carbon layer, forming a stable inner support and outer confinement system. The mechanical integrity is enhanced by the porous structure and the rigid SiO 2 particles, which collectively inhibit pore collapse and mitigate volume expansion. Meanwhile, the N‐doped carbon layer not only facilitates rapid charge transfer but also promotes the formation of a stable SEI enriched with LiF and Li 3 N in liquid electrolyte systems. Finite element simulation further verifies that this synergistic dual‐armor design enables low stress strain and high structural stability during cycling. As a result, the composite anode demonstrates exceptional lithium storage performance, achieving a high capacity retention of 94.4% after 250 cycles at 0.5 C in the LFP||p‐Ge/SiO 2 /NC‐2 full cells. Notably, the p‐Ge/SiO 2 /NC‐2||LPSC||Li all‐solid‐state lithium‐ion batteries (ASSLIBs) with a sulfide solid electrolyte maintain stable cycling, delivering a specific capacity of 449 mAh g −1 at 0.5 A g −1 . This work highlights the crucial role of rational structural design in advancing Ge‐based anodes for high‐performance energy storage systems.
Chen et al. (Sun,) studied this question.