Honeycomb-Like Porous Carbon Framework with Consecutive Conductive Channels for Stable SiOx/C Anodes

Silicon oxide (SiO_x) materials have been extensively researched. However, slow intrinsic kinetics and significant volume changes hinder the practical deployment of SiO_x anodes. Herein, an in situ molecular polymerization strategy, in which a loading substrate (PM) is introduced into a mixed solution of silane, is devised to construct SiO_x/C composites with honeycomb porous frameworks through one-step condensation followed by carbonization at 900 °C without any template or additive. The uniform dispersion of SiO_x/C facilitates rapid Li⁺ transport and stress dissipation, while abundant pore volume accommodates SiO_x/C expansion during lithiation/delithiation, thereby alleviating mechanical stress and enhancing electrode–electrolyte wettability. The continuous honeycomb-like channel changes capacitive behavior of the anode, improving lithium-ion diffusion kinetics and electrochemical performances at high current densities. The PM@SiO_x/C anode delivers 95.8% capacity retention after 500 cycles at 2 A g^–1, which is attributed to the dual protection from both well-dispersed carbon and honeycomb porous frameworks. This molecular polymerization strategy facilitates the scalable production of Si-based porous materials, simultaneously establishing a distinctive way to prepare template-free porous frameworks.