Benchmarking the Match of Porous Carbon Substrate Pore Volume on Silicon Anode Materials for Lithium‐Ion Batteries

Abstract Silicon (Si) is one of the most promising anode materials for high‐energy‐density lithium‐ion batteries. However, the huge volume expansion hinders its commercial application. Embedding amorphous Si nanoparticles in a porous carbon framework is an effective way to alleviate Si volume expansion, with the pore volume of the carbon substrates playing a pivotal role. This work demonstrates the impact of pore volume on the electrochemical performance of the silicon/carbon porous composites from two perspectives: 1) pore volume affects the loadings of Si particles; 2) pore volume affects the structural stability and mechanical properties. The smaller pore volume of the carbon substrate cannot support the high Si loadings, which results in forming a thick Si shell on the surface, thereby being detrimental to cycling stability and the diffusion of electrons and ions. On top of that, the carbon substrate with a larger pore volume has poor structural stability due to its fragility, which is also not conducive to realizing long cycle life and high rate performance. Achieving excellent electrochemical performances should match the proper pore volume with Si content. This study will provide important insights into the rational design of the silicon/carbon porous composites based on the pore volume of the carbon substrates.