A Micrometer‐Sized Silicon/Carbon Composite Anode Synthesized by Impregnation of Petroleum Pitch in Nanoporous Silicon

Porous silicon (Si)/carbon nanocomposites have been extensively explored as a promising anode material for high-energy lithium (Li)-ion batteries (LIBs). However, shrinking of the pores and sintering of Si in the nanoporous structure during fabrication often diminishes the full benefits of nanoporous Si. Herein, a scalable method is reported to preserve the porous Si nanostructure by impregnating petroleum pitch inside of porous Si before high-temperature treatment. The resulting micrometer-sized Si/C composite maintains a desired porosity to accommodate large volume change and high conductivity to facilitate charge transfer. It also forms a stable surface coating that limits the penetration of electrolyte into nanoporous Si and minimizes the side reaction between electrolyte and Si during cycling and storage. A Si-based anode with 80% of pitch-derived carbon/nanoporous Si enables very stable cycling of a Si||Li(Ni0.5Co0.2Mn0.3)O₂ (NMC532) battery (80% capacity retention after 450 cycles). It also leads to low swelling in both particle and electrode levels required for the next generation of high-energy LIBs. The process also can be used to preserve the porous structure of other nanoporous materials that need to be treated at high temperatures.