Si has been regarded as one of the most promising next generation lithium-ion battery (LIB) anodes due to its exceptional capacity and proper working voltage. However, the dramatic volume change during lithiation/delithiation processes has caused severe detrimental consequences, leading to very poor cyclic stability. It has been one of the critical problems hampering the practical applications of the silicon based LIB anode. Extensive research has been carried out to resolve the problem since early 1990s. For the first time, the studies on the Si anode in the time frame more than two decades are summarized and discussed in this review with a novel chronicle perspective. Through this article, the evolution of the concept, fundamental scientific and technology development of the silicon LIB anode are clearly presented. It 2 provides unique eyesight into this rapid developing field and will shed light on the future trend of the Si LIB anode research.

Porous silicon has found wide applications in many different fields including catalysis and lithium-ion batteries. Three-dimensional hierarchical macro-/mesoporous silicon is synthesized from zero-dimensional Stöber silica particles through a facile and scalable magnesiothermic reduction process. By systematic structure characterization of the macro-/mesoporous silicon, a self-templating mechanism governing the formation of the porous silicon is proposed. Applications as lithium-ion battery anode and photocatalytic hydrogen evolution catalyst are demonstrated. It is found that the macro-/mesoporous silicon shows significantly improved cyclic and rate performance over the commercial nanosized and micrometer-sized silicon particles. After 300 cycles at 0.2 A g, the reversible specific capacity is still retained as much as 959 mAh g with a high mass loading density of 1.4 mg cm. With the large current density of 2 A g, a reversible capacity of 632 mAh g is exhibited. The coexistence of both macro- and mesoporous structures is responsible for the enhanced performance. The macro-/mesoporous silicon also shows superior catalytic performance for photocatalytic hydrogen evolution compared to the silicon nanoparticles.

Silicon (Si) has been regarded as one of the most promising anodes for next-generation lithium-ion batteries (LIBs) due to its exceptional capacity, appropriate voltage profile, and reliable operation safety. However, poor cyclic stability and moderate rate performance have been critical drawbacks to hamper the practical application of Si-based anodes. It has been one of the central issues to develop new strategies to improve the cyclic and rate performance of the Si-based lithium-ion battery anodes. In this work, super-small metal nanoparticles (2.9 nm in diameter) are in situ synthesized and homogeneously embedded in the in situ formed nitrogen-doped carbon matrix, as demonstrated by the Si/Ag/C nanohybrid, where epoxy resin monomers are used as solvent and carbon source. With tiny amount of silver (2.59% by mass), the Si/Ag/C nanohybrid exhibits superior rate performance compared to the bare Si/C sample. Systematic structure characterization and electrochemical performance tests of the Si/Ag/C nanohybrids have been performed. The mechanism for the enhanced rate performance is investigated and elaborated. The temperature-dependent I-V behavior of the Si/Ag/C nanohybrids with tuned silver contents is measured. Based on the model, it is found that the super-small silver nanoparticles mainly increase charge carrier mobility instead of the charge carrier density in the Si/Ag/C nanohybrids. The evaluation of the total electron transportation length provided by the silver nanoparticles within the electrode also suggests significantly enhanced charge carrier mobility. The existence of tremendous amounts of super-small silver nanoparticles with excellent mechanical properties also contributes to the slightly improved cyclic stability compared to that of simple Si/C anodes.