Densification of Alloying Anodes for High Energy Lithium-Ion Batteries: Critical Perspective on Inter- Versus Intra-Particle Porosity.

High Li-storage-capacity particles such as alloying-based anodes (Si, Sn, Ge, etc.) are core components for next-generation Li-ion batteries (LIBs) but are crippled by their intrinsic volume expansion issues. While pore pre-plantation represents a mainstream solution, seldom do this strategy fully satisfy the requirements in practical LIBs. One prominent issue is that porous particles reduce electrode density and negate volumetric performance (Wh L) despite aggressive electrode densification strategies. Moreover, the additional liquid electrolyte dosage resulting from porosity increase is rarely noticed, which has a significant negative impact on cell gravimetric energy density (Wh kg). Here, the concept of judicious porosity control is introduced to recalibrate existing particle design principles in order to concurrently boost gravimetric and volumetric performance, while also maintaining the battery's cycle life. The critical is emphasized but often neglected role that intraparticle pores play in dictating battery performance, and also highlight the superiority of closed pores over the open pores that are more commonly referred to in the literature. While the analysis and case studies focus on silicon-carbon composites, the overall conclusions apply to the broad class of alloying anode chemistries.