Beyond intercalation based sodium-ion batteries: the role of alloying anodes, efficient sodiation mechanisms and recent progress

Sodium-ion batteries (SIBs) have received renewed interest in recent years and are projected as an alternative to the existing lithium-ion battery (LIB) system. Research on SIBs is impelled by the low cost and abundant supply of sodium resources, the similar electrochemistry of SIBs and LIBs and the competing electrochemical performance achieved in recent years. Significant progress has been made in the development of alloying anodes for SIBs which offer high gravimetric and volumetric energy densities when compared to the conventional intercalation based anodes. Recent progress in the field of advanced operando and ex situ characterization techniques as well as theoretical computational studies has shed light on the sodiation mechanism of these alloying anodes. Herein, we review the recent developments in alloying anodes for SIBs. Primarily Sn, Sb, and P based alloying anodes are focused on and the progress in Bi, Ge and Si is also discussed. We focus on the sodiation mechanism of these alloying anodes, recently revealed by means of advanced experimental and computational tools, to enable the design of efficient strategies for enhanced electrochemical performance. We also discuss synthetic methodologies and novel approaches adopted for alloying anodes to mitigate the challenges faced during the (de)sodiation cycles. The future outlook and issues to be addressed to realize the practical implementation of alloying anodes are also discussed.