Real-Time TEM Study of Nanopore Evolution in Battery Materials and Their Suppression for Enhanced Cycling Performance

Battery materials, which store energy by combining mechanisms of intercalation, conversion, and alloying, provide promisingly high energy density but usually suffer from fast capacity decay due to the drastic volume change upon cycling. Particularly, the significant volume shrinkage upon mass (Li⁺, Na⁺, etc.) extraction inevitably leads to the formation of pores in materials and their final pulverization after cycling. It is necessary to explore the failure mechanism of such battery materials from the microscopic level in order to understand the evolution of porous structures. Here, prototyped Sb₂Se₃ nanowires are targeted to understand the structural failures during repetitive (de)­sodiation, which exhibits mainly alloying and conversion mechanisms. The fast growing nanosized pores embedded in the nanowire during desodiation are identified to be the key factor that weakens the mechanical strength of the material and thus cause a rapid capacity decrease. To suppress the pore development, we further limit the cutoff charge voltage in a half-cell against Na below a critical value where the conversion reaction of such a material system is yet happening, the result of which demonstrates significantly improved battery performance with well-maintained structural integrity. These findings may shed some light on electrode failure investigation and rational design of advanced electrode materials with long cycling life.