Electrochemical Atomic Force Microscopy of Black Phosphorus Composite Anodes: Electrode Destabilization and Degradation Mechanisms in Alkali-Ion Batteries.

Despite their higher capacity compared to common intercalation- and conversion-type anodes, black phosphorus (BP) based anodes suffer from significant capacity fading attributed to the large volume expansion (∼300%) during lithiation. Downsizing BP into nanosheets has been proposed to mitigate this issue, and various methods, particularly mechanical mixing with graphitic materials (BP-C), have been explored to enhance electrochemical performance. However, the understanding of BP-C hybridization is hindered by the lack of studies focusing on fundamental degradation mechanisms within operational battery environments. Here we address this challenge by employing electrochemical atomic force microscopy (EC-AFM) to study the morphological and mechanical evolution of BP-C composite anodes during lithiation. The results reveal that BP-C binding interactions alone are insufficient to withstand the structural reorganization of BP during its alloying reaction with lithium. Furthermore, the study emphasizes the critical role of the solid electrolyte interphase (SEI) and BP-C interface evolution in determining the long-term performance of these composites, shedding light on the disparity in final electrode morphologies between binder-inclusive and binder-free BP-C composites. These findings provide crucial insights into the challenges associated with BP-based anodes and underscore the need for a deeper understanding of the dynamic behavior within operating cells for the development of stable and high-performance battery materials.