Visualization and Quantification of State of Charge-Dependent Young’s Modulus of LiMn₂O₄ Nanosized Particles by Bimodal AFM

Abstract

Mechanical damage of LiMn 2 O 4 active material caused by volume change, phase transition, and lithium diffusion-induced stress is the main degradation mechanism in lithium-ion batteries. Young's modulus is a key parameter of mechanical property, and its variation with lithium content x or state of charge (SOC) at the nanoscale is an important issue because such variation may have influences on the stress level and lithium-ion transport. In this study, we successfully developed bimodal atomic force microscopy (bimodal AFM) and related approaches to carry out surface topography imaging and Young's modulus mapping of Li x Mn 2 O 4 nanosized particles. It was validated that the size of particles decreased with decreasing SOC due to delithiation during the charging cycle. The variation in Young's modulus with SOC was quantitatively determined using the silicon material as a reference, and the trend of the variation is consistent with the reported results of molecular dynamics simulation. Furthermore, spatially nonuniform distribution of Young's modulus on the nanosized particle surface was found even upon completion of charging. This phenomenon could be attributed to the coexistence of two phases during the charging process. Our experimental study reveals the correlation between Young's modulus of LiMn 2 O 4 and SOC at the nanosized particle level, and we believe that the bimodal AFM will be widely used in the nanocharacterization of the electrode materials because lithium content-or SOC-dependent mechanical properties are common in battery electrode materials.