期刊
Langmuir
标题
Operando Imaging of Over-Discharge-Induced Surface Morphology Evolutions of LiMn2O4 Submicron-Sized Particles by Electrochemical High-Speed Atomic Force Microscopy
作者
Peifa Yang, Zhuanfang Bi, and Guangyi Shang
摘要
Spinel LiMn2O4 is a promising cathode material but suffers from severe capacity fading during battery operation. One of capacity fade mechanisms results from changes in its morphology and structure due to over-discharge. In this work, for the first time, we successfully tracked the morphologic evolution of LiMn2O4 submicron-sized particles during over-discharging by our home-made electrochemical high-speed atomic force microscopy (EC-HS-AFM). Seven hundred and sixty successive EC-HS-AFM images were stably captured at an imaging speed of ∼0.85 fps at corresponding potentials during over-discharging in ∼15 min, from which evolutions of nanoscale wrinkle-like and step-like structures on the particle surface were clearly observed. The phenomena could be resulted from the complex stresses due to structural distortion during the phase transformation from cubic (LiMn2O4) to tetragonal (Li2Mn2O4), and the formation of the Li2Mn2O4 phase was confirmed by ex situ XRD. Moreover, the particle surface area as a function of the potential was quantitatively extracted from the EC-HS-AFM images, revealing the irreversible expansion/contraction of the particles, and this finding obtained at the nanoscale was consistent with the macroscopic results tested by cyclic voltammetry and galvanostatic charge/discharge methods. These results demonstrate that the EC-HS-AFM is a powerful tool to establish the correlation between the over-discharge-induced surface morphology changes and irreversibility of the Li-ion insertion/extraction as well as capacity fading.
原文链接
