Invited: Surface Modification of Positive Electrode and its Effect to Bulk

Improvement technique of the life of Li-ion batteries has been intensively studied. Modification of the surface of positive electrode material including coating is effective to this purpose. In that process, it is very important to compare the bulk and surface structure of the positive electrode with/without surface modification to understand this effect.

For basic information concerning the effect of surface modification, authors have applied Transmission Electron Microscopy (TEM) to visualize the structural distribution inside the positive electrode particles after degradation [1]. As a model material, we synthesized sub-micron size particle of positive electrode such as LiCoO₂ by Pechini sol-gel method [2, 3] that could provide the suitable sample for TEM observation without damages from sample preparation like ion-milling or FIB. Analytical TEM measurements by scanning transmission microscopy (STEM) with electron energy-loss spectroscopy (EELS) equipped with monochromator were applied. Li-K EELS peak around 62 eV was clearly found and this peak intensity changed with Li charge-discharge state. The EELS mapping from the spectrum imaging method using this Li-K region spectra showed a distribution of Li in the particle or among particles during the charge discharge cycle. We discuss precisely the change of chemical states at the surface and Li ion distribution inside particles of positive electrode material with/without surface modification using Si, Zr, Al, Mg oxide during charge-discharge cycle.

References

[1] N. Taguchi, T. Akita, H. Sakaebe, K. Tatsumi, Z. Ogumi, J. Electrochem. Soc., 160, A2293 (2013).

[2] Y. Sun, I. Oh, S. Hong, J. Mat. Sci., 31, 3617 (1996).