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Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li1-xCo1/3Ni1/3MN1/3O2 Electrode System by Combination of Soft and Hard X-Ray Absorption Spectroscopy

Published

Author(s)

W S. Yoon, Kyung Y. Chung, Xiao-Qing Yang, James McBreen, Mahalingam Balasubramanian, C P. Grey, Daniel A. Fischer

Abstract

In situ hard X-ray absorption spectroscopy (XAS) at metal K-edges and soft XAS at O K-edge and metal L-edges have been carried out during the first charging process for the layered Li1-2Co1/3Ni1/3Mn1/3O2 cathode material. The metal K-edge XANES results show that the major charge compensation at the metal site during Li-ion deintercalation is achieved by the oxidation of Ni2+ ions, while the manganese ions and the cobalt ions remain mostly unchanged in the Mn4+ and Co3+ state. These conclusions are in good agreement with the results of the metal K-edge EXAFS data. Metal L-edge XAS results at different charge states in both the FY and PEY modes show that unlike Mn and Co ions, Ni ions at the surface are oxidized to Ni3+ during charge whereas Ni ions in the bulk are further oxidized to Ni4+ during charge. From the observation of O K-edge XAS results, we can conclude that large portion of the charge compensation during Li-ion deintercalation is achieved in the oxygen site. By comparison to our earlier results on the Li1-xNi0.5Mn0.5O2 system, we attribute the active participation of oxygen in the redox process in Li1-xCo1/3Ni1/3Mn1/3O2, to be related to the presence of Co in this system.
Citation
Journal of the American Chemical Society
Volume
127

Keywords

lithium rechargeable batteries, NEXAFS, XAS

Citation

Yoon, W. , Chung, K. , Yang, X. , McBreen, J. , Balasubramanian, M. , Grey, C. and Fischer, D. (2005), Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li<sub>1-x</sub>Co<sub>1/3</sub>Ni<sub>1/</sub>3MN<sub>1/3</sub>O<sub>2</sub> Electrode System by Combination of Soft and Hard X-Ray Absorption Spectroscopy, Journal of the American Chemical Society (Accessed February 26, 2024)
Created January 10, 2005, Updated October 12, 2021