title: 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.
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-xCo1/3Ni1/3Mn1/3O2 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 a 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.
authors.affiliation: Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, USA. wonsuby@bnl.gov
authors.forename: Won-Sub
authors.initials: WS
authors.lastname: Yoon
authors.forename: Mahalingam
authors.initials: M
authors.lastname: Balasubramanian
authors.forename: Kyung Yoon
authors.initials: KY
authors.lastname: Chung
authors.forename: Xiao-Qing
authors.initials: XQ
authors.lastname: Yang
authors.forename: James
authors.initials: J
authors.lastname: McBreen
authors.forename: Clare P
authors.initials: CP
authors.lastname: Grey
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Fischer