Resonant Soft X-Ray Emission Spectroscopy and X-Ray Absorption Spectroscopy on the Cathode Material LiNi0.65Co0.25Mn0.1O2

We present a study of the charge-state behavior of the Li-ion battery cathode material LixNi(0.65)Co(0.25)Mn(0.1)O(2) as observed by X-ray absorption spectroscopy (XAS) and resonant soft X-ray emission (RSXE). A set of six identical Li//LixNi0.65Co0.25Mn0.1O2 batteries has been cycled and is studied in different states of charge in the range of x = 1.0, ... ,0.2 before disassembly in an Ar glove box. Site and symmetry selective information about the electronic structure of the conduction and valence bands reveals that Ni as well as Co ions participate in the uptake and release of the extra electron charge that the inserted Li ions provide, but the Ni ion is much less than expected. The net amount of charge on the oxygen varies approximately 0.24 charge units in the range of x, and dramatic changes in the hybridization are evident in XAS and in particular in RSXE at the O K edge. We attribute this to a strong screening behavior of the Li ions between the oxide layers. Structural integrity effects limit the extraction of Li ions to a value of about x = 0.2-0.4. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3454739] All rights reserved.