Abstract
Layered Li‐Mn oxide‐based materials 
with the unconventional O2 structure were prepared by ion exchanging Na for Li in the corresponding P2 structure sodium bronzes, 
. Powder X‐ray diffraction (XRD) was used to confirm the purity and structure of the phase. The Bragg peaks from 
can be indexed based on a hexagonal unit cell with dimensions a = 2.8609 Å and c = 10.061 Å, and the diffraction pattern can be approximately matched assuming that the atoms are in 2a and 2b positions of space group 
. However, the initial structure is more complex, because some observed diffraction peaks (i.e., 111) are forbidden in this space group. In situ XRD and electrochemical testing were used to investigate the behavior of O2‐type 
as a cathode for rechargeable lithium batteries. It exhibits a large reversible capacity of approximately 180 mAh/g divided into two plateaus centered near 2.8 and 3.9 V. In situ XRD proves that after an initial phase transformation, during which all forbidden diffraction peaks vanish, the extraction and insertion of lithium occurs without any first order phase transitions. The material remains layered and does not transform to the spinel structure during cycling. It shows good capacity retention vs. cycle number at both 30 and 55°C. Differential scanning calorimetry measurements on charged electrodes show exotherms that are about one order of magnitude less intense than those from charged 
electrodes. © 2000 The Electrochemical Society. All rights reserved.