In this paper, it is demonstrated that all the lithium cannot he removed el
ectrochemically from Li-2/3[Ni1/3Mn2/3]O-2 at room temperature below 5.4 V
vs. Li/Li+. On the contrary, all the Na atoms can he extracted and reinsert
ed reversibly from P2-Na-2/3[Ni1/3Mn2/3]O-2 electrochemically to form Na-x[
Ni1/3Mn2/3]O-2 with 0 < x 0.67. Both of these results have been confirmed b
y X-ray diffraction measurements. Furthermore, when all the Na is removed,
<square>[Ni1/3Mn2/3]O-2 adopts the O2 structure with random stacking faults
. The diffraction pattern can be well matched by simulations of these stack
ing faults using the DIFFaX program. Lithium can be inserted into square [N
i1/3Mn2/3]O-2, however. only about one-half of the lithium which is inserte
d can be removed. X-ray diffraction shows that when the Li is inserted into
square [Ni1/3Mn2/3]O-2, the structure transforms from O2 with stacking fau
lts to O2 without stacking faults. We speculate upon the reasons for the di
fference between the behavior of Li and Na in this host system. (C) 2001 Th
e Electrochemical Society.