Ad. Robertson et al., Li-x(Mn1-yCoy)O-2 intercalation compounds as electrodes for lithium batteries: influence of ion exchange on structure and performance, J MAT CHEM, 11(1), 2001, pp. 113-118
LixMn1-yCoyO2 compounds were synthesised by a low temperature route involvi
ng ion exchange from sodium precursors. Neutron diffraction confirmed that
the structures are layered (space group R (3) over barm). Materials synthes
ised from the precursors by ion exchange using LiBr in ethanol at 80 degree
sC possess vacancies on the transition metal sites which pin residual Na+ i
ons. Such transition metal vacancies and Na+ ions are not observed on reflu
xing at 160 degreesC in hexanol. We show that lithium intercalation accompa
nies the ion exchange process. The presence of Na+ in the Li+ layered mater
ials induces disorder perpendicular to the layers and this has been modelle
d. The performance of the materials depends on the ion exchange conditions.
The y = 0.025 compound obtained in ethanol exhibits a particularly high ca
pacity to cycle lithium. The initial discharge capacity is 200 mA h g(-1) w
ith a fade rate of only 0.08% per charge/discharge cycle on extended cyclin
g. This performance is delivered despite conversion to a spinel-like phase
during cycling and is markedly superior to the cycling ability of directly
prepared spinels over a similar composition range.