The electrochemical and transport properties of the intercalation of L
i and Na into (PbS)1.14-(NbS2)2, a misfit layer compound, have been in
vestigated. The open-circuit voltage (OCV) of the lithium cell gradual
ly decreases with increasing lithium content, while the OCV of Nax(PbS
)1.14-(NbS2)2 shows the appearance of a voltage plateau in the range o
f composition 0.1 < x < 0.25. This different behavior has been correla
ted with the chemical diffusion coefficients obtained by a long-pulse
galvanostatic technique. While the chemical diffusivity of lithium inc
reased with composition and had a maximum of approximately 1.3 X 10(-9
) cm2 s-1 for composition 0.4 < x < 0.5, the diffusion coefficients of
Na+ were found to decrease slowly in the range 0.05 < x < 0.2, where
the voltage-composition curve showed a two-phase region supported by t
he related X-ray data. On the other hand, the standard free energies o
f intercalation for sodium intercalates are less negative than those f
ound for the respective lithium intercalated compounds.