Electrochemical lithium intercalation into WO3 and lithium tungstates Li x WO3+ x /2 of various structures

Hexagonal and monoclinic tungsten trioxides WO₃ and hexagonal lithium tungstates Li _x WO_{3+ x /2} (x = 0.10–0.42) from a soft chemistry route were used as the active cathode material in secondary lithium batteries. The hexagonal structures, regardless of their being an oxide or a tungstate, showed higher specific capacities and better cycling behavior in Li⁺ intercalation reactions than the monoclinic form. The presence of pre-allocated lithium (as Li₂O) in hexagonal tungstates decreased the capacity for lithium intercalation. Additionally, the plot of open-circuit voltage (OCV) against the depth of intercalation (n) for anhydrous tungstates showed two straight lines with different slopes that can be related to the structural changes in lithium intercalation. The effective diffusion coefficients of lithium insertion into the host structure, D˜, were also found to be dependent on the structure and the composition of these compounds. Received: 28 November 1997 / Accepted: 6 March 1998