HRTEM and neutron diffraction study of LixMo5O17: From the ribbon (x=5) structure to the rock salt (x=12) structure

Abstract Structure determination of the fully intercalated phase Li 12 Mo 5 O 17 and of the deintercalated oxide Li 5 Mo 5 O 17 has been carried out by electron microscopy and neutron powder diffraction. The reversible topotactic transformation between the ordered rock salt structure of the former and the ribbon structure of the latter (closely related to that of Li 4 Mo 5 O 17 ) is explained on the following basis: both structures can be described as strips built up as an assembly of infinite ribbons of MoO 6 octahedra that are five octahedra thick, and that differ by slight displacements of the octahedral ribbons. We show that the electrochemical behavior of the Li x Mo 5 O 17 system is based on two sorts of Li + sites; those that are located within the strips between the ribbons, and those that are located at the border of the strips. The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure.