Topotactic insertion of lithium in the layered structure Li4VO(PO4)2: The tunnel structure Li5VO(PO4)2

A new V(III) lithium phosphate Li5VO(PO4)2 has been synthesized by electrochemical insertion of lithium into Li4VO(PO4)2. This phase, which crystallizes in the space group I4/mcm, exhibits a tunnel structure closely related to the layered structure of Li4VO(PO4)2 and to the tunnel structure of VO(H2PO4)2. The topotactic reactions that take place during lithium exchange and intercalation, starting from VO(H2PO4)2 and going to the final phase Li5VO(PO4)2 are explained on the basis of the flexible coordinations of V4+ and V3+ species. The electrochemical and magnetic properties of this new phase are also presented and explained on the basis of the structure dimensionality.