A new potentially interesting material as a positive electrode for lithium-ion batteries, Li2V(III)(H0.5PO4)2, was obtained by hydrothermal synthesis. Its crystal structure was solved thanks to single-crystal X-ray diffraction. This material is isostructural to Li2Fe(III)(PO4)(HPO4) and also closely related to Li2Fe(II)(SO4)2. It can be described as a VO6 octahedron sharing corners with six PO4 tetrahedra to form a 3D framework. One oxygen atom of each phosphate group is unshared with a vanadium octahedron and as such linked to a hydrogen atom. The arrangement of these polyhedra generates large channels running along [100] in which lithium cations are located. The close structural relationship between Li2Fe(III)(PO4)(HPO4) and Li2Fe(II)(SO4)2 allows one to investigate, by comparison, the effect of the hydrogen atoms lying on lithium diffusion pathways.
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