Crystal Structure and Lithium Diffusion Pathways of a Potential Positive Electrode Material for Lithium-Ion Batteries: Li2VIII(H0.5PO4)2

Edouard Boivin; Christian Masquelier; Laurence Croguennec; Jean-Noël Chotard

doi:10.1021/acs.inorgchem.7b00792

Crystal Structure and Lithium Diffusion Pathways of a Potential Positive Electrode Material for Lithium-Ion Batteries: Li₂V^III(H_0.5PO₄)₂

Inorg Chem. 2017 Jun 19;56(12):6776-6779. doi: 10.1021/acs.inorgchem.7b00792. Epub 2017 May 30.

Authors

Edouard Boivin^{1

2

3}, Christian Masquelier^{1

3

4}, Laurence Croguennec^{2

3

4}, Jean-Noël Chotard^{1

3

4}

Affiliations

¹ Laboratoire de Réactivité et de Chimie des Solides, CNRS, UMR 7314, Université de Picardie Jules Verne , F-80039 Amiens Cedex 1, France.
² CNRS, Université de Bordeaux, Bordeaux INP, ICMCB UPR 9048 , F-33600 Pessac, France.
³ RS2E, Réseau Français sur le Stockage Electrochimique de l'Energie, FR CNRS 3459 ,F-80039 Amiens Cedex 1, France.
⁴ ALISTORE-ERI European Research Institute, FR CNRS 3104 , F-80039 Amiens Cedex 1, France.

PMID: 28557425
DOI: 10.1021/acs.inorgchem.7b00792

Abstract

A new potentially interesting material as a positive electrode for lithium-ion batteries, Li₂V^III(H_0.5PO₄)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.