Synthesis, Structure and Electrochemistry of Lithium Vanadium Phosphate Cathode Materials

The Li-ion battery positive electrode materials, alpha-LiVOPO(4), beta-LiVOPO(4), and Li(3)V(2)(PO(4))(3) have been prepared as individual phases from a common precursor mixture by controlling the synthesis conditions. These phases result because of their distinct crystal symmetries and V oxidation states. The synthesis involves the decomposition of a precursor mixture prepared from NH(4)VO(3), NH(4)H(2)PO(4), LiF and hexanoic acid which when heat-treated under different conditions produced the three Li(w)V(x)O(y)(PO(4))(z) products. The materials were characterized by means of elemental analysis, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and Li cell data. The Li cycling performance and the accompanying structural effects on alpha- and beta-LiVOPO(4) were also studied under normal and deep discharge conditions using XAS to probe the local vanadium environment. XANES and EXAFS confirm reversible changes in the two structures when intercalation does not exceed 1Li/VOPO(4). Deeper discharge revealed more disruption to both structures, including an additional 0.25 angstrom increase to the V=O bond length. A greater range in the VO(6) symmetry of alpha-LiVOPO(4) resulted in a more flexible accommodating host, in agreement with its improved low voltage performance compared to beta-LiVOPO(4). (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.003112jes] All rights reserved.