The layered transition metal oxide composition series of Li1+xV1-xO2 was synthesized using the solid state synthesis technique. X-ray diffraction was used to determine the dependence of structure on composition and clearly indicated a structural anomaly at x = 0 caused by the unusual magnetic ordering on the triangular lattice of the V3+ layer. To prevent magnetic frustration V3+ cations undergo orbital ordering and subsequent periodic displacent to form “trimers”. The periodicity of this phenomena results in a superlattice structure that can be observed as a faint peak in XRD spectra. The relationship between composition, superlattice peak intensity and lattice parameters was clearly documented for the first time.
Li/Li1+xV1-xO2 cells were made and tested. Recent literature has shown that the transformation to 1T Li2VO2 upon lithiation is dependant on a nonzero x (ideally x = 0.07 for maximum capacity) to make a small number of tetrahedrally coordinated Li sites accessible. These sites then act as a trigger for shearing into the 1T phase. The cells described within this work intercalated significant amounts of lithium at a higher potential than the to 1T transition, possibly signifying occupation of a large number of the tetrahedral sites.
LiVO2 is known to undergo delithiation even in ambient conditons and this can lead to cationic disorder. Cationic disorder is an inhibitor of anion sheet shearing and this suggests that sample handling could be a cause of the observed electrochemical behaviour. The effects of air and water exposure were investigated.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:NSHD.ca#10222/13337 |
| Date | 03 February 2011 |
| Creators | Gaudet, James Michael |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
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