Spectroscopic and Computational Study of Structural Changes in γ-LiV₂O₅Cathodic Material Induced by Lithium Intercalation

Abstract

Structure, electronic states, and vibrational dynamics of γ-LiV 2 O 5 were studied by combined use of the quantum-chemical calculations and Raman spectroscopy. The spin-polarized DFT+U calculations correctly mimic the structural changes induced by the Li intercalation into the V 2 O 5 framework. The analysis of the density of electronic states shows that the electrons of Li atoms are transferred to the Vb atoms and are aligned in ferromagnetic order. The charge distribution in the system reflects the change of valence state of the Vb atoms from 5+ to 4+ and it is in line with changes of Vb-O bond lengths. The calculated Raman spectrum of the γ-LiV 2 O 5 structure is in line with the experimental Raman spectra that allows a reliable assignment of all prominent Raman peaks. The comparison of the spectra of γ-LiV 2 O 5 and γ ′ -V 2 O 5 indicates spectral signatures of structural changes induced by the Li insertion into the γ ′ -V 2 O 5 lattice. Results of the study opens the opportunity of using the Raman spectroscopy for characterization of structural modifications of the vanadate framework upon intercalation of guest species.

A porous puckered V2O5 polymorph as new high performance cathode material for aqueous rechargeable zinc batteries

“…5b), a minor contraction in a parameter (1%) and a moderate expansion in c parameter Raman fingerprint of the electroformed phase matches perfectly that reported for γ-Li1V2O5 formed during electrochemical lithiation of γ'-V2O5 in non-aqueous lithiated electrolyte [40] as well as chemically synthesized γ-LiV2O5 [43]. The whole assignment of the Raman spectrum of the γ-LiV2O5 bronze can be found in [43].…”

Structural Evolution of Disordered LixV2O5 Bronzes in V2O5 Cathodes for Li-Ion Batteries

“…only brings a minor structural change by increasing the buckering of the V 2 O 5 layers, while δ-and γ-Li x V 2 O 5 (1.0 < x < 2.0) are significantly different structures with every other V 2 O 5 -layer shifted and severe buckering of the layers. 4,[9][10][11][12] These crystalline-to-crystalline phase transitions are summarized in Figures S2 in the supporting information. As the known crystalline Li x V 2 O 5 polymorphs are not the focus of this study, these will not be discussed in further detail herein.…”

A Novel Ultrafast Rechargeable Multi‐Ions Battery

“…[1] Currently, lithium-ion batteries (LIBs) are the most successfully commercialized rechargeable batteries due to their relatively high energy densities, good stability, and low selfdischarge. [11][12][13][14][15] All of these materials are based on the intercalation and deintercalation of lithium ions in both the cathode and anode materials. [6][7][8][9] As the cobalt oxide cathode is expensive and toxic, a variety of other materials [2,10] are being extensively studied to replace the original materials.…”