Elucidating Structural Transformations in LixV2O5 Electrochromic Thin Films by Multimodal Spectroscopies

Vanadium oxides are widely seen as strong candidates for next-generation energy-saving electrochemical devices, ranging from their use as cathode materials in inherently safe high energy all-solid-state batteries to smart windows that employ their wide color range of electrochromic response. However, critical questions about these materials remain largely unanswered: interfacial reactions and the evolution of the electrode material as delithiation takes place. Distinguishing between topotactic (i.e., reversible) intercalation, conversion, and alloying reactions in ion tunable vanadium oxide devices, in operando, at a resolution that matches the size of structural building units, is a particularly challenging task. In this work, we investigated the effects of lithiation on the structural and optical characteristics of a model thin film system - LixV2O5 - as a function of depth, using several highly sensitive and nondestructive spectroscopic methods with different depth sensitivities. We exploit (1) LixV2O5 electrochromic properties to utilize in operando optical response, (2) depth-resolved cathodoluminescence spectroscopy (DRCLS), and (3) Raman spectroscopy to monitor the changes in LixV2O5 electronic structure from the surface to the bulk of the thin film with nanoscale resolution. We find that the degradation of electrochemical performance with deep discharge of LixV2O5 is associated with drastic band structure changes that accompany octahedral distortion, rather than with a chemical conversion reaction. Elongation along the c axis and charge redistribution induced by varying levels of V(3d)-O(2p) hybridization in the presence of the Li considerably affect the electronic band structure. The coexistence of multiple metastable phases, strong electron correlation, and deviation from an ideal cubic symmetry results in lower structural reversibility with a higher bandgap. Beyond these specific inferences, these results suggest that these optical techniques-Raman, optical absorption/reflection, and cathodoluminescence-can be a powerful combination to reveal electrochemical behavior of ion-tunable transition metal oxides materials and associated reaction mechanisms.