Nanoscale depth and lithiation dependence of V<sub>2</sub>O<sub>5</sub> band structure by cathodoluminescence spectroscopy

Walker, Mitchell J.; Jarry, Angélique; Pronin, Nick; Ballard, Jake D.; Rubloff, Gary W.; Brillson, L. J.

doi:10.1039/d0ta03204b

Cited by 10 publications

(21 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this work, we are then efficiently probing the partial V 3d t 2g and O 2p density of states (DOS). In our previous work, we confirmed the excellent agreement between partial V 3d t 2g DOS of α-V 2 O 5 calculated by DFT and measured by CL. We highlighted that the 1.8–2 eV peaks is associated with the strong V 3d xy -O 2p x /2p y hybridization states and is very sensitive to any lattice distortion as well as reduction of vanadium associated with lithiation.…”

Section: Resultssupporting

confidence: 87%

“…In our previous work, we extensively discussed the origin of the shift/disappearance of the ∼1.8-2 eV peaks during the first lithiation from the DRCLS spectra and correlated it with crystallographic distortions of the V 2 O 5 ’s structure along its three axes. Further insight regarding the local atomic and electronic structure of the Li x V 2 O 5 phases can be deduced from the DRCLS results.…”

Section: Discussion: Topotactic Versus Conversion Reactions In LI X V2o5mentioning

confidence: 99%

“…However, our results imply that a nonfully uniform topochemical lithium insertion is occurring, with the coexistence of multiple metastable phases that blend at the macroscale, below the ∼1 μm spatial resolution of our Raman system. In our previous work, 47 we extensively discussed the origin of the shift/disappearance of the ∼1.8-2 eV peaks during the first lithiation from the DRCLS spectra and correlated it with crystallographic distortions of the V 2 O 5 's structure along its three axes. Further insight regarding the local atomic and electronic structure of the Li x V 2 O 5 phases can be deduced from the DRCLS results.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 2 more Smart Citations

Elucidating Structural Transformations in Li_xV₂O₅ Electrochromic Thin Films by Multimodal Spectroscopies

et al. 2020

Self Cite

View full text Add to dashboard Cite

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 -Li x V 2 O 5 -as a function of depth, using several highly sensitive and nondestructive spectroscopic methods with different depth sensitivities. We exploit (1) Li x V 2 O 5 electrochromic properties to utilize in operando optical response, (2) depthresolved cathodoluminescence spectroscopy (DRCLS), and (3) Raman spectroscopy to monitor the changes in Li x V 2 O 5 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 Li x V 2 O 5 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.

show abstract

Section: Resultssupporting

confidence: 87%

Section: Discussion: Topotactic Versus Conversion Reactions In LI X V2o5mentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 1 more Smart Citation

Elucidating Structural Transformations in Li_xV₂O₅ Electrochromic Thin Films by Multimodal Spectroscopies

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…[123,155,156] Li intecalation in V 2 O 5 has been extensively studied in the context of Li-battery cathodes but leads to somewhat larger distortions of the lattice than Na intercalation, related to formation of the γform [157] of V 2 O 5 . [52,158,159] Mg-intercalated V 2 O 5 in the β-form [160] has also recently been considered as a battery material.…”

Section: P-type Transport and Low Dimensional Scattering Inmentioning

confidence: 99%

Ultrathin 2D-oxides: A perspective on fabrication, structure, defect, transport, electron, and phonon properties

Radha

Crowley

Holler

et al. 2021

Journal of Applied Physics

View full text Add to dashboard Cite

for electronic devices. Oxides constitute a broad family of materials with a wide range of potential applications, from catalysis to electronic, photonic, ferroelectric, magnetic and multiferroic functionalities. Understanding structure-property relations in free-standing, supported, and confined two-dimensional ceramics or "ceramic flatlands" has been identified as one of the challenges for future work in ceramics by a recent National Science Foundation workshop. [9] Nonetheless, over the last decade, there have been many reviews on 2D oxides either as the main focus or as a part of a more general nano-materials focused review papers or books. One of the earlier reviews of nanosheets of oxides and hydroxides focused on synthesis, properties -especially photon-induced behavior -and their assembly, was published in 2010 by Ma et al. [11], followed by a second review [12] as a part of a special issue on "2D Nanomaterials beyond Graphene" in 2015. Around the same time (2011) another review by Mas-Balleste et al.[13] also emphasized the importance and variety of 2D oxides. A more recent focused review on 2D oxides can be found in 2019 paper of Hinterding et al.

show abstract

“…15 shows the recombined transition (depth-resolved cathodoluminescence (DRCL) spectroscopy) spectra of Li x V 2 O 5 . 221 The DRCL spectra of a-V 2 O 5 with an electron beam energy (E B = 0.5 kV) showed peaks at 1.8-2, 3.2, 3.6-3.7, and 4.0 eV, with a wide feature of approximately 2 eV and 3.6 eV as E B increased (Fig. 15A).…”

Section: Electrochromic Process Inmentioning

confidence: 97%

Recent advances in vanadium pentoxide (V₂O₅) towards related applications in chromogenics and beyond: fundamentals, progress, and perspectives

Pham

Dong

et al. 2022

J. Mater. Chem. C

View full text Add to dashboard Cite

show abstract

Nanoscale depth and lithiation dependence of V₂O₅ band structure by cathodoluminescence spectroscopy

Abstract: V2O5 electronic band structure from cathodoluminescence reveals how lithiation creates octahedral distortion and not oxygen vacancies or conversion reactions.

Cited by 10 publications

References 50 publications

Elucidating Structural Transformations in Li_xV₂O₅ Electrochromic Thin Films by Multimodal Spectroscopies

Elucidating Structural Transformations in Li_xV₂O₅ Electrochromic Thin Films by Multimodal Spectroscopies

Ultrathin 2D-oxides: A perspective on fabrication, structure, defect, transport, electron, and phonon properties

Recent advances in vanadium pentoxide (V₂O₅) towards related applications in chromogenics and beyond: fundamentals, progress, and perspectives

Contact Info

Product

Resources

About

Nanoscale depth and lithiation dependence of V2O5 band structure by cathodoluminescence spectroscopy

Abstract: V2O5 electronic band structure from cathodoluminescence reveals how lithiation creates octahedral distortion and not oxygen vacancies or conversion reactions.

Cited by 10 publications

References 50 publications

Elucidating Structural Transformations in LixV2O5 Electrochromic Thin Films by Multimodal Spectroscopies

Elucidating Structural Transformations in LixV2O5 Electrochromic Thin Films by Multimodal Spectroscopies

Ultrathin 2D-oxides: A perspective on fabrication, structure, defect, transport, electron, and phonon properties

Recent advances in vanadium pentoxide (V2O5) towards related applications in chromogenics and beyond: fundamentals, progress, and perspectives

Contact Info

Product

Resources

About

Nanoscale depth and lithiation dependence of V₂O₅ band structure by cathodoluminescence spectroscopy

Elucidating Structural Transformations in Li_xV₂O₅ Electrochromic Thin Films by Multimodal Spectroscopies

Elucidating Structural Transformations in Li_xV₂O₅ Electrochromic Thin Films by Multimodal Spectroscopies

Recent advances in vanadium pentoxide (V₂O₅) towards related applications in chromogenics and beyond: fundamentals, progress, and perspectives