Single crystal growth and characterization of nearly stoichiometric LiVO2

Wang, Tian; Chisholm, M. F.; Khalifah, Peter G.; Jin, Rongying; Sales, B. C.; Nagler, S. E.; Mandrus, David

doi:10.1016/j.materresbull.2004.03.024

Cited by 49 publications

(39 citation statements)

References 13 publications

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“…The calculated spin moments are strongly reduced from the value of 2 µ B expected for the S = 1 spins due to localized V 3+ (d 2 ) electrons. This reduction of moments is at odds with the results of magnetic susceptibility measurements that show the effective moment to have a value µ eff ≈ 3.3 µ B , 12,22 which is close to the value of µ eff = 2.8 µ B due to a localized S = 1 moment. This disagreement suggests that the itinerant picture of magnetism given by DFT may not be adequate to describe the high-temperature phase of LiVO 2 .…”

Section: A High-temperature Phasecontrasting

confidence: 61%

“…21 Tian et al were able to grow single crystals of LiVO 2 in 2004. 22 Their structural, magnetic, and transport studies confirm the first-order paramagnetic-to-nonmagnetic transition in this material. Resistivity measurements show that both phases exhibit activated behavior with small gaps of 0.14 and 0.18 eV in the low-and hightemperature phases, respectively.…”

Section: Introductionmentioning

confidence: 59%

“…8, displays a band gap of 0.78 eV, which is larger than the experimental value of 0.14 eV obtained from transport measurements. 22 I did not find any magnetic instabilities in this phase. The calculated total energy of this phase is 244 and 138 meV per formula unit lower than the non-spin-polarized and the 120 • ordered high-temperature rhombohedral phases, respectively.…”

Section: B Low-temperature Phasementioning

confidence: 68%

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Mott-to-Goodenough insulator-insulator transition inLiVO2

Subedi

2017

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Section: A High-temperature Phasecontrasting

confidence: 61%

Section: Introductionmentioning

confidence: 59%

Section: B Low-temperature Phasementioning

confidence: 68%

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Mott-to-Goodenough insulator-insulator transition inLiVO2

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2017

Phys. Rev. B

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“…Among ABX 2 , LiVO 2 has been extensively investigated as a candidate of VBS. [10][11][12][13][14] The crystal structure is comprised of the triangular lattice of V 3+ (3d 2 ) ions in a rhombohedral R3c structure [ Fig. 1(a)].…”

mentioning

confidence: 99%

“…[11][12][13][14] We define δν as an average of the splitting frequency independently fitted to the sinusoidal function and plot as a function of the rotation angle in Fig. 3.…”

mentioning

confidence: 99%

Orbital reformation with vanadium trimerization ind2triangular lattice LiVO2revealed by51V NMR

et al. 2013

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LiVO 2 is a model system of the valence bond solid (VBS) in 3d 2 triangular lattice. The origin of the VBS formation has remained controversial. We investigate the microscopic mechanism by elucidating the d orbital character via on-site 51 V NMR measurements in a single crystal up to 550 K across a structural transition temperature T c . The Knight shift, K, and nuclear quadrupole frequency, δν, show that the 3d orbital with local trigonal symmetry are reconstructed into a d yz d zx orbital order below T c . Together with the NMR spectra with three-fold rotational symmetry, we confirm a vanadium trimerization with d-d σ bonds. The Knight shift extracts the large Van-Vleck orbital susceptibility, χ VV = 3.6 × 10 −4 , in a paramagnetic state above T c , which is comparable to the spin susceptibility. The results suggest that orbitally induced Peierls transition in the proximity of the frustrated itinerant state is the dominant driving force of the trimerization transition. PACS numbers: 71.30.+h, 75.40.Gb Valence bond ordering in two-and three-dimensional systems is a manifestation of geometrical frustration.1 Across Mott transition, a valence bond solid (VBS) phase resides nearby unconventional metal 2,3 and superconducting phases 3 in triangular lattice systems. The VBS transition can accompany by d orbital orders with versatile textures, depending on lattice geometry and band filling. 4-9 However, d orbital orders governed by frustrated intersite interactions are not apparent from lattice distortions and need to be detected by microscopic probes. Here we show a tool for detailed characterization of d 2 orbital ordering in a model material LiVO 2 with the triangular lattice.ABX 2 (A:alkali metal; B: transition metal; X: chalcogen ion) with an ordered lock-type structure is a prototype of triangular-lattice antiferromagnet. 9 For Ti 3+ and V 3+ , t 2g orbital degrees of freedom play crucial roles in determining magnetic ground states. Among ABX 2 , LiVO 2 has been extensively investigated as a candidate of VBS.10-14 The crystal structure is comprised of the triangular lattice of V 3+ (3d 2 ) ions in a rhombohedral R3c structure [ Fig. 1(a)]. A trigonal elongation of VO 6 along the c axis splits the t 2g sublevel into a lower a 1g singlet and an upper e15 Calculated orbital occupations are almost equivalent in the a 1g and e ′ g orbitals due to the small trigonal field of 25 meV compared to the bandwidth.15 Below a first-order structural transition temperature T c ∼ 450-500 K, a superlattice Fig. 1(a)] appears in x-ray and electron diffraction measurements.11-14 Recent pair distribution function analyses of synchrotron data propose lowersymmetry lattice distortions depending on the layers. 16 Although the way of displacements of vanadium ions is compatible to trimerization, 12,13,16 the orbital character has not been accessible by the diffraction measurements due to Li deficiency and crystal twinning. Thus, the origin of the spin-singlet state in LiVO 2 remains controversial and to be elucidated via direct obse...

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Electrochemical Performance of B‐Type Vanadium Dioxide as a Sodium‐Ion Battery Cathode: A Combined Experimental and Theoretical Study

et al. 2020

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B‐type vanadium dioxide is a frequently investigated lithium‐ion battery material because of its appreciable gravimetric capacity, energy density, rate capability and cycling stability, but investigations of its performance with sodium working metal are scarce. We present a combined experimental‐theoretical study exploring the underlying mechanism of the electrochemical sodiation of B‐type vanadium dioxide. We find agreement between theoretical and experimental results, which complement each other and map out a detailed mechanistic picture. We are able to identify the sluggish diffusion of sodium ions in the vanadium dioxide host material, especially at low concentrations, as a key obstacle to the utilization of the pristine material as a high‐performance cathode for sodium‐ion batteries. Our findings provide context for previously reported results and can be used for a more targeted vanadium dioxide electrode design in the future.

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Single crystal growth and characterization of nearly stoichiometric LiVO2

Cited by 49 publications

References 13 publications

Mott-to-Goodenough insulator-insulator transition inLiVO2

Mott-to-Goodenough insulator-insulator transition inLiVO2

Orbital reformation with vanadium trimerization ind2triangular lattice LiVO2revealed by51V NMR

Electrochemical Performance of B‐Type Vanadium Dioxide as a Sodium‐Ion Battery Cathode: A Combined Experimental and Theoretical Study

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