Energy storage mechanisms in vacancy-ordered Wadsley–Roth layered niobates

McColl, Kit; Griffith, Kent J.; Dally, Rebecca; Li, Runze; Douglas, Jason E.; Poeppelmeier, Kenneth R.; Corà, Furio; Levin, Igor; Butala, Megan M.

doi:10.1039/d1ta02992d

Cited by 14 publications

(20 citation statements)

References 64 publications

(101 reference statements)

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“…In the past reports, low-dimensional KNb 3 O 8 materials synthesized via sol-gel or hydrothermal methods were widely applied in photocatalysis and lithium ion battery. [39][40][41][42][43] However, the disordered morphology of thick KNb 3 O 8 nanoflakes synthesized by the above methods cannot be used in micro-nano devices due to incompatibility with semiconductor processing technology. The low crystallinity, numerous oxygen defects, and unavoidable surface contamination of the liquidphase synthesized KNb 3 O 8 nanoflakes also hinder its development in optoelectronic devices.…”

Section: Introductionmentioning

confidence: 99%

Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb₃O₈ Nanobelt with Fringe‐Like Atomic Lattice

Yue

Long

Liu

et al. 2022

Adv Funct Materials

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Low-dimensional ultrawide bandgap semiconductors demonstrate great potential in fabricating solar-blind ultraviolet photodetectors. However, the widespread use of detectors is still limited by the low responsivity, large noise, and dark current, and especially few detectors can fulfill the solarblind ultraviolet detection and the polarization dependence simultaneously. Herein, a polarization sensitive solar-blind ultraviolet photodetector based on ultrathin KNb 3 O 8 nanobelts synthesized via chemical vapor deposition growth, is reported. By selecting suitable substrate and tuning the growth temperature, the nonlayered KNb 3 O 8 crystal is grown into the quasi-1D ultrathin nanobelt with thickness in the range of 4.8-120 nm. Density functional theory calculations and experimental results indicate that the ultrathin KNb 3 O 8 nanobelt possesses an ultrawide bandgap (4.15 eV) as well as unusual in-plane structural anisotropy. Benefiting from the above features, the ultrathin KNb 3 O 8 nanobelt-based device exhibits superior photodetection performances with high responsivity (30 A W −1 ), high detectivity (5.95 × 10 11 Jones), and ultralow dark current (7.1 × 10 −15 A) in the solar-blind ultraviolet region (230-280 nm). In addition, the KNb 3 O 8 photodetector displays strong polarization sensitive photoresponse with a linear dichroic ratio of 1.62 at 254 nm. With these remarkable features, the ultrathin KNb 3 O 8 nanobelt provides great opportunities for designing the next-generation multifunctional solar-blind ultraviolet optoelectronic devices.

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Section: Introductionmentioning

confidence: 99%

Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb₃O₈ Nanobelt with Fringe‐Like Atomic Lattice

Yue

Long

Liu

et al. 2022

Adv Funct Materials

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“…Crystallographic shear phases, including the Wadsley–Roth structures − possess crystallographic shear and have emerged as a promising and broad class of materials that display exemplary performance as electrodes. These materials are diverse in elemental constitution and block size, and even large particles of these materials are capable of impressive rates. − Computational and experimental efforts have suggested that a combination of corner and edge-sharing polyhedra promote metallic conductivity and fast Li + diffusion, while suppressing large structural changes. − …”

Section: Introductionmentioning

confidence: 99%

Metal–Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo₃O₈

et al. 2022

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Electrode materials for Li + -ion batteries require optimization along several disparate axes related to cost, performance, and sustainability. One of the important performance axes is the ability to retain structural integrity though cycles of charge/discharge. Metal-metal bonding is a distinct feature of some refractory metal oxides that has been largely underutilized in electrochemical energy storage, but that could potentially impact structural integrity. Here LiScMo 3 O 8 , a compound containing triangular clusters of metal-metal bonded Mo atoms, is studied as a potential anode material in Li + -ion batteries. Electrons inserted though lithiation are localized across rigid Mo 3 triangles (rather than on individual metal ions), resulting in minimal structural change as suggested by operando diffraction. The unusual chemical bonding allows this compound to be cycled with Mo atoms below a formally +4 valence state, resulting in an acceptable voltage regime that is appropriate for an anode material.Several characterization methods including potentiometric entropy measurements indicate two-phase regions, which are attributed through extensive first-principles modeling to Li + ordering. This study of LiScMo 3 O 8 provides valuable insights for design principles for structural motifs that stably and reversibly permit Li + (de)insertion.

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“…Shear-phase oxides contain regions of edge-sharing and corner-sharing transition metal octahedra, which promote electronic and ionic conductivity, respectively, and have emerged as promising high-rate Li + -ion battery electrode materials. − Nearly all of these oxides are Nb-based, and since Nb 5+ , Nb 4+ , and Nb 3+ are all accessible oxidation states, they are capable of multielectron redox and therefore high capacities. The voltage associated with these couples (on average 1.5 V vs Li/Li + ) is suitably in the regime expected for anodes.…”

Section: Introductionmentioning

confidence: 99%

High-Rate Lithium Cycling and Structure Evolution in Mo₄O₁₁

et al. 2022

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Shear-phase early transition metal oxides, mostly of Nb, and comprising edge-and corner-shared metal−oxygen octahedra have seen a resurgence in recent years as fast-charging, low-voltage electrodes for Li + -ion batteries. Mo oxides, broadly, have been less well studied as fast-charging electrodes.Here we examine a reduced Mo oxide, Mo 4 O 11 , that has a structure comprising only corner-connected MoO 4 tetrahedra and MoO 6 octahedra. We show that an electrode formed using micrometer-sized particles of Mo 4 O 11 as the active material can function as a high-rate Li + -ion electrode against Li metal, with a stable capacity of over 200 mAh g −1 at the high rate of 5C. Operando X-ray diffraction (XRD), entropic potential measurements, and ex situ Raman spectroscopy are employed to understand the nature of the charge storage. The crystal structure dramatically changes upon the first lithiation, and subsequent cycling is completely reversible with low capacity fade. It is the newly formed and potentially more layered structure that demonstrates high-rate cycling and small voltage polarization. A space group and unit cell for the new structure is proposed. This finding expands the scope of candidate highrate electrode materials to those beyond the expected Nb-containing shear-phase oxide materials.

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Energy storage mechanisms in vacancy-ordered Wadsley–Roth layered niobates

Abstract: Layered niobates with vacancy-ordered Wadsley–Roth structures were investigated as Li-ion battery anodes. Using operando and ex situ methods and DFT, we identify an intercalation mechanism dominated by Li-diffusion kinetics and layer evolution.

Cited by 14 publications

References 64 publications

Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb₃O₈ Nanobelt with Fringe‐Like Atomic Lattice

Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb₃O₈ Nanobelt with Fringe‐Like Atomic Lattice

Metal–Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo₃O₈

High-Rate Lithium Cycling and Structure Evolution in Mo₄O₁₁

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Energy storage mechanisms in vacancy-ordered Wadsley–Roth layered niobates

Abstract: Layered niobates with vacancy-ordered Wadsley–Roth structures were investigated as Li-ion battery anodes. Using operando and ex situ methods and DFT, we identify an intercalation mechanism dominated by Li-diffusion kinetics and layer evolution.

Cited by 14 publications

References 64 publications

Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb3O8 Nanobelt with Fringe‐Like Atomic Lattice

Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb3O8 Nanobelt with Fringe‐Like Atomic Lattice

Metal–Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo3O8

High-Rate Lithium Cycling and Structure Evolution in Mo4O11

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Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb₃O₈ Nanobelt with Fringe‐Like Atomic Lattice

Polarization Sensitive Solar‐Blind Ultraviolet Photodetectors Based on Ultrawide Bandgap KNb₃O₈ Nanobelt with Fringe‐Like Atomic Lattice

Metal–Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo₃O₈

High-Rate Lithium Cycling and Structure Evolution in Mo₄O₁₁