The synthesis,structure, and electrochemical properties of Li<Subscript>2</Subscript>FeSiO<Subscript>4</Subscript>-based lithium-accumulating electrode material

Different approaches to synthesis of Li₂FeSiO₄-based electrode materials for lithium intercalation, using low-cost and abundant Li-, Si-, and Fe-containing parent substances, are discussed. XRD, SEM, and a laser-diffraction analyzer of particle size were used for structure and morphology characterization of the composite electrode materials. Li₂FeSiO₄ was shown to be the main lithium-accumulating crystalline phase; minor LiFeO₂ and Li₂SiO₃ admixtures are also present. The material microparticles’ average size was shown to vary from tenths of micrometer to 1 μm. Larger objects sized ca. 2–4 μm are the microparticles’ agglomerates. The material electrochemical properties were studied by dc chronopotentiometry (galvanostatic charging–discharging) and cyclic voltammetry with potential linear sweeping. The initial reversible cycled capacity of the best samples is 170 mA h/g. The anodic and cathodic processes manifest obvious hysteresis caused by the presence of several different lithium ion energy states in the material; the transition between the states is kinetically hindered. The dependences of the specific capacity and its stability under cycling on the current load and the conductive carbon component content in the composite were elucidated.     

Sodium-Vanadium Bronze Na9V14O35: An Electrode Material for Na-Ion Batteries

Na₉V₁₄O₃₅ (η-Na_xV₂O₅) has been synthesized via solid-state reaction in an evacuated sealed silica ampoule and tested as electroactive material for Na-ion batteries. According to powder X-ray diffraction, electron diffraction and atomic resolution scanning transmission electron microscopy, Na₉V₁₄O₃₅ adopts a monoclinic structure consisting of layers of corner- and edge-sharing VO₅ tetragonal pyramids and VO₄ tetrahedra with Na cations positioned between the layers, and can be considered as sodium vanadium(IV,V) oxovanadate Na₉V₁₀^4.1+O₁₉(V⁵⁺O₄)₄. Behavior of Na₉V₁₄O₃₅ as a positive and negative electrode in Na half-cells was investigated by galvanostatic cycling against metallic Na, synchrotron powder X-ray diffraction and electron energy loss spectroscopy. Being charged to 4.6 V vs. Na⁺/Na, almost 3 Na can be extracted per Na₉V₁₄O₃₅ formula, resulting in electrochemical capacity of ~60 mAh g⁻¹. Upon discharge below 1 V, Na₉V₁₄O₃₅ uptakes sodium up to Na:V = 1:1 ratio that is accompanied by drastic elongation of the separation between the layers of the VO₄ tetrahedra and VO₅ tetragonal pyramids and volume increase of about 31%. Below 0.25 V, the ordered layered Na₉V₁₄O₃₅ structure transforms into a rock-salt type disordered structure and ultimately into amorphous products of a conversion reaction at 0.1 V. The discharge capacity of 490 mAh g⁻¹ delivered at first cycle due to the conversion reaction fades with the number of charge-discharge cycles.     

Nonexponential Photoluminescence Dynamics in an Inhomogeneous Ensemble of Excitons in WSe2 Monolayers

The spectral and spatiotemporal dynamics of photoluminescence in monolayers of transition metal dichalcogenide WSe₂ obtained by mechanical exfoliation on a Si/SiO₂ substrate is studied over a wide range of temperatures and excitation powers. It is shown that the dynamics is nonexponential and, for times t exceeding ∼50 ps after the excitation pulse, is described by a dependence of the form 1/(t + t₀). Photoluminescence decay is accelerated with a decrease in the temperature and in the energy of emitting states. It is shown that the observed dynamics cannot be described by a bimolecular recombination process, such as exciton—exciton annihilation. A model that describes the nonexponential photoluminescence dynamics by taking into account the spread of radiative recombination times of localized exciton states in a random potential gives good agreement with experimental data.

     

Effect of a Low-Temperature Si Underlayer on the Photoluminescence of Misfit Dislocations in Si(001)Si<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Heterostructures with Ge-Rich Alloy Layers

The effect a low-temperature Si underlayer has on the photoluminescence of misfit dislocations in Si(001)Si_{1 – x}Ge _x heterostructures with high Ge contents in a SiGe alloy layer is investigated. It is found that the introduction of this layer prevents the formation of dislocations in the alloy layer.